Sample records for surface catalytic efficiency
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NASA Technical Reports Server (NTRS)
Stewart, David A.
1996-01-01
The catalytic efficiency (atom recombination coefficients) for advanced ceramic thermal protection systems was calculated using arc-jet data. Coefficients for both oxygen and nitrogen atom recombination on the surfaces of these systems were obtained to temperatures of 1650 K. Optical and chemical stability of the candidate systems to the high energy hypersonic flow was also demonstrated during these tests.
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Xiao, Junwu; Kuang, Qin; Yang, Shihe; Xiao, Fei; Wang, Shuai; Guo, Lin
2013-01-01
Catalytic activity is primarily a surface phenomenon, however, little is known about Co3O4 nanocrystals in terms of the relationship between the oxygen reduction reaction (ORR) catalytic activity and surface structure, especially when dispersed on a highly conducting support to improve the electrical conductivity and so to enhance the catalytic activity. Herein, we report a controllable synthesis of Co3O4 nanorods (NR), nanocubes (NC) and nano-octahedrons (OC) with the different exposed nanocrystalline surfaces ({110}, {100}, and {111}), uniformly anchored on graphene sheets, which has allowed us to investigate the effects of the surface structure on the ORR activity. Results show that the catalytically active sites for ORR should be the surface Co2+ ions, whereas the surface Co3+ ions catalyze CO oxidation, and the catalytic ability is closely related to the density of the catalytically active sites. These results underscore the importance of morphological control in the design of highly efficient ORR catalysts. PMID:23892418
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Influence of surface phenomena in oxidative desulfurization with WOx/ZrO2 catalysts
NASA Astrophysics Data System (ADS)
Torres-García, E.; Canizal, G.; Velumani, S.; Ramírez-Verduzco, L. F.; Murrieta-Guevara, F.; Ascencio, J. A.
2004-12-01
Oil refinery related catalysis, particularly hydro desulfurization is viewed as a mature technology, but still we view that more efforts have to be made to boost the efficiency of the existing catalysts. So in this article we report the use of WOx/ZrO2 catalysts for the oxidation of dibenzothiophene (DBT) as a more effective material in nanometer scales. The WOx/ZrO2 samples were prepared by solid impregnation of ZrO2-x(OH)2x with ammonium metatungstate solution maintaining the pH at 10. Detailed structural and surface morphological analyses were carried out using Raman spectroscopy and Atomic force microscopy. In order to understand the catalytic activity which is largely influenced by the surface morphology, an interpretation based on the experimental results is given. The results showed an important correlation between the catalytic efficiency with the morphology of the surface which is identified as arrays of planes with steps of around 10 nm with the structures showing faceting with a preferential angle of 90°. It was established that when the number of W atoms in the surface increase the catalytic efficiency also increases. Thus we conclude that the material efficiency as a catalyst is directly related with the surface structure.
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NASA Astrophysics Data System (ADS)
Gao, Wei; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan
2015-07-01
Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications.Controllable surface properties of nanocerias are desired for various catalytic processes. There is a lack of efficient approaches to adjust the surface properties of ceria to date. Herein, a redox chemical etching method was developed to controllably engineer the surface properties of ceria nanorods. Ascorbic acid and hydrogen peroxide were used to perform the redox chemical etching process, resulting in a rough surface and/or pores on the surface of ceria nanorods. Increasing the etching cycles induced a steady increase of the specific surface area, oxygen vacancies and surface Ce3+ fractions. As a result, the etched nanorods delivered enhanced catalytic activity for CO oxidation, compared to the non-etched ceria nanorods. Our method provides a novel and facile approach to continuously adjust the surface properties of ceria for practical applications. Electronic supplementary information (ESI) available: Diameter distributions of as-prepared and etched samples, optical images, specific catalytic data of CO oxidation and comparison of CO oxidation. See DOI: 10.1039/c5nr01846c
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Liu, Hu; Yu, Yongsheng; Yang, Weiwei; Lei, Wenjuan; Gao, Manyi; Guo, Shaojun
2017-07-13
Controlling the surface defects of nanocrystals is a new way of tuning/boosting their catalytic properties. Herein, we report networked PdAg nanowires (NWs) with high-density defects as catalytic hot spots for efficient catalytic dehydrogenation of formic acid (FA) and catalytic reduction of nitrates. The networked PdAg NWs exhibit composition-dependent catalytic activity for the dehydrogenation reaction of FA without any additive, with Pd 5 Ag 5 NWs exhibiting the highest activity. They also show good durability, reflected by the retention of their initial activity during the dehydrogenation reaction of FA even after five cycles. Their initial TOF is 419 h -1 at 60 °C in water solution, much higher than those of the most Pd-based catalysts with a support. Moreover, they can efficiently reduce nitrates to alleviate nitrate pollution in water (conversion yield >99%). This strategy opens up a new green synthetic technique to design support-free heterogeneous catalysts with high-density defects as catalytic hot spots for efficient dehydrogenation catalysis of FA to meet the requirement of fuel cell applications and catalytic reduction of nitrates in water polluted with nitrates.
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Zhu, Xinbo; Tu, Xin; Mei, Danhua; Zheng, Chenghang; Zhou, Jinsong; Gao, Xiang; Luo, Zhongyang; Ni, Mingjiang; Cen, Kefa
2016-07-01
In this work, plasma-catalytic removal of low concentrations of acetone over CuO/γ-Al2O3 catalysts was carried out in a cylindrical dielectric barrier discharge (DBD) reactor. The combination of plasma and the CuO/γ-Al2O3 catalysts significantly enhanced the removal efficiency of acetone compared to the plasma process using the pure γ-Al2O3 support, with the 5.0 wt% CuO/γ-Al2O3 catalyst exhibiting the best acetone removal efficiency of 67.9%. Catalyst characterization was carried out to understand the effect the catalyst properties had on the activity of the CuO/γ-Al2O3 catalysts in the plasma-catalytic reaction. The results indicated that the formation of surface oxygen species on the surface of the catalysts was crucial for the oxidation of acetone in the plasma-catalytic reaction. The effects that various operating parameters (discharge power, flow rate and initial concentration of acetone) and the interactions between these parameters had on the performance of the plasma-catalytic removal of acetone over the 5.0 wt% CuO/γ-Al2O3 catalyst were investigated using central composite design (CCD). The significance of the independent variables and their interactions were evaluated by means of the Analysis of Variance (ANOVA). The results showed that the gas flow rate was the most significant factor affecting the removal efficiency of acetone, whilst the initial concentration of acetone played the most important role in determining the energy efficiency of the plasma-catalytic process. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Predicting Catalytic Activity of Nanoparticles by a DFT-Aided Machine-Learning Algorithm.
Jinnouchi, Ryosuke; Asahi, Ryoji
2017-09-07
Catalytic activities are often dominated by a few specific surface sites, and designing active sites is the key to realize high-performance heterogeneous catalysts. The great triumphs of modern surface science lead to reproduce catalytic reaction rates by modeling the arrangement of surface atoms with well-defined single-crystal surfaces. However, this method has limitations in the case for highly inhomogeneous atomic configurations such as on alloy nanoparticles with atomic-scale defects, where the arrangement cannot be decomposed into single crystals. Here, we propose a universal machine-learning scheme using a local similarity kernel, which allows interrogation of catalytic activities based on local atomic configurations. We then apply it to direct NO decomposition on RhAu alloy nanoparticles. The proposed method can efficiently predict energetics of catalytic reactions on nanoparticles using DFT data on single crystals, and its combination with kinetic analysis can provide detailed information on structures of active sites and size- and composition-dependent catalytic activities.
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Regulating the surface of nanoceria and its applications in heterogeneous catalysis
NASA Astrophysics Data System (ADS)
Ma, Yuanyuan; Gao, Wei; Zhang, Zhiyun; Zhang, Sai; Tian, Zhimin; Liu, Yuxuan; Ho, Johnny C.; Qu, Yongquan
2018-03-01
Ceria (CeO2) as a support, additive, and active component for heterogeneous catalysis has been demonstrated to have great catalytic performance, which includes excellent thermal structural stability, catalytic efficiency, and chemoselectivity. Understanding the surface properties of CeO2 and the chemical reactions occurred on the corresponding interfaces is of great importance in the rational design of heterogeneous catalysts for various reactions. In general, the reversible Ce3+/Ce4+ redox pair and the surface acid-base properties contribute to the superior intrinsic catalytic capability of CeO2, and hence yield enhanced catalytic phenomenon in many reactions. Particularly, nanostructured CeO2 is characterized by a large number of surface-bound defects, which are primarily oxygen vacancies, as the surface active catalytic sites. Many efforts have therefore been made to control the surface defects and properties of CeO2 by various synthetic strategies and post-treatments. The present review provides a comprehensive overview of recent progress in regulating the surface structure and composition of CeO2 and its applications in catalysis.
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NASA Astrophysics Data System (ADS)
Li, Jingying; Tang, Xiaolong; Yi, Honghong; Yu, Qingjun; Gao, Fengyu; Zhang, Runcao; Li, Chenlu; Chu, Chao
2017-08-01
Different copper-precursors were used to prepare Cu/graphene catalysts by an impregnation method. XRD, Raman spectra, TEM, BET, XPS, H2-TPR, NH3-TPD, DRIFTS and catalytic activity test were used to characterize and study the effect of precursors on the catalytic activity of Cu/graphene catalysts for NH3-SCO reaction. The large specific surface area of Cu/graphene catalysts and high dispersion of the metal particles on the graphene caused the well catalytic activity of NH3-SCO reaction. Compared to Cu/GE(AC), Cu/GE(N) showed better catalytic performance, and the complete NH3 removal efficiency was obtained at 250 °C with N2 selectivity of 85%. The copper-precursors had influence on the distribution of surface Cu species and further affected the catalytic activity of Cu/GE catalysts. The more amount of surface Cu species and highly dispersed CuO particles on the graphene surface formed by using copper nitrate as precursor could significantly improve the reducibility of catalysts and enhance NH3 adsorption, thereby improving the catalytic activity of Cu/graphene catalyst.
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Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi; ...
2017-01-06
Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less
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Silver nanocluster catalytic microreactors for water purification
NASA Astrophysics Data System (ADS)
Da Silva, B.; Habibi, M.; Ognier, S.; Schelcher, G.; Mostafavi-Amjad, J.; Khalesifard, H. R. M.; Tatoulian, M.; Bonn, D.
2016-07-01
A new method for the elaboration of a novel type of catalytic microsystem with a high specific area catalyst is developed. A silver nanocluster catalytic microreactor was elaborated by doping a soda-lime glass with a silver salt. By applying a high power laser beam to the glass, silver nanoclusters are obtained at one of the surfaces which were characterized by BET measurements and AFM. A microfluidic chip was obtained by sealing the silver coated glass with a NOA 81 microchannel. The catalytic activity of the silver nanoclusters was then tested for the efficiency of water purification by using catalytic ozonation to oxidize an organic pollutant. The silver nanoclusters were found to be very stable in the microreactor and efficiently oxidized the pollutant, in spite of the very short residence times in the microchannel. This opens the way to study catalytic reactions in microchannels without the need of introducing the catalyst as a powder or manufacturing complex packed bed microreactors.
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Bai, Zhiyong; Wang, Jianlong; Yang, Qi
2018-04-01
Sulfonamide antibiotics are ubiquitous pollutants in aquatic environments due to their large production and extensive application. In this paper, the iron doped fibrous-structured silica (KCC-1) nanospheres (Fe-KCC-1) was prepared, characterized, and applied as a catalyst for catalytic ozonation of sulfamethazine (SMT). The effects of ozone dosage, catalyst dosage, and initial concentration of SMT were examined. The experimental results showed that Fe-KCC-1 had large surface area (464.56 m2 g -1 ) and iron particles were well dispersed on the catalyst. The catalyst had high catalytic performance especially for the mineralization of SMT, with mineralization ratio of about 40% in a wide pH range. With addition of Fe-KCC-1, the ozone utilization increased nearly two times than single ozonation. The enhancement of SMT degradation was mainly due to the surface reaction, and the increased mineralization of SMT was due to radical mechanism. Fe-KCC-1 was an efficient catalyst for SMT degradation in catalytic ozonation system.
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Zhang, Sai; Huang, Zheng-Qing; Ma, Yuanyuan; Gao, Wei; Li, Jing; Cao, Fangxian; Li, Lin; Chang, Chun-Ran; Qu, Yongquan
2017-01-01
Identification on catalytic sites of heterogeneous catalysts at atomic level is important to understand catalytic mechanism. Surface engineering on defects of metal oxides can construct new active sites and regulate catalytic activity and selectivity. Here we outline the strategy by controlling surface defects of nanoceria to create the solid frustrated Lewis pair (FLP) metal oxide for efficient hydrogenation of alkenes and alkynes. Porous nanorods of ceria (PN-CeO2) with a high concentration of surface defects construct new Lewis acidic sites by two adjacent surface Ce3+. The neighbouring surface lattice oxygen as Lewis base and constructed Lewis acid create solid FLP site due to the rigid lattice of ceria, which can easily dissociate H–H bond with low activation energy of 0.17 eV. PMID:28516952
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Catalytic biofilms on structured packing for the production of glycolic acid.
Li, Xuan Zhong; Hauer, Bernhard; Rosche, Bettina
2013-02-01
While structured packing modules are known to be efficient for surface wetting and gas-liquid exchange in abiotic surface catalysis, this model study explores structured packing as a growth surface for catalytic biofilms. Microbial biofilms have been proposed as self-immobilized and self-regenerating catalysts for the production of chemicals. A concern is that the complex and dynamic nature of biofilms may cause fluctuations in their catalytic performance over time or may affect process reproducibility. An aerated continuous trickle-bed biofilm reactor system was designed with a 3 L structured packing, liquid recycling and pH control. Pseudomonas diminuta established a biofilm on the stainless steel structured packing with a specific surface area of 500 m2 m-3 and catalyzed the oxidation of ethylene glycol to glycolic acid for over two months of continuous operation. A steady-state productivity of up to 1.6 gl-1h-1 was achieved at a dilution rate of 0.33 h-1. Process reproducibility between three independent runs was excellent, despite process interruptions and activity variations in cultures grown from biofilm effluent cells. The results demonstrate the robustness of a catalytic biofilm on structured packing, despite its dynamic nature. Implementation is recommended for whole-cell processes that require efficient gas-liquid exchange, catalyst retention for continuous operation, or improved catalyst stability.
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Surface-immobilized DNAzyme-type biocatalysis
NASA Astrophysics Data System (ADS)
Stefan, Loic; Lavergne, Thomas; Spinelli, Nicolas; Defrancq, Eric; Monchaud, David
2014-02-01
The structure of the double helix of deoxyribonucleic acid (DNA, also called duplex-DNA) was elucidated sixty years ago by Watson, Crick, Wilkins and Franklin. Since then, DNA has continued to hold a fascination for researchers in diverse fields including medicine and nanobiotechnology. Nature has indeed excelled in diversifying the use of DNA: beyond its canonical role of repository of genetic information, DNA could also act as a nanofactory able to perform some complex catalytic tasks in an enzyme-mimicking manner. The catalytic capability of DNA was termed DNAzyme; in this context, a peculiar DNA structure, a quadruple helix also named quadruplex-DNA, has recently garnered considerable interest since its autonomous catalytic proficiency relies on its higher-order folding that makes it suitable to interact efficiently with hemin, a natural cofactor of many enzymes. Quadruplexes have thus been widely studied for their hemoprotein-like properties, chiefly peroxidase-like activity, i.e., their ability to perform hemin-mediated catalytic oxidation reactions. Recent literature is replete with applications of quadruplex-based peroxidase-mimicking DNAzyme systems. Herein, we take a further leap along the road to biochemical applications, assessing the actual efficiency of catalytic quadruplexes for the detection of picomolar levels of surface-bound analytes in an enzyme-linked immunosorbent (ELISA)-type assay. To this end, we exploit an innovative strategy based on the functionalization of DNA by a multitasking platform named RAFT (for regioselectivity addressable functionalized template), whose versatility enables the grafting of DNA whatever its nature (duplex-DNA, quadruplex-DNA, etc.). We demonstrate that the resulting biotinylated RAFT/quadruplex systems indeed acquire catalytic properties that allow for efficient luminescent detection of picomoles of surface-bound streptavidin. We also highlight some of the pitfalls that have to be faced during optimization, notably demonstrating that highly optimized experimental conditions can make DNA pre-catalysts catalytically competent whatever their secondary structures.
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Itoh, Takafumi; Hibi, Takao; Suzuki, Fumiko; Sugimoto, Ikumi; Fujiwara, Akihiro; Inaka, Koji; Tanaka, Hiroaki; Ohta, Kazunori; Fujii, Yutaka; Taketo, Akira; Kimoto, Hisashi
2016-01-01
The Gram-positive bacterium Paenibacillus sp. str. FPU-7 effectively hydrolyzes chitin by using a number of chitinases. A unique chitinase with two catalytic domains, ChiW, is expressed on the cell surface of this bacterium and has high activity towards various chitins, even crystalline chitin. Here, the crystal structure of ChiW at 2.1 Å resolution is presented and describes how the enzyme degrades chitin on the bacterial cell surface. The crystal structure revealed a unique multi-modular architecture composed of six domains to function efficiently on the cell surface: a right-handed β-helix domain (carbohydrate-binding module family 54, CBM-54), a Gly-Ser-rich loop, 1st immunoglobulin-like (Ig-like) fold domain, 1st β/α-barrel catalytic domain (glycoside hydrolase family 18, GH-18), 2nd Ig-like fold domain and 2nd β/α-barrel catalytic domain (GH-18). The structure of the CBM-54, flexibly linked to the catalytic region of ChiW, is described here for the first time. It is similar to those of carbohydrate lyases but displayed no detectable carbohydrate degradation activities. The CBM-54 of ChiW bound to cell wall polysaccharides, such as chin, chitosan, β-1,3-glucan, xylan and cellulose. The structural and biochemical data obtained here also indicated that the enzyme has deep and short active site clefts with endo-acting character. The affinity of CBM-54 towards cell wall polysaccharides and the degradation pattern of the catalytic domains may help to efficiently decompose the cell wall chitin through the contact surface. Furthermore, we clarify that other Gram-positive bacteria possess similar cell-surface-expressed multi-modular enzymes for cell wall polysaccharide degradation. PMID:27907169
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Buonanno, Martina; Di Fiore, Anna; Langella, Emma; D'Ambrosio, Katia; Supuran, Claudiu T; Monti, Simona Maria; De Simone, Giuseppina
2018-05-24
Although important progress has been achieved in understanding the catalytic mechanism of Carbonic Anhydrases, a detailed picture of all factors influencing the catalytic efficiency of the various human isoforms is still missing. In this paper we report a detailed structural study and theoretical pKa calculations on a hCA VII variant. The obtained data were compared with those already known for another thoroughly investigated cytosolic isoform, hCA II. Our structural studies show that in hCA VII the network of ordered water molecules, which connects the zinc bound solvent molecule to the proton shuttle His64, is altered compared to hCA II, causing a reduction of the catalytic efficiency. Theoretical calculations suggest that changes in solvent network are related to the difference in pKa of the proton shuttle in the two enzymes. The residue that plays a major role in determining the diverse pKa values of the proton shuttle is the one in position four, namely His for hCA II and Gly for hCA VII. This residue is located on the protein surface, outside of the active site cavity. These findings are in agreement with our previous studies that highlighted the importance of histidines on the protein surface of hCA II (among which His4) as crucial residues for the high catalytic efficiency of this isoform.
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Analytic Corrections to CFD Heating Predictions Accounting for Changes in Surface Catalysis. Part II
NASA Technical Reports Server (NTRS)
Gnoffo, Peter A.; Inger, George R.
1996-01-01
A new approach for combining the insight afforded by integral boundary-layer analysis with comprehensive (but time intensive) computational fluid dynamic (CFD) flowfield solutions of the thin-layer Navier-Stokes equations is described. The approach extracts CFD derived quantities at the wall and at the boundary layer edge for inclusion in a post-processing boundary-layer analysis. It allows a designer at a work-station to address two questions, given a single CFD solution. (1) How much does the heating change for a thermal protection system (TPS) with different catalytic properties than was used in the original CFD solution? (2) How does the heating change at the interface of two different TPS materials with an abrupt change in catalytic efficiency? The answer to the second question is particularly important, because abrupt changes from low to high catalytic efficiency can lead to localized increase in heating which exceeds the usually conservative estimate provided by a fully catalytic wall assumption. Capabilities of this approach for application to Reusable Launch Vehicle (RLV) design are demonstrated. If the definition of surface catalysis is uncertain early in the design process, results show that fully catalytic wall boundary conditions provide the best baseline for CFD design points.
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NASA Astrophysics Data System (ADS)
Shen, Meng; Han, Ali; Wang, Xijun; Ro, Yun Goo; Kargar, Alireza; Lin, Yue; Guo, Hua; Du, Pingwu; Jiang, Jun; Zhang, Jingyu; Dayeh, Shadi A.; Xiang, Bin
2015-02-01
Catalysts play a significant role in clean renewable hydrogen fuel generation through water splitting reaction as the surface of most semiconductors proper for water splitting has poor performance for hydrogen gas evolution. The catalytic performance strongly depends on the atomic arrangement at the surface, which necessitates the correlation of the surface structure to the catalytic activity in well-controlled catalyst surfaces. Herein, we report a novel catalytic performance of simple-synthesized porous NiO nanowires (NWs) as catalyst/co-catalyst for the hydrogen evolution reaction (HER). The correlation of catalytic activity and atomic/surface structure is investigated by detailed high resolution transmission electron microscopy (HRTEM) exhibiting a strong dependence of NiO NW photo- and electrocatalytic HER performance on the density of exposed high-index-facet (HIF) atoms, which corroborates with theoretical calculations. Significantly, the optimized porous NiO NWs offer long-term electrocatalytic stability of over one day and 45 times higher photocatalytic hydrogen production compared to commercial NiO nanoparticles. Our results open new perspectives in the search for the development of structurally stable and chemically active semiconductor-based catalysts for cost-effective and efficient hydrogen fuel production at large scale.
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Shen, Huazhen; Ie, Iau-Ren; Yuan, Chung-Shin; Hung, Chung-Hsuang; Chen, Wei-Hsiang
2016-03-01
The catalytic removal of Hg(0) was investigated to ascertain whether the catalysts could simultaneously possess both thermo- and photo-catalytic reactivity. The immobilized V2O5/TiO2 and WO3/TiO2 catalysts were synthesized by sol-gel method and then coated on the surface of glass beads for catalytic removal of Hg(0). They were also characterized by SEM, BET, XRD, UV-visible, and XPS analysis, and their catalytic reactivity was tested under 100-160 °C under the near-UV irradiation. The results indicated that V2O5/TiO2 solely possessed the thermo-catalytic reactivity while WO3/TiO2 only had photo-catalytic reactivity. Although the synthesis catalytic reactivity has not been found for these catalysts up to date, but compared with TiO2, the removal efficiencies of Hg(0) at 140 and 160 °C were enhanced; particularly, the efficiency was improved from 20 % at 160 °C by TiO2 to nearly 90 % by WO3/TiO2 under the same operating conditions. The effects of doping amount of V2O5 and WO3 were also investigated, and the results showed that 10 % V2O5 and 5 % WO3/TiO2 were the best immobilized catalysts for thermo- and photo-catalytic reactivity, respectively. The effect of different influent concentrations of Hg(0) was demonstrated that the highest concentration of Hg(0) led to the best removal efficiencies for V2O5/TiO2 and WO3/TiO2 at 140 and 160 °C, because high Hg(0) concentration increased the mass transfer rate of Hg(0) toward the surface of catalysts and drove the reaction to proceed. At last, the effect of single gas component on the removal of Hg(0) was also investigated.
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Chou, Chih-Wei; Hsieh, Hui-Hsuan; Hseu, You-Cheng; Chen, Ko-Shao; Wang, Gou-Jen; Chang, Hsien-Chang; Pan, Yong-Li; Wei, Yi-Syuan; Chang, Ko Hsin; Harn, Yeu-Wei
2013-07-21
This study deals with the preparation of multi-shaped nanoscale gold crystals under synthetically simple, green, and efficient conditions using a seed-mediated growth approach in the presence of hyaluronic acid (HA). These highly biocompatible multi-shaped gold nanocrystals were examined to evaluate their catalytic and surface enhanced Raman scattering (SERS) properties. The results show that the size and shape of the nanocrystals are mainly correlated to the amount of seed, seed size, HA concentration, and reaction temperature. Gold seeds accelerate the reduction of the gold precursor to form gold nanocrystals using HA. The HA serves as a reducing agent and a growth template for the reduction of Au(III) and nanocrystal stabilization. The multi-shaped gold nanocrystals showed superior catalytic properties and higher SERS performance. The simple, green approach efficiently controls the nanocrystals and creates many opportunities for future applications.
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de Vasconcellos, Adriano; Miller, Alex Henrique; Aranda, Donato A G; Nery, José Geraldo
2018-05-01
Nanozeolites with different crystallographic structures (Nano/TS1, Nano/GIS, Nano/LTA, Nano/BEA, Nano/X, and Nano-X/Ni), functionalized with (3-aminopropyl)trimethoxysilane (APTMS) and crosslinked with glutaraldehyde (GA), were studied as solid supports for Thermomyces lanuginosus lipase (TLL) immobilization. Physicochemical characterizations of the surface-functionalized nanozeolites and nanozeolite-enzyme complexes were performed using XRD, SEM, AFM, ATR-FTIR, and zeta potential measurements. The experimental enzymatic activity results indicated that the nanozeolitic supports functionalized with APTMS and GA immobilized larger amounts of enzymes and provided higher enzymatic activities, compared to unfunctionalized supports. Correlations were observed among the nanozeolite surface charges, the enzyme immobilization efficiencies, and the biocatalyst activities. The catalytic performance and reusability of these enzyme-nanozeolite complexes were evaluated in the ethanolysis transesterification of microalgae oil to fatty acid ethyl esters (FAEEs). TLL immobilized on the nanozeolite supports functionalized with APTMS and GA provided the most efficient biocatalysis, with FAEEs yields above 93% and stability during five reaction cycles. Lower FAEEs yields and poorer catalytic stability were found for nanozeolite-enzyme complexes prepared only by physical adsorption. The findings indicated the viability of designing highly efficient biocatalysts for biofuel production by means of chemical modulation of nanozeolite surfaces. The high biocatalyst catalytic efficiency observed in ethanolysis reactions using a lipid feedstock that does not compete with food production is an advantage that should encourage the industrial application of these biocatalysts. Copyright © 2018 Elsevier B.V. All rights reserved.
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Synthesis of ternary oxide for efficient photo catalytic conversion of CO2
NASA Astrophysics Data System (ADS)
Wan, Lijuan
2018-01-01
Zn2GeO4 Nan rods were prepared by solution phase route. The morphology and structure of the as-prepared products were characterized by scanning electron microscopy (SEM) and Bruner-Emmett-Teller (BET) surface area measurements. The results revealed that Zn2GeO4 Nan rods with higher surface area have higher photo catalytic activity in photo reduction of CO2 than Zn2GeO4 prepared through solid-state reaction.
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Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia
2012-11-05
LaMnO(3), either pure or doped with 10 mol % Sr, has been prepared by flame pyrolysis in nanostructured form. Such catalysts have been tested for the catalytic flameless combustion of methane, achieving very high catalytic activity. The resistance toward poisoning by some model N-containing impurities has been checked in order to assess the possibility of operating the flameless catalytic combustion with biogas, possibly contaminated by S- or N-based compounds. This would be a significant improvement from the environmental point of view because the application of catalytic combustion to gas turbines would couple improved energy conversion efficiency and negligible noxious emissions, while the use of biogas would open the way to energy production from a renewable source by means of very efficient technologies. A different behavior has been observed for the two catalysts; namely, the undoped sample was more or less heavily poisoned, whereas the Sr-doped sample showed slightly increasing activity upon dosage of N-containing compounds. A possible reaction mechanism has been suggested, based on the initial oxidation of the organic backbone, with the formation of NO. The latter may adsorb more or less strongly depending on the availability of surface oxygen vacancies (i.e., depending on doping). Decomposition of NO may leave additional activated oxygen species on the surface, available for low-temperature methane oxidation and so improving the catalytic performance.
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Hexagonal tungsten oxide nanoflowers as enzymatic mimetics and electrocatalysts.
Park, Chan Yeong; Seo, Ji Min; Jo, Hongil; Park, Juhyun; Ok, Kang Min; Park, Tae Jung
2017-01-27
Tungsten oxide (WO x ) has been widely studied for versatile applications based on its photocatalytic, intrinsic catalytic, and electrocatalytic properties. Among the several nanostructures, we focused on the flower-like structures to increase the catalytic efficiency on the interface with both increased substrate interaction capacities due to their large surface area and efficient electron transportation. Therefore, improved WO x nanoflowers (WONFs) with large surface areas were developed through a simple hydrothermal method using sodium tungstate and hydrogen chloride solution at low temperature, without any additional surfactant, capping agent, or reducing agent. Structural determination and electrochemical analyses revealed that the WONFs have hexagonal Na 0.17 WO 3.085 ·0.17H 2 O structure and exhibit peroxidase-like activity, turning from colorless to blue by catalyzing the oxidation of a peroxidase substrate, such as 3,3',5,5'-tetramethylbenzidine, in the presence of H 2 O 2 . Additionally, a WONF-modified glassy carbon electrode was adopted to monitor the electrocatalytic reduction of H 2 O 2 . To verify the catalytic efficiency enhancement by the unique shape and structure of the WONFs, they were compared with calcinated WONFs, cesium WO x nanoparticles, and other peroxidase-like nanomaterials. The results indicated that the WONFs showed a low Michaelis-Menten constant (k m ), high maximal reaction velocity (v max ), and large surface area.
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Synthesis and catalytic performance of SiO2@Ni and hollow Ni microspheres
NASA Astrophysics Data System (ADS)
Liu, Xin; Liu, Yanhua; Shi, Xueting; Yu, Zhengyang; Feng, Libang
2016-11-01
Nickel (Ni) catalyst has been widely used in catalytic reducing reactions such as catalytic hydrogenation of organic compounds and catalytic reduction of organic dyes. However, the catalytic efficiency of pure Ni is low. In order to improve the catalytic performance, Ni nanoparticle-loaded microspheres can be developed. In this study, we have prepared Ni nanoparticle-loaded microspheres (SiO2@Ni) and hollow Ni microspheres using two-step method. SiO2@Ni microspheres with raspberry-like morphology and core-shell structure are synthesized successfully using SiO2 microsphere as a template and Ni2+ ions are adsorbed onto SiO2 surfaces via electrostatic interaction and then reduced and deposited on surfaces of SiO2 microspheres. Next, the SiO2 cores are removed by NaOH etching and the hollow Ni microspheres are prepared. The NaOH etching time does no have much influence on the crystal structure, shape, and surface morphology of SiO2@Ni; however, it can change the phase composition evidently. The hollow Ni microspheres are obtained when the NaOH etching time reaches 10 h and above. The as-synthesized SiO2@Ni microspheres exhibit much higher catalytic performance than the hollow Ni microspheres and pure Ni nanoparticles in the catalytic reduction of methylene blue. Meanwhile, the SiO2@Ni catalyst has high stability and hence it can be recycled for reuse.
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NASA Astrophysics Data System (ADS)
Knysh, Yu A.; Xanthopoulou, G. G.
2018-01-01
The object of the study is a catalytic combustion chamber that provides a highly efficient combustion process through the use of effects: heat recovery from combustion, microvortex heat transfer, catalytic reaction and acoustic resonance. High efficiency is provided by a complex of related technologies: technologies for combustion products heat transfer (recuperation) to initial mixture, catalytic processes technology, technology for calculating effective combustion processes based on microvortex matrices, technology for designing metamaterials structures and technology for obtaining the required topology product by laser fusion of metal powder compositions. The mesoscale level structure provides combustion process with the use of a microvortex effect with a high intensity of heat and mass transfer. High surface area (extremely high area-to-volume ratio) created due to nanoscale periodic structure and ensures catalytic reactions efficiency. Produced metamaterial is the first multiscale product of new concept which due to combination of different scale level periodic topologies provides qualitatively new set of product properties. This research is aimed at solving simultaneously two global problems of the present: ensure environmental safety of transport systems and power industry, as well as the economy and rational use of energy resources, providing humanity with energy now and in the foreseeable future.
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Liu, Mengran; Fan, Guoli; Yu, Jiaying; Yang, Lan; Li, Feng
2018-04-17
Tuning the surface properties of supported metal catalysts is of vital importance for governing their catalytic performances in nanocatalysis. Here, we report highly dispersed nanometric gold nanoparticles (NPs) supported on Ni-Ti layered double hydroxides (NiTi-LDHs), which were employed in solvent-free and base-free selective oxidation of benzyl alcohol. A series of characterization techniques demonstrated that defect-rich NiTi-LDHs could efficiently stabilize Au NPs and decrease surface electron density of Au NPs. The as-formed Au/NiTi-LDH catalyst with a Ni/Ti molar ratio of 3 : 1 and an Au loading of 0.71 wt% yielded the highest turnover frequency value of ∼4981 h-1 at 120 °C among tested Au/NiTi-LDH catalysts with different Ni/Ti molar ratios, along with a high benzaldehyde selectivity of 98%. High catalytic efficiency of the catalyst was mainly correlated with surface cooperation between unique defects (i.e. defective Ti3+ species and oxygen vacancies) and abundant hydroxyl groups on the brucite-like layers of the NiTi-LDH support, which could lead to the preferential adsorption and activation of an alcohol hydroxyl moiety in benzyl alcohol and oxygen molecule, as well as the formation of more electron-deficient Ni3+ and Au0 species on the catalyst surface. Furthermore, the present Au/NiTi-LDH catalyst tolerated the oxidation of a wide variety of substrate structures into the corresponding aldehydes, acids or ketones. Our primary results illustrate that defect-rich NiTi-LDHs are promising supports which can efficiently modify surface structure and electronic properties of supported metal catalysts and consequently improve their catalytic performances.
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Leandro, João; Stokka, Anne J; Teigen, Knut; Andersen, Ole A; Flatmark, Torgeir
2017-07-01
Mammalian phenylalanine hydroxylase (PAH) is a key enzyme in l-phenylalanine (l-Phe) metabolism and is active as a homotetramer. Biochemical and biophysical work has demonstrated that it cycles between two states with a variably low and a high activity, and that the substrate l-Phe is the key player in this transition. X-ray structures of the catalytic domain have shown mobility of a partially intrinsically disordered Tyr 138 -loop to the active site in the presence of l-Phe. The mechanism by which the loop dynamics are coupled to substrate binding at the active site in tetrameric PAH is not fully understood. We have here conducted functional studies of four Tyr 138 point mutants. A high linear correlation ( r 2 = 0.99) was observed between their effects on the catalytic efficiency of the catalytic domain dimers and the corresponding effect on the catalytic efficiency of substrate-activated full-length tetramers. In the tetramers, a correlation ( r 2 = 0.96) was also observed between the increase in catalytic efficiency (activation) and the global conformational change (surface plasmon resonance signal response) at the same l-Phe concentration. The new data support a similar functional importance of the Tyr 138 -loop in the catalytic domain and the full-length enzyme homotetramer.
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Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G
2017-07-03
Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.
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Zhang, Zhen; Sèbe, Gilles; Wang, Xiaosong; Tam, Kam C
2018-02-15
pH-responsive poly(4-vinylpyridine) (P4VP) grafted cellulose nanocrystals (P4VP-g-CNC) were prepared by Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) and subsequently used to stabilize gold nanoparticles (Au NPs) as efficient and recyclable nanocatalysts for the reduction of 4-nitrophenol (4NP). The presence of P4VP brushes on the CNC surface controlled the growth of Au NPs yielding smaller averaged diameter compared to Au NPs deposited directly on pristine CNC. The catalytic performances of pristine Au NPs, Au@CNC and Au@P4VP-g-CNC were compared by measuring the turnover frequency (TOF) for the catalytic reduction of 4NP. Compared to pristine Au NPs, the catalytic activity of Au@CNC and Au@P4VP-g-CNC were 10 and 24 times better. Moreover, the Au@P4VP-g-CNC material could be recovered via flocculation at pH>5, and the recycled nanocatalyst remained highly active. Copyright © 2017 Elsevier Ltd. All rights reserved.
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High aspect ratio catalytic reactor and catalyst inserts therefor
Lin, Jiefeng; Kelly, Sean M.
2018-04-10
The present invention relates to high efficient tubular catalytic steam reforming reactor configured from about 0.2 inch to about 2 inch inside diameter high temperature metal alloy tube or pipe and loaded with a plurality of rolled catalyst inserts comprising metallic monoliths. The catalyst insert substrate is formed from a single metal foil without a central supporting structure in the form of a spiral monolith. The single metal foil is treated to have 3-dimensional surface features that provide mechanical support and establish open gas channels between each of the rolled layers. This unique geometry accelerates gas mixing and heat transfer and provides a high catalytic active surface area. The small diameter, high aspect ratio tubular catalytic steam reforming reactors loaded with rolled catalyst inserts can be arranged in a multi-pass non-vertical parallel configuration thermally coupled with a heat source to carry out steam reforming of hydrocarbon-containing feeds. The rolled catalyst inserts are self-supported on the reactor wall and enable efficient heat transfer from the reactor wall to the reactor interior, and lower pressure drop than known particulate catalysts. The heat source can be oxygen transport membrane reactors.
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Bio-inspired nanocatalysts for the oxygen reduction reaction.
Grumelli, Doris; Wurster, Benjamin; Stepanow, Sebastian; Kern, Klaus
2013-01-01
Electrochemical conversions at fuel cell electrodes are complex processes. In particular, the oxygen reduction reaction has substantial overpotential limiting the electrical power output efficiency. Effective and inexpensive catalytic interfaces are therefore essential for increased performance. Taking inspiration from enzymes, earth-abundant metal centres embedded in organic environments present remarkable catalytic active sites. Here we show that these enzyme-inspired centres can be effectively mimicked in two-dimensional metal-organic coordination networks self-assembled on electrode surfaces. Networks consisting of trimesic acid and bis-pyridyl-bispyrimidine coordinating to single iron and manganese atoms on Au(111) effectively catalyse the oxygen reduction and reveal distinctive catalytic activity in alkaline media. These results demonstrate the potential of surface-engineered metal-organic networks for electrocatalytic conversions. Specifically designed coordination complexes at surfaces inspired by enzyme cofactors represent a new class of nanocatalysts with promising applications in electrocatalysis.
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Outstanding catalytic activity of ultra-pure platinum nanoparticles.
Januszewska, Aneta; Dercz, Grzegorz; Piwowar, Justyna; Jurczakowski, Rafal; Lewera, Adam
2013-12-09
Small (4 nm) nanoparticles with a narrow size distribution, exceptional surface purity, and increased surface order, which exhibits itself as an increased presence of basal crystallographic planes, can be obtained without the use of any surfactant. These nanoparticles can be used in many applications in an as-received state and are threefold more active towards a model catalytic reaction (oxidation of ethylene glycol). Furthermore, the superior properties of this material are interesting not only due to the increase in their intrinsic catalytic activity, but also due to the exceptional surface purity itself. The nanoparticles can be used directly (i.e., as-received, without any cleaning steps) in biomedical applications (i.e., as more efficient drug carriers due to an increased number of adsorption sites) and in energy-harvesting/data-storage devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Yang, Sena; Lee, Hangil
2017-11-01
The modified TiO2 nanoparticles (NPs) to enhance their catalytic activities by doping them with the five transition metals (Cr, Mn, Fe, Co, and Ni) have been investigated using various surface analysis techniques such as scanning electron microscopy (SEM), Raman spectroscopy, scanning transmission X-ray microscopy (STXM), and high-resolution photoemission spectroscopy (HRPES). To compare catalytic activities of these transition metal-doped TiO2 nanoparticles (TM-TiO2) with those of TiO2 NPs, we monitored their performances in the catalytic oxidation of 2-aminothiophenol (2-ATP) by using HRPES and on the oxidation of 2-ATP in aqueous solution by taking electrochemistry (EC) measurements. As a result, we clearly investigate that the increased defect structures induced by the doped transition metal are closely correlated with the enhancement of catalytic activities of TiO2 NPs and confirm that Fe- and Co-doped TiO2 NPs can act as efficient catalysts.
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NASA Astrophysics Data System (ADS)
Song, Shaoqing; Wu, Xi; Lu, Changhai; Wen, Meicheng; Le, Zhanggao; Jiang, Shujuan
2018-06-01
Solid strong base nano-catalytic system of K-modification NaY zeolite supported 0.08% Pt (K-Pt/NaY) were constructed for eliminating HCHO at room temperature. In the catalytic process, activation energy over K-Pt/NaY nano-catalytic system was greatly decreased along with the enhanced reaction rate. Characterization and catalytic tests revealed the surface electron structure of K-Pt/NaY was improved, as reflected by the enhanced HCHO adsorption capability, high sbnd OH concentration, and low-temperature reducibility. Therefore, the optimal K-Pt/NaY showed high catalytic efficiency and strong H2O tolerance for HCHO elimination by directly promoting the reaction between active sbnd OH and formate species. These results may suggest a new way for probing the advanced solid strong base nano-catalytic system for the catalytic elimination of indoor HCHO.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi
Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less
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Resonances of nanoparticles with poor plasmonic metal tips
NASA Astrophysics Data System (ADS)
Ringe, Emilie; Desantis, Christopher J.; Collins, Sean M.; Duchamp, Martial; Dunin-Borkowski, Rafal E.; Skrabalak, Sara E.; Midgley, Paul A.
2015-11-01
The catalytic and optical properties of metal nanoparticles can be combined to create platforms for light-driven chemical energy storage and enhanced in-situ reaction monitoring. However, the heavily damped plasmon resonances of many catalytically active metals (e.g. Pt, Pd) prevent this dual functionality in pure nanostructures. The addition of catalytic metals at the surface of efficient plasmonic particles thus presents a unique opportunity if the resonances can be conserved after coating. Here, nanometer resolution electron-based techniques (electron energy loss, cathodoluminescence, and energy dispersive X-ray spectroscopy) are used to show that Au particles incorporating a catalytically active but heavily damped metal, Pd, sustain multiple size-dependent localized surface plasmon resonances (LSPRs) that are narrow and strongly localized at the Pd-rich tips. The resonances also couple with a dielectric substrate and other nanoparticles, establishing that the full range of plasmonic behavior is observed in these multifunctional nanostructures despite the presence of Pd.
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NASA Astrophysics Data System (ADS)
Rao, Xi; Guyon, Cédric; Ognier, Stephanie; Da Silva, Bradley; Chu, Chenglin; Tatoulian, Michaël; Hassan, Ali Abou
2018-05-01
Immobilization of colloidal particles (e.g. gold nanoparticles (AuNps)) on the inner surface of micro-/nano- channels has received a great interest for catalysis. A novel catalytic ozonation setup using a gold-immobilized microchannel reactor was developed in this work. To anchor AuNps, (3-aminopropyl) triethoxysilane (APTES) with functional amine groups was deposited using plasma enhanced chemical vapor deposition (PECVD) process. The results clearly evidenced that PECVD processing exhibited relatively high efficiency for grafting amine groups and further immobilizing AuNPs. The catalytic activity of gold immobilized microchannel was evaluated by pyruvic acid ozonation. The decomposition rate calculated from High Performance Liquid Chromatography (HPLC) indicated a much better catalytic performance of gold in microchannel than that in batch. The results confirmed immobilizing gold nanoparticles on plasma deposited APTES for preparing catalytic microreactors is promising for the wastewater treatment in the future.
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A graded catalytic–protective layer for an efficient and stable water-splitting photocathode
Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne; ...
2017-01-09
Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less
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NASA Astrophysics Data System (ADS)
Fang, Minfeng
Despite the aggressive development and deployment of new renewable and nuclear technologies, petroleum-derived transportation fuels---gasoline, diesel and jet fuels---will continue to dominate the markets for decades. Environmental legislation imposes severe limits on the tolerable proportion of aromatics, sulfur and nitrogen contents in transportation fuels, which is difficult to achieve with current refining technologies. Catalytic hydrogenation plays an important role in the production of cleaner fuels, both as a direct means to reduce the aromatics and as a key step in the hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) processes. However, conventional catalysts require drastic conditions and/or are easily poisoned by S or N aromatics. Therefore, there is still a need for new efficient catalysts for hydrogenation reactions relevant to the production of cleaner fossil fuels. Our catalyst design involves metallic nanoparticles intimately associated with a basic support, with the aim of creating a nanostructure capable of promoting the heterolytic activation of hydrogen and ionic hydrogenation mechanisms, as a strategy to avoid catalyst poisoning and enhance catalytic activity. We have designed and prepared a new nanostructured catalytic material composed of RuNPs immobilized on the basic polymer P4VPy. We have demonstrated that the Ru/P4VPy catalyst can promote heterolytic hydrogen activation and a unique surface ionic hydrogenation mechanism for the efficient hydrogenation of N-aromatics. This is the first time these ionic hydrogenation pathways have been demonstrated on solid surfaces. For the RuNPs surfaces without basic sites in close proximity, the conventional homolytic H2 splitting is otherwise involved. Using the mechanistic concepts from Ru/P4VPy, we have designed and prepared the Ru/MgO catalyst, with the aim to improve the catalytic efficiency for the hydrogenation of heteroatom aromatics operating by the ionic hydrogenation mechanism. The Ru/MgO catalyst significantly improves the catalytic efficiency for hydrogenation of a variety of N-/S-heteroaromatics and mono-/polycyclic aromatic hydrocarbons representative of components of petroleum-derived fuels. The catalyst is superior to the few other known supported noble metal catalysts for these reactions. Mechanistic studies also point to the ionic hydrogenation mechanism on the Ru/MgO surfaces. In addition, the Ru/MgO catalyst is highly recyclable and long-lived.
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Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements
NASA Technical Reports Server (NTRS)
Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.
2016-01-01
This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.
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Ishida, Tamao; Kume, Kurumi; Kinjo, Kota; Honma, Tetsuo; Nakada, Kengo; Ohashi, Hironori; Yokoyama, Takushi; Hamasaki, Akiyuki; Murayama, Haruno; Izawa, Yusuke; Utsunomiya, Masaru; Tokunaga, Makoto
2016-12-20
Decarbonylation of furfural to furan was efficiently catalyzed by ZrO 2 -supported Pd clusters in the liquid phase under a N 2 atmosphere without additives. Although Pd/C and Pd/Al 2 O 3 have frequently been used for decarbonylation, Pd/ZrO 2 exhibited superior catalytic performance compared with these conventional catalysts. Transmission electron microscopy and X-ray absorption fine structure measurements revealed that the size of the Pd particles decreased with an increase in the specific surface area of ZrO 2 . ZrO 2 with a high surface area immobilized Pd as clusters consisting of several (three to five) Pd atoms, whereas Pd aggregated to form nanoparticles on other supports such as carbon and Al 2 O 3 despite their high surface areas. The catalytic activity of Pd/ZrO 2 was enhanced with a decrease in particle size, and the smallest Pd/ZrO 2 was the most active catalyst for decarbonylation. When CeO 2 was used as the support, a decrease in Pd particle size with an increase in surface area was also observed. Single Pd atoms were deposited on CeO 2 with a high surface area, with a strong interaction through the formation of a Pd-O-Ce bond, which led to a lower catalytic activity than that of Pd/ZrO 2 . This result suggests that zero-valent small Pd clusters consisting of more than one Pd atom are the active species for the decarbonylation reaction. Recycling tests proved that Pd/ZrO 2 maintained its catalytic activity until its sixth use. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Photocatalytic generation of hydrogen from water
NASA Technical Reports Server (NTRS)
Bottoms, W. R.; Miles, R. B.
1976-01-01
A concept designed to overcome the problems encountered when using photodissociation for the generation of hydrogen is discussed. The problems limiting the efficiency of photodissociation of water are the separation of the photolysis products and the high energy photons necessary for the reaction. It is shown that the dissociation energy of a large number of molecules is catalytically reduced when these molecules are in intimate contact with the surface of certain metals. It is proposed to develop a surface which will take advantage of this catalytic shift in dissociation energies to reduce the photon energy required to produce hydrogen. This same catalytic surface can be used to separate the reaction products if it is made so that one of the dissociations products is soluble in the metal and others are not. This condition is met by many metal systems such as platinum group metals which have been used commercially to separate hydrogen from other gases and liquids.
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Zhang, Xiaodong; Li, Hongxin; Lv, Xutian; Xu, Jingcheng; Wang, Yuxin; He, Chi; Liu, Ning; Yang, Yiqiong; Wang, Yin
2018-06-21
A comprehensive study was carried out on amorphous metal-organic frameworks Mn-MIL-100 as efficient catalysts for CO oxidation. This study focused on explaining the crystalline-amorphous-crystalline transformations during thermolysis of Mn-MIL-100 and studying the structure changes during the CO oxidation reaction. A possible formation mechanism of amorphous Mn-MIL-100 was proposed. Amorphous Mn-MIL-100 obtained by calcination at 250 °C (a-Mn-250) showed a smaller specific surface area (4 m 2 g -1 ) but high catalytic activity. Furthermore, the structure of amorphous Mn-MIL-100 was labile during the reaction. When a-Mn-250 was treated with reaction atmosphere at high temperature (giving used-a-Mn-250-S), the amorphous catalysts transformed into Mn 2 O 3 . Meanwhile, the BET surface area (164 m 2 g -1 ) and catalytic performance both sharply increased. In addition, used-a-Mn-250-S catalyst transformed from Mn 2 O 3 into Mn 3 O 4 , and this resulted in a slight decrease of catalytic activity in the presence of 1 vol % water vapor in the feed stream. A schematic mechanism of the structure changes during the reaction process was proposed. The success of the synthesis relies on the increase in BET surface area by using CO as retreatment atmosphere, and the enhanced catalytic activity was attributed to the unique structure, a large quantity of surface active oxygen species, oxygen vacancies, and good low-temperature reduction behavior. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Chitosan-microreactor: a versatile approach for heterogeneous organic synthesis in microfluidics.
Basavaraju, K C; Sharma, Siddharth; Singh, Ajay K; Im, Do Jin; Kim, Dong-Pyo
2014-07-01
Microreactors have been proven to be efficient tools for a variety of homogeneous organic transformations due to their mixing efficiency, which results in very fast reactions, better heat and mass transfer, and simple scale-up. However, in heterogeneous catalytic reactions each catalyst needs an individual substrate as support. Herein, a versatile approach to immobilize metal catalysts on chitosan as a common substrate is presented. Chitosan, accommodating many metal catalysts, is grafted onto the microchannel surface as nanobrush. The versatility, catalytic efficiency, and stability/durability of the microreactor are demonstrated for a number of organic transformations involving various metal compounds as catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water
Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei
2017-01-01
An iron-manganese co-oxide filter film (MeOx) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeOx was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeOx was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6–8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeOx included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeOx was formed by abiotic ways and the main elements on the surface of MeOx were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeOx as both ammonia molecules and ammonium ions and the active species of O2 were possibly •O and O2−. PMID:28753939
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Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water.
Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei
2017-07-19
An iron-manganese co-oxide filter film (MeO x ) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeO x was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeO x was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6-8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeO x included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeO x was formed by abiotic ways and the main elements on the surface of MeO x were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeO x as both ammonia molecules and ammonium ions and the active species of O₂ were possibly • O and O₂ - .
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Graphene as a thin-film catalyst booster: graphene-catalyst interface plays a critical role.
Chae, Sieun; Jin Choi, Won; Sang Chae, Soo; Jang, Seunghun; Chang, Hyunju; Lee, Tae Il; Kim, Youn Sang; Lee, Jeong-O
2017-12-08
Due to its extreme thinness, graphene can transmit some surface properties of its underlying substrate, a phenomenon referred to as graphene transparency. Here we demonstrate the application of the transparency of graphene as a protector of thin-film catalysts and a booster of their catalytic efficiency. The photocatalytic degradation of dye molecules by ZnO thin films was chosen as a model system. A ZnO thin film coated with monolayer graphene showed greater catalytic efficiency and long-term stability than did bare ZnO. Interestingly, we found the catalytic efficiency of the graphene-coated ZnO thin film to depend critically on the nature of the bottom ZnO layer; graphene transferred to a relatively rough, sputter-coated ZnO thin film showed rather poor catalytic degradation of the dye molecules while a smooth sol-gel-synthesized ZnO covered with monolayer graphene showed enhanced catalytic degradation. Based on a systematic investigation of the interface between graphene and ZnO thin films, we concluded the transparency of graphene to be critically dependent on its interface with a supporting substrate. Graphene supported on an atomically flat substrate was found to efficiently transmit the properties of the substrate, but graphene suspended on a substrate with a rough nanoscale topography was completely opaque to the substrate properties. Our experimental observations revealed the morphology of the substrate to be a key factor affecting the transparency of graphene, and should be taken into account in order to optimally apply graphene as a protector of catalytic thin films and a booster of their catalysis.
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Glycine Polymerization on Oxide Minerals.
Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru
2017-06-01
It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.
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NASA Astrophysics Data System (ADS)
Mao, Bao-Hua; Liu, Chang-Hai; Gao, Xu; Chang, Rui; Liu, Zhi; Wang, Sui-Dong
2013-10-01
The room-temperature ionic liquid assisted sputtering method is utilized to achieve the Pd-nanoparticle (NP)-graphene hybrid. The supported Pd NPs possess uniformly small sizes of 1-2 nm, which create huge surface area with ultralow Pd consumption and high NP stability. The Pd-NP-graphene hybrid is in situ characterized by the ambient pressure X-ray photoelectron spectroscopy using synchrotron radiation, and the results demonstrate high catalytic activity of the hybrid for CO oxidation. The catalytic behavior is reproducible for several catalytic cycles. The present simple and clean approach is promising to produce metal-NP-based high-efficiency catalysts for CO oxidation.
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NASA Astrophysics Data System (ADS)
Zhang, Zhen; Jiang, Yanzhou; Chi, Maoqiang; Yang, Zezhou; Nie, Guangdi; Lu, Xiaofeng; Wang, Ce
2016-02-01
This article reports the fabrication of magnetically responsive Au nanoparticles supported on CoFe2O4 nanotubes through polyaniline (PANI) assisted self-assembly strategy which can be used as an efficient magnetically recoverable nanocatalyst. The central magnetic CoFe2O4 nanotubes possess a strong magnetic response under an externally magnetic field, enabling an easy and efficient separation from the reaction system for reuse. The thorn-like PANI layer on the surface of CoFe2O4 nanotubes provides large surface area for supporting Au nanocatalysts due to the electrostatic interactions. The as-prepared CoFe2O4/PANI/Au nanotube assemblies exhibit a high catalytic activity for the hydrogenation of 4-nitrophenol by sodium borohydride (NaBH4) at room temperature, with an apparent kinetic rate constant (Kapp) of about 7.8 × 10-3 s-1. Furthermore, the composite nanocatalyst shows a good recoverable property during the catalytic process. This work affords a reliable way in developing multifunctional nanocomposite for catalysis and other potential applications in many fields.
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Thabit, Mohamed; Liu, Huiling; Zhang, Jian; Wang, Bing
2017-10-01
Pd-MnO 2 /TiO 2 nanotube arrays (NTAs) photo-electrodes were successfully fabricated via anodization and electro deposition subsequently; the obtained Pd-MnO 2 /TiO 2 NTAs photo electrodes were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and characterized accordingly. Moreover, the light harvesting and absorption properties were investigated via ultraviolet-visible diffuse reflectance spectrum (DRS); photo degradation efficiency was investigated via analyzing the photo catalytic degradation of Rhodamine B under visible illumination (xenon light). The performed analyses illustrated that Pd-MnO 2 codoped particles were successfully deposited onto the surface of the TiO 2 nanotube arrays; DRS results showed significant improvement in visible light absorption which was between 400 and 700nm. Finally, the photo catalytic degradation efficiency results of the designated organic pollutant (Rhodamine B) illustrated a superior photocatalytic (PC) efficiency of approximately 95% compared to the bare TiO 2 NTAs, which only exhibited a photo catalytic degradation efficiency of approximately 61%, thus it indicated the significant enhancement of the light absorption properties of fabricated photo electrodes and their yield of OH radicals. Copyright © 2017. Published by Elsevier B.V.
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Zhong, Hong; Liu, Caiping; Zhou, Hanghui; Wang, Yangxin; Wang, Ruihu
2016-08-22
Three porous organic polymers (POPs) containing H, COOMe, and COO(-) groups at 2,6-bis(1,2,3-triazol-4-yl)pyridyl (BTP) units (i.e., POP-1, POP-2, and POP-3, respectively) were prepared for the immobilization of metal nanoparticles (NPs). The ultrafine palladium NPs are uniformly encapsulated in the interior pores of POP-1, whereas uniform- and dual-distributed palladium NPs are located on the external surface of POP-2 and POP-3, respectively. The presence of carboxylate groups not only endows POP-3 an outstanding dispersibility in H2 O/EtOH, but also enables the palladium NPs at the surface to show the highest catalytic activity, stability, and recyclability in dehalogenation reactions of chlorobenzene at 25 °C. The palladium NPs on the external surface are effectively stabilized by the functionalized POPs containing BTP units and carboxylate groups, which provides a new insight for highly efficient catalytic systems based on surface metal NPs of porous materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Li, Ziyu; Jia, Zhigang; Ni, Tao; Li, Shengbiao
2017-12-01
Natural cotton, featuring abundant oxygen-containing functional groups, has been utilized as a reductant to synthesize Ag nanoparticles on its surface. Through the facile and environment-friendly reduction process, the fibrous Ag/cotton composite (FAC) was conveniently synthesized. Various characterization techniques including XRD, XPS, TEM, SEM, EDS and FT-IR had been utilized to study the material microstructure and surface properties. The resulting FAC exhibited favorable activity on the catalytic reduction of 4-nitrophenol with high reaction rate. Moreover, the fibrous Ag/cotton composites were capable to form a desirable catalytic mat for catalyzing and simultaneous product separation. Reactants passing through the mat could be catalytically transformed to product, which is of great significance for water treatment. Such catalyst (FAC) was thus expected to have the potential as a highly efficient, cost-effective and eco-friendly catalyst for industrial applications. More importantly, this newly developed synthetic methodology could serve as a general tool to design and synthesize other metal/biomass composites catalysts for a wider range of catalytic applications.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne
Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less
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NASA Astrophysics Data System (ADS)
Nekouei, Farzin; Nekouei, Shahram; Noorizadeh, Hossein
2018-03-01
In this study, we synthesized a new nanocomposite catalyst comprising Ag/AgCl@N-doped activated carbon (Ag/AgCl@N-AC) and demonstrated its high efficiency during the enhanced adsorptive removal and catalytic oxidation of ciprofloxacin (CIP) with peroxymonosulfate (PMS) and persulfate (PS) as oxidants in aqueous solution. The efficiency of the new nanocomposite was compared with those of both pristine AC and N-AC under the same conditions. Furthermore, the effects of oxidants on the catalytic oxidation of CIP were assessed using PMS and PS. We found that the degradation efficiency of CIP with Ag/AgCl@N-AC was higher when using PS as an oxidant, whereas the use of PMS obtained relatively better results with both AC and N-AC. The adsorption processes for AC, N-AC, and Ag/AgCl@N-AC were dominated not only by electrostatic attraction but also by π-π interactions, which had higher impacts on the adsorption processes than the specific surface area.
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Sheng, Jun; Ji, Xiaofeng; Zheng, Yuan; Wang, Zhipeng; Sun, Mi
2016-10-01
To determine the effects of artificial disulfide bridges on the thermostability and catalytic efficiency of chitosanase EAG1. Five artificial disulfide bridges were designed based on the structural information derived from the three-dimensional (3-D) model of chitosanase EAG1. Two beneficial mutants (G113C/D116C, A207C-L286C) were located in the flexible surface loop region, whereas the similar substitutions introduced in α-helices regions had a negligible effect. Mut5, the most active mutant, had a longer half-life at 50 °C (from 10.5 to 69.3 min) and a 200 % higher catalytic efficiency (K cat/K m) than that of the original EAG1. The contribution of disulfide bridges to enzyme thermostability is mainly dependent on its location within the polypeptide chain. Strategical placement of a disulfide bridge in flexible regions provides a rigid support and creation of a protected microenvironment, which is effective in improving enzyme's thermostability and catalytic efficiency.
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NASA Astrophysics Data System (ADS)
Moqbel, Redhwan A.; Gondal, Mohammed A.; Qahtan, Talal F.; Dastageer, Mohamed A.
2018-03-01
In this work the synthesis of visible light active zinc oxide/reduced graphene oxide (ZnO/rGO) nanocomposite by laser induced fragmentation of particulates in liquid, its morphological/optical characterizations, and its application in the process of photo-catalytic degradation of toxic Rhodamine B (RhB) dye under visible radiation were studied. It is observed from the optical and morphological characterization that the anchoring of ZnO on the rGO sheets in ZnO/rGO nanocomposite considerably reduced the aggregation of ZnO (increased surface area), reduced the recombination of photo-induced charge carriers, promoted more adsorption of reactants on the catalytic surface and also enhanced and extended the light absorption in the visible spectral region. With all these improved characteristics of ZnO/rGO nanocomposite, it was found that this material as a photo-catalyst yielded an RhB degradation efficiency of 86%, as compared to the 40% degradation with pure ZnO NPs under the same experimental conditions. In the ZnO/rGO nanocomposite, rGO functions as an electron acceptor to promote charge separation, an aggregation inhibitor to enhance the active surface area, a co-catalyst, a good dye adsorber and also as a supporting matrix for ZnO.
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Wang, Zhili; Liu, Pan; Han, Jiuhui; Cheng, Chun; Ning, Shoucong; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei
2017-10-20
Tuning surface structures by bottom-up synthesis has been demonstrated as an effective strategy to improve the catalytic performances of nanoparticle catalysts. Nevertheless, the surface modification of three-dimensional nanoporous metals, fabricated by a top-down dealloying approach, has not been achieved despite great efforts devoted to improving the catalytic performance of three-dimensional nanoporous catalysts. Here we report a surfactant-modified dealloying method to tailor the surface structure of nanoporous gold for amplified electrocatalysis toward methanol oxidation and oxygen reduction reactions. With the assistance of surfactants, {111} or {100} faceted internal surfaces of nanoporous gold can be realized in a controllable manner by optimizing dealloying conditions. The surface modified nanoporous gold exhibits significantly enhanced electrocatalytic activities in comparison with conventional nanoporous gold. This study paves the way to develop high-performance three-dimensional nanoporous catalysts with a tunable surface structure by top-down dealloying for efficient chemical and electrochemical reactions.
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Harnessing catalytic pumps for directional delivery of microparticles in microchambers
DOE Office of Scientific and Technical Information (OSTI.GOV)
Das, Sambeeta; Shklyaev, Oleg E.; Altemose, Alicia
The directed transport of microparticles in microfluidic devices is vital for efficient bioassays and fabrication of complex microstructures. There remains, but, a need for methods to propel and steer microscopic cargo that do not require modifying these particles. By using theory and experiments, we show that catalytic surface reactions can be used to deliver microparticle cargo to specified regions in microchambers. Here reagents diffuse from a gel reservoir and react with the catalyst-coated surface. Fluid density gradients due to the spatially varying reagent concentration induce a convective flow, which carries the suspended particles until the reagents are consumed. Consequently, themore » cargo is deposited around a specific position on the surface. The velocity and final peak location of the cargo can be tuned independently. And by increasing the local particle concentration, highly sensitive assays can be performed efficiently and rapidly. Moreover, the process can be repeated by introducing fresh reagent into the microchamber.« less
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Harnessing catalytic pumps for directional delivery of microparticles in microchambers
Das, Sambeeta; Shklyaev, Oleg E.; Altemose, Alicia; ...
2017-02-17
The directed transport of microparticles in microfluidic devices is vital for efficient bioassays and fabrication of complex microstructures. There remains, but, a need for methods to propel and steer microscopic cargo that do not require modifying these particles. By using theory and experiments, we show that catalytic surface reactions can be used to deliver microparticle cargo to specified regions in microchambers. Here reagents diffuse from a gel reservoir and react with the catalyst-coated surface. Fluid density gradients due to the spatially varying reagent concentration induce a convective flow, which carries the suspended particles until the reagents are consumed. Consequently, themore » cargo is deposited around a specific position on the surface. The velocity and final peak location of the cargo can be tuned independently. And by increasing the local particle concentration, highly sensitive assays can be performed efficiently and rapidly. Moreover, the process can be repeated by introducing fresh reagent into the microchamber.« less
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NASA Astrophysics Data System (ADS)
Tian, Meng; Cui, Xueliang; Dong, Chunxu; Dong, Zhengping
2016-12-01
In this study, a novel catalyst has been prepared through supporting Pd nanoparticles (NPs) on the surface of boehmite (γ-AlOOH) based hollow aluminosilicate microspheres (HAM@γ-AlOOH). The prepared Pd/HAM@γ-AlOOH catalyst has high catalytic activity for the hydrogenation of nitroarenes to their corresponding amino derivatives with high yields at ambient conditions. The high catalytic efficiency is attributed to the large pore size of the flower-like hierarchical flakes structure of HAM@γ-AlOOH, that gives Pd NPs on the support surface easy accessibility. Moreover, the Pd/HAM@γ-AlOOH catalyst can also be easily recycled at least five times without obvious decrease of catalytic activity. This work may provide a useful method for the fabrication of supported noble metal NP-based catalysts on the surface of mesoporous hierarchical structure materials with easy accessibility and superior activity.
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NASA Astrophysics Data System (ADS)
Han, Weiliang; Huang, Xiaosheng; Lu, Gongxuan; Tang, Zhicheng
2018-04-01
In this paper, the support surface properties (surface oxygen-containing functional groups and structure defects) of porous carbon spheres (PCSs) were carefully designed by as UV assisted O3 technology. CO catalytic oxidation reactions performed over the supported Pd-Ce catalysts on modified porous carbon spheres. Results illustrated that the Pd-Ce/PCSs catalysts exhibited high CO catalytic activity, which were increased at first, and then decreased with UV assistant-O3 treatment time. The Pd-Ce/PCSs-30 catalyst exhibited superior activity and T100 was only 15 °C. Moreover, the Pd-Ce/PCSs-30 catalyst obtained an excellent stability, and 100% CO conversion could be maintained as the time on stream evolutes up to 16h in the presence of H2O in the feed. Based on characterization results, there were two main factors: (a) the surface area and pore volume were decreased with UV-O3 treatment, leading to the enhancement of Pd-Ce particle size, and the decrease of Pd-Ce nanoparticle dispersion and mass transfer efficiency, as well as the decrease of catalytic activity of Pd-Ce/PCSs, (b) the surface oxygen content and defect sites of PCSs were raised by UV-O3 treatment, which could improve surface loading of Pd, Ce and enhance Pdsbnd Osbnd Ce bonding interactions, thereby increasing the activity of Pd-Ce/PCSs.
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NASA Astrophysics Data System (ADS)
Tsai, Chih-Hung; Shih, Chun-Jyun; Wang, Wun-Shiuan; Chi, Wen-Feng; Huang, Wei-Chih; Hu, Yu-Chung; Yu, Yuan-Hsiang
2018-03-01
In this study, macrocyclic Co complexes were successfully grafted onto graphene oxide (GO) to produce GO/Co nanocomposites with a large surface area, high electrical conductivity, and excellent catalytic properties. The novel GO/Co nanocomposites were applied as counter electrodes for Pt-free dye-sensitized solar cells (DSSCs). Various ratios of macrocyclic Co complexes were used as the reductant to react with the GO, with which the surface functional groups of the GO were reduced and the macrocyclic ligand of the Co complexes underwent oxidative dehydrogenation, after which the conjugated macrocyclic Co systems were grafted onto the surface of the reduced GO to form GO/Co nanocomposites. The surface morphology, material structure, and composition of the GO/Co composites and their influences on the power-conversion efficiency of DSSC devices were comprehensively investigated. The results showed that the GO/Co (1:10) counter electrode (CE) exhibited an optimal power conversion efficiency of 7.48%, which was higher than that of the Pt CE. The GO/Co (1:10) CE exhibited superior electric conductivity, catalytic capacity, and redox capacity. Because GO/Co (1:10) CEs are more efficient and cheaper than Pt CEs, they could potentially be used as a replacement for Pt electrodes.
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Deebasree, J P; Maheskumar, V; Vidhya, B
2018-07-01
Visible light induced photocatalyst BiVO 4 with monoclinic scheelite structure has been synthesised via sol gel method assisted by ultrasonication. The prepared samples were characterised using X-ray diffraction (XRD), scanning electron microscope (SEM), UV-Vis diffused reflectance spectroscopy (DRS) techniques. The photocatalytic efficiency was evaluated by decolourisation of MB under visible light irradiation. The effect of ultrasound output power on the properties of BiVO 4 during and after preparation by sol-gel method has been compared with normal agitated sample (As prepared). The power of ultrasonic vibration has been varied and an ideal output power which yields better catalytic efficiency is determined. BiVO 4 sonicated with 80 W during preparation 80 W (D) exhibited relatively high surface area, better surface morphology and better catalytic efficiency compared to other samples which were sonicated with 100, 160 and 200 W. The results signify that the photodegradation rate of BiVO 4 80 W (D) sample is high up to 96% in 90 min compared to other samples. Change in morphology leading to better catalytic efficiency was obtained just by exposing the sample to ultrasonic radiation without addition of any surfactant. The recovery test showed that the sample was stable for four consecutive cycles. Using radical test, a reasonable mechanism for photodegradation has been proposed. Copyright © 2018 Elsevier B.V. All rights reserved.
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Wen, Xin; Ma, Zhenhua; Zhang, Lei; Sha, Xiangling; He, Huibin; Zeng, Tianyou; Wang, Yusu; Chen, Jihao
2017-01-01
Selective catalytic oxidation (SCO) method is commonly used in wet denitration technology; NO after the catalytic oxidation can be removed with SO2 together by wet method. Among the SCO denitration catalysts, pyrolysis coke is favored by the advantages of low cost and high catalytic activity. In this paper, SCO method combined with pyrolysis coke catalyst was used to remove NO from flue gas. The effects of different SCO operating conditions and different pyrolysis coke catalyst made under different process conditions were studied. Besides, the specific surface area of the catalyst and functional groups were analyzed with surface area analyzer and Beohm titration. The results are: (1) The optimum operating conditions of SCO is as follows: the reaction temperature is 150°C and the oxygen content is 6%. (2) The optimum pyrolysis coke catalyst preparation processes are as follows: the pyrolysis final temperature is 750°C, and the heating rate is 44°C / min. (3) The characterization analysis can be obtained: In the denitration reaction, the basic functional groups and the phenolic hydroxyl groups of the catalyst play a major role while the specific surface area not. PMID:28793346
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Heat Transfer to Surfaces of Finite Catalytic Activity in Frozen Dissociated Hypersonic Flow
NASA Technical Reports Server (NTRS)
Chung, Paul M.; Anderson, Aemer D.
1961-01-01
The heat transfer due to catalytic recombination of a partially dissociated diatomic gas along the surfaces of two-dimensional and axisymmetric bodies with finite catalytic efficiencies is studied analytically. An integral method is employed resulting in simple yet relatively complete solutions for the particular configurations considered. A closed form solution is derived which enables one to calculate atom mass-fraction distribution, therefore catalytic heat transfer distribution, along the surface of a flat plate in frozen compressible flow with and without transpiration. Numerical calculations are made to determine the atom mass-fraction distribution along an axisymmetric conical body with spherical nose in frozen hypersonic compressible flow. A simple solution based on a local similarity concept is found to be in good agreement with these numerical calculations. The conditions are given for which the local similarity solution is expected to be satisfactory. The limitations on the practical application of the analysis to the flight of the blunt bodies in the atmosphere are discussed. The use of boundary-layer theory and the assumption of frozen flow restrict application of the analysis to altitudes between about 150,000 and 250,000 feet.
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Design and functionalization of photocatalytic systems within mesoporous silica.
Qian, Xufang; Fuku, Kojirou; Kuwahara, Yasutaka; Kamegawa, Takashi; Mori, Kohsuke; Yamashita, Hiromi
2014-06-01
In the past decades, various photocatalysts such as TiO2, transition-metal-oxide moieties within cavities and frameworks, or metal complexes have attracted considerable attention in light-excited catalytic processes. Owing to high surface areas, transparency to UV and visible light as well as easily modified surfaces, mesoporous silica-based materials have been widely used as excellent hosts for designing efficient photocatalytic systems under the background of environmental remediation and solar-energy utilization. This Minireview mainly focuses on the surface-chemistry engineering of TiO2/mesoporous silica photocatalytic systems and fabrication of binary oxides and nanocatalysts in mesoporous single-site-photocatalyst frameworks. Recently, metallic nanostructures with localized surface plasmon resonance (LSPR) have been widely studied in catalytic applications harvesting light irradiation. Accordingly, silver and gold nanostructures confined in mesoporous silica and their corresponding catalytic activity enhanced by the LSPR effect will be introduced. In addition, the integration of metal complexes within mesoporous silica materials for the construction of functional inorganic-organic supramolecular photocatalysts will be briefly described. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Yang, Qiu; Liu, Wenxian; Wang, Bingqing; ...
2017-02-14
Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. We report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing themore » encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.« less
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Catalytic reaction processes revealed by scanning probe microscopy. [corrected].
Jiang, Peng; Bao, Xinhe; Salmeron, Miquel
2015-05-19
Heterogeneous catalysis is of great importance for modern society. About 80% of the chemicals are produced by catalytic reactions. Green energy production and utilization as well as environmental protection also need efficient catalysts. Understanding the reaction mechanisms is crucial to improve the existing catalysts and develop new ones with better activity, selectivity, and stability. Three components are involved in one catalytic reaction: reactant, product, and catalyst. The catalytic reaction process consists of a series of elementary steps: adsorption, diffusion, reaction, and desorption. During reaction, the catalyst surface can change at the atomic level, with roughening, sintering, and segregation processes occurring dynamically in response to the reaction conditions. Therefore, it is imperative to obtain atomic-scale information for understanding catalytic reactions. Scanning probe microscopy (SPM) is a very appropriate tool for catalytic research at the atomic scale because of its unique atomic-resolution capability. A distinguishing feature of SPM, compared to other surface characterization techniques, such as X-ray photoelectron spectroscopy, is that there is no intrinsic limitation for SPM to work under realistic reaction conditions (usually high temperature and high pressure). Therefore, since it was introduced in 1981, scanning tunneling microscopy (STM) has been widely used to investigate the adsorption, diffusion, reaction, and desorption processes on solid catalyst surfaces at the atomic level. STM can also monitor dynamic changes of catalyst surfaces during reactions. These invaluable microscopic insights have not only deepened the understanding of catalytic processes, but also provided important guidance for the development of new catalysts. This Account will focus on elementary reaction processes revealed by SPM. First, we will demonstrate the power of SPM to investigate the adsorption and diffusion process of reactants on catalyst surfaces at the atomic level. Then the dynamic processes, including surface reconstruction, roughening, sintering, and phase separation, studied by SPM will be discussed. Furthermore, SPM provides valuable insights toward identifying the active sites and understanding the reaction mechanisms. We also illustrate here how both ultrahigh vacuum STM and high pressure STM provide valuable information, expanding the understanding provided by traditional surface science. We conclude with highlighting remarkable recent progress in noncontact atomic force microscopy (NC-AFM) and inelastic electron tunneling spectroscopy (IETS), and their impact on single-chemical-bond level characterization for catalytic reaction processes in the future.
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Khan, Farman Ullah; Asimullah; Khan, Sher Bahadar; Kamal, Tahseen; Asiri, Abdullah M; Khan, Ihsan Ullah; Akhtar, Kalsoom
2017-09-01
A very simple and low-cost procedure has been adopted to synthesize efficient copper (Cu), silver (Ag) and copper-silver (Cu-Ag) mixed nanoparticles on the surface of pure cellulose acetate (CA) and cellulose acetate-copper oxide nanocomposite (CA-CuO). All nanoparticles loaded onto CA and CA-CuO presented excellent catalytic ability, but Cu-Ag nanoparticles loaded onto CA-CuO (Cu 0 -Ag 0 /CA-CuO) exhibited outstanding catalytic efficiency to convert 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) in the presence of NaBH 4 . Additionally, the Cu 0 -Ag 0 /CA-CuO can be easily recovered by removing the sheet from the reaction media, and can be recycled several times, maintaining high catalytic ability for four cycles. Copyright © 2017 Elsevier B.V. All rights reserved.
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Yuan, Xiangjuan; Qin, Wenlei; Lei, Xiaoman; Sun, Lei; Li, Qiang; Li, Dongya; Xu, Haiming; Xia, Dongsheng
2018-08-01
A functional organic-metal composite material zero-valent zinc immobilized graphitic carbon nitride (ZVZ-g-C 3 N 4 ) was prepared by a fast and facile two-step synthetic approach with an optimal ZVZ content of 5.4 wt%. The structure, surface morphology and chemical composition of the as-synthesized ZVZ-g-C 3 N 4 were characterized by BET surface area, XRD, FT-IR, SEM, TEM, and XPS, respectively. ZVZ-g-C 3 N 4 composite exhibited superior catalytic ozonation activity with an improvement of 61.2% on atrazine (ATZ) degradation efficiency in 1.5 min reaction, more than 12 times of the pseudo-first-order rate constant, and almost 16-fold of the R ct value obtained in O 3 /ZVZ-g-C 3 N 4 process compared to O 3 alone. Meanwhile, the ATZ degradation efficiency was gradually enhanced with increasing ZVZ-g-C 3 N 4 dosage and initial solution pH in the range from 3.0 to 9.0, and a higher amount of ATZ was degraded when the initial concentration of ATZ rose from 1 to 10 mg L -1 . The enhanced catalytic ozonation activity of ZVZ-g-C 3 N 4 is attributed to the synergistic effects among ZVZ, ZnO and g-C 3 N 4 , as well as the improved dispersibility, increased surface area, and intensive electron-transfer ascribed to the electronic and surface properties modification. The radical scavengers experiments demonstrated that O 2 - , OH, and 1 O 2 were the dominant reactive radical species in the multifunctional processes. Moreover, an empirical kinetic model was proposed to predict ATZ degradation. The results indicated that the ZVZ-g-C 3 N 4 composite was a highly efficient, recoverable, and durable catalyst, which would provide a promising alternative in catalytic ozonation. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Competing reaction processes on a lattice as a paradigm for catalyst deactivation
NASA Astrophysics Data System (ADS)
Abad, E.; Kozak, J. J.
2015-02-01
We mobilize both a generating function approach and the theory of finite Markov processes to compute the probability of irreversible absorption of a randomly diffusing species on a lattice with competing reaction centers. We consider an N-site lattice populated by a single deep trap, and N -1 partially absorbing traps (absorption probability 0
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Yang, Tao; Fukuda, Ryoichi; Hosokawa, Saburo; Tanaka, Tsunehiro; Sakaki, Shigeyoshi; Ehara, Masahiro
2017-04-07
Single-atom catalysts have attracted much interest recently because of their excellent stability, high catalytic activity, and remarkable atom efficiency. Inspired by the recent experimental discovery of a highly efficient single-atom catalyst Pd 1 /γ-Al 2 O 3 , we conducted a comprehensive DFT study on geometries, stabilities and CO oxidation catalytic activities of M 1 /γ-Al 2 O 3 (M=Pd, Fe, Co, and Ni) by using slab-model. One of the most important results here is that Ni 1 /Al 2 O 3 catalyst exhibits higher activity in CO oxidation than Pd 1 /Al 2 O 3 . The CO oxidation occurs through the Mars van Krevelen mechanism, the rate-determining step of which is the generation of CO 2 from CO through abstraction of surface oxygen. The projected density of states (PDOS) of 2 p orbitals of the surface O, the structure of CO-adsorbed surface, charge polarization of CO and charge transfer from CO to surface are important factors for these catalysts. Although the binding energies of Fe and Co with Al 2 O 3 are very large, those of Pd and Ni are small, indicating that the neighboring O atom is not strongly bound to Pd and Ni, which leads to an enhancement of the reactivity of the O atom toward CO. The metal oxidation state is suggested to be one of the crucial factors for the observed catalytic activity.
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Guo, Zhuang; Cao, Hongbin; Wang, Yuxian; Xie, Yongbing; Xiao, Jiadong; Yang, Jin; Zhang, Yi
2018-06-01
Three kinds of graphitic carbon nitride materials (bulk, porous and nanosheet g-C 3 N 4 ) were composited with a multiwall carbon nanotube (MWCNT) by a hydrothermal method, and the obtained b-C 3 N 4 /CNT, p-C 3 N 4 /CNT and n-C 3 N 4 /CNT materials were used in the electrodes for electro-peroxone process. It was found that the n-C 3 N 4 /CNT composite exhibited the highest efficiency in oxalate degradation, though it performed the worst in the oxygen-reduction reaction for H 2 O 2 production. The n-C 3 N 4 /CNT composite exhibited higher activity than CNT and other composites in catalytic ozonation experiments, due to the higher pyrrolic-N content modified on the CNT surface and higher surface area. It also has higher electron transfer ability, which benefited to the electro-reduction of both O 2 and O 3 . The result confirmed that catalytic ozonation process was an important means to enhance the degradation efficiency in the electro-peroxone process, besides peroxone process and O 3 -electrolysis. Copyright © 2018 Elsevier Ltd. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Rodríguez-Maciá, Patricia; Priyadarshani, Nilusha; Dutta, Arnab
Hydrogenases are a diverse group of metalloenzymes which catalyze the reversible conversion between molecular hydrogen and protons at high rates. The catalytic activity of these enzymes does not require overpotential because their active site has been evolutionarily optimized to operate fast and efficiently. These enzymes have inspired the development of molecular catalysts, which have dramatically improved in efficiency in recent years, to the point that some synthetic catalysts even outperform hydrogenases under certain conditions. In this work, we use a reversible noble-metal-free homogeneous catalyst, the [Ni(PCy2NPhe2)2]2+ complex, and we covalently immobilize it on a functionalized highly oriented pyrolytic graphite “edge”more » (HOPGe) electrode surface. This catalyst is not water soluble, but once it is surface-confined on the electrode, it maintains its catalytic properties in aqueous solutions, showing reversibility for H2 oxidation/reduction. Immobilization of the [Ni(PCy2NPhe2)2]2+ complex onto a multi-walled carbon nanotubes coated electrode leads to even higher catalytic current densities and enhanced stability.« less
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NASA Astrophysics Data System (ADS)
Serra, José M.; Buchkremer, Hans-Peter
Solid oxide fuel cells (SOFCs) are highly efficient energy converters for both stationary and mobile purposes. However, their market introduction still demands the reduction of manufacture costs and one possible way to reach this goal is the decrease of the operating temperatures, which entails the improvement of the cathode electrocatalytic properties. An ideal cathode material may have mixed ionic and electronic conductivity as well as proper catalytic properties. Nanostructuring and catalytic promotion of mixed conducting perovskites (e.g. La 0.58Sr 0.4Fe 0.8Co 0.2O 3- δ) seem to be promising approaches to overcoming cathode polarization problems and are briefly illustrated here. The preparation of nanostructured cathodes with relatively high surface area and enough thermal stability enables to improve the oxygen exchange rate and therefore the overall SOFC performance. A similar effect was obtained by catalytic promoting the perovskite surface, allowing decoupling the catalytic and ionic-transport properties in the cathode design. Noble metal incorporation may improve the reversibility of the reduction cycles involved in the oxygen reduction. Under the cathode oxidizing conditions, Pd seems to be partially dissolved in the perovskite structure and as a result very well dispersed.
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Rogers, Cameron; Perkins, Wade S.; Veber, Gregory; ...
2017-02-24
Regulating the complex environment accounting for the stability, selectivity, and activity of catalytic metal nanoparticle interfaces represents a challenge to heterogeneous catalyst design. Here in this paper, we demonstrate the intrinsic performance enhancement of a composite material composed of gold nanoparticles (AuNPs) embedded in a bottom-up synthesized graphene nanoribbon (GNR) matrix for the electrocatalytic reduction of CO 2. Electrochemical studies reveal that the structural and electronic properties of the GNR composite matrix increase the AuNP electrochemically active surface area (ECSA), lower the requisite CO 2 reduction overpotential by hundreds of millivolts (catalytic onset > -0.2 V versus reversible hydrogen electrodemore » (RHE)), increase the Faraday efficiency (>90%), markedly improve stability (catalytic performance sustained over >24 h), and increase the total catalytic output (>100-fold improvement over traditional amorphous carbon AuNP supports). The inherent structural and electronic tunability of bottom-up synthesized GNR-AuNP composites affords an unrivaled degree of control over the catalytic environment, providing a means for such profound effects as shifting the rate-determining step in the electrocatalytic reduction of CO 2 to CO, and thereby altering the electrocatalytic mechanism at the nanoparticle surface.« less
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Li, Xukai; Chen, Weirui; Tang, Yiming; Li, Laisheng
2018-05-12
Fe-MCM-48 catalyst with a three-dimensional cubic pore structure was directly synthesized via a hydrothermal method, and the mineralization efficiency of diclofenac (DCF) in the catalytic ozonation process (Fe-MCM-48/O 3 ) was assessed. X-ray diffraction (XRD), N 2 adsorption desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) characterizations revealed that Fe existed in the framework of MCM-48, and Fe-MCM-48 possessed a large surface area and a highly ordered cubic mesoporous structure, which could accelerate reactants and products diffusion. Regarding mineralization efficiency, the addition of Fe-MCM-48 significantly improved total organic carbon (TOC) removal, and approximately 49.9% TOC were removed through the Fe-MCM-48/O 3 process at 60 min, which was 2.0 times higher than that in single ozonation. Due to this catalyst's superior structure, Fe-MCM-48 showed the better catalytic activity compared with Fe-MCM-41 and Fe loaded MCM-48 (Fe/MCM-48, Fe existed on the surface of MCM-48). DCF removal in the Fe-MCM-48/O 3 process was primarily based on ozone direct oxidation. The improvement of mineralization efficiency was attributed to the function of generated hydroxyl radicals (•OH), which indicated that the presence of Fe-MCM-48 accelerated ozone decomposition. Moreover, the negatively charged surface of Fe-MCM-48 and the proper pH value of the DCF solution played an essential role in OH generation. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Preparation of immobilized coating Fenton-like catalyst for high efficient degradation of phenol.
Wang, Jiankang; Yao, Zhongping; Wang, Yajing; Xia, Qixing; Chu, Huiya; Jiang, Zhaohua
2017-05-01
In this study, solid acid amorphous Fe 3 O 4 /SiO 2 ceramic coating decorated with sulfur on Q235 carbon steel as Fenton-like catalyst for phenol degradation was successfully prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte containing Na 2 S 2 O 8 as sulfur source. The surface morphology and phase composition were characterized by SEM, EDS, XRD and XPS analyses. NH 3 -TPD was used to evaluate surface acidity of PEO coating. The results indicated that sulfur decorated amorphous Fe 3 O 4 /SiO 2 ceramic coatings with porous structure and higher acid strength had the similar pore size and the surface became more and more uneven with the increase of Na 2 S 2 O 8 in the silicate electrolyte. The Fenton-like catalytic activity of sulfur decorated PEO coatings was also evaluated. In contrast to negligible catalytic activity of sulfur undecorated PEO coating, catalytic activity of sulfur decorated PEO coating was excellent and PEO coating prepared with 3.0 g Na 2 S 2 O 8 had the highest catalytic activity which could degrade 99% of phenol within 8 min under circumneutral pH. The outstanding performance of sulfur decorated PEO coating was attributed to strong acidic microenvironment and more Fe 2+ on the surface. The strong acid sites played a key factor in determining catalytic activity of catalyst. In conclusion, rapid phenol removal under circumneutral pH and easier separation endowed it potential application in wastewater treatment. In addition, this strategy of preparing immobilized solid acid coating could provide guidance for designing Fenton-like catalyst with excellent catalytic activity and easier separation. Copyright © 2017 Elsevier Ltd. All rights reserved.
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NOx Binding and Dissociation: Enhanced Ferroelectric Surface Chemistry by Catalytic Monolayers
NASA Astrophysics Data System (ADS)
Kakekhani, Arvin; Ismail-Beigi, Sohrab
2013-03-01
NOx molecules are regulated air pollutants produced during automotive combustion. As part of an effort to design viable catalysts for NOx decomposition operating at higher temperatures that would allow for improved fuel efficiency, we examine NOx chemistry on ferroelectric perovskite surfaces. Changing the direction of ferroelectric polarization can modify surface electronic properties and may lead to switchable surface chemistry. Here, we describe our recent work on potentially enhanced surface chemistry using catalytic RuO2 monolayers on perovskite ferroelectric substrates. In addition to thermodynamic stabilization of the RuO2 layer, we present results on the polarization-dependent binding of NO, O2, N2, and atomic O and N. We present results showing that one key problem with current catalysts, involving the difficulty of releasing dissociation products (especially oxygen), can be ameliorated by this method. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.
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Barroo, Cedric; Janvelyan, Nare; Zugic, Branko; ...
2016-07-25
To improve the understanding of catalytic processes, the surface structure and composition of the active materials need to be determined before and after reaction. Morphological changes may occur under reaction conditions and can dramatically influence the reactivity and/or selectivity of a catalyst. Goldbased catalysts with different architectures are currently being developed for selective oxidation reactions at low temperatures. Specifically, nanoporous Au (npAu) with a composition of Au 97-Ag 3 is obtained by dealloying a Ag 70-Au 30 bulk alloy. Recent studies highlight the efficiency of npAu catalysts for methanol oxidation using ozone to activate the catalysts before methanol oxidation. Inmore » this paper, we studied the morphological and compositional changes occurring at the surface of Au-based catalysts in certain conditions.« less
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Wang, Huan-Jiang; Wang, Yong-Cheng
2014-06-01
Carbon monoxide (CO) and oxygen (O2) catalyzed by small neutral iron oxide clusters (FeO(1-3)) was investigated at the density functional level of theory using the Becke-Perdew-Wang functional (BPW91). Three reaction pathways along with singlet, triplet and quintet states were calculated for ascertaining the presence of some spin inversion during the catalytic cycle. The catalytic cycle was found to be "two state reactivity" resulting from the crossing among the multistate energetic profiles. The Landau-Zener equation was used to calculate the thermally-averaged spin transition probabilities for the non-adiabatic surface crossing reaction. In order to predict the efficiency of catalyst the energetic span model developed by Kozuch was implemented, whereas this model is not suitable for handling the diabatic reaction, this feature we must take into consideration. To this end, a kinetic assessment is carried out with an expansion of the energetic span model, including the spin-crossing effects. This approximation enables one to measure the efficiency of catalytic cycle including spin-crossing effects by quantum mechanical computation.
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Sun, Fugen; Wang, Jitong; Chen, Huichao; Qiao, Wenming; Ling, Licheng; Long, Donghui
2013-01-01
We demonstrate a sustainable and efficient approach to produce high performance sulfur/carbon composite cathodes via a bottom-up catalytic approach. The selective oxidation of H2S by a nitrogen-enriched mesoporous carbon catalyst can produce elemental sulfur as a by-product which in-situ deposit onto the carbon framework. Due to the metal-free catalytic characteristic and high catalytic selectivity, the resulting sulfur/carbon composites have almost no impurities that thus can be used as cathode materials with compromising battery performance. The layer-by-layer sulfur deposition allows atomic sulfur binding strongly with carbon framework, providing efficient immobilization of sulfur. The nitrogen atoms doped on the carbon framework can increase the surface interactions with polysulfides, leading to the improvement in the trapping of polysulfides. Thus, the composites exhibit a reversible capacity of 939 mAh g−1 after 100 cycles at 0.2 C and an excellent rate capability of 527 mAh g−1 at 5 C after 70 cycles. PMID:24084754
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Analytic corrections to CFD heating predictions accounting for changes in surface catalysis
NASA Technical Reports Server (NTRS)
Gnoffo, Peter A.; Inger, George R.
1996-01-01
Integral boundary-layer solution techniques applicable to the problem of determining aerodynamic heating rates of hypersonic vehicles in the vicinity of stagnation points and windward centerlines are briefly summarized. A new approach for combining the insight afforded by integral boundary-layer analysis with comprehensive (but time intensive) computational fluid dynamic (CFD) flowfield solutions of the thin-layer Navier-Stokes equations is described. The approach extracts CFD derived quantities at the wall and at the boundary layer edge for inclusion in a post-processing boundary-layer analysis. It allows a designer at a workstation to address two questions, given a single CFD solution. (1) How much does the heating change for a thermal protection system with different catalytic properties than was used in the original CFD solution? (2) How does the heating change at the interface of two different TPS materials with an abrupt change in catalytic efficiency? The answer to the second question is particularly important, because abrupt changes from low to high catalytic efficiency can lead to localized increase in heating which exceeds the usually conservative estimate provided by a fully catalytic wall assumption.
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Arab Chamjangali, M; Bagherian, G; Javid, A; Boroumand, S; Farzaneh, N
2015-11-05
In this study, the photo-decolorization of a mixture of methylene blue (MB) and methyl orange (MO) was investigated using Ag-ZnO multipods. The photo-catalyst used, ZnO multipods, was successfully synthesized. The surface of ZnO microstructure was modified by deposition of different amounts of Ag nanoparticles (Ag NPs) using the photo-reduction method. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-Vis and atomic absorption spectroscopy. The photo-catalytic efficiency of Ag-ZnO is mainly controlled by the amount of Ag NPs deposited on the ZnO surface. The results obtained suggest that Ag-ZnO containing 6.5% Ag NPs, has the highest photo-catalytic performance in the simultaneous photo-degradation of dyes at a shorter time. Copyright © 2015 Elsevier B.V. All rights reserved.
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Metal oxide composite enabled nanotextured Si photoanode for efficient solar driven water oxidation.
Sun, Ke; Pang, Xiaolu; Shen, Shaohua; Qian, Xueqiang; Cheung, Justin S; Wang, Deli
2013-05-08
We present a study of a transition metal oxide composite modified n-Si photoanode for efficient and stable water oxidation. This sputter-coated composite functions as a protective coating to prevent Si from photodecomposition, a Schottky heterojunction, a hole conducting layer for efficient charge separation and transportation, and an electrocatalyst to reduce the reaction overpotential. The formation of mixed-valence oxides composed of Ni and Ru effectively modifies the optical, electrical, and catalytic properties of the coating material, as well as the interfaces with Si. The successful application of this oxide composite on nanotextured Si demonstrates improved conversion efficiency due to enhanced catalytic activity, minimized reflection, and increased surface reaction sites. Although the coated nanotextured Si shows a noticeable degradation from 500 cycles of operation, the oxide composite provides a simple method to enable unstable photoanode materials for solar fuel conversion.
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Huang, Hsu-Hui; Lu, Ming-Chun; Chen, Jong-Nan; Lee, Cheng-Te
2003-06-01
The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.
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Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts
Zugic, Branko; Wang, Lucun; Heine, Christian; ...
2016-12-19
Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver–gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changesmore » occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Finally, our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.« less
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Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zugic, Branko; Wang, Lucun; Heine, Christian
Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver–gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changesmore » occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Finally, our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.« less
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Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study
Li, Liang; Zhang, Rui; Vinson, John; ...
2018-03-05
Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO 2 reduction. While photoreduction of CO 2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu 2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO 2 and the Cu 2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu 2O (110) surface stoichiometry that favors CO 2 reduction. To facilitate interpretation ofmore » scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO 2 reduction reaction on, and rational surface engineering of, Cu 2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.« less
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Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study
DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Liang; Zhang, Rui; Vinson, John
Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO 2 reduction. While photoreduction of CO 2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu 2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO 2 and the Cu 2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu 2O (110) surface stoichiometry that favors CO 2 reduction. To facilitate interpretation ofmore » scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO 2 reduction reaction on, and rational surface engineering of, Cu 2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.« less
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Catalytic activity of carbon nanotubes in the conversion of aliphatic alcohols
NASA Astrophysics Data System (ADS)
Zhitnev, Yu. N.; Tveritinova, E. A.; Chernyak, S. A.; Savilov, S. V.; Lunin, V. V.
2016-06-01
Carbon nanotubes (CNTs) obtained via the catalytic pyrolysis of hexane at 750°C were studied as the catalysts in conversion of C2-C4 alcohols. The efficiency of CNTs as catalysts in dehydration and dehydrogenation of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol was studied by means of pulse microcatalysis. The surface and structural characteristics of CNTs are investigated via SEM, TEM, DTA, BET, and XPS. CNTs are shown to be effective catalysts in the conversion of alcohols and do not require additional oxidative treatment. The regularities of the conversion of aliphatic alcohols, related to the properties of the CNTs surface and the structure of the alcohols are identified.
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Wang, Feifan; Huang, Yanjie; Chai, Zhigang; Zeng, Min; Li, Qi; Wang, Yuan; Xu, Dongsheng
2016-12-01
Conventional semiconductor photocatalysis based on band-edge absorption remains inefficient due to the limited harvesting of solar irradiation and the complicated surface/interface chemistry. Herein, novel photothermal-enhanced catalysis was achieved in a core-shell hierarchical Cu 7 S 4 nano-heater@ZIF-8 heterostructures via near-infrared localized surface plasmon resonance. Our results demonstrated that both the high surface temperature of the photothermal Cu 7 S 4 core and the close-adjacency of catalytic ZIF-8 shell contributed to the extremely enhanced catalytic activity. Under laser irradiation (1450 nm, 500 mW), the cyclocondensation reaction rate increased 4.5-5.4 fold compared to that of the process at room temperature, in which the 1.6-1.8 fold enhancement was due to the localized heating effect. The simulated sunlight experiments showed a photothermal activation efficiency (PTAE) of 0.07%, further indicating the validity of photothermal catalysis based on the plasmonic semiconductor nanomaterials. More generally, this approach provides a platform to improve reaction activity with efficient utilization of solar energy, which can be readily extended to other green-chemistry processes.
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Probing Ultrafast Electron Dynamics at Surfaces Using Soft X-Ray Transient Reflectivity Spectroscopy
NASA Astrophysics Data System (ADS)
Baker, L. Robert; Husek, Jakub; Biswas, Somnath; Cirri, Anthony
The ability to probe electron dynamics with surface sensitivity on the ultrafast time scale is critical for understanding processes such as charge separation, injection, and surface trapping that mediate efficiency in catalytic and energy conversion materials. Toward this goal, we have developed a high harmonic generation (HHG) light source for femtosecond soft x-ray reflectivity. Using this light source we investigated the ultrafast carrier dynamics at the surface of single crystalline α-Fe2O3, polycrystalline α-Fe2O3, and the mixed metal oxide, CuFeO2. We have recently demonstrated that CuFeO2 in particular is a selective catalyst for photo-electrochemical CO2 reduction to acetate; however, the role of electronic structure and charge carrier dynamics in mediating catalytic selectivity has not been well understood. Soft x-ray reflectivity measurements probe the M2,3, edges of the 3d transition metals, which provide oxidation and spin state resolution with element specificity. In addition to chemical state specificity, these measurements are also surface sensitive, and by independently simulating the contributions of the real and imaginary components of the complex refractive index, we can differentiate between surface and sub-surface contributions to the excited state spectrum. Accordingly, this work demonstrates the ability to probe ultrafast carrier dynamics in catalytic materials with element and chemical state specificity and with surface sensitivity.
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NASA Astrophysics Data System (ADS)
Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan
2017-10-01
Heterogeneous catalytic reactions on surface and interfaces are renowned for ample intermediate adsorbates and complex reaction networks. The common practice to reveal the reaction mechanism is via theoretical computation, which locates all likely transition states based on the pre-guessed reaction mechanism. Here we develop a new theoretical method, namely, stochastic surface walking (SSW)-Cat method, to resolve the lowest energy reaction pathway of heterogeneous catalytic reactions, which combines our recently developed SSW global structure optimization and SSW reaction sampling. The SSW-Cat is automated and massively parallel, taking a rough reaction pattern as input to guide reaction search. We present the detailed algorithm, discuss the key features, and demonstrate the efficiency in a model catalytic reaction, water-gas shift reaction on Cu(111) (CO + H2O → CO2 + H2). The SSW-Cat simulation shows that water dissociation is the rate-determining step and formic acid (HCOOH) is the kinetically favorable product, instead of the observed final products, CO2 and H2. It implies that CO2 and H2 are secondary products from further decomposition of HCOOH at high temperatures. Being a general purpose tool for reaction prediction, the SSW-Cat may be utilized for rational catalyst design via large-scale computations.
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NASA Astrophysics Data System (ADS)
Zhang, Sufeng; Zhao, Dongyan; Hou, Chen; Liang, Chen; Li, Hao
2018-06-01
A facile and efficient one-pot method for the synthesis of well-dispersed hollow CuFe2O4 nanoparticles (H-CuFe2O4 NPs) in the presence of cellulose nanocrystals (CNC) as the support was described. Based on the one-pot solvothermal condition control, magnetic H-CuFe2O4 NPs were in-situ grown on the CNC surface uniformly. TEM images indicated good dispersity of H-CuFe2O4 NPs with uniform size of 300 nm. The catalytic activity of H-CuFe2O4/CNC was tested in the catalytic reduction of 4-nitrophenol (4-NP) in aqueous solution. Compared with most CNC-based ferrite catalysts, H-CuFe2O4/CNC catalyst exhibited an excellent catalytic activity toward the reduction of 4-NP. The catalytic performance of H-CuFe2O4/CNC catalyst was remarkably enhanced with the rate constant of 3.24 s-1 g-1, which was higher than H-CuFe2O4 NPs (0.50 s-1 g-1). The high catalytic activity was attributed to the introduction of CNC and the special hollow mesostructure of H-CuFe2O4 NPs. In addition, the H-CuFe2O4/CNC catalyst promised good conversion efficiency without significant decrease even after 10 cycles, confirming relatively high stability. Because of its environmental sustainability and magnetic separability, H-CuFe2O4/CNC catalyst was shown to indicate that the ferrite nanoparticles supported on CNC were acted as a promising catalyst and exhibited potential applications in numerous ferrite based catalytic reactions.
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High efficiency tantalum-based ceramic composite structures
NASA Technical Reports Server (NTRS)
Stewart, David A. (Inventor); Leiser, Daniel B. (Inventor); DiFiore, Robert R. (Inventor); Katvala, Victor W. (Inventor)
2010-01-01
Tantalum-based ceramics are suitable for use in thermal protection systems. These composite structures have high efficiency surfaces (low catalytic efficiency and high emittance), thereby reducing heat flux to a spacecraft during planetary re-entry. These ceramics contain tantalum disilicide, molybdenum disilicide and borosilicate glass. The components are milled, along with a processing aid, then applied to a surface of a porous substrate, such as a fibrous silica or carbon substrate. Following application, the coating is then sintered on the substrate. The composite structure is substantially impervious to hot gas penetration and capable of surviving high heat fluxes at temperatures approaching 3000.degree. F. and above.
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Yang, Tao; Fukuda, Ryoichi; Hosokawa, Saburo; Tanaka, Tsunehiro
2017-01-01
Abstract Single‐atom catalysts have attracted much interest recently because of their excellent stability, high catalytic activity, and remarkable atom efficiency. Inspired by the recent experimental discovery of a highly efficient single‐atom catalyst Pd1/γ‐Al2O3, we conducted a comprehensive DFT study on geometries, stabilities and CO oxidation catalytic activities of M1/γ‐Al2O3 (M=Pd, Fe, Co, and Ni) by using slab‐model. One of the most important results here is that Ni1/Al2O3 catalyst exhibits higher activity in CO oxidation than Pd1/Al2O3. The CO oxidation occurs through the Mars van Krevelen mechanism, the rate‐determining step of which is the generation of CO2 from CO through abstraction of surface oxygen. The projected density of states (PDOS) of 2p orbitals of the surface O, the structure of CO‐adsorbed surface, charge polarization of CO and charge transfer from CO to surface are important factors for these catalysts. Although the binding energies of Fe and Co with Al2O3 are very large, those of Pd and Ni are small, indicating that the neighboring O atom is not strongly bound to Pd and Ni, which leads to an enhancement of the reactivity of the O atom toward CO. The metal oxidation state is suggested to be one of the crucial factors for the observed catalytic activity. PMID:28515795
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NASA Astrophysics Data System (ADS)
Kakekhani, Arvin; Ismail-Beigi, Sohrab
2014-03-01
NOx are regulated pollutants produced during automotive combustion. As part of an effort to design catalysts for NOx decomposition that operate in oxygen rich environment and permit greater fuel efficiency, we study chemistry of NOx on (001) ferroelectric surfaces. Changing the polarization at such surfaces modifies electronic properties and leads to switchable surface chemistry. Using first principles theory, our previous work has shown that addition of catalytic RuO2 monolayer on ferroelectric PbTiO3 surface makes direct decomposition of NO thermodynamically favorable for one polarization. Furthermore, the usual problem of blockage of catalytic sites by strong oxygen binding is overcome by flipping polarization that helps desorb the oxygen. We describe a thermodynamic cycle for direct NO decomposition followed by desorption of N2 and O2. We provide energy barriers and transition states for key steps of the cycle as well as describing their dependence on polarization direction. We end by pointing out how a switchable order parameter of substrate,in this case ferroelectric polarization, allows us to break away from some standard compromises for catalyst design(e.g. the Sabatier principle). This enlarges the set of potentially catalytic metals. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.
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Qi, Wei; Yan, Pengqiang; Su, Dang Sheng
2018-03-20
Sustainable and environmentally benign catalytic processes are vital for the future to supply the world population with clean energy and industrial products. The replacement of conventional metal or metal oxide catalysts with earth abundant and renewable nonmetallic materials has attracted considerable research interests in the field of catalysis and material science. The stable and efficient catalytic performance of nanocarbon materials was discovered at the end of last century, and these materials are considered as potential alternatives for conventional metal-based catalysts. With its rapid development in the past 20 years, the research field of carbon catalysis has been experiencing a smooth transition from the discovery of novel nanocarbon materials or related new reaction systems to the atomistic-level mechanistic understanding on the catalytic process and the subsequent rational design of the practical catalytic reaction systems. In this Account, we summarize the recent progress in the kinetic and mechanistic studies on nanocarbon catalyzed alkane oxidative dehydrogenation (ODH) reactions. The paper attempts to extract general concepts and basic regularities for carbon catalytic process directing us on the way for rational design of novel efficient metal-free catalysts. The nature of the active sites for ODH reactions has been revealed through microcalorimetric analysis, ambient pressure X-ray photoelectron spectroscopy (XPS) measurement, and in situ chemical titration strategies. The detailed kinetic analysis and in situ catalyst structure characterization suggests that carbon catalyzed ODH reactions involve the redox cycles of the ketonic carbonyl-hydroxyl pairs, and the key physicochemical parameters (activation energy, reaction order, and rate/equilibrium constants, etc.) of the carbon catalytic systems are proposed and compared with conventional transition metal oxide catalysts. The proposal of the intrinsic catalytic activity (TOF) provides the possibility for the fair comparisons of different nanocarbon catalysts and the consequent structure-function relation regularity. Surface modification and heteroatom doping are proved as the most effective strategies to adjust the catalytic property (activity and product selectivity etc.) of the nanocarbon catalysts. Nanocarbon is actually a proper candidate platform helping us to understand the classical catalytic reaction mechanism better, since there is no lattice oxygen and all the catalytic process happens on nanocarbon surface. This Account also exhibits the importance of the in situ structural characterizations for heterogeneous nanocarbon catalysis. The research strategy and methods proposed for carbon catalysts may also shed light on other complicated catalytic systems or fields concerning the applications of nonmetallic materials, such as energy storage and environment protection etc.
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Hierarchical Nanoporous Gold-Platinum with Heterogeneous Interfaces for Methanol Electrooxidation
Xiao, Shuang; Xiao, Fei; Hu, Yuan; Yuan, Songliu; Wang, Shuai; Qian, Lihua; Liu, Yunqi
2014-01-01
The electrocatalysts utilized as the prospective electrodes in fuel cells and high efficient energy conversion devices require both the interconnected channels for efficient electrolyte transportation and the superior catalytic activity with long service life. In this work, nanoporous gold with the rigid skeletons in three dimensions is partially decorated by porous platinum shell containing nanoscale interstitials, aiming to create the heterogeneous gold-platinum interfaces and facilitate the electrolyte transportation as well. In comparison with no catalytic activity of bare nanoporous gold, the catalytic activity of hierarchical nanoporous gold-platinum towards electrochemical oxidation of methanol increases with the loading level of platinum shells, resulting in the highest electrochemical area of 70.4 m2·g−1 after the normalization by the mass of platinum. Heterogeneous gold-platinum interfaces affect the tolerance of the absorbed intermediate species because of the oxidization by the oxygenated species absorbed on the gold surface and the enhanced ion transportation within the porous platinum shell. PMID:24621809
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Li, Yifeng; Zhang, Wenqiang; Zheng, Yun; Chen, Jing; Yu, Bo; Chen, Yan; Liu, Meilin
2017-10-16
Solid oxide cell (SOC) based energy conversion systems have the potential to become the cleanest and most efficient systems for reversible conversion between electricity and chemical fuels due to their high efficiency, low emission, and excellent fuel flexibility. Broad implementation of this technology is however hindered by the lack of high-performance electrode materials. While many perovskite-based materials have shown remarkable promise as electrodes for SOCs, cation enrichment or segregation near the surface or interfaces is often observed, which greatly impacts not only electrode kinetics but also their durability and operational lifespan. Since the chemical and structural variations associated with surface enrichment or segregation are typically confined to the nanoscale, advanced experimental and computational tools are required to probe the detailed composition, structure, and nanostructure of these near-surface regions in real time with high spatial and temporal resolutions. In this review article, an overview of the recent progress made in this area is presented, highlighting the thermodynamic driving forces, kinetics, and various configurations of surface enrichment and segregation in several widely studied perovskite-based material systems. A profound understanding of the correlation between the surface nanostructure and the electro-catalytic activity and stability of the electrodes is then emphasized, which is vital to achieving the rational design of more efficient SOC electrode materials with excellent durability. Furthermore, the methodology and mechanistic understanding of the surface processes are applicable to other materials systems in a wide range of applications, including thermo-chemical photo-assisted splitting of H 2 O/CO 2 and metal-air batteries.
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Briggs, Beverly D.; Bedford, Nicholas M.; Seifert, Soenke; ...
2015-07-23
C–C coupling reactions are of great importance in the synthesis of numerous organic compounds, where Pd nanoparticle catalyzed systems represent new materials to efficiently drive these reactions. Despite their pervasive utility, the catalytic mechanism of these particle-based reactions remains highly contested. Herein we present evidence of an atom leaching mechanism for Stille coupling under aqueous conditions using peptide-capped Pd nanoparticles. EXAFS analysis revealed Pd coordination changes in the nanoparticle consistent with Pd atom abstraction, where sizing analysis by SAXS confirmed particle size changes associated with a leaching process. It is likely that recently discovered highly disordered surface Pd atoms aremore » the favored catalytic active sites and are leached during oxidative addition, resulting in smaller particles. Thus, probing the mechanism of nanoparticle-driven C–C coupling reactions through structural analyses provides fundamental information concerning these active sites and their reactivity at the atomic-scale, which can be used to improve catalytic performance to meet important sustainability goals.« less
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A Mesopore-Dependent Catalytic Cracking of n-Hexane Over Mesoporous Nanostructured ZSM-5.
Qamar, M; Ahmed, M I; Qamaruddin, M; Asif, M; Sanhoob, M; Muraza, O; Khan, M Y
2018-08-01
Herein, pore size, crystalinity, and Si/Al ratio of mesoporous ZSM-5 (MFI) nanocrystals was controlled by synthesis parameters, such as surfactant concentration ([3-(trimethoxysilyl)propyl] hexa-decyl dimethyl ammonium chloride), sodium hydroxide concentrations, synthesis temperature and time. The morphology, surface structure and composition of the MFI particles was systematically investigated. More notably, the mesopore-dependent catalytic activity of ZSM-5 was evaluated by studying the cracking of n-hexane. The findings suggest the porosity has pronounced impact on the catalytic activity, selectivity and stability of ZSM-5 nanocrystals. Critical surface attributes such as nature of acid sites (Brønsted and Lewis), concentration, and strength are obtained by the infrared study of adsorbed probe molecules (pyridine) and the temperature programmed desorption. In spite of being weaker in Si/Al ratio or acidic strength, mesoporous catalysts showed more stable and efficient cracking of n-hexane suggesting that acidity seems not the predominant factor operative in the activity, selectivity and stability.
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NASA Astrophysics Data System (ADS)
Yoshida, K.; Shiju, N.; Brown, R.; Wright, I.; Boyes, E. D.; Gai, P. L.
2012-07-01
We report nanostructural and physico-chemical studies in the development of an efficient low temperature heterogeneous catalytic process for nonsteroidal anti-inflammatory drugs (NSAIDS) such as N-acetyl-p-aminophenol (paracetamol or acetaminophen) on tungstated zirconia nanocatalysts. Using a double-aberration corrected TEM/STEM, modified in-house for in-situ studies at the sub-Angstrom level, we directly observed in real-time, the dynamic precursor transformation to the active catalyst. We quantified the observations with catalytic activity studies for the NSAIDS. The studies have provided the direct evidence for single tungsten promoter atoms and surface WOx species of <= 0.35 nm, with nanoclusters of WOx (0.6 to 1nm), located at grain boundaries on the surface of the zirconia nanoparticles. The correlation between the nanostructure and catalytic activity indicates that the species create Brønsted acid sites highly active for the low temperature process. The results open up opportunities for developing green heterogeneous methods for pharmaceuticals.
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NASA Astrophysics Data System (ADS)
García-Meseguer, Rafael; Martí, Sergio; Ruiz-Pernía, J. Javier; Moliner, Vicent; Tuñón, Iñaki
2013-07-01
Conformational changes are known to be able to drive an enzyme through its catalytic cycle, allowing, for example, substrate binding or product release. However, the influence of protein motions on the chemical step is a controversial issue. One proposal is that the simple equilibrium fluctuations incorporated into transition-state theory are insufficient to account for the catalytic effect of enzymes and that protein motions should be treated dynamically. Here, we propose the use of free-energy surfaces, obtained as a function of both a chemical coordinate and an environmental coordinate, as an efficient way to elucidate the role of protein structure and motions during the reaction. We show that the structure of the protein provides an adequate environment for the progress of the reaction, although a certain degree of flexibility is needed to attain the full catalytic effect. However, these motions do not introduce significant dynamical corrections to the rate constant and can be described as equilibrium fluctuations.
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Few-layer MoSe₂ possessing high catalytic activity towards iodide/tri-iodide redox shuttles.
Lee, Lawrence Tien Lin; He, Jian; Wang, Baohua; Ma, Yaping; Wong, King Young; Li, Quan; Xiao, Xudong; Chen, Tao
2014-02-14
Due to the two-dimensional confinement of electrons, single- and few-layer MoSe₂ nanostructures exhibit unusual optical and electrical properties and have found wide applications in catalytic hydrogen evolution reaction, field effect transistor, electrochemical intercalation, and so on. Here we present a new application in dye-sensitized solar cell as catalyst for the reduction of I₃(-) to I(-) at the counter electrode. The few-layer MoSe₂ is fabricated by surface selenization of Mo-coated soda-lime glass. Our results show that the few-layer MoSe₂ displays high catalytic efficiency for the regeneration of I(-) species, which in turn yields a photovoltaic energy conversion efficiency of 9.00%, while the identical photoanode coupling with "champion" electrode based on Pt nanoparticles on FTO glass generates efficiency only 8.68%. Thus, a Pt- and FTO-free counter electrode outperforming the best conventional combination is obtained. In this electrode, Mo film is found to significantly decrease the sheet resistance of the counter electrode, contributing to the excellent device performance. Since all of the elements in the electrode are of high abundance ratios, this type of electrode is promising for the fabrication of large area devices at low materials cost.
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Zhu, Feng-Xia; Wang, Wei; Li, He-Xing
2011-08-03
An operationally simple approach for the preparation of a new class of bifunctional Au nanoparticle-acid catalysts has been developed. In situ reduction of Au(3+) with HS-functionalized periodic mesoporous organosilicas (PMOs) creates robust, fine Au nanoparticles and concomitantly produces a sulfonic acid moiety strongly bonded to PMOs. Characterizations of the nanostructures reveal that Au nanoparticles are formed with uniformed, narrow size distribution around 1-2 nm, which is very critical for essential catalytic activities. Moreover, the Au nanoparticles are mainly attached onto the pore surface rather than onto the outer surface with ordered mesoporous channels, allowing for maximal exposure to reaction substrates while minimizing Au nanoparticle leaching. Their higher S(BET), V(P), and D(P) than either the Au-HS-PMO(Et) or the Au/SO(3)H-PMO(Et) render the catalyst with comparably even higher catalytic efficiency than its homogeneous counterparts. Furthermore, the unique amphiphilic compartment of the Au-HS/SO(3)H-PMO(Et) nanostructures enables organic reactions to proceed efficiently in a pure aqueous solution without using any organic solvents or even without water. As demonstrated experimentally, remarkably, the unique bifunctional Au-HS/SO(3)H-PMO(Et) catalyst displays higher efficiencies in promoting water-medium alkyne hydration, intramolecular hydroamination, styrene oxidation, and three-component coupling reactions and even the solvent-free alkyne hydration process than its homogeneous catalysts. The robust catalyst can be easily recycled and used repetitively at least 10 times without loss of catalytic efficiency. These features render the catalyst particularly attractive in the practice of organic synthesis in an environmentally friendly manner.
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Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste
Liu, Wu-Jun; Tian, Ke; Jiang, Hong; Yu, Han-Qing
2013-01-01
In this work, sawdust, a biomass waste, is converted into a magnetic porous carbonaceous (MPC) solid acid catalyst by an integrated fast pyrolysis–sulfonation process. The resultant magnetic solid acid has a porous structure with high surface area of 296.4 m2 g−1, which can be attributed to the catalytic effect of Fe. The catalytic activity and recyclability of the solid acid catalyst are evaluated during three typical acid-catalyzed reactions: esterification, dehydration, and hydrolysis. The favorable catalytic performance in all three reactions is attributed to the acid's high strength with 2.57 mmol g−1 of total acid sites. Moreover, the solid acid can be reused five times without a noticeable decrease in catalytic activity, indicating the stability of the porous carbon (PC)–sulfonic acid group structure. The findings in the present work offer effective alternatives for environmentally friendly utilization of abundant biomass waste. PMID:23939253
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Lee, Hyosun; Lim, Juhyung; Lee, Changhwan; Back, Seoin; An, Kwangjin; Shin, Jae Won; Ryoo, Ryong; Jung, Yousung; Park, Jeong Young
2018-06-08
Despite numerous studies, the origin of the enhanced catalytic performance of bimetallic nanoparticles (NPs) remains elusive because of the ever-changing surface structures, compositions, and oxidation states of NPs under reaction conditions. An effective strategy for obtaining critical clues for the phenomenon is real-time quantitative detection of hot electrons induced by a chemical reaction on the catalysts. Here, we investigate hot electrons excited on PtCo bimetallic NPs during H 2 oxidation by measuring the chemicurrent on a catalytic nanodiode while changing the Pt composition of the NPs. We reveal that the presence of a CoO/Pt interface enables efficient transport of electrons and higher catalytic activity for PtCo NPs. These results are consistent with theoretical calculations suggesting that lower activation energy and higher exothermicity are required for the reaction at the CoO/Pt interface.
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NASA Astrophysics Data System (ADS)
Gao, Zhiyong; Liu, Xiao; Chang, Jiuli; Wu, Dapeng; Xu, Fang; Zhang, Lingcui; Du, Weimin; Jiang, Kai
2017-01-01
Graphene incorporated, N doped activated carbons (GNACs) are synthesized by alkali activation of graphene-polypyrrole composite (G-PPy) at different temperatures for application as electrode materials of supercapacitors. Under optimal activation temperature of 700 °C, the resultant samples, labeled as GNAC700, owns hierarchically porous texture with high specific surface area and efficient ions diffusion channels, N, O functionalized surface with apparent pseudocapacitance contribution and high wettability, thus can deliver a moderate capacitance, a high rate capability and a good cycleability when used as supercapacitor electrode. Additionally, the GNAC700 electrode demonstrates high catalytic activity for the redox reaction of pyrocatechol/o-quinone pair in H2SO4 electrolyte, thus enables a high pseudocapacitance from electrolyte. Under optimal pyrocatechol concentration in H2SO4 electrolyte, the electrode capacitance of GNAC700 increases by over 4 folds to 512 F g-1 at 1 A g-1, an excellent cycleability is also achieved simultaneously. Pyridinic- N is deemed to be responsible for the high catalytic activity. This work provides a promising strategy to ameliorate the capacitive performances of supercapacitors via the synergistic interaction between redox-active electrolyte and catalytic electrodes.
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Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi
2008-01-01
Formic acid (HCOOH) decomposes efficiently to afford H2 and CO2 selectively in the presence of a catalytic amount of a water-soluble rhodium aqua complex, [Rh(III)(Cp*)(bpy)(H2O)]2+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) in aqueous solution at 298 K. No CO was produced in this catalytic decomposition of HCOOH. The decomposition rate reached a maximum value at pH 3.8. No deterioration of the catalyst was observed during the catalytic decomposition of HCOOH, and the catalytic activity remained the same for the repeated addition of HCOOH. The rhodium-hydride complex was detected as the catalytic active species that undergoes efficient H/D exchange with water. When the catalytic decomposition of HCOOH was performed in D2O, D2 was produced selectively. Such an efficient H/D exchange and the observation of a deuterium kinetic isotope effect in the catalytic decomposition of DCOOH in H2O provide valuable mechanistic insight into this efficient and selective decomposition process.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Chaleshtori, Maryam Zarei, E-mail: mzarei@utep.edu; Hosseini, Mahsa; Edalatpour, Roya
2013-10-15
Graphical abstract: The photocatalytic activity of different porous titanium–niobium oxides was evaluated toward degradation of bromocresol green (BG) under UV light. A better catalytic activity was observed for all samples at lower pH. Catalysts have a stronger ability for degradation of BG in acid media than in alkaline media. - Highlights: • Different highly structured titanium–niobium oxides have been prepared using improved methods of synthesis. • Photo-degradation of bromocresol green dye (BG) with nanostructure titanium–niobium oxide catalysts was carried out under UV light. • The photo-catalytic activity of all catalysts was higher in lower pH. • Titanium–niobium oxide catalysts aremore » considerably stable and reusable. - Abstract: In this study, high surface area semiconductors, non porous and porous titanium–niobium oxides derived from KTiNbO{sub 5} were synthesized, characterized and developed for their utility as photocatalysts for decontamination with sunlight. These materials were then used in the photocatalytic degradation of bromocresol green dye (BG) in aqueous solution using UV light and their catalytic activities were evaluated at various pHs. For all catalysts, the photocatalytic degradation of BG was most efficient in acidic solutions. Results show that the new porous oxides have large porous and high surface areas and high catalytic activity. A topotactic dehydration treatment greatly improves catalyst performance at various pHs. Stability and long term activity of porous materials (topo and non-topo) in photocatalysis reactions was also tested. These results suggest that the new materials can be used to efficiently purify contaminated water.« less
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Yihan, Sun; Mingming, Liu; Guo, Zhiguang
2018-05-19
Herein, a catalytic mesh with unique wettability, high oil-water separation efficiency and excellent catalytic performance towards aromatic dyes was fabricated. Polypyrrole (PPy) was firstly pre-coated on pristine stainless-steel mesh (SSM) surface via cyclic voltammetry approach. Subsequently, a simple electrodeposition process was performed to prepare and anchor Ag nanoparticles (AgNPs) onto the PPy-coated SSM surface. The PPy-coated mesh with anchored AgNPs was denoted as PPy/AgNPs-coated SSM. The obtained PPy/AgNPs-coated SSM exhibited dual superlyophobic properties and were able to achieve on-demand separation to deal with various of light oil (ρ oil < ρ water ) and heavy oil (ρ oil > ρ water )-water mixtures. Importantly, benefitting from AgNPs on mesh surface, the obtained PPy/AgNPs-coated SSM exhibits exceptional catalytic activity. As proof-of-concept three typical aromatic dye molecules (methylene blue, rhodamine B and Congo red) can be effectivity degraded. Additionally, the degradation of aromatic dyes and oil-water separation were achieved simultaneously when the PPy/AgNPs-coated SSM was converted to water-removing mode. Therefore, the present work is of great significance to the development of novel oil-water filtration membranes and can open a new avenue towards the practicability of metal nanoparticle catalysts in wastewater treatment. Copyright © 2018 Elsevier Inc. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Rappe, Andrew
This research project explored the catalytic properties of complex surfaces of functional materials. The PI used first-principles density functional theory (DFT) calculations to explore a tightly integrated set of properties. The physical properties of complex functional materials that influence surface chemistry were explored, including bulk and surface electric dipoles, and surface conductivity. The energetic, compositional, electronic, and chemical properties of the surfaces of these materials were explored in detail, and connections between material properties and chemical reactivity were established. This project led to 28 publications, including Nat. Comm., JACS, 3 PRL, 7 PRB, 2 ACS Nano, 2 Nano Lett., 4more » JPCL, 2 JCP, Chem. Mater., ACS Appl. Mater. Interfaces, Phys. Rev. Appl., and a U.S. Patent on surface catalysts. The key accomplishments in this project involved work in six coordinated areas: pioneering ways to control bulk dipoles in order to dynamically affect catalysis, exploring novel ways of bringing charge to the surface for redox catalysis, nonstoichiometric surfaces offering new sites for heterogeneous catalysis, illustrating how surface catalysis responds to applied pressure, catalytic growth of carbon-based materials, and new computational methods allowing more accurate exploration of molecule-surface interactions« less
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Gomes, Diego E B; Lins, Roberto D; Pascutti, Pedro G; Lei, Chenghong; Soares, Thereza A
2010-01-14
The enzyme organophosphorous hydrolase (OPH) catalyzes the hydrolysis of a wide variety of organophosphorous compounds with high catalytic efficiency and broad substrate specificity. The immobilization of OPH in functionalized mesoporous silica (FMS) surfaces increases significantly its catalytic specific activity, as compared to the enzyme in solution, with important applications for the detection and decontamination of insecticides and chemical warfare agents. Experimental measurements of immobilization efficiency as a function of the charge and coverage percentage of different functional groups have been interpreted as electrostatic forces being the predominant interactions underlying the adsorption of OPH onto FMS surfaces. Explicit solvent molecular dynamics simulations have been performed for OPH in bulk solution and adsorbed onto two distinct interaction potential models of the FMS functional groups to investigate the relative contributions of nonbonded interactions to the conformational dynamics and adsorption of the protein. Our results support the conclusion that electrostatic interactions are responsible for the binding of OPH to the FMS surface. However, these results also show that van der Waals forces are detrimental for interfacial adhesion. In addition, it is found that OPH adsorption onto the FMS models favors a protein conformation whose active site is fully accessible to the substrate, in contrast to the unconfined protein.
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Highly flexible sub-1 nm tungsten oxide nanobelts as efficient desulfurization catalysts.
He, Jie; Liu, Huiling; Xu, Biao; Wang, Xun
2015-03-01
Ultrathin tungsten oxide nanobelts are successfully synthesized via a facile solvothermal method. Sub-1 nm thickness and hydrophobic surface property endow the nanobelts with flexibility, viscosity, gelation, and good catalytic performance in oxidative desulfurization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Hod, Idan; Sampson, Matthew D.; Deria, Pravas; ...
2015-09-18
Realization of heterogeneous electrochemical CO 2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO 2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~10 15 sites/cm 2). The chemical products of the reduction, obtained withmore » ~100% Faradaic efficiency, are mixtures of CO and H 2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.« less
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NASA Astrophysics Data System (ADS)
Chen, Xi; Lin, Zheng-Zhe
2018-05-01
In recent years, two-dimensional confined catalysis, i.e., the enhanced catalytic reactions in confined space between metal surface and two-dimensional overlayer, makes a hit and opens up a new way to enhance the performance of catalysts. In this work, graphdiyne overlayer was proposed as a more excellent material than graphene or hexagonal boron nitride for two-dimensional confined catalysis on Pt(111) surface. Density functional theory calculations revealed the superiority of graphdiyne overlayer originates from the steric hindrance effect which increases the catalytic ability and lowers the reaction barriers. Moreover, with the big triangle holes as natural gas tunnels, graphdiyne possesses higher efficiency for the transit of gaseous reactants and products than graphene or hexagonal boron nitride. The results in this work would benefit future development of two-dimensional confined catalysis. [Figure not available: see fulltext.
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NASA Astrophysics Data System (ADS)
Liu, Ying; Zhang, Kun; Yin, Xiaoshuang; Yang, Wenzhong; Zhu, Hongjun
2016-04-01
The metal-deposited magnetic catalyst microspheres (MCM-MPs) were successfully synthesized by one facile, high yield and controllable approach. Here, the bare magnetic microspheres were firstly synthesized according to the solvothermal method. Then silica shell were coated on the surface of the magnetic microspheres via sol-gel method, and subsequently with surface modifying with amino in the purpose to form SiO2-NH2 shell. Thus, metal particles were easily adsorbed into the SiO2-NH2 shell and in-situ reduced by NaBH4 solution. All the obtained products (MCM-Cu, MCM-Ag, MCM-Pd) which were monodisperse and constitutionally stable were exhibited high magnetization and excellent catalytic activity towards dyes solution reduction. The catalytic rate ratio of MCM-Pd: MCM-Cu: MCM-Ag could be 10:3:1. Besides, some special coordination compound Cu2(OH)3Br had been generated in the in-situ reduced process of MCM-Cu, which produced superior cyclical stability (>20 times) than that of MCM-Ag and MCM-Pd. In all, those highly reusability and great catalytic efficiency of MCM-MPs show promising and great potential for treatment of dye-contaminated water.
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NASA Astrophysics Data System (ADS)
Huang, Xiaohua; El-Sayed, Ivan H.; El-Sayed, Mostafa A.
2005-08-01
Gold nanoparticles with unique optical properties offer useful applications in biotechnology. In this article two applications that we have developed are summarized, in one they are used in cancer cell diagnostics and in the other they are found to have catalytic property for the NADH oxidation reaction which is important in ATP formations. By conjugation with anti-EGFR antibodies which specifically target EGFR that are usually overexpressed on most cancer cells, gold nanoparticles are used as a molecular contrast agent for cancer cell diagnostics using their both strong surface plasmon absorption and efficient Mie scattering properties. Au nanoparticles are also good catalysts for many reactions due to their high surface to volume ratio. Au nanoparticles are found to be the catalyst for the NADH oxidation reaction. This was studied by monitoring the effect of the nanoparticles on NADH fluorescence intensity and lifetime as well as the change of the surface plasmon absorption band during the reaction.
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Fabrication of superhydrophobic Pt3Fe/Fe surface for its application
NASA Astrophysics Data System (ADS)
Cui, Shuo; Lu, Shixiang; Xu, Wenguo; Wu, Bei
2017-10-01
Well-defined Pt3Fe/Fe superhydrophobic materials on iron sheet with special properties, such as corrosion resistance, superhydrophobicity and superoleophilicity, was fabricated. The fabrication process involved etching in hydrochloric acid aqueous solution and simple replacement deposition process without using any seed and organic solvent, and then annealing. The electrochemical measurements show that the resultant surface in 3.5% sodium chloride solution displays good corrosion resistance. Also, it is proved that the obtained surface has better mechanical abrasion resistance via scratch test. The superoleophilicity and low water adhesion force of the obtained surface endow it high oil/water separation capacity. The as-prepared nanocomposites display enhanced catalytic activity and kinetics toward degradation of methyl orange. In particular, it possesses the most efficient degradation capacity (95%) towards methyl orange at a high concentration (17.5 mg/L) in 80 min. The improved stability and excellent catalytic activity of the Pt3Fe/Fe nanocomposites promise new opportunities for the development of waste water treatment.
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Zhang, Hua; Wang, Chen; Sun, Han-Lei; Fu, Gang; Chen, Shu; Zhang, Yue-Jiao; Chen, Bing-Hui; Anema, Jason R.; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun
2017-01-01
Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd–C/Pt–C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis. PMID:28537269
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Yang, Jin; Wang, Wei David; Dong, Zhengping
2018-08-15
In the present work, a facile and environment-friendly route is illustrated for the efficient fabrication of highly dispersed PdCo nanoparticles (NPs) by modified cotton-derived carbon fibers (PdCo/CCF). Firstly, commercial cotton was impregnated with CoCl 2 , followed by pyrolysis under high calcination temperature to obtain the Co NPs modified CCF sample (Co/CCF). Secondly, Co/CCF was treated with Pd(AcO) 2 aqueous solution, wherein, through a spontaneous replacement reaction process, Pd 2+ is reduced to metallic Pd and mostly covered on the surface of the Co NPs. Thus, the PdCo/CCF catalyst was obtained avoiding the use of toxic reductants like NaBH 4 , NH 2 NH 2 and HCHO. The PdCo/CCF catalyst exhibits excellent catalytic activity and recyclability for the reduction of 4-nitrophenol and other nitroarenes compared with Pd/CCF, PdCo NPs and many other noble metals based catalysts. The reasons could be attributed to the uniformly dispersed and accessible PdCo NPs on the surface of the CCF, and the Pd atoms deposited on the Co NPs surface that makes the Pd active sites available for optimum use. The PdCo/CCF catalyst also exhibits potential application for catalytic reduction of nitroarenes in a fixed bed reactor under mild reaction conditions. Furthermore, the PdCo/CCF catalyst can be magnetically recycled and reused for at least ten cycles without either losing catalytic activity or leaching of Pd active sites, thereby confirming its superior stability. Copyright © 2018 Elsevier Inc. All rights reserved.
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Zeng, Xianwei; Xiong, Dehua; Zhang, Wenjun; Ming, Liqun; Xu, Zhen; Huang, Zhanfeng; Wang, Mingkui; Chen, Wei; Cheng, Yi-Bing
2013-08-07
In this paper, low-cost counter electrodes (CEs) based on water-soluble multiwall carbon nanotube (MWCNT) and Cu2ZnSnSe4 nanoparticle (CZTSe NP) composites have been successfully introduced into a quantum dot-sensitized solar cell (QDSC) system. Suitable surface modification allows the MWCNTs and CZTSe NPs to be homogeneously dispersed in water, facilitating the subsequent low-temperature spray deposition of high quality composite films with different composite ratios. The electrochemical catalytic activity of the composite CEs has been critically compared by electrochemical impedance spectroscopy and Tafel-polarization analysis. It is found that the composite CE at the MWCNT : CZTSe ratio of 0.1 offers the best performance, leading to an optimal solar cell efficiency of 4.60%, which is 50.8% higher than that of the Pt reference CE. The as-demonstrated higher catalytic activity of the composite CEs compared to their single components could be ascribed to the combination of the fast electron transport of the MWCNTs and the high catalytic activity of CZTSe NPs.
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Zhang, Yongqi; Ouyang, Bo; Xu, Kun; Xia, Xinhui; Zhang, Zheng; Rawat, Rajdeep Singh; Fan, Hong Jin
2018-04-01
Prereduction of transition metal oxides is a feasible and efficient strategy to enhance their catalytic activity for hydrogen evolution. Unfortunately, the prereduction via the common H 2 annealing method is unstable for nanomaterials during the hydrogen evolution process. Here, using NiMoO 4 nanowire arrays as the example, it is demonstrated that carbon plasma (C-plasma) treatment can greatly enhance both the catalytic activity and the long-term stability of transition metal oxides for hydrogen evolution. The C-plasma treatment has two functions at the same time: it induces partial surface reduction of the NiMoO 4 nanowire to form Ni 4 Mo nanoclusters, and simultaneously deposits a thin graphitic carbon shell. As a result, the C-plasma treated NiMoO 4 can maintain its array morphology, chemical composition, and catalytic activity during long-term intermittent hydrogen evolution process. This work may pave a new way for simultaneous activation and stabilization of transition metal oxide-based electrocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Method to monitor HC-SCR catalyst NOx reduction performance for lean exhaust applications
Viola, Michael B [Macomb Township, MI; Schmieg, Steven J [Troy, MI; Sloane, Thompson M [Oxford, MI; Hilden, David L [Shelby Township, MI; Mulawa, Patricia A [Clinton Township, MI; Lee, Jong H [Rochester Hills, MI; Cheng, Shi-Wai S [Troy, MI
2012-05-29
A method for initiating a regeneration mode in selective catalytic reduction device utilizing hydrocarbons as a reductant includes monitoring a temperature within the aftertreatment system, monitoring a fuel dosing rate to the selective catalytic reduction device, monitoring an initial conversion efficiency, selecting a determined equation to estimate changes in a conversion efficiency of the selective catalytic reduction device based upon the monitored temperature and the monitored fuel dosing rate, estimating changes in the conversion efficiency based upon the determined equation and the initial conversion efficiency, and initiating a regeneration mode for the selective catalytic reduction device based upon the estimated changes in conversion efficiency.
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NASA Astrophysics Data System (ADS)
Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep
2016-07-01
For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.
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Development of a para-orthohydrogen catalytic converter for a solid hydrogen cooler
NASA Technical Reports Server (NTRS)
Nast, T. C.; Hsu, I. C.
1984-01-01
Design features of a tested catalytic converter for altering vented cryogenic parahydrogen used as a coolant on spacecraft into a para-ortho equilibrium for channeling to other cooling functions are described. The hydrogen is expected to be stored in either liquid or solid form. A high surface area Ni-on-Si catalyst was selected for tests at an operating pressure of 2 torr at a ratio of 1000 gr catalyst for a gr/sec hydrogen flow. Cylindrical and radial flow geometries were tried and measurements centered on the converter efficiencies at different operating temperatures when the converter was placed in the vent line of the H2 cooler. Efficiencies ranging from 10-100 percent were obtained for varying flow rates. Further testing is necessary to characterize the converter performance under a wider range of operating temperatures and environments.
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NASA Astrophysics Data System (ADS)
Wang, Tehua; Chong, Siying; Wang, Tongtong; Lu, Huiyi; Ji, Min
2018-01-01
In order to correlate the physicochemical properties of carbon-covered alumina (CCA) materials with their catalytic performance for oxidative dehydrogenation of ethylbenzene with CO2 (CO2-ODEB), a series of CCA materials with diverse carbon contents (8.7-31.3 wt%) and pyrolysis temperatures (600-800 °C), which were synthesized via an impregnation method followed by pyrolysis, were applied. These catalytic materials were characterized by TGA, N2 physisorption, XRD, Raman spectroscopy and XPS techniques. It was found that the catalytic performance of these CCA materials highly depended on their physicochemical properties, and the optimum CCA catalyst exhibited much better catalytic stability than conventional hydroxyl carbon nanotubes. Below an optimum value of carbon content, the CCA catalyst preserved the main pore characteristics of the Al2O3 support and its catalytic activity increased with the carbon content. Excessive carbon loading resulted in significant textural alterations and thereby decreased both the ethylbenzene conversion and styrene selectivity. On the other hand, high pyrolysis temperature was detrimental to the ordered graphitic structure of the carbon species within the Al2O3 pore. The decreased ordered graphitic degree was found to be associated with the loss of the surface active carbonyl groups, consequently hampering the catalytic efficiency of the CCA catalyst.
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Few-Layer MoSe2 Possessing High Catalytic Activity towards Iodide/Tri-iodide Redox Shuttles
Lee, Lawrence Tien Lin; He, Jian; Wang, Baohua; Ma, Yaping; Wong, King Young; Li, Quan; Xiao, Xudong; Chen, Tao
2014-01-01
Due to the two-dimensional confinement of electrons, single- and few-layer MoSe2 nanostructures exhibit unusual optical and electrical properties and have found wide applications in catalytic hydrogen evolution reaction, field effect transistor, electrochemical intercalation, and so on. Here we present a new application in dye-sensitized solar cell as catalyst for the reduction of I3− to I− at the counter electrode. The few-layer MoSe2 is fabricated by surface selenization of Mo-coated soda-lime glass. Our results show that the few-layer MoSe2 displays high catalytic efficiency for the regeneration of I− species, which in turn yields a photovoltaic energy conversion efficiency of 9.00%, while the identical photoanode coupling with “champion” electrode based on Pt nanoparticles on FTO glass generates efficiency only 8.68%. Thus, a Pt- and FTO-free counter electrode outperforming the best conventional combination is obtained. In this electrode, Mo film is found to significantly decrease the sheet resistance of the counter electrode, contributing to the excellent device performance. Since all of the elements in the electrode are of high abundance ratios, this type of electrode is promising for the fabrication of large area devices at low materials cost. PMID:24525919
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NASA Astrophysics Data System (ADS)
Rangel-Rivera, Pedro; Bachiller-Baeza, María Belén; Galindo-Esquivel, Ignacio; Rangel-Porras, Gustavo
2018-07-01
The interactions between the clay surface and the organic molecules play an important role in the efficient of these materials in adsorption and catalytic processes. These materials are often modified with the inclusion of other catalytic particles for the purpose of enhancing the activity. In this study, commercial clay K10 was modified with the particles inclusion of titanium and zirconium. The solid surfaces were examined by infrared spectroscopy, scanning electron microscopy (SEM) coupled to an energy-dispersive X-ray spectroscopy device (EDS), and X-ray photoelectron spectroscopy (XPS). Temperature programmed desorption of ammonia (TPD-NH3) and propan-2-ol decomposition test reaction were performed to probe the acid properties. The adsorption of acetic acid, ethanol, and propan-2-ol on the surface of each solid and their thermal stability were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). Finally, these materials were used in the esterification of acetic acid with penta-1-ol. The real effect over the incorporation of titanium species and zirconium species on clay surface for interacting with the organic molecules was discussed.
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Graphite-Conjugated Rhenium Catalysts for Carbon Dioxide Reduction
DOE Office of Scientific and Technical Information (OSTI.GOV)
Oh, Seokjoon; Gallagher, James R.; Miller, Jeffrey T.
2016-02-17
Condensation of fac-Re(5,6-diamino-1,10-phenanthroline)(CO)(3)Cl to o-quinone edge defects on graphitic carbon surfaces generates graphite-conjugated rhenium (GCC-Re) catalysts that are highly active for CO2 reduction to CO in acetonitrile electrolyte. X-ray photo-electron and X-ray absorption spectroscopies establish the formation of surface-bound Re centers with well-defined coordination environments. GCC-Re species on glassy carbon surfaces display catalytic currents greater than 50 mA cm(-2) with 96 +/- 3% Faradaic efficiency for CO production. Normalized for the number of Re active sites, GCC-Re catalysts exhibit higher turnover frequencies than that of a soluble molecular analogue, fac-Re(1,10-phenanthroline)(CO)(3)Cl, and turnover numbers greater than 12,000. In contrast to themore » molecular analogue, GCC-Re surfaces display a Tafel slope of 150 mV/decade, indicative of a catalytic mechanism involving rate-limiting one-electron transfer. This work establishes graphite conjugation as a powerful strategy for generating well-defined, tunable, heterogeneous electrocatalysts on ubiquitous graphitic carbon surfaces.« less
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NASA Astrophysics Data System (ADS)
Li, Wenge; Hu, Yanjie; Jiang, Hao; Jiang, Yi; Wang, Yang; Huang, Su; Biswas, Pratim; Li, Chunzhong
2018-06-01
Constructing a porous architecture is a considerable strategy to enhance the catalytic activity of metal oxides catalysts for CO oxidation. In this work, we have developed porous sponge-like Fe2O3 microspheres by employing a facile aerosol spray pyrolysis. The NaNO3 salt in the spray solution plays a crucial role as a fluxing sacrifice template in the formation of the sponge-like structure, in which a high surface area of 216.2 m2 g-1 and an average pore size of 4 nm are obtained. This novel Fe2O3 catalyst exhibits an improved catalytic activity compared to usual iron oxides catalysts. Nearly 50% CO conversion at a relatively low temperature of 200 °C and 100% CO conversion at 300 °C at a space velocity of 60 000 ml h-1 g-1 are achieved. Furthermore, it displays an outstanding catalytic stability without distinct decay for 1000 min in a continuous stream at 300 °C. In addition to the effect of plentiful adsorption sites for the gas reactant, the promoted catalytic performance is also attributed to the function of abundant OH groups rooted in the large surface of the sponge-like structure, which induces faster reaction rate of CO oxidation via a bicarbonate route.
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Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong
2013-06-01
Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.
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Unravelling Site-Specific Photo-Reactions of Ethanol on Rutile TiO2(110)
Hansen, Jonas Ø.; Bebensee, Regine; Martinez, Umberto; Porsgaard, Soeren; Lira, Estephania; Wei, Yinying; Lammich, Lutz; Li, Zheshen; Idriss, Hicham; Besenbacher, Flemming; Hammer, Bjørk; Wendt, Stefan
2016-01-01
Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2. PMID:26915303
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Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao; ...
2016-08-30
Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao
Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less
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NASA Astrophysics Data System (ADS)
Anushree; Kumar, S.; Sharma, C.
2017-11-01
Here we report the catalytic property of ZnO-CeO2 nanoparticles towards oxidative degradation of organic pollutants present in industrial wastewater. The catalysts were prepared by co-precipitation method without using any surfactant. The physicochemical properties of catalysts were studied by XRD, Raman, XPS, N2-sorption, FE-SEM, TEM and EDX techniques. The characterization results confirmed the formation of porous ZnO-CeO2 nanocatalysts with high surface area, pore volume and oxygen vacancies. ZnO-CeO2 nanocatalysts exhibited appreciable efficiency in CWAO of industrial wastewater under mild conditions. The Ce40Zn60 catalyst was found to be most efficient with 72% color, 64% chemical oxygen demand (COD) and 63% total organic carbon (TOC) removal. Efficient removal of chlorophenolics (CHPs, 59%) and adsorbable organic halides (AOX, 54%) indicated the feasibility of using ZnO-CeO2 nanocatalysts in degradation of non-biodegradable and toxic chlorinated compounds.
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NASA Astrophysics Data System (ADS)
Ma, Tao; Fan, Qun; Tao, Hengcong; Han, Zishan; Jia, Mingwen; Gao, Yunnan; Ma, Wangjing; Sun, Zhenyu
2017-11-01
Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.
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Self-Propulsion Of Catalytic Conical Micro-Swimmer
NASA Astrophysics Data System (ADS)
Gallino, Giacomo; Gallaire, Francois; Lauga, Eric; Michelin, Sebastien
2017-11-01
Self-propelled artificial micro-motors have attracted much attention both as fundamental examples of active matter and for their potential biomedical applications (e.g. drug delivery, cell sorting). A popular design exploits the catalytic decomposition of a fuel (e.g. hydrogen peroxide) on the active surface of the motor to produce oxygen bubbles that propel the swimmer, effectively converting chemical energy into swimming motion. We focus here on a conical shape swimmer with chemically-active inner surfaces. Using numerical simulations of the chemical problem and viscous hydrodynamics, we analyze the formation, growth and motion of the bubbles inside the micro-motor and the resulting swimming motion. Our results shed light on the fundamental hydrodynamics of the propulsion of conical swimmers and may help to improve the efficiency of these machines. G.G. aknowledges support from the Swiss National Science Fundation.
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Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces
NASA Astrophysics Data System (ADS)
McBriarty, Martin E.
Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.
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Chen, Yaxin; Huang, Zhiwei; Zhou, Meijuan; Ma, Zhen; Chen, Jianmin; Tang, Xingfu
2017-02-21
The involvement of a great amount of active oxygen species is a crucial requirement for catalytic oxidation of benzene, because complete mineralization of one benzene molecule needs 15 oxygen atoms. Here, we disperse single silver adatoms on nanostructured hollandite manganese oxide (HMO) surfaces by using a thermal diffusion method. The single-atom silver catalyst (Ag 1 /HMO) shows high catalytic activity in benzene oxidation, and 100% conversion is achieved at 220 °C at a high space velocity of 23 000 h -1 . The Mars-van Krevelen mechanism is valid in our case as the reaction orders for both benzene and O 2 approach one, according to reaction kinetics data. Data from H 2 temperature-programmed reduction and O core-level X-ray photoelectron spectra (XPS) reveal that Ag 1 /HMO possesses a great amount of active surface lattice oxygen available for benzene oxidation. Valence-band XPS and density functional theoretical calculations demonstrate that the single Ag adatoms have the upshifted 4d orbitals, thus facilitating the activation of gaseous oxygen. Therefore, the excellent activation abilities of Ag 1 /HMO toward both surface lattice oxygen and gaseous oxygen account for its high catalytic activity in benzene oxidation. This work may assist with the rational design of efficient metal-oxide catalysts for the abatement of volatile organic compounds such as benzene.
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NASA Astrophysics Data System (ADS)
Wang, Shan; Gao, Shasha; Tang, Yakun; Wang, Lei; Jia, Dianzeng; Liu, Lang
2018-04-01
Coal-based activated carbons (AC) were acted as the support, Cu/AC catalysts were synthesized by a facile solid-state reaction combined with subsequent heat treatment. In Cu/AC composites, highly dispersed Cu nanospheres were anchored on AC. The catalytic activity for 4-nitrophenol (4-NP) was investigated, the effects of activation temperature and copper loading on the catalytic performance were studied. The catalysts exhibited very high catalytic activity and moderate chemical stability due to the unique characteristics of the particle-assembled nanostructures, the high surface area and the porous structure of coal-based AC and the good dispersion of metal particles. Design and preparation of non-noble metal composite catalysts provide a new direction for improving the added value of coal.
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Shah, Rachit M; Maize, Kimberly M; West, Harrison T; Strom, Alexander M; Finzel, Barry C; Wagner, Carston R
2018-05-19
Inherited peripheral neuropathies are a group of neurodegenerative disorders that clinically affect 1 in 2500 individuals. Recently, genetic mutations in human histidine nucleotide-binding protein 1 (hHint1) have been strongly and most frequently associated with patients suffering from axonal neuropathy with neuromyotonia. However, the correlation between the impact of these mutations on the hHint1 structure, enzymatic activity and in vivo function has remained ambiguous. Here, we provide detailed biochemical characterization of a set of these hHint1 mutations. Our findings indicate that half of the mutations (R37P, G93D and W123*) resulted in a destabilization of the dimeric state and a significant decrease in catalytic activity and HINT1 inhibitor binding affinity. The H112N mutant was found to be dimeric, but devoid of catalytic activity, due to the loss of the catalytically essential histidine; nevertheless, it exhibited high affinity to AMP and a HINT1 inhibitor. In contrast to the active-site mutants, the catalytic activity and dimeric structure of the surface mutants, C84R and G89V, were found to be similar to the wild-type enzyme. Taken together, our results suggest that the pathophysiology of inherited axonal neuropathy with neuromyotonia can be induced by conversion of HINT1 from a homodimer to monomer, by modification of select surface residues or by a significant reduction of the enzyme's catalytic efficiency. Copyright © 2018. Published by Elsevier Ltd.
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Yang, Guang; Yao, Hua; Mozzicafreddo, Matteo; Ballarini, Patrizia; Pucciarelli, Sandra
2017-01-01
ABSTRACT The α-amylases are endo-acting enzymes that hydrolyze starch by randomly cleaving the 1,4-α-d-glucosidic linkages between the adjacent glucose units in a linear amylose chain. They have significant advantages in a wide range of applications, particularly in the food industry. The eukaryotic α-amylase isolated from the Antarctic ciliated protozoon Euplotes focardii (EfAmy) is an alkaline enzyme, different from most of the α-amylases characterized so far. Furthermore, EfAmy has the characteristics of a psychrophilic α-amylase, such as the highest hydrolytic activity at a low temperature and high thermolability, which is the major drawback of cold-active enzymes in industrial applications. In this work, we applied site-directed mutagenesis combined with rational design to generate a cold-active EfAmy with improved thermostability and catalytic efficiency at low temperatures. We engineered two EfAmy mutants. In one mutant, we introduced Pro residues on the A and B domains in surface loops. In the second mutant, we changed Val residues to Thr close to the catalytic site. The aim of these substitutions was to rigidify the molecular structure of the enzyme. Furthermore, we also analyzed mutants containing these combined substitutions. Biochemical enzymatic assays of engineered versions of EfAmy revealed that the combination of mutations at the surface loops increased the thermostability and catalytic efficiency of the enzyme. The possible mechanisms responsible for the changes in the biochemical properties are discussed by analyzing the three-dimensional structural model. IMPORTANCE Cold-adapted enzymes have high specific activity at low and moderate temperatures, a property that can be extremely useful in various applications as it implies a reduction in energy consumption during the catalyzed reaction. However, the concurrent high thermolability of cold-adapted enzymes often limits their applications in industrial processes. The α-amylase from the psychrophilic Antarctic ciliate Euplotes focardii (named EfAmy) is a cold-adapted enzyme with optimal catalytic activity in an alkaline environment. These unique features distinguish it from most α-amylases characterized so far. In this work, we engineered a novel EfAmy with improved thermostability, substrate binding affinity, and catalytic efficiency to various extents, without impacting its pH preference. These characteristics can be considered important properties for use in the food, detergent, and textile industries and in other industrial applications. The enzyme engineering strategy developed in this study may also provide useful knowledge for future optimization of molecules to be used in particular industrial applications. PMID:28455329
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Yang, Guang; Yao, Hua; Mozzicafreddo, Matteo; Ballarini, Patrizia; Pucciarelli, Sandra; Miceli, Cristina
2017-07-01
The α-amylases are endo-acting enzymes that hydrolyze starch by randomly cleaving the 1,4-α-d-glucosidic linkages between the adjacent glucose units in a linear amylose chain. They have significant advantages in a wide range of applications, particularly in the food industry. The eukaryotic α-amylase isolated from the Antarctic ciliated protozoon Euplotes focardii ( Ef Amy) is an alkaline enzyme, different from most of the α-amylases characterized so far. Furthermore, Ef Amy has the characteristics of a psychrophilic α-amylase, such as the highest hydrolytic activity at a low temperature and high thermolability, which is the major drawback of cold-active enzymes in industrial applications. In this work, we applied site-directed mutagenesis combined with rational design to generate a cold-active Ef Amy with improved thermostability and catalytic efficiency at low temperatures. We engineered two Ef Amy mutants. In one mutant, we introduced Pro residues on the A and B domains in surface loops. In the second mutant, we changed Val residues to Thr close to the catalytic site. The aim of these substitutions was to rigidify the molecular structure of the enzyme. Furthermore, we also analyzed mutants containing these combined substitutions. Biochemical enzymatic assays of engineered versions of Ef Amy revealed that the combination of mutations at the surface loops increased the thermostability and catalytic efficiency of the enzyme. The possible mechanisms responsible for the changes in the biochemical properties are discussed by analyzing the three-dimensional structural model. IMPORTANCE Cold-adapted enzymes have high specific activity at low and moderate temperatures, a property that can be extremely useful in various applications as it implies a reduction in energy consumption during the catalyzed reaction. However, the concurrent high thermolability of cold-adapted enzymes often limits their applications in industrial processes. The α-amylase from the psychrophilic Antarctic ciliate Euplotes focardii (named Ef Amy) is a cold-adapted enzyme with optimal catalytic activity in an alkaline environment. These unique features distinguish it from most α-amylases characterized so far. In this work, we engineered a novel Ef Amy with improved thermostability, substrate binding affinity, and catalytic efficiency to various extents, without impacting its pH preference. These characteristics can be considered important properties for use in the food, detergent, and textile industries and in other industrial applications. The enzyme engineering strategy developed in this study may also provide useful knowledge for future optimization of molecules to be used in particular industrial applications. Copyright © 2017 Yang et al.
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NASA Astrophysics Data System (ADS)
Abbas, Mohamed; Torati, Sri Ramulu; Kim, Cheolgi
2015-07-01
A novel sonochemical approach was developed for the synthesis of different core/shell structures of Fe3O4/SiO2/Ag nanocubes and SiO2/Ag nanospheres. The total reaction time of the three sonochemical steps for the synthesis of Fe3O4/SiO2/Ag nanocubes is shorter than that of the previously reported methods. A proposed reaction mechanism for the sonochemical functionalization of the silica and the silver on the surface of magnetic nanocubes was discussed in detail. Transmission electron microscopy revealed that the surface of Fe3O4/SiO2 nanocubes was decorated with small Ag nanoparticles of approximately 10-20 nm in size, and the energy dispersive spectroscopy mapping analysis confirmed the morphology of the structure. Additionally, X-ray diffraction data were used to confirm the formation of both phases of a cubic inverse spinel structure for Fe3O4 and bcc structures for Ag in the core/shell structure of the Fe3O4/SiO2/Ag nanocubes. The as-synthesized Fe3O4/SiO2/Ag nanocubes showed a high efficiency in the catalytic reduction reaction of 4-nitroaniline to 4-phenylenediamine and a better performance than both Ag and SiO2/Ag nanoparticles. The grafted silver catalyst was recycled and reused at least fifteen times without a significant loss of catalytic efficiency.A novel sonochemical approach was developed for the synthesis of different core/shell structures of Fe3O4/SiO2/Ag nanocubes and SiO2/Ag nanospheres. The total reaction time of the three sonochemical steps for the synthesis of Fe3O4/SiO2/Ag nanocubes is shorter than that of the previously reported methods. A proposed reaction mechanism for the sonochemical functionalization of the silica and the silver on the surface of magnetic nanocubes was discussed in detail. Transmission electron microscopy revealed that the surface of Fe3O4/SiO2 nanocubes was decorated with small Ag nanoparticles of approximately 10-20 nm in size, and the energy dispersive spectroscopy mapping analysis confirmed the morphology of the structure. Additionally, X-ray diffraction data were used to confirm the formation of both phases of a cubic inverse spinel structure for Fe3O4 and bcc structures for Ag in the core/shell structure of the Fe3O4/SiO2/Ag nanocubes. The as-synthesized Fe3O4/SiO2/Ag nanocubes showed a high efficiency in the catalytic reduction reaction of 4-nitroaniline to 4-phenylenediamine and a better performance than both Ag and SiO2/Ag nanoparticles. The grafted silver catalyst was recycled and reused at least fifteen times without a significant loss of catalytic efficiency. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02680f
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Bhunia, Subhajit; Banerjee, Biplab; Bhaumik, Asim
2015-03-25
We have designed a new hypercrosslinked supermicroporous polymer (HMP-1) with a BET surface area of 913 m(2) g(-1) by FeCl3 via a catalyzed Friedel-Crafts alkylation reaction between carbazole and α,α'-dibromo-p-xylene. Upon sulfonation HMP-1 yielded a very efficient solid acid catalyst for the production of biodiesels via esterification/transesterification of free fatty acids (FFA)/esters at room temperature.
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NASA Astrophysics Data System (ADS)
Dumée, Ludovic F.; Yi, Zhifeng; Tardy, Blaise; Merenda, Andrea; Des Ligneris, Elise; Dagastine, Ray R.; Kong, Lingxue
2017-03-01
Nano-porous metallic matrixes (NMMs) offer superior surface to volume ratios as well as enhanced optical, photonic, and electronic properties to bulk metallic materials. Such behaviours are correlated to the nano-scale inter-grain metal domains that favour the presence of electronic vacancies. In this work, continuous 3D NMMs were synthesized for the first time through a simple diffusion-reduction process whereby the aerogel matrix was functionalized with (3-Mercaptopropyl)trimethoxysilane. The surface energy of the silica monolith templates was tuned to improve the homogeneity of the reduction process while thiol functionalization facilitated the formation of a high density of seeding points for metal ions to reduce. The diameter of NMMs was between 2 and 1000 nm, corresponding to a silver loading between 1.23 and 41.16 at.%. A rates of catalytic degradation kinetics of these NMMS which is three orders of magnitude higher than those of the non-functionalized silver-silica structures. Furthermore, the enhancement in mechanical stability at nanoscale which was evaluated by Atomic Force Microscopy force measurements, electronic density and chemical inertness was assessed and critically correlated to their catalytic potential. This strategy opens up new avenues for design of complex architectures of either single or multi-metal alloy NMMs with enhanced surface properties for various applications.
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Dumée, Ludovic F.; Yi, Zhifeng; Tardy, Blaise; Merenda, Andrea; des Ligneris, Elise; Dagastine, Ray R.; Kong, Lingxue
2017-01-01
Nano-porous metallic matrixes (NMMs) offer superior surface to volume ratios as well as enhanced optical, photonic, and electronic properties to bulk metallic materials. Such behaviours are correlated to the nano-scale inter-grain metal domains that favour the presence of electronic vacancies. In this work, continuous 3D NMMs were synthesized for the first time through a simple diffusion-reduction process whereby the aerogel matrix was functionalized with (3-Mercaptopropyl)trimethoxysilane. The surface energy of the silica monolith templates was tuned to improve the homogeneity of the reduction process while thiol functionalization facilitated the formation of a high density of seeding points for metal ions to reduce. The diameter of NMMs was between 2 and 1000 nm, corresponding to a silver loading between 1.23 and 41.16 at.%. A rates of catalytic degradation kinetics of these NMMS which is three orders of magnitude higher than those of the non-functionalized silver-silica structures. Furthermore, the enhancement in mechanical stability at nanoscale which was evaluated by Atomic Force Microscopy force measurements, electronic density and chemical inertness was assessed and critically correlated to their catalytic potential. This strategy opens up new avenues for design of complex architectures of either single or multi-metal alloy NMMs with enhanced surface properties for various applications. PMID:28332602
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Pentsak, E. O.; Kashin, A. S.; Polynski, M. V.; Kvashnina, K. O.; Glatzel, P.
2015-01-01
Gaining insight into Pd/C catalytic systems aimed at locating reactive centers on carbon surfaces, revealing their properties and estimating the number of reactive centers presents a challenging problem. In the present study state-of-the-art experimental techniques involving ultra high resolution SEM/STEM microscopy (1 Å resolution), high brilliance X-ray absorption spectroscopy and theoretical calculations on truly nanoscale systems were utilized to reveal the role of carbon centers in the formation and nature of Pd/C catalytic materials. Generation of Pd clusters in solution from the easily available Pd2dba3 precursor and the unique reactivity of the Pd clusters opened an excellent opportunity to develop an efficient procedure for the imaging of a carbon surface. Defect sites and reactivity centers of a carbon surface were mapped in three-dimensional space with high resolution and excellent contrast using a user-friendly nanoscale imaging procedure. The proposed imaging approach takes advantage of the specific interactions of reactive carbon centers with Pd clusters, which allows spatial information about chemical reactivity across the Pd/C system to be obtained using a microscopy technique. Mapping the reactivity centers with Pd markers provided unique information about the reactivity of the graphene layers and showed that >2000 reactive centers can be located per 1 μm2 of the surface area of the carbon material. A computational study at a PBE-D3-GPW level differentiated the relative affinity of the Pd2 species to the reactive centers of graphene. These findings emphasized the spatial complexity of the carbon material at the nanoscale and indicated the importance of the surface defect nature, which exhibited substantial gradients and variations across the surface area. The findings show the crucial role of the structure of the carbon support, which governs the formation of Pd/C systems and their catalytic activity. PMID:29511504
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Supported versus colloidal zinc oxide for advanced oxidation processes
NASA Astrophysics Data System (ADS)
Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep
2017-07-01
Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.
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An alternative synthetic approach for efficient catalytic conversion of syngas to ethanol.
Yue, Hairong; Ma, Xinbin; Gong, Jinlong
2014-05-20
Ethanol is an attractive end product and a versatile feedstock because a widespread market exists for its commercial use as a fuel additive or a potential substitute for gasoline. Currently, ethanol is produced primarily by fermentation of biomass-derived sugars, particularly those containing six carbons, but coproducts 5-carbon sugars and lignin remain unusable. Another major process for commercial production of ethanol is hydration of ethylene over solid acidic catalysts, yet not sustainable considering the depletion of fossil fuels. Catalytic conversion of synthetic gas (CO + H2) could produce ethanol in large quantities. However, the direct catalytic conversion of synthetic gas to ethanol remains challenging, and no commercial process exists as of today although the research has been ongoing for the past 90 years, since such the process suffers from low yield and poor selectivity due to slow kinetics of the initial C-C bond formation and fast chain growth of the C2 intermediates. This Account describes recent developments in an alternative approach for the synthesis of ethanol via synthetic gas. This process is an integrated technology consisting of the coupling of CO with methanol to form dimethyl oxalate and the subsequent hydrogenation to yield ethanol. The byproduct of the second step (methanol) can be separated and used in circulation as the feedstock for the coupling step. The coupling reaction of carbon monoxide for producing dimethyl oxalate takes place under moderate reaction conditions with high selectivity (∼95%), which ideally leads to a self-closing, nonwaste, catalytic cycling process. This Account also summarizes the progress on the development of copper-based catalysts for the hydrogenation reaction with remarkable efficiencies and stability. The unique lamellar structure and the cooperative effect between surface Cu(0) and Cu(+) species are responsible for the activity of the catalyst with high yield of ethanol (∼91%). The understanding of nature of valence states of Cu could also guide the rational design of Cu-based catalysts for other similar reactions, particularly for hydrogenation catalytic systems. In addition, by regulating the reaction condition and the surface structure of the catalysts, the products in the hydrogenation steps, such as ethanol, methyl glycolate, and ethylene glycol, could be tuned efficiently. This synthetic approach enables a more sustainable ethanol, methyl glycolate, and ethylene glycol synthesis in industry and greatly reduces the dependence on petroleum resources and the emission of the greenhouse gas.
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BLIMPK/Streamline Surface Catalytic Heating Predictions on the Space Shuttle Orbiter
NASA Technical Reports Server (NTRS)
Marichalar, Jeremiah J.; Rochelle, William C.; Kirk, Benjamin S.; Campbell, Charles H.
2006-01-01
This paper describes the results of an analysis of localized catalytic heating effects to the U.S. Space Shuttle Orbiter Thermal Protection System (TPS). The analysis applies to the High-temperature Reusable Surface Insulation (HRSI) on the lower fuselage and wing acreage, as well as the critical Reinforced Carbon-Carbon on the nose cap, chin panel and the wing leading edge. The object of the analysis was to use a modified two-layer approach to predict the catalytic heating effects on the Orbiter windward HRSI tile acreage, nose cap, and wing leading edge assuming localized highly catalytic or fully catalytic surfaces. The method incorporated the Boundary Layer Integral Matrix Procedure Kinetic (BLIMPK) code with streamline inputs from viscous Navier-Stokes solutions to produce heating rates for localized fully catalytic and highly catalytic surfaces as well as for nominal partially catalytic surfaces (either Reinforced Carbon-Carbon or Reaction Cured Glass) with temperature-dependent recombination coefficients. The highly catalytic heating results showed very good correlation with Orbiter Experiments STS-2, -3, and -5 centerline and STS-5 wing flight data for the HRSI tiles. Recommended catalytic heating factors were generated for use in future Shuttle missions in the event of quick-time analysis of damaged or repaired TPS areas during atmospheric reentry. The catalytic factors are presented along the streamlines as well as a function of stagnation enthalpy so they can be used for arbitrary trajectories.
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Coupling catalytic hydrolysis and oxidation on Mn/TiO2-Al2O3 for HCN removal
NASA Astrophysics Data System (ADS)
Wang, Langlang; Wang, Xueqian; Cheng, Jinhuan; Ning, Ping; Lin, Yilong
2018-05-01
The manganese-modified titania-alumina (Mn/TiO2-Al2O3) catalyst synthesized by sol-gol method was used to remove hydrogen cyanide (HCN) from simulated flue gas. Further, effects of the mass ratios of Ti/Al, Mn loading, calcination temperature, and relative humidity on HCN conversion efficiency and catalytic activity were systematically investigated. The results indicated that the Mn/TiO2-Al2O3 catalyst exhibited significantly enhanced HCN removal efficiency, and the maximum yield of N2 increased to 68.02% without the participation of water vapor. When water vapor was added into the flue gas, the yield of N2 decreased and the formation of NOx was also inhibited. The XRD and XPS results indicated that Mn was mainly present in the form of Mn2+, Mn3+, and Mn4+ on the surface of catalyst and chemisorbed oxygen played a major role in the HCN catalytic oxidation process. The results of DSC-TGA analysis and H2-TPR indicated that the catalyst also exhibited a good thermal and chemical stability. NH3-TPD and CO2-TPD indicated that the surface of the catalyst mainly contained acidic sites. During the reaction, part of NH3 was adsorbed by Brönsted and Lewis acid sites. NH3 adsorbed on Lewis acid sites participated in NH3-SCR, which reduced the amount of NOx produced and resulted in a high N2 yield.
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O'Hare, Stephen A.
1978-01-01
A catalytic device for use in a conventional coal gasification process which includes a tubular substrate having secured to its inside surface by expansion a catalytic material. The catalytic device is made by inserting a tubular catalytic element, such as a tubular element of a nickel-aluminum alloy, into a tubular substrate and heat-treating the resulting composite to cause the tubular catalytic element to irreversibly expand against the inside surface of the substrate.
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Development and assessment of photo-catalytic membranes for water purification using solar radiation
NASA Astrophysics Data System (ADS)
Coto, M.; Troughton, S. C.; Duan, J.; Kumar, R. V.; Clyne, T. W.
2018-03-01
This paper describes a novel set-up for characterization of the performance of membranes designed for purification of water. It involves a recirculatory system, with continuous monitoring of the concentration in the water of a representative pollutant (Methylene Blue). Pressures, flow rates and temperatures are also measured. Results, in the form of rate constants for reduction in pollutant concentration, are presented for three different types of membrane, all of which incorporate relatively high surface areas of titania and have permeability values in a range making them suitable for this type of processing (∼10-11 m2). These results are rationalized in terms of the surface areas of the membranes, and the likely water flow characteristics within them. It is concluded that all of the titania surfaces within them have similar efficiencies for photo-catalytic oxidation of pollutants, but there are significant differences in the ways that the water is exposed to these surfaces, and hence in the pollutant oxidation rates. These points are relevant to the optimization of membrane design for this purpose.
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Ferroelectric based catalysis: Switchable surface chemistry
NASA Astrophysics Data System (ADS)
Kakekhani, Arvin; Ismail-Beigi, Sohrab
2015-03-01
We describe a new class of catalysts that uses an epitaxial monolayer of a transition metal oxide on a ferroelectric substrate. The ferroelectric polarization switches the surface chemistry between strongly adsorptive and strongly desorptive regimes, circumventing difficulties encountered on non-switchable catalytic surfaces where the Sabatier principle dictates a moderate surface-molecule interaction strength. This method is general and can, in principle, be applied to many reactions, and for each case the choice of the transition oxide monolayer can be optimized. Here, as a specific example, we show how simultaneous NOx direct decomposition (into N2 and O2) and CO oxidation can be achieved efficiently on CrO2 terminated PbTiO3, while circumventing oxygen (and sulfur) poisoning issues. One should note that NOx direct decomposition has been an open challenge in automotive emission control industry. Our method can expand the range of catalytically active elements to those which are not conventionally considered for catalysis and which are more economical, e.g., Cr (for NOx direct decomposition and CO oxidation) instead of canonical precious metal catalysts. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.
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Nickel hydroxide/cobalt-ferrite magnetic nanocatalyst for alcohol oxidation.
Bhat, Pooja B; Inam, Fawad; Bhat, Badekai Ramachandra
2014-08-11
A magnetically separable, active nickel hydroxide (Brønsted base) coated nanocobalt ferrite catalyst has been developed for oxidation of alcohols. High surface area was achieved by tuning the particle size with surfactant. The surface area of 120.94 m2 g(-1) has been achieved for the coated nanocobalt ferrite. Improved catalytic activity and selectivity were obtained by synergistic effect of transition metal hydroxide (basic hydroxide) on nanocobalt ferrite. The nanocatalyst oxidizes primary and secondary alcohols efficiently (87%) to corresponding carbonyls in good yields.
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Tang, Shoufeng; Yuan, Deling; Zhang, Qi; Liu, Yameng; Zhang, Qi; Liu, Zhengquan; Huang, Haiming
2016-09-01
A Fe-Mn bi-metallic oxide supported on granular activated carbon (Fe-Mn GAC) has been fabricated by an impregnation-desiccation method and tested in the catalytic ozonation of methyl orange (MO) degradation and mineralization. X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy characterizations revealed that Fe-Mn oxides were successfully loaded and uniformly distributed on the GAC, and nitrogen adsorption isotherms showed that the supported GAC retained a large surface area and a high pore volume compared with the pristine GAC. The catalytic activity was systematically assessed by monitoring the MO removal efficiencies at different operational parameters, such as catalyst dosage, initial solution pH, and ozone flow rate. The Fe-Mn GAC exhibited better catalytic activity relative to ozone alone and GAC alone, improving the TOC removal by 24.5 and 11.5 % and COD removal by 13.6 and 7.3 %, respectively. The reusability of the hybrid was examined over five consecutive cyclic treatments. The Fe-Mn GAC catalytic activity was only a slight loss in the cycles, showing good stability. The addition of Na2CO3 as hydroxyl radicals (•OH) scavengers proved that the catalytic ozonation mechanism was the enhanced generation of •OH by the Fe-Mn GAC. The above results render the Fe-Mn GAC an industrially promising candidate for catalytic ozonation of dye contaminant removal.
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Positron Annihilation Induced Auger and Gamma Spectroscopy of Catalytically Important Surfaces
NASA Astrophysics Data System (ADS)
Weiss, A. H.; Nadesalingam, M. P.; Sundaramoorthy, R.; Mukherjee, S.; Fazleev, N. G.
2006-10-01
The annihilation of positrons with core electrons results in unique signatures in the spectra of Auger-electron and annihilation-gamma rays that can be used to make clear chemical identification of atoms at the surface. Because positrons implanted at low energies are trapped with high efficiency in the image-correlation well where they are localized just outside the surface it is possible to use annihilation induced Auger and Gamma signals to probe the surfaces of solids with single atomic layer depth resolution. In this talk we will report recent applications of Positron Annihilation Induced Auger Electron Spectroscopy (PAES) and Auger-Gamma Coincidence Spectroscopy (AGCS) to the study of surface structure and surface chemistry. Our research has demonstrated that PAES spectra can provide new information regarding the composition of the top-most atomic layer. Applications of PAES to the study of catalytically important surfaces of oxides and wide band-gap semiconductors including TiO2, SiO2,Cu2O, and SiC will be presented. We conclude with a discussion of the use of Auger-Gamma and Gamma-Gamma coincidence spectroscopy for the study of surfaces at pressures closer to those found in practical chemical reactors. Research supported by the Welch Foundation Grant Number Y-1100.
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Ma, Jie; Yang, Mingxuan; Yu, Fei; Chen, Junhong
2015-04-15
We report a facile solid method to synthesize efficient carbon-based Fenton-like catalyst (CNTs/FeS) using as-prepared carbon nanotubes (APCNTs), which makes full use of the iron nanoparticles in APCNTs without needless purification. Furthermore, the CNTs/FeS was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric (TG) and other analysis techniques, and then the CNTs/FeS was used as a Fenton-like catalyst for removing ciprofloxacin from aqueous solution. Response Surface Methodology (RSM) was applied to find the effect of the reaction parameter and the optimum operating condition. Results shows the catalytic reaction had better suitability than previous studies in a wide range of pH values (pH 3-8) and the Fenton-like catalyst CNTs/FeS exhibits good catalytic activity for removing of antibiotic, which be attributed to the synergistic effect of adsorption-advanced oxidation and significantly improves efficiency of advanced oxidation. More importantly, the CNTs/FeS catalyst exhibit good regeneration performance and retains a high catalytic capacity (>75%) even after four reaction cycles. The catalytic mechanism were also studied further, the removal mechanism of ciprofloxacin by a CNTs/FeS heterogeneous Fenton-like process primarily involves three removal pathways occurring simultaneously: (a) adsorption removal by CNTs, (b) Fenton-like degradation catalyzed by FeS, (c) catalytic degradation by CNTs catalyst. And these actions also have synergistic effects for ciprofloxacin removal. Copyright © 2014 Elsevier Inc. All rights reserved.
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NASA Astrophysics Data System (ADS)
Piotrowski, Piotr; Pawłowska, Joanna; Sadło, Jarosław Grzegorz; Bilewicz, Renata; Kaim, Andrzej
2017-05-01
C60TEMPO10 catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C60TEMPO10@Au composite catalyst had a particle size of 0.5-0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79-98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O2/Fe3+ system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.
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NASA Astrophysics Data System (ADS)
Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao
2016-02-01
Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology.
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Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W.; Liu, Yan; Walter, Nils G.; Yan, Hao
2016-01-01
Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology. PMID:26861509
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Zhao, Zhao; Fu, Jinglin; Dhakal, Soma; Johnson-Buck, Alexander; Liu, Minghui; Zhang, Ting; Woodbury, Neal W; Liu, Yan; Walter, Nils G; Yan, Hao
2016-02-10
Cells routinely compartmentalize enzymes for enhanced efficiency of their metabolic pathways. Here we report a general approach to construct DNA nanocaged enzymes for enhancing catalytic activity and stability. Nanocaged enzymes are realized by self-assembly into DNA nanocages with well-controlled stoichiometry and architecture that enabled a systematic study of the impact of both encapsulation and proximal polyanionic surfaces on a set of common metabolic enzymes. Activity assays at both bulk and single-molecule levels demonstrate increased substrate turnover numbers for DNA nanocage-encapsulated enzymes. Unexpectedly, we observe a significant inverse correlation between the size of a protein and its activity enhancement. This effect is consistent with a model wherein distal polyanionic surfaces of the nanocage enhance the stability of active enzyme conformations through the action of a strongly bound hydration layer. We further show that DNA nanocages protect encapsulated enzymes against proteases, demonstrating their practical utility in functional biomaterials and biotechnology.
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NASA Astrophysics Data System (ADS)
Wu, Siduo; Teng, Chao; Cai, Sheng; Jiang, Biwang; Wang, Yong; Meng, Hong; Tao, Huchun
2017-11-01
A novel triphenylphosphine-based porous polymer (TPDB) with a high Brunauer-Emmett-Teller (BET) surface area was synthesized through Friedel-Crafts alkylation of triphenylphosphine and α-dibromo- p-xylene. Then, the functional hydroxyl groups were successfully grafted onto the polymer framework by post modification of TPDB with 3-bromo-1-propanol (BP) and triethanolamine (TEA). The resulting sample TPDB-BP-TEA was characterized by various techniques such as FT-IR, TG, SEM, EDS mapping, ICP-MS, and N2 adsorption-desorption. This new polymer was tested as the catalyst in the solvent-free cycloaddition reaction of CO2 with epoxides, which exhibited excellent performance, with high yield, selectivity, and stable recyclability for several catalytic cycles. The comparison experiment results demonstrate that the bromide ions and hydroxyl groups, as well as high surface area, are key factors in improving the catalytic activity of this new catalyst.
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Zhang, Miao; Frei, Heinz
2017-05-05
Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. Combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.
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Highly active catalytic Ru/TiO2 nanomaterials for continuous flow production of γ-valerolactone.
Ouyang, Weiyi; Munoz-Batista, Mario; Fernandez-Garcia, Marcos; Luque, Rafael
2018-05-29
Green energy production from renewable sources is an attractive but challenging topic to face the likely energy crisis scenario in the future. In the current work, a series of versatile Ru/TiO2 catalysts were simply synthesized and employed in continuous flow catalytic transfer hydrogenation of industrially derived methyl levulinate biowaste (from Avantium Chemicals B.V.) to γ-valerolactone. Different analytical techniques were applied in the characterization of the as-synthesized catalysts, including XRD, SEM, EDX, TEM and XPS etc. The effects of various reaction conditions (e.g. temperature, concentration and flow rate) were investigated. Results suggested that optimum dispersion and distribution of Ru on the TiO2 surface could efficiently promote production of γ-valerolactone, with 5% Ru/TiO2 catalyst providing excelling catalytic performance and stability as compared to commercial Ru catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao
2017-10-01
The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.
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Roberts, Christopher C; Chang, Chia-en A
2015-01-13
Colocalized multistep enzymatic reaction pathways within biological catabolic and metabolic processes occur with high yield and specificity. Spatial organization on membranes or surfaces may be associated with increased efficiency of intermediate substrate transfer. Using a new Brownian dynamics package, GeomBD, we explored the geometric features of a surface-anchored enzyme system by parallel coarse-grained Brownian dynamics simulations of substrate diffusion over microsecond (μs) to millisecond (ms) time scales. We focused on a recently developed glucose oxidase (GOx), horseradish peroxidase (HRP), and DNA origami-scaffold enzyme system, where the H2O2 substrate of HRP is produced by GOx. The results revealed and explained a significant advantage in catalytic enhancement by optimizing interenzyme distance and orientation in the presence of the scaffold model. The planar scaffold colocalized the enzymes and provided a diffusive barrier that enhanced substrate transfer probability, becoming more relevant with increasing interenzyme distance. The results highlight the importance of protein geometry in the proper assessment of distance and orientation dependence on the probability of substrate transfer. They shed light on strategies for engineering multienzyme complexes and further investigation of enhanced catalytic efficiency for substrate diffusion between membrane-anchoring proteins.
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An, Junjian; Huang, Mengxuan; Wang, Mengling; Chen, Jiali; Wang, Peng
2018-04-12
Fe-doped NaBiO 3 nanoscaled compounds were prepared by hydrothermal method and evaluated as a highly efficient photo-Fenton-like catalyst under visible light irradiation. The Fe-doped NaBiO 3 compound had a specific surface area of 41.42 m 2 g -1 , which is considerably larger than that of NaBiO 3 nanoparticles (28.81 m 2 g -1 ). The compound exhibited an excellent visible light-Fenton-like catalysis activity, which is influenced by the iron content of the compound and the pH value of the solution. Under the optimal conditions, the Fe-doped NaBiO 3 compound led to fast degradation of Nonylphenol with an apparent rate constant of 5.71 × 10 -2 min -1 , which was 8.23-fold of that achieved by using NaBiO 3 . The significantly enhanced visible light-Fenton-like catalytic property of the Fe-doped NaBiO 3 was attributed to the large surface area and the high adsorption capacity of the compound, and the Fenton catalytic ability of iron in the compound.
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Huang, Gang; Yang, Li; Ma, Xiao; Jiang, Jun; Yu, Shu-Hong; Jiang, Hai-Long
2016-03-01
Metal-free catalysts are of great importance and alternative candidates to conventional metal-based catalysts for many reactions. Herein, several types of metal-organic frameworks have been exploited as templates/precursors to afford porous carbon materials with various nitrogen dopant forms and contents, degrees of graphitization, porosities, and surface areas. Amongst these materials, the PCN-224-templated porous carbon material optimized by pyrolysis at 700 °C (denoted as PCN-224-700) is composed of amorphous carbon coated with well-defined graphene layers, offering a high surface area, hierarchical pores, and high nitrogen content (mainly, pyrrolic nitrogen species). Remarkably, as a metal-free catalyst, PCN-224-700 exhibits a low activation energy and superior activity to most metallic catalysts in the catalytic reduction of 4-nitrophenol to 4-aminophenol. Theoretical investigations suggest that the content and type of the nitrogen dopant play crucial roles in determining the catalytic performance and that the pyrrolic nitrogen species makes the dominant contribution to this activity, which explains the excellent efficiency of the PCN-224-700 catalyst well. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Shrestha, Ruben; Chen, Xuejie; Ramyar, Kasra X.
Dye-decolorizing peroxidases (DyPs) are a family of heme peroxidases in which a catalytic distal aspartate is involved in H 2O 2 activation to catalyze oxidations under acidic conditions. They have received much attention due to their potential applications in lignin compound degradation and biofuel production from biomass. However, the mode of oxidation in bacterial DyPs remains unknown. We have recently reported that the bacterial TcDyP from Thermomonospora curvata is among the most active DyPs and shows activity toward phenolic lignin model compounds. On the basis of the X-ray crystal structure solved at 1.75 Å, sigmoidal steady-state kinetics with Reactive Bluemore » 19 (RB19), and formation of compound II like product in the absence of reducing substrates observed with stopped-flow spectroscopy and electron paramagnetic resonance (EPR), we hypothesized that the TcDyP catalyzes oxidation of large-size substrates via multiple surface-exposed protein radicals. Among 7 tryptophans and 3 tyrosines in TcDyP consisting of 376 residues for the matured protein, W263, W376, and Y332 were identified as surface-exposed protein radicals. Only the W263 was also characterized as one of the surface-exposed oxidation sites. SDS-PAGE and size-exclusion chromatography demonstrated that W376 represents an off-pathway destination for electron transfer, resulting in the cross-linking of proteins in the absence of substrates. Mutation of W376 improved compound I stability and overall catalytic efficiency toward RB19. While Y332 is highly conserved across all four classes of DyPs, its catalytic function in A-class TcDyP is minimal, possibly due to its extremely small solvent-accessible areas. Identification of surface-exposed protein radicals and substrate oxidation sites is important for understanding the DyP mechanism and modulating its catalytic functions for improved activity on phenolic lignin.« less
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Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren
2013-01-01
Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures.
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Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren
2013-01-01
Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures. PMID:23383368
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Ma, Xuejuan; Zhang, Lin; Xia, Mengfan; Zhang, Xiaohong; Zhang, Yaodong
2018-05-15
The degradation of organophosphorous nerve agents is of primary concern due to the severe toxicity of these agents. Based on the active center of organophosphorus hydrolase (OPH), a bimetallic nuclear ligand, (5-vinyl-1,3-phenylene)bis(di(1H-imidazol-2-yl) methanol) (VPIM), was designed and synthesized, which contains four imidazole groups to mimic the four histidines at OPH active center. By grafting VPIM on graphene oxide (GO) surface via polymerization, the VPIM-polymer beads@GO was produced. The obtained OPH mimics has an impressive activity in dephosphorylation reactions (turnover frequency (TOF) towards paraoxon: 2.3 s -1 ). The synergistic catalytic effect of the bimetallic Zn 2+ nuclear center and carboxyl groups on surface of GO possibly contributes to the high hydrolysis on organophosphate substrate. Thus, a biomimetic catalyst for efficient degradation of some organophosphorous nerve agent simulants, such as paraoxon and chlorpyrifos, was prepared by constructing catalytic active sites. The proposed mechanism and general synthetic strategy open new avenues for the engineering of functional GOs for biomimetic catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.
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Dedzo, Gustave K; Ngnie, Gaëlle; Detellier, Christian
2016-02-01
The synthesis of selectively deposited palladium nanoparticles (PdNPs) inside tubular halloysite lumens is reported. This specific localization was directed by the selective modification of the aluminol surfaces of the clay mineral through stable Al-O-C bonds. An ionic liquid (1-(2-hydroxyethyl)-3-methylimidazolium) was grafted onto halloysite following the guest displacement method (generally used for kaolinite) using halloysite-DMSO preintercalate. The characterization of this clay nanohybrid material (XRD, NMR, TGA) showed characteristics reminiscent of similar materials synthesized from kaolinite. The grafting on halloysite lumens was also effective without using the DMSO preintercalate. The presence of these new functionalities in halloysite directs the synthesis of uniform PdNPs with size ranging between 3 and 6 nm located exclusively in the lumens. This results from the selective adsorption of PdNPs precursors in functionalized lumens through an anion exchange mechanism followed by in situ reduction. In contrast, the unmodified clay mineral displayed nanoparticles both inside and outside the tubes. These catalysts showed significant catalytic activity for the reduction of 4-nitrophenol (4-NP). The most efficient catalysts were recycled up to three times without reducing significantly the catalytic activities.
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NASA Astrophysics Data System (ADS)
Borade, Ravikumar M.; Shinde, Pavan R.; Kale, Swati B.; Pawar, Rajendra P.
2018-05-01
A highly efficient magnetically recoverable cobalt ferrite nano-catalyst was prepared by sol-gel autocombustion method using glycine as green fuel. The prepared material has been characterized by X-ray powder diffraction and scanning. An investigation of its catalytic activity showed it to be a heterogeneous Lewis acid catalyst for the synthesis of substituted benzimidazoles. The aqueous ethanol used as green solvent for the reaction. The nm size range of these particles facilitates the catalysis process, as an increased surface area available for the reaction. The easy separation of the catalyst by an external magnet and their recovery and reuse in next cycle reaction are additional benefits.
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Wang, Qiu-lin; Huang, Qun-xing; Wu, Hui-fan; Lu, Sheng-yong; Wu, Hai-long; Li, Xiao-dong; Yan, Jian-hua
2016-02-01
Gaseous 1,2-dichlorobenzene (1,2-DCBz) was catalytically decomposed in a fixed-bed catalytic reactor using composite copper-based titanium oxide (CuOx/TiO2) catalysts with different copper ratios. Carbon nanotubes (CNTs) were introduced to produce novel CuOx/TiO2-CNTs catalysts by the sol-gel method. The catalytic performances of CuOx/TiO2 and CuOx/TiO2-CNTs on 1,2-DCBz oxidative destruction under different temperatures (150-350 °C) were experimentally examined and the correlation between catalyst structure and catalytic activity was characterized and the role of oxygen in catalytic reaction was discussed. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generation during 1,2-DCBz catalytic oxidation by CuOx/TiO2-CNTs composite catalyst was also examined. Results indicate that the 1,2-DCBz destruction/removal efficiencies of CuOx (4 wt%)/TiO2 catalyst at 150 °C and 350 °C with a GHSV of 3400 h(-1) are 59% and 94% respectively and low-temperature (150 °C) catalytic activity of CuOx/TiO2 on 1,2-DCBz oxidation can be improved from 59 to 77% when CNTs are introduced. Furthermore, oxygen either in catalyst or from reaction atmosphere is indispensible in reaction. The former is offered to activate and oxidize the 1,2-DCBz adsorbed on catalyst, thus can be generally consumed during reaction and the oxygen content in catalyst is observed lost from 39.9 to 35.0 wt% after reacting under inert atmosphere; the latter may replenish the vacancy in catalyst created by the consumed oxygen thus extends the catalyst life and raises the destruction/removal efficiency. The introduction of CNTs also increases the Cu(2+)/Cu(+) ratio, chemisorbed oxygen concentration and surface lattice oxygen binding energy which are closely related with catalytic activity. PCDD/Fs is confirmed to be formed when 1,2-DCBz catalytically oxidized by CuOx/TiO2-CNTs composite catalyst with sufficient oxygen (21%), proper temperature (350 °C) and high concentration of 1,2-DCBz feed (120 ppm). Copyright © 2015 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Liu, Xiong; Cheng, Yuming; Li, Xuefeng; Dong, Jinfeng
2018-05-01
In this work, we developed a new type of photo-catalysts composed of the urchin-like cupric oxide (CuO) microparticle and polyvinylidene fluoride (PVDF) hybrid composites by the convenient organic-inorganic hybrid strategy, which show high-efficiency and conveniently recyclable for dye degradation including methylene blue (MB), Congo red (CR), and malachite green (MG) by visible light irradiation. The micro-structural characteristics of urchin-like CuO microparticles are crucial and dominant over the photo-degrading efficiency of hybrid catalyst because of their highly exposed {0 0 2} facet and larger specific surface area. Simultaneously, the intrinsic porous framework of PVDF membrane not only remains the excellent photo-catalytic activity of urchin-like CuO microparticles but also facilitates the enrichment of dyes on the membrane, and thereby synergistically contributing to the photo-catalytic efficiency. The microstructures of both urchin-like CuO microparticles and hybrid catalysts are systematically characterized by various techniques including scanning electron microscopy (SEM), transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorption/desorption isotherms, which evidently support the mentioned mechanism.
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Chang, Shu Hao; Yeh, Jhy Wei; Chein, Hung Min; Hsu, Li Yeh; Chi, Kai Hsien; Chang, Moo Been
2008-08-01
Catalytic destruction has been applied to control polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) emissions from different facilities. The cost of carbon-based catalysts is considerably lower than that of the metal oxide or zeolite-based catalysts used in the selective catalytic reduction (SCR) system. In this study, destruction and adsorption efficiencies of PCDD/Fs achieved with Cu/C and Fe/C catalysts from flue gas streams of a metal smelting plant (MSP) and a large-scale municipal waste incinerator (MWI), respectively, are evaluated via the pilot-scale catalytic reactor system (PCRS). The results indicate that Cu and Fe catalysts supported on carbon surface are capable of decomposing and adsorbing PCDD/ Fs from gas streams. In the testing sources of MSP and MWI, the PCDD/F removal efficiencies achieved with Cu/C catalyst at 250 degrees C reach 96%, however, the destruction efficiencies are negative (-1,390% and -112%, respectively) due to significant PCDD/F formation on catalyst promoted by copper. In addition, Fe/C catalyst is of higher removal and destruction efficiencies compared with Cu/C catalyst in both testing sources. The removal efficiencies of PCDD/Fs achieved with Fe/C catalyst are 97 and 94% for MSP and MWI, respectively, whereas the destruction efficiencies are both higher than 70%. Decrease of PCDD/F destruction efficiency and increase of adsorption efficiency with increasing chlorination of dioxin congeners is also observed in the test via three-layer Fe/C catalyst. Furthermore, the mass of 2,3,7,8-PCDD/Fs retained on catalyst decreases on the order of first to third layer of catalyst. Each gram Fe/C catalyst in first layer adsorbs 10.9, 6.91, and 3.04 ng 2,3,7,8-PCDD/Fs in 100 min testing duration as the operating temperature is controlled at 150, 200, and 250 degrees C, respectively.
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Fang, Xian; Wang, Xueting; Li, Guiling; Zeng, Jun; Li, Jian; Liu, Jingwen
2018-05-01
PEGylation is one of the most promising and extensively studied strategies for improving the properties of proteins as well as enzymic physical and thermal stability. Phospholipase C, hydrolyzing the phospholipids offers tremendous applications in diverse fields. However, the poor thermal stability and higher cost of production have restricted its industrial application. This study focused on improving the stabilization of recombinant PLC by chemical modification with methoxypolyethylene glycol-Succinimidyl Succinate (SS-mPEG, MW 5000). PLC gene from isolate Bacillus cereus HSL3 was fused with SUMO, a novel small ubiquitin-related modifier expression vector and over expressed in Escherichia coli. The soluble fraction of SUMO-PLC reached 80% of the total recombinant protein. The enzyme exhibited maximum catalytic activity at 80 °C and was relatively thermostable at 40-70 °C. It showed extensive substrate specificity pattern and marked activity toward phosphatidylcholine, which made it a typical non-specific PLC for industrial purpose. SS-mPEG-PLC complex exhibited an enhanced thermal stability at 70-80 °C and the catalytic efficiency (K cat /K m ) had increased by 3.03 folds compared with free PLC. CD spectrum of SS-mPEG-PLC indicated a possible enzyme aggregation after chemical modification, which contributed to the higher thermostability of SS-mPEG-PLC. The increase of antiparallel β sheets in secondary structure also made it more stable than parallel β sheets. The presence of SS-mPEG chains on the enzyme molecule surface somewhat changed the binding rate of the substrates, leading to a significant improvement in catalytic efficiency. This study provided an insight into the addition of SS-mPEG for enhancing the industrial applications of phospholipase C at higher temperature. Copyright © 2018 Elsevier B.V. All rights reserved.
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Wang, Fan; Mo, Junyong; Huang, Aimin; Zhang, Min; Ma, Lin
2018-06-15
Polyethyleneimine (PEI) has long been considered as "golden standard" for polymeric gene delivery carrier, however also induces cytotoxicity. To make a further insight into the molecular basis of PEI cytotoxicity, fluorescence, absorption and circular dichroism spectroscopy were conducted to investigate the influence of PEI (average molecular weight 25,000 and 1800 Da) on the conformation of pig heart lactate dehydrogenase (LDH) and its catalytic efficiency. Zeta-potential measurement and isothermal titration calorimetry were used to reveal the interaction between PEI and LDH. PEI was found to bind onto the surface of LDH predominantly via hydrophobic interaction, inducing a more compact conformation and an increased surface hydrophobicity of the enzyme. The conformational change of LDH induced by PEI binding had little influence on the complex formation between LDH and reduced nicotinamide adenine dinucleotide (NADH, the co-enzyme). However, the nonspecific binding of PEI on the surface of LDH retarded the turnover of the enzyme. Meanwhile, the large quantity of amine groups on the polymer chain made PEI subject to form complexes with NADH and pyruvate (the substrate) via hydrogen bond and electrostatic interaction, which greatly reduced the binding efficient of LDH. The polymer size played an important role in PEI-LDH interaction. The smaller size of lower molecular weight PEI facilitated the close contact with LDH and consequential reduction of the turnover number of the enzyme. However, higher molecular weight PEI was more favorable for competitive binding with NADH and pyruvate and generally decreased the catalytic efficient of LDH. Copyright © 2018. Published by Elsevier B.V.
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Production of bio-oil and biochar from soapstock via microwave-assisted co-catalytic fast pyrolysis.
Dai, Leilei; Fan, Liangliang; Liu, Yuhuan; Ruan, Roger; Wang, Yunpu; Zhou, Yue; Zhao, Yunfeng; Yu, Zhenting
2017-02-01
In this study, production of bio-oil and biochar from soapstock via microwave-assisted co-catalytic fast pyrolysis combining the advantages of in-situ and ex-situ catalysis was performed. The effects of catalyst and pyrolysis temperature on product fractional yields and bio-oil chemical compositions were investigated. From the perspective of bio-oil yield, the optimal pyrolysis temperature was 550°C. The use of catalysts reduced the water content, and the addition of bentonite increased the bio-oil yield. Up to 84.16wt.% selectivity of hydrocarbons in the bio-oil was obtained in the co-catalytic process. In addition, the co-catalytic process can reduce the proportion of oxygenates in the bio-oil to 15.84wt.% and eliminate the N-containing compounds completely. The addition of bentonite enhanced the BET surface area of bio-char. In addition, the bio-char removal efficiency of Cd 2+ from soapstock pyrolysis in presence of bentonite was 27.4wt.% higher than without bentonite. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Fouad, Dina Mamdouh; Mohamed, Mona Bakr
2011-11-11
This work is devoted to the synthesis of different semiconductor nanoparticles and their metal core-shell nanocomposites such as TiO2, Au/TiO2, ZnO, and Au/ZnO. The morphology and crystal structures of the developed nanomaterials were characterized by transmission electron microscopy (TEM) and x-ray diffraction (XRD). These materials were used as catalysts for the photodegradation of malathion, which is one of the most commonly used pesticides in developing countries. The degradation of 10 ppm malathion under ultraviolet (UV) and visible light in the presence of different synthesized nanocomposites was analyzed using high performance liquid chromatography (HPLC) and UV-visible spectra. A comprehensive study was carried out for the catalytic efficiency of the prepared nanoparticles. Moreover, the effects of different factors that could influence catalytic photodegradation, such as different light sources, surface coverage and the nature of the organic contaminants, were investigated. The results indicate that the core-shell nanocomposite of semiconductor-gold serves as a better catalytic system than the semiconductor nanoparticles themselves.
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Gondal, Mohammed A; Sadullah, Muhammad S; Qahtan, Talal F; Dastageer, Mohamed A; Baig, Umair; McKinley, Gareth H
2017-05-10
Superhydrophilic and underwater superoleophobic surfaces were fabricated by facile spray coating of nanostructured WO 3 on stainless steel meshes and compared its performance in oil-water separation with ZnO coated meshes. The gravity driven oil-water separation system was designed using these surfaces as the separation media and it was noticed that WO 3 coated stainless steel mesh showed high separation efficiency (99%), with pore size as high as 150 µm, whereas ZnO coated surfaces failed in the process of oil-water separation when the pore exceeded 50 µm size. Since, nanostructured WO 3 is a well known catalyst, the simultaneous photocatalytic degradation of organic pollutants present in the separated water from the oil water separation process were tested using WO 3 coated surfaces under UV radiation and the efficiency of this degradation was found to be quite significant. These results assure that with little improvisation on the oil water separation system, these surfaces can be made multifunctional to work simultaneously for oil-water separation and demineralization of organic pollutants from the separated water. Fabrication of the separating surface, their morphological characteristics, wettability, oil water separation efficiency and photo-catalytic degradation efficiency are enunciated.
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NASA Astrophysics Data System (ADS)
Sun, Dong; Le, Yao; Jiang, Chuanjia; Cheng, Bei
2018-05-01
Two-dimensional (2D) ultrathin bismuth tungstate (Bi2WO6) nanosheets (BWO-NS) with a thickness of approximately 4.0 nm were synthesized by a one-step hydrothermal method, and decorated with platinum (Pt) nanoparticles (NPs) via an impregnation/borohydride-reduction approach. The as-prepared ultrathin Pt-BWO-NS exhibited superior catalytic activity for removing gaseous formaldehyde (HCHO) at ambient temperature, in comparison with bulk counterpart with Bi2WO6 sheet thickness of tens of nanometers. The ultrathin structure endowed the Pt-BWO-NS sample with larger specific surface area, which can provide abundant surface active sites for HCHO adsorption and facilitate the homogeneous dispersion of Pt NPs. X-ray photoelectron spectroscopy and hydrogen temperature-programmed reduction analyses revealed the interaction between the Bi2WO6 support and Pt species, which is crucial for activating surface oxygen atoms to participate in the catalytic HCHO oxidation process. By conducting in situ diffuse reflectance infrared Fourier transform spectroscopy under different atmospheres, i.e., gaseous HCHO in nitrogen or oxygen (O2), the reaction mechanism and the role of O2 were elucidated, with dioxymethylene, formate and linearly adsorbed carbon monoxide identified as the main reaction intermediates. This study may provide new enlightenment on fabricating novel 2D nanomaterials for efficient indoor air purification and potentially other environmental applications.
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Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao
2016-01-01
Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199
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NASA Astrophysics Data System (ADS)
Taft, Michael J., Sr.
Alcohol conversion to hydrogen, via steam reforming, is an alternative energy process that is promising for the future of clean energy economies. With advancements in fuel cell technologies, on-board hydrogen reforming could leverage already existing automotive designs and fuel infrastructure. The design of catalytic materials with tunable properties requires a level of insight that has yet to be achieved experimentally. The central objective of this project is to develop a working model of metal-oxide surface mediated copper clusters, since such catalytic beds have a wide-range of applications. More specifically, we investigate the catalytic framework of this process with theoretical models of the active metal (Cu) and metaloxide support (TiO2). We employ a Density Functional Theory (DFT)-Generalized Gradient Approximation (GGA) approach for the quantum level electronic structure calculations of Cu, TiO2 and CH3OH. Additionally, we have generated anatase (A(001), A(101)) and rutile (R(100), R(110)) surface morphologies and 7atom copper cluster complexes with those planes. To examine the possible influence of TiO2 on the adsorption properties of our active metal, Cu7, we have carried out adsorption studies with CH3OH. Our final data and observations predict that the Cu7 cluster adopts a symmetric pentagonal bipyramidal geometry with D5h symmetry. We find that the anatase morphology has a greater overall stability than rutile. The adsorption strength of the Cu7 cluster has been predicted in this study to be according to the following order: A(001) > A(101)> R(110). Indeed, the R(100) surface appears to be an unfavorable surface for metal cluster binding. Our data indicates that copper cluster stabilization on the metal-oxide surface depends on the nature of the crystal face. Again, we studied the adsorption properties of methanol on nascent Cu7 cluster, Cu7-TiO 2 complex and on pure TiO2-surface in A(001) polymorphic form. The calculations revealed that methanol adsorbs more efficiently on TiO2-bound copper clusters than either the copper cluster alone or the surface of TiO2. Additionally, we find that the metal-oxide support plays a significant role in stabilizing the catalytic reactions of CH3OH adsorption. Here, we have shown that TiO2 clearly enhances the catalytic properties of copper clusters.
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NASA Astrophysics Data System (ADS)
Al-Adwani, Hamad A. H.
Supercritically dried silico-alumino-titanate (Si-Al-Ti) mixed oxides (T2CT) were successfully synthesized by a sol-gel method with hydrothermal synthesis temperatures less than 200°C and autogenic pressure. High-surface-area T2CT aerogels with meso- to macroporosity were obtained. All solid products, after calcination at 450°C, are semicrystalline. In addition, successful scale-up of T2CT synthesis in a one-gallon reactor yielding 500 g was achieved. Surface areas, pore volumes, and average pore diameters are greatly influenced by the drying method. Supercritical drying had no effect on the crystalline or molecular structure of the materials. The synthesized materials were characterized by means of nitrogen physisorption, X-ray diffraction (XRD), thermal analysis, and diffuse reflectance FTIR spectroscopy. The addition of different amounts of phosphorous and antimony affected neither the textural nor the structural aspects of T2CT. However, a decrease in surface area occurred. The catalytic activity of these materials was evaluated after being loaded with nickel and molybdenum by the incipient wetness method. Cyclohexene hydrogenation and thiophene hydrodesulfurization reactions are used in the catalytic activity study. The activities of some of the catalyst prepared in this study are in the same range as the commercial catalyst, Shell 324, but with lower metal loadings than the commercial catalysts. Thus, more efficient use of Mo and Ni was observed.
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Roylance, John J.; Kim, Tae Woo; Choi, Kyoung-Shin
2016-02-17
Reductive biomass conversion has been conventionally conducted using H 2 gas under high-temperature and-pressure conditions. Here, efficient electrochemical reduction of 5-hydroxymethylfurfural (HMF), a key intermediate for biomass conversion, to 2,5-bis(hydroxymethyl)furan (BHMF), an important monomer for industrial processes, was demonstrated using Ag catalytic electrodes. This process uses water as the hydrogen source under ambient conditions and eliminates the need to generate and consume H 2 for hydrogenation, providing a practical and efficient route for BHMF production. By systematic investigation of HMF reduction on the Ag electrode surface, BHMF production was achieved with the Faradaic efficiency and selectivity nearing 100%, and plausiblemore » reduction mechanisms were also elucidated. Furthermore, construction of a photoelectrochemical cell (PEC) composed of an n-type BiVO 4 semiconductor anode, which uses photogenerated holes for water oxidation, and a catalytic Ag cathode, which uses photoexcited electrons from BiVO 4 for the reduction of HMF to BHMF, was demonstrated to utilize solar energy to significantly decrease the external voltage necessary for HMF reduction. This shows the possibility of coupling electrochemical HMF reduction and solar energy conversion, which can provide more efficient and environmentally benign routes for reductive biomass conversion.« less
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Li, Jiayuan; Li, Jing; Zhou, Xuemei; Xia, Zhaoming; Gao, Wei; Ma, Yuanyuan; Qu, Yongquan
2016-05-04
To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h.
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Robinson, David M; Go, Yong Bok; Mui, Michelle; Gardner, Graeme; Zhang, Zhijuan; Mastrogiovanni, Daniel; Garfunkel, Eric; Li, Jing; Greenblatt, Martha; Dismukes, G Charles
2013-03-06
Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ≫ λ-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and λ-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface.
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Martí, Sergio; Andrés, Juan; Moliner, Vicent; Silla, Estanislao; Tuñón, Iñaki; Bertrán, Juan
2008-01-01
The Diels-Alder reaction is one of the most important and versatile transformations available to organic chemists for the construction of complex natural products, therapeutics agents, and synthetic materials. Given the lack of efficient enzymes capable of catalyzing this kind of reaction, it is of interest to ask whether a biological catalyst could be designed from an antibody-combining site. In the present work, a theoretical study of the different behavior of a germline catalytic antibody (CA) and its matured form, 39 A-11, that catalyze a Diels-Alder reaction has been carried out. A free-energy perturbation technique based on a hybrid quantum-mechanics/molecular-mechanics scheme, together with internal energy minimizations, has allowed free-energy profiles to be obtained for both CAs. The profiles show a smaller barrier for the matured form, which is in agreement with the experimental observation. Free-energy profiles were obtained with this methodology, thereby avoiding the much more demanding two-dimensional calculations of the energy surfaces that are normally required to study this kind of reaction. Structural analysis and energy evaluations of substrate-protein interactions have been performed from averaged structures, which allows understanding of how the single mutations carried out during the maturation process can be responsible for the observed fourfold enhancement of the catalytic rate constant. The conclusion is that the mutation effect in this studied germline CA produces a complex indirect effect through coupled movements of the backbone of the protein and the substrate.
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Cherepanov, Pavel V; Andreeva, Daria V
2017-03-01
High intensity ultrasound (HIUS) is a novel and efficient tool for top-down nanostructuring of multi-phase metal systems. Ultrasound-assisted structuring of the phase in metal alloys relies on two main mechanisms including interfacial red/ox reactions and temperature driven solid state phase transformations which affect surface composition and morphology of metals. Physical and chemical properties of sonication medium strongly affects the structuring pathways as well as morphology and composition of catalysts. HIUS can serve as a simple, fast, and effective approach for the tuning of structure and surface properties of metal particles, opening the new perspectives in design of robust and efficient catalysts. Copyright © 2016 Elsevier B.V. All rights reserved.
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Yang, Haiquan; Liu, Long; Shin, Hyun-dong; Li, Jianghua; Du, Guocheng; Chen, Jian
2013-01-01
High oxidative stability and catalytic efficiency are required for the alkaline α-amylases to keep the enzymatic performance under the harsh conditions in detergent industries. In this work, we attempted to significantly improve both the oxidative stability and catalytic efficiency of an alkaline α-amylase from Alkalimonas amylolytica by engineering the five oxidation-prone methionine residues around the catalytic domain via a systematic approach. Specifically, based on the tertiary structure analysis, five methionines (Met 145, Met 214, Met 229, Met 247 and Met 317) were individually substituted with oxidation-resistant threonine, isoleucine and alaline, respectively. Among the created 15 mutants, 7 mutants M145A, M145I, M214A, M229A, M229T, M247T and M317I showed significantly enhanced oxidative stability or catalytic efficiency. In previous work, we found that the replacement of M247 with leucine could significantly improve the oxidative stability. Thus, these 8 positive mutants (M145A, M145I, M214A, M229A, M229T, M247T, M247L and M317I) were used to conduct the second round of combinational mutations. Among the constructed 85 mutants (25 two-point mutants, 36 three-point mutants, 16 four-point mutants and 8 five-point mutants), the mutant M145I-214A-229T-247T-317I showed a 5.4-fold increase in oxidative stability and a 3.0-fold increase in catalytic efficiency. Interestingly, the specific activity, alkaline stability and thermal stability of this mutant were also increased. The increase of salt bridge and hydrogen bonds around the catalytic domain contributed to the significantly improved catalytic efficiency and stability, as revealed by the three-dimensional structure model of wild-type alkaline α-amylase and its mutant M145I-214A-229T-247T-317I. With the significantly improved oxidative stability and catalytic efficiency, the mutant M145I-214A-229T-247T-317I has a great potential as a detergent additive, and this structure-guided systems engineering strategy may be useful for the protein engineering of the other microbial enzymes to fulfill industrial requirements.
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Raugei, Simone; Helm, Monte L; Hammes-Schiffer, Sharon; Appel, Aaron M; O'Hagan, Molly; Wiedner, Eric S; Bullock, R Morris
2016-01-19
Understanding how to control the movement of protons and electrons is crucial to the design of fast, efficient electrocatalysts for H2 production and oxidation based on earth-abundant metals. Our work seeks to address fundamental questions about proton movement. We have demonstrated that incorporating a pendant amine functioning as a proton relay in the second coordination sphere of a metal complex helps proton mobility, resulting in faster and more energy-efficient catalysts. Proton-transfer reactions can be rate-limiting and are influenced by several factors, such as pKa values, steric effects, hydrogen bonding, and solvation/desolvation of the exogenous base and acid employed. The presence of multiple protonation sites introduces branching points along the catalytic cycle, making less productive pathways accessible or leading to the formation of stable off-cycle species. Using ligands with only one pendant amine mitigates this problem and results in catalysts with high rates for production of H2, although generally at higher overpotentials. For H2 oxidation catalysts, iron complexes with a high H2 binding affinity were developed. However, these iron complexes had a pKa mismatch between the protonated metal center and the protonated pendant amine, and consequently intramolecular proton movement was slow. Taken altogether, our results demonstrate the necessity of optimizing the entire catalytic cycle because optimization of a specific catalytic step can negatively influence another step and not necessarily lead to a better catalytic performance. We discuss a general procedure, based on thermodynamic arguments, which allows the simultaneous minimization of the free-energy change of each catalytic step, yielding a nearly flat free-energy surface, with no large barriers due to energy mismatches from either high- or low-energy intermediates.
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Improvement of activity and stability of chloroperoxidase by chemical modification
Liu, Jian-Zhong; Wang, Min
2007-01-01
Background Enzymes show relative instability in solvents or at elevated temperature and lower activity in organic solvent than in water. These limit the industrial applications of enzymes. Results In order to improve the activity and stability of chloroperoxidase, chloroperoxidase was modified by citraconic anhydride, maleic anhydride or phthalic anhydride. The catalytic activities, thermostabilities and organic solvent tolerances of native and modified enzymes were compared. In aqueous buffer, modified chloroperoxidases showed similar Km values and greater catalytic efficiencies kcat/Km for both sulfoxidation and oxidation of phenol compared to native chloroperoxidase. Of these modified chloroperoxidases, citraconic anhydride-modified chloroperoxidase showed the greatest catalytic efficiency in aqueous buffer. These modifications of chloroperoxidase increased their catalytic efficiencies for sulfoxidation by 12%~26% and catalytic efficiencies for phenol oxidation by 7%~53% in aqueous buffer. However, in organic solvent (DMF), modified chloroperoxidases had lower Km values and higher catalytic efficiencies kcat/Km than native chloroperoxidase. These modifications also improved their thermostabilities by 1~2-fold and solvent tolerances of DMF. CD studies show that these modifications did not change the secondary structure of chloroperoxidase. Fluorescence spectra proved that these modifications changed the environment of tryptophan. Conclusion Chemical modification of epsilon-amino groups of lysine residues of chloroperoxidase using citraconic anhydride, maleic anhydride or phthalic anhydride is a simple and powerful method to enhance catalytic properties of enzyme. The improvements of the activity and stability of chloroperoxidase are related to side chain reorientations of aromatics upon both modifications. PMID:17511866
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A catalytic surface for amyloid fibril formation
NASA Astrophysics Data System (ADS)
Hammarström, P.; Ali, M. M.; Mishra, R.; Svensson, S.; Tengvall, P.; Lundström, I.
2008-03-01
A hydrophobic surface incubated in a solution of protein molecules (insulin monomers) was made into a catalytic surface for amyloid fibril formation by repeatedly incubate, rinse and dry the surface. The present contribution describes how this unexpected transformation occurred and its relation to rapid fibrillation of insulin solutions in contact with the surface. A tentative model of the properties of the catalytic surface is given, corroborated by ellipsometric measurements of the thickness of the organic layer on the surface and by atomic force microscopy. The surfaces used were spontaneously oxidized silicon made hydrophobic through treatment in dichlorodimethylsilane.
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Hoffeditz, William L; Katz, Michael J; Deria, Pravas; Martinson, Alex B F; Pellin, Michael J; Farha, Omar K; Hupp, Joseph T
2014-06-11
Dye-sensitized solar cell (DSC) redox shuttles other than triiodide/iodide have exhibited significantly higher charge transfer resistances at the dark electrode. This often results in poor fill factor, a severe detriment to device performance. Rather than moving to dark electrodes of untested materials that may have higher catalytic activity for specific shuttles, the surface area of platinum dark electrodes could be increased, improving the catalytic activity by simply presenting more catalyst to the shuttle solution. A new copper-based redox shuttle that experiences extremely high charge-transfer resistance at conventional Pt dark electrodes yields cells having fill-factors of less than 0.3. By replacing the standard Pt dark electrode with an inverse opal Pt electrode fabricated via atomic layer deposition, the dark electrode surface area is boosted by ca. 50-fold. The resulting increase in interfacial electron transfer rate (decrease in charge-transfer resistance) nearly doubles the fill factor and therefore the overall energy conversion efficiency, illustrating the utility of this high-area electrode for DSCs.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Thi, Trinh Cham, E-mail: s1240009@jaist.ac.jp; Koyama, Koichi; Ohdaira, Keisuke
We improve the passivation property of n-type crystalline silicon (c-Si) surface passivated with a catalytic chemical vapor deposited (Cat-CVD) Si nitride (SiN{sub x}) film by inserting a phosphorous (P)-doped layer formed by exposing c-Si surface to P radicals generated by the catalytic cracking of PH{sub 3} molecules (Cat-doping). An extremely low surface recombination velocity (SRV) of 2 cm/s can be achieved for 2.5 Ω cm n-type (100) floating-zone Si wafers passivated with SiN{sub x}/P Cat-doped layers, both prepared in Cat-CVD systems. Compared with the case of only SiN{sub x} passivated layers, SRV decreases from 5 cm/s to 2 cm/s. The decrease in SRVmore » is the result of field effect created by activated P atoms (donors) in a shallow P Cat-doped layer. Annealing process plays an important role in improving the passivation quality of SiN{sub x} films. The outstanding results obtained imply that SiN{sub x}/P Cat-doped layers can be used as promising passivation layers in high-efficiency n-type c-Si solar cells.« less
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NASA Technical Reports Server (NTRS)
1998-01-01
Under an SBIR (Small Business Innovative Research) from Lewis Research Center, Precision Combustion, Inc. (PCI) developed the Advanced Technology Catalytic Combustor. The research proved the viability of efficient, cost-effective catalytic reduction of gas turbine nitrogen oxide emissions along with fuel efficiency. PCI has signed agreements with Westinghouse, other gas turbine manufacturers, including Capstone Turbine Corporation to develop a catalytic combustor for their hybrid electric vehicle.
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NASA Astrophysics Data System (ADS)
Li, Chao; Sun, Jun-Jie; Chen, Duo; Han, Guang-Bing; Yu, Shu-Yun; Kang, Shi-Shou; Mei, Liang-Mo
2016-08-01
A facile step-by-step approach is developed for synthesizing the high-efficiency and magnetic recyclable Fe3O4@SiO2@Ag@Ni trepang-like nanocomposites. This method involves coating Fe2O3 nanorods with a uniform silica layer, reduction in 10% H2/Ar atmosphere to transform the Fe2O3 into magnetic Fe3O4, and finally depositing Ag@Ni core-shell nanoparticles on the L-lysine modified surface of Fe3O4@SiO2 nanorods. The fabricated nanocomposites are further characterized by x-ray diffraction, transmission electron microscopy, scanning electron microscope, Fourier transform infrared spectroscopy, and inductively coupled plasma mass spectroscopy. The Fe3O4@SiO2@Ag@Ni trepang-like nanocomposites exhibit remarkably higher catalytic efficiency than monometallic Fe3O4@SiO2@Ag nanocomposites toward the degradation of Rhodamine B (RhB) at room temperature, and maintain superior catalytic activity even after six cycles. In addition, these samples could be easily separated from the catalytic system by an external magnet and reused, which shows great potential applications in treating waste water. Project supported by the National Basic Research Program of China (Grant No. 2015CB921502), the National Natural Science Foundation of China (Grant Nos. 11474184 and 11174183), the 111 Project (Grant No. B13029), and the Fundamental Research Funds of Shandong University, China.
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NASA Astrophysics Data System (ADS)
Zhao, Qi; Li, Yingjun; Li, Yetong; Huang, Keke; Wang, Qin; Zhang, Jun
2017-04-01
Novel nickel nitride (Ni3N) nanoparticles supported on nitrogen-doped reduced graphene oxide nanosheets (N-RGOs) are synthesized via a facile strategy including hydrothermal and subsequent calcination methods, in which the reduced graphene oxide nanosheets (RGOs) are simultaneously doped with nitrogen species. By varying the content of the RGOs, a series of Ni3N/N-RGO nanocomposites are obtained. The Ni3N/N-RGO-30% hybrid nanocomposite exhibits superior catalytic activity towards oxygen reduction reaction (ORR) under alkaline condition (0.1 M KOH). Furthermore, this hybrid catalyst also demonstrates high tolerance to methanol poisoning. The RGO containing rich N confers the nanocomposite with large specific surface area and high electronic conduction ability, which can enhance the catalytic efficiency of Ni3N nanoparticles. The enhanced catalytic activity can be attributed to the synergistic effect between Ni3N and nitrogen doped reduced graphene oxide. In addition, the sufficient contact between Ni3N nanoparticles and the N-RGO nanosheets simultaneously promotes good nanoparticle dispersion and provides a consecutive activity sites to accelerate electron transport continuously, which further enhance the ORR performance. The Ni3N/N-RGO may be further an ideal candidate as efficient and inexpensive noble metal-free ORR electrocatalyst in fuel cells.
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NASA Astrophysics Data System (ADS)
Liu, Bing; Tian, Lihong; Wang, Ran; Yang, Jinfeng; Guan, Rong; Chen, Xiaobo
2017-11-01
Though α-Fe2O3 has attracted much attention in photocatalytic or Fenton-catalytic degradation of organic contaminants, its performance is still unsatisfactory due to fast recombination of electrons and holes in photocatalytic process and the difficult conversion of Fe(II) and Fe(III) in Fenton reaction. Herein, a pyrrolic N-doped graphene oxide/Fe2O3 mesocrystal (NG-Fe2O3) nanocomposite with good distribution is synthesized by a simple solvothermal method and adjusting the oxygen-containing groups on graphene oxide. The morphology of NG-Fe2O3 contributes to a relatively large BET surface area and an intimate contact between NG and Fe2O3. These two important factors along with the excellent electro-conductivity of pyrrolic-N doped GO result in the efficient separation of electron-hole pairs and fast conversion of Fe(II)and Fe(III) in photo-Fenton synergistic reaction. Thus, a remarkably improved photo-Fenton catalytic activity of NG-Fe2O3 is obtained. The degrading rate on methyl blue increases by 1.5 times and the conversion rate of glyphosate increases by 2.3 times under visible light irradiation, compared to pristine α-Fe2O3 mesocrystals.
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Anchoring and promotion effects of metal oxides on silica supported catalytic gold nanoparticles.
Luo, Jingjie; Ersen, Ovidiu; Chu, Wei; Dintzer, Thierry; Petit, Pierre; Petit, Corinne
2016-11-15
The understanding of the interactions between the different components of supported metal doped gold catalysts is of crucial importance for selecting and designing efficient gold catalysts for reactions such as CO oxidation. To progress in this direction, a unique supported nano gold catalyst Au/SS was prepared, and three doped samples (Au/SS@M) were elaborated. The samples before and after test were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). It is found that the doping metal species prefer to be located on the surface of gold nanoparticles and that a small amount of additional reductive metal leads to more efficient reaction. During the catalytic test, the nano-structure of the metal species transforms depending on its chemical nature. This study allows one to identify and address the contribution of each metal on the CO reaction in regard to oxidative species of gold, silica and dopants. Metal doping leads to different exposure of interface sites between Au and metal oxide, which is one of the key factors for the change of the catalytic activity. The metal oxides help the activation of oxygen by two actions: mobility inside the metal bulk and transfer of water species onto of gold nanoparticles. Copyright © 2016. Published by Elsevier Inc.
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Guo, Xiaolei; Wan, Jiafeng; Yu, Xiujuan; Lin, Yuhui
2016-12-01
In order to improve the electro-catalytic activity and catalytic reaction rate of graphite-like material, Tin dioxide-Titanium dioxide/Nano-graphite (SnO 2 -TiO 2 /Nano-G) composite was synthesized by a sol-gel method and SnO 2 -TiO 2 /Nano-G electrode was prepared in hot-press approach. The composite was characterized by X-ray photoelectron spectroscopy, fourier transform infrared, Raman, N 2 adsorption-desorption, scanning electrons microscopy, transmission electron microscopy and X-ray diffraction. The electrochemical performance of the SnO 2 -TiO 2 /Nano-G anode electrode was investigated via cyclic voltammetry and electrochemical impedance spectroscopy. The electro-catalytic performance was evaluated by the degradation of ceftriaxone sodium and the yield of ·OH radicals in the reaction system. The results demonstrated that TiO 2 , SnO 2 and Nano-G were composited successfully, and TiO 2 and SnO 2 particles dispersed on the surface and interlamination of the Nano-G uniformly. The specific surface area of SnO 2 modified anode was higher than that of TiO 2 /Nano-G anode and the degradation rate of ceftriaxone sodium within 120 min on SnO 2 -TiO 2 /Nano-G electrode was 98.7% at applied bias of 2.0 V. The highly efficient electro-chemical property of SnO 2 -TiO 2 /Nano-G electrode was attributed to the admirable conductive property of the Nano-G and SnO 2 -TiO 2 /Nano-G electrode. Moreover, the contribution of reactive species ·OH was detected, indicating the considerable electro-catalytic activity of SnO 2 -TiO 2 /Nano-G electrode. Copyright © 2016 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Zhang, Lihong; Hu, Chenhui; Mei, Weigang; Zhang, Junfeng; Cheng, Liyuan; Xue, Nianhua; Ding, Weiping; Chen, Jing; Hou, Wenhua
2015-12-01
Sulfated Zr-doped titanoniobate nanoplates were prepared and evaluated as a solid acid catalyst in the alcoholysis of styrene epoxide at room temperature. Compared with undoped and Zr-doped nanosheets, the resulting sulfated catalyst exhibited an excellent catalytic performance to afford corresponding β-alkoxyalcohols (99% yield with methanol as nucleophile in only 10 min) due to the high dispersion of zirconia species on nanosheets, appropriate Lewis acid strength and amount from the strong interaction between zirconia and sulfate species, and greatly increased surface area arisen from the exfoliation and house-of-cards restacking of nanosheets. The corresponding catalytic mechanism was proposed and discussed. The obtained material may act as a promising catalyst in many acid catalyzed reactions.
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Gao, Wenpei; Hood, Zachary D; Chi, Miaofang
2017-04-18
Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell, between separate phases and twinned grains, between the catalyst surface and gas, and between metal and support are discussed. We also provide an outlook on how emerging electron microscopy techniques, such as vibrational spectroscopy and electron ptychography, will impact future catalysis research.
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Highly efficient catalytic systems based on Pd-coated microbeads
NASA Astrophysics Data System (ADS)
Lim, Jin Hyun; Cho, Ahyoung; Lee, Seung Hwan; Park, Bumkyo; Kang, Dong Woo; Koo, Chong Min; Yu, Taekyung; Park, Bum Jun
2018-01-01
The efficiency of two prototype catalysis systems using palladium (Pd)-coated microparticles was investigated with regard to the recovery and recyclability of the catalytic particles. One such system was the interface-adsorption method, in which polymer particles coated with Pd nanoparticles strongly and irreversibly attach to the oil-water interface. Due to the irreversible adsorption of the catalytic particles to the interface, particle loss was completely prevented while mixing the aqueous solution and while collecting the products. The other system was based on the magnetic field-associated particle recovery method. The use of polymeric microparticles containing Pd nanoparticles and magnetite nanoparticles accelerated the sedimentation of the particles in the aqueous phase by applying a strong magnetic field, consequently suppressing drainage of the particles from the reactor along the product stream. Upon multiple runs of the catalytic reactions, it was found that conversion does not change significantly, demonstrating the excellent recyclability and performance efficiency in the catalytic processes.
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Cheng, Ya; Li, Ye; Huang, Tinglin; Sun, Yuankui; Shi, Xinxin; Shao, Yuezong
2018-03-01
As an efficient method for ammonium (NH 4 + ) removal, contact catalytic oxidation technology has drawn much attention recently, due to its good low temperature resistance and short start-up period. Two identical filters were employed to compare the process for ammonium removal during the start-up period for ammonium removal in groundwater (Filter-N) and surface water (Filter-S) treatment. Two types of source water (groundwater and surface water) were used as the feed waters for the filtration trials. Although the same initiating method was used, Filter-N exhibited much better ammonium removal performance than Filter-S. The differences in catalytic activity among these two filters were probed using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and compositional analysis. XRD results indicated that different manganese oxide species were formed in Filter-N and Filter-S. Furthermore, the Mn3p XPS spectra taken on the surface of the filter films revealed that the average manganese valence of the inactive manganese oxide film collected from Filter-S (FS-MnO x ) was higher than in the film collected from Filter-N (FN-MnO x ). Mn(IV) was identified as the predominant oxidation state in FS-MnO x and Mn(III) was identified as the predominant oxidation state in FN-MnO x . The results of compositional analyses suggested that polyaluminum ferric chloride (PAFC) used during the surface water treatment was an important factor in the mineralogy and reactivity of MnO x . This study provides the theoretical basis for promoting the wide application of the technology and has great practical significance. Copyright © 2017. Published by Elsevier B.V.
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NASA Astrophysics Data System (ADS)
González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.
2016-08-01
A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.
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NASA Astrophysics Data System (ADS)
Chen, Jinshe; Duan, Zunbin; Song, Zhaoyang; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong
2017-12-01
The amorphous NiP nanoparticles were synthesized and a novel amorphous NiP/Hβ catalyst was prepared successfully further. Due to the superior surface property of amorphous NiP/Hβ catalyst, it exhibited good catalytic application for n-hexane isomerization. The catalytic activity of amorphous NiP/Hβ catalyst was close to that of the prepared Pt/Hβ sample, and better than that of commercial catalyst and crystalline Ni2P/Hβ catalyst. What's more, the amorphous NiP/Hβ catalyst shows high resistance to different sulfur compounds and water on account of its unique surface property. The effect of loading amounts on surface property and catalytic performance was investigated, and the structure-function relationship among them was studied ulteriorly. The results demonstrate that loading amounts have effect on textural property and surface acid property, which further affect the catalytic performance. The 10 wt.% NiP/Hβ sample has appropriate pore structure and acid property with uniformly dispersed NiP nanoparticles on surface, which is helpful for providing suitable synergistic effect. The effects of reaction conditions on surface reactions and the mechanism for n-hexane isomerization were investigated further. Based on these results, the amorphous NiP/Hβ catalyst with superior surface property probably pavesa way to overcome the drawbacks of traditional noble metal catalyst, which shows good catalytic application prospects.
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Wang, Qiulin; Tang, Minghui; Peng, Yaqi; Du, Cuicui; Lu, Shengyong
2018-05-01
Ozone assisted carbon nanotubes (CNTs) supported vanadium oxide/titanium dioxide (V/Ti-CNTs) or vanadium oxide-manganese oxide/titanium dioxide (V-Mn/Ti-CNTs) catalysts towards gaseous PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) catalytic oxidations at low temperature (150 °C) were investigated. The removal efficiency (RE) and decomposition efficiency (DE) of PCDD/Fs achieved with V-Mn/Ti-CNTs alone were 95% and 45% at 150 °C under a space velocity (SV) of 14000 h -1 ; yet, these values reached 99% and 91% when catalyst and low concentration (50 ppm) ozone were used in combined. The ozone promotion effect on catalytic activity was further enhanced with the addition of manganese oxide (MnO x ) and CNTs. Adding MnO x and CNTs in V/Ti catalysts facilitated the ozone decomposition (creating more active species on catalyst surface), thus, improved ozone utilization (demanding relatively lower ozone addition concentration). On the other hand, this study threw light upon ozone promotion mechanism based on the comparison of catalyst properties (i.e. components, surface area, surface acidity, redox ability and oxidation state) before and after ozone treatment. The experimental results indicate that a synergistic effect exists between catalyst and ozone: ozone is captured and decomposed on catalyst surface; meanwhile, the catalyst properties are changed by ozone in return. Reactive oxygen species from ozone decomposition and the accompanied catalyst properties optimization are crucial reasons for catalyst activation at low temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Novel Acid Catalysts from Waste-Tire-Derived Carbon: Application in Waste-to-Biofuel Conversion
Hood, Zachary D.; Adhikari, Shiba P.; Li, Yunchao; ...
2017-06-21
Many inexpensive biofuel feedstocks, including those containing free fatty acids (FFAs) in high concentrations, are typically disposed of as waste due to our inability to efficiently convert them into usable biofuels. Here we demonstrate that carbon derived from waste tires could be functionalized with sulfonic acid (-SO 3H) to effectively catalyze the esterification of oleic acid or a mixture of fatty acids to usable biofuels. Waste tires were converted to hard carbon, then functionalized with catalytically active -SO 3H groups on the surface through an environmentally benign process that involved the sequential treatment with L-cysteine, dithiothreitol, and H 2O 2.more » In conclusion, when benchmarked against the same waste-tire derived carbon material treated with concentrated sulfuric acid at 150 °C, similar catalytic activity was observed. Both catalysts could also effectively convert oleic acid or a mixture of fatty acids and soybean oil to usable biofuels at 65 °C and 1 atm without leaching of the catalytic sites.« less
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microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G
NASA Astrophysics Data System (ADS)
Li, Zhan Jun; Ali, Ghafar; Kim, Hyun Jin; Yoo, Seong Ho; Cho, Sung Oh
2014-05-01
We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hood, Zachary D.; Adhikari, Shiba P.; Li, Yunchao
Many inexpensive biofuel feedstocks, including those containing free fatty acids (FFAs) in high concentrations, are typically disposed of as waste due to our inability to efficiently convert them into usable biofuels. Here we demonstrate that carbon derived from waste tires could be functionalized with sulfonic acid (-SO 3H) to effectively catalyze the esterification of oleic acid or a mixture of fatty acids to usable biofuels. Waste tires were converted to hard carbon, then functionalized with catalytically active -SO 3H groups on the surface through an environmentally benign process that involved the sequential treatment with L-cysteine, dithiothreitol, and H 2O 2.more » In conclusion, when benchmarked against the same waste-tire derived carbon material treated with concentrated sulfuric acid at 150 °C, similar catalytic activity was observed. Both catalysts could also effectively convert oleic acid or a mixture of fatty acids and soybean oil to usable biofuels at 65 °C and 1 atm without leaching of the catalytic sites.« less
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Liang, Jia; Li, Jia; Zhu, Hongfei; Han, Yuxiang; Wang, Yanrong; Wang, Caixing; Jin, Zhong; Zhang, Gengmin; Liu, Jie
2016-09-21
Here we report a facile one-step solution-phase process to directly grow ultrathin MoS2 nanofilms on a transparent conductive glass as a novel high-performance counter electrode for dye-sensitized solar cells. After an appropriate reaction time, the entire surface of the conductive glass substrate was uniformly covered by ultrathin MoS2 nanofilms with a thickness of only several stacked layers. Electrochemical impedance spectroscopy and cyclic voltammetry reveal that the MoS2 nanofilms possess excellent catalytic activity towards tri-iodide reduction. When used in dye-sensitized solar cells, the MoS2 nanofilms show an impressive energy conversion efficiency of 8.3%, which is higher than that of a Pt-based electrode and very promising to be a desirable alternative counter electrode. Considering their ultrathin thickness, superior catalytic activity, simple preparation process and low cost, the as-prepared MoS2 nanofilms with high photovoltaic performance are expected to be widely employed in dye-sensitized solar cells.
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NASA Astrophysics Data System (ADS)
Leman, A. M.; Jajuli, Afiqah; Rahman, Fakhrurrazi; Feriyanto, Dafit; Zakaria, Supaat
2017-09-01
Enforcement of a stricter regulation on exhaust emission by many countries has led to utilization of catalytic converter to reduce the harmful pollutant emission. Ceramic and metallic catalytic converters are the most common type of catalytic converter used. The purpose of this study is to evaluate the performance of the ceramic and metallic catalytic converter on its conversion efficiency using experimental measurement. Both catalysts were placed on a modified exhaust system equipped with a Mitshubishi 4G93 single cylinder petrol engine that was tested on an eddy current dynamometer under steady state conditions for several engine speeds. The experimental results show that the metallic catalytic converter reduced a higher percentage of CO up to 98.6% reduction emissions while ceramic catalytic converter had a better reduction efficiency of HC up to 85.4% and 87.2% reduction of NOx.
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Dehalogenation and coupling of a polycyclic hydrocarbon on an atomically thin insulator.
Dienel, Thomas; Gómez-Díaz, Jaime; Seitsonen, Ari P; Widmer, Roland; Iannuzzi, Marcella; Radican, Kevin; Sachdev, Hermann; Müllen, Klaus; Hutter, Jürg; Gröning, Oliver
2014-07-22
Catalytic activity is of pivotal relevance in enabling efficient and selective synthesis processes. Recently, covalent coupling reactions catalyzed by solid metal surfaces opened the rapidly evolving field of on-surface chemical synthesis. Tailored molecular precursors in conjunction with the catalytic activity of the metal substrate allow the synthesis of novel, technologically highly relevant materials such as atomically precise graphene nanoribbons. However, the reaction path on the metal substrate remains unclear in most cases, and the intriguing question is how a specific atomic configuration between reactant and catalyst controls the reaction processes. In this study, we cover the metal substrate with a monolayer of hexagonal boron nitride (h-BN), reducing the reactivity of the metal, and gain unique access to atomistic details during the activation of a polyphenylene precursor by sequential dehalogenation and the subsequent coupling to extended oligomers. We use scanning tunneling microscopy and density functional theory to reveal a reaction site anisotropy, induced by the registry mismatch between the precursor and the nanostructured h-BN monolayer.
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Platinum-coated non-noble metal-noble metal core-shell electrocatalysts
Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir
2015-04-14
Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.
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Moghaddam, Hadi Mahmoudi; Beitollahi, Hadi; Tajik, Somayeh; Malakootian, Mohammad; Maleh, Hassan Karimi
2014-11-01
The electrochemical oxidation of hydroxylamine on the surface of a carbon paste electrode modified with carbon nanotubes and 2,7-bis(ferrocenyl ethyl)fluoren-9-one is studied. The electrochemical response characteristics of the modified electrode toward hydroxylamine and phenol were investigated. The results showed an efficient catalytic activity of the electrode for the electro-oxidation of hydroxylamine, which leads to lowering its overpotential. The modified electrode exhibits an efficient electron-mediating behavior together with well-separated oxidation peaks for hydroxylamine and phenol. Also, the modified electrode was used for determination of hydroxylamine and phenol in some real samples.
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Woodman, Zenda L; Schwager, Sylva L U; Redelinghuys, Pierre; Carmona, Adriana K; Ehlers, Mario R W; Sturrock, Edward D
2005-08-01
sACE (somatic angiotensin-converting enzyme) consists of two homologous, N and C domains, whereas the testis isoenzyme [tACE (testis ACE)] consists of a single C domain. Both isoenzymes are shed from the cell surface by a sheddase activity, although sACE is shed much less efficiently than tACE. We hypothesize that the N domain of sACE plays a regulatory role, by occluding a recognition motif on the C domain required for ectodomain shedding and by influencing the catalytic efficiency. To test this, we constructed two mutants: CNdom-ACE and CCdom-ACE. CNdom-ACE was shed less efficiently than sACE, whereas CCdom-ACE was shed as efficiently as tACE. Notably, cleavage occurred both within the stalk and the interdomain bridge in both mutants, suggesting that a sheddase recognition motif resides within the C domain and is capable of directly cleaving at both positions. Analysis of the catalytic properties of the mutants and comparison with sACE and tACE revealed that the k(cat) for sACE and CNdom-ACE was less than or equal to the sum of the kcat values for tACE and the N-domain, suggesting negative co-operativity, whereas the kcat value for the CCdom-ACE suggested positive co-operativity between the two domains. Taken together, the results provide support for (i) the existence of a sheddase recognition motif in the C domain and (ii) molecular flexibility of the N and C domains in sACE, resulting in occlusion of the C-domain recognition motif by the N domain as well as close contact of the two domains during hydrolysis of peptide substrates.
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Woodman, Zenda L.; Schwager, Sylva L. U.; Redelinghuys, Pierre; Carmona, Adriana K.; Ehlers, Mario R. W.; Sturrock, Edward D.
2005-01-01
sACE (somatic angiotensin-converting enzyme) consists of two homologous, N and C domains, whereas the testis isoenzyme [tACE (testis ACE)] consists of a single C domain. Both isoenzymes are shed from the cell surface by a sheddase activity, although sACE is shed much less efficiently than tACE. We hypothesize that the N domain of sACE plays a regulatory role, by occluding a recognition motif on the C domain required for ectodomain shedding and by influencing the catalytic efficiency. To test this, we constructed two mutants: CNdom-ACE and CCdom-ACE. CNdom-ACE was shed less efficiently than sACE, whereas CCdom-ACE was shed as efficiently as tACE. Notably, cleavage occurred both within the stalk and the interdomain bridge in both mutants, suggesting that a sheddase recognition motif resides within the C domain and is capable of directly cleaving at both positions. Analysis of the catalytic properties of the mutants and comparison with sACE and tACE revealed that the kcat for sACE and CNdom-ACE was less than or equal to the sum of the kcat values for tACE and the N-domain, suggesting negative co-operativity, whereas the kcat value for the CCdom-ACE suggested positive co-operativity between the two domains. Taken together, the results provide support for (i) the existence of a sheddase recognition motif in the C domain and (ii) molecular flexibility of the N and C domains in sACE, resulting in occlusion of the C-domain recognition motif by the N domain as well as close contact of the two domains during hydrolysis of peptide substrates. PMID:15813703
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Singh, Archana; Fekete, Monika; Gengenbach, Thomas; Simonov, Alexandr N; Hocking, Rosalie K; Chang, Shery L Y; Rothmann, Mathias; Powar, Satvasheel; Fu, Dongchuan; Hu, Zheng; Wu, Qiang; Cheng, Yi-Bing; Bach, Udo; Spiccia, Leone
2015-12-21
We report that films screen printed from nickel oxide (NiO) nanoparticles and microballs are efficient electrocatalysts for water oxidation under near-neutral and alkaline conditions. Investigations of the composition and structure of the screen-printed films by X-ray diffraction, X-ray absorption spectroscopy, and scanning electron microscopy confirmed that the material was present as the cubic NiO phase. Comparison of the catalytic activity of the microball films to that of films fabricated by using NiO nanoparticles, under similar experimental conditions, revealed that the microball films outperform nanoparticle films of similar thickness owing to a more porous structure and higher surface area. A thinner, less-resistive NiO nanoparticle film, however, was found to have higher activity per Ni atom. Anodization in borate buffer significantly improved the activity of all three films. X-ray photoelectron spectroscopy showed that during anodization, a mixed nickel oxyhydroxide phase formed on the surface of all films, which could account for the improved activity. Impedance spectroscopy revealed that surface traps contribute significantly to the resistance of the NiO films. On anodization, the trap state resistance of all films was reduced, which led to significant improvements in activity. In 1.00 m NaOH, both the microball and nanoparticle films exhibit high long-term stability and produce a stable current density of approximately 30 mA cm(-2) at 600 mV overpotential. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al2O 3 catalyst.
Chen, Chunmao; Yoza, Brandon A; Wang, Yandan; Wang, Ping; Li, Qing X; Guo, Shaohui; Yan, Guangxu
2015-04-01
There is of great interest to develop an economic and high-efficient catalytic ozonation system (COS) for the treatment of biologically refractory wastewaters. Applications of COS require options of commercially feasible catalysts. Experiments in the present study were designed to prepare and investigate a novel manganese-iron-copper oxide-supported alumina-assisted COS (Mn-Fe-Cu/Al2O3-COS) for the pretreatment of petroleum refinery wastewater. The highly dispersed composite metal oxides on the catalyst surface greatly promoted the performance of catalytic ozonation. Hydroxyl radical mediated oxidation is a dominant reaction in Mn-Fe-Cu/Al2O3-COS. Mn-Fe-Cu/Al2O3-COS enhanced COD removal by 32.7% compared with a single ozonation system and by 8-16% compared with Mn-Fe/Al2O3-COS, Mn-Cu/Al2O3-COS, and Fe-Cu/Al2O3-COS. The O/C and H/C ratios of oxygen-containing polar compounds significantly increased after catalytic ozonation, and the biodegradability of petroleum refinery wastewater was significantly improved. This study illustrates potential applications of Mn-Fe-Cu/Al2O3-COS for pretreatment of biologically refractory wastewaters.
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A Hybrid Co Quaterpyridine Complex/Carbon Nanotube Catalytic Material for CO2 Reduction in Water.
Wang, Min; Chen, Lingjing; Lau, Tai-Chu; Robert, Marc
2018-06-25
Associating a metal-based catalyst to a carbon-based nanomaterial is a promising approach for the production of solar fuels from CO 2 . Upon appending a Co II quaterpyridine complex [Co(qpy)] 2+ at the surface of multi-walled carbon nanotubes, CO 2 conversion into CO was realized in water at pH 7.3 with 100 % catalytic selectivity and 100 % Faradaic efficiency, at low catalyst loading and reduced overpotential. A current density of 0.94 mA cm -2 was reached at -0.35 V vs. RHE (240 mV overpotential), and 9.3 mA cm -2 could be sustained for hours at only 340 mV overpotential with excellent catalyst stability (89 095 catalytic cycles in 4.5 h), while 19.9 mA cm -2 was met at 440 mV overpotential. Such a hybrid material combines the high selectivity of a homogeneous molecular catalyst to the robustness of a heterogeneous material. Catalytic performances compare well with those of noble-metal-based nano-electrocatalysts and atomically dispersed metal atoms in carbon matrices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Novel catalytic micromotor of porous zeolitic imidazolate framework-67 for precise drug delivery.
Wang, Linlin; Zhu, Hongli; Shi, Ying; Ge, You; Feng, Xiaomiao; Liu, Ruiqing; Li, Yi; Ma, Yanwen; Wang, Lianhui
2018-06-07
Micromotors hold promise as drug carriers for targeted drug delivery owing to the characteristics of self-propulsion and directional navigation. However, several defects still exist, including high cost, short movement life, low drug loading and slow release rate. Herein, a novel catalytic micromotor based on porous zeolitic imidazolate framework-67 (ZIF-67) synthesized by a greatly simplified wet chemical method assisted with ultrasonication is described as an efficient anticancer drug carrier. These porous micromotors display effective autonomous motion in hydrogen peroxide and long durable movement life of up to 90 min. Moreover, the multifunctional micromotor ZIF-67/Fe3O4/DOX exhibits excellent performance in precise drug delivery under external magnetic field with high drug loading capacity of fluorescent anticancer drug DOX up to 682 μg mg-1 owing to its porous nature, high surface area and rapid drug release based on dual stimulus of catalytic reaction and solvent effects. Therefore, these porous ZIF-67-based catalytic micromotors combine the domains of metal-organic frameworks (MOFs) and micomotors, thus developing potential resources for micromotors and holding great potential as label-free and precisely controlled high-quality candidates of drug delivery systems for biomedical applications.
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Shahbazy, Mohammad; Kompany-Zareh, Mohsen; Najafpour, Mohammad Mahdi
2015-11-01
Water oxidation is among the most important reactions in artificial photosynthesis, and nano-sized layered manganese-calcium oxides are efficient catalysts toward this reaction. Herein, a quantitative structure-activity relationship (QSAR) model was constructed to predict the catalytic activities of twenty manganese-calcium oxides toward water oxidation using multiple linear regression (MLR) and genetic algorithm (GA) for multivariate calibration and feature selection, respectively. Although there are eight controlled parameters during synthesizing of the desired catalysts including ripening time, temperature, manganese content, calcium content, potassium content, the ratio of calcium:manganese, the average manganese oxidation state and the surface of catalyst, by using GA only three of them (potassium content, the ratio of calcium:manganese and the average manganese oxidation state) were selected as the most effective parameters on catalytic activities of these compounds. The model's accuracy criteria such as R(2)test and Q(2)test in order to predict catalytic rate for external test set experiments; were equal to 0.941 and 0.906, respectively. Therefore, model reveals acceptable capability to anticipate the catalytic activity. Copyright © 2015 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Cao, Houbao, E-mail: caohoubao66@163.com; Du, Pingfan; Song, Lixin
2013-11-15
Graphical abstract: - Highlights: • The core–sheath TiO{sub 2}/SiO{sub 2} nanofibers were fabricated by co-electrospinning technique. • The catalytic property of nanofibers with different sheath thickness was studied. • The potential methods of improving catalytic efficiency are suggested. - Abstract: In this paper, core/sheath TiO{sub 2}/SiO{sub 2} nanofibers with tunable sheath thickness were directly fabricated via a facile co-electrospinning technique with subsequent calcination at 500 °C. The morphologies and structures of core/sheath TiO{sub 2}/SiO{sub 2} nanofibers were characterized by TGA, FESEM, TEM, FTIR, XPS and BET. It was found that the 1D core/sheath nanofibers are made up of anatase–rutile TiO{submore » 2} core and amorphous SiO{sub 2} sheath. The influences of SiO{sub 2} sheath and its thickness on the photoreactivity were evaluated by observing photo-degradation of methylene blue aqueous solution under the irradiation of UV light. Compared with pure TiO{sub 2} nanofibers, the core/sheath TiO{sub 2}/SiO{sub 2} nanofibers performed a better catalytic performance. That was attributed to not only efficient separation of hole–electron pairs resulting from the formation of heterojunction but also larger surface area and surface silanol group which will be useful to provide higher capacity for oxygen adsorption to generate more hydroxyl radicals. And the optimized core/sheath TiO{sub 2}/SiO{sub 2} nanofibers with a sheath thickness of 37 nm exhibited the best photocatalytic performance.« less
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Si, Jiaqi; Ouyang, Wenbing; Zhang, Yanji; Xu, Wentao; Zhou, Jicheng
2017-04-28
Supported metal as a type of heterogeneous catalysts are the most widely used in industrial processes. High dispersion of the metal particles of supported catalyst is a key factor in determining the performance of such catalysts. Here we report a novel catalyst Pd/Ⓕ-MeO x /AC with complex nanostructured, Pd nanoparticles supported on the platelike nano-semiconductor film/activated carbon, prepared by the photocatalytic reduction method, which exhibited high efficient catalytic performance for selective hydrogenation of phenol to cyclohexanone. Conversion of phenol achieved up to more than 99% with a lower mole ratio (0.5%) of active components Pd and phenol within 2 h at 70 °C. The synergistic effect of metal nanoparticles and nano-semiconductors support layer and the greatly increasing of contact interface of nano-metal-semiconductors may be responsible for the high efficiency. This work provides a clear demonstration that complex nanostructured catalysts with nano-metal and nano-semiconductor film layer supported on high specific surface AC can yield enhanced catalytic activity and can afford promising approach for developing new supported catalyst.
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NASA Astrophysics Data System (ADS)
Xu, Huan-Yan; Wang, Yuan; Shi, Tian-Nuo; Zhao, Hang; Tan, Qu; Zhao, Bo-Chao; He, Xiu-Lan; Qi, Shu-Yan
2018-03-01
Multi-walled carbon nanotubes (MWCNTs) can act not only as a support for Fe3O4 nanoparticles (NPs) but also as a coworker with synergistic effect, accordingly improving the heterogeneous Fenton-like efficiency of Fe3O4 NPs. In this study, Fe3O4 NPs were in situ anchored onto MWCNTs by a moderate co-precipitation method and the as-prepared Fe3O4/MWCNTs nanocomposites were employed as the highly efficient Fenton-like catalysts. The analyses of XRD, FTIR, Raman, FESEM, TEM and HRTEM results indicated the formation of Fe3O4 crystals in Fe3O4/MWCNTs nanocomposites prepared at different conditions and the interaction between Fe3O4 NPs and MWCNTs. Over a wide pH range, the surface of modified MWCNTs possessed negative charges. Based on these results, the possible combination mechanism between Fe3O4 NPs and MWCNTs was discussed and proposed. Moreover, the effects of preparation and catalytic conditions on the Fenton-like catalytic efficiency were investigated in order to gain further insight into the heterogeneous Fenton-like reaction catalyzed by Fe3O4/MWCNTs nanocomposites.
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Li, Yue; Machala, Libor; Yan, Weile
2016-02-02
Heterogeneous iron species at the mineral/water interface are important catalysts for the generation of reactive oxygen species at circumneutral pH. One significant pathway leading to the formation of such species arises from deposition of dissolved iron onto mineral colloids due to changes in redox conditions. This study investigates the catalytic properties of Fe impregnated on silica, alumina, and titania nanoparticles (as prototypical mineral colloids). Fe impregnation was carried out by immersing the mineral nanoparticles in dilute Fe(II) or Fe(III) solutions at pH 6 and 3, respectively, in an aerobic environment. The uptake of iron per unit surface area follows the order of nTiO2 > nAl2O3 > nSiO2 for both types of Fe precursors. Impregnation of mineral particles in Fe(II) solutions results in predominantly Fe(III) species due to efficient surface-mediated oxidation. The catalytic activity of the impregnated solids to produce hydroxyl radical (·OH) from H2O2 decomposition was evaluated using benzoic acid as a probe compound under dark conditions. Invariably, the rates of benzoic acid oxidation with different Fe-laden particles increase with the surface density of Fe until a critical density above which the catalytic activity approaches a plateau, suggesting active Fe species are formed predominantly at low surface loadings. The critical surface density of Fe varies with the mineral substrate as well as the aqueous Fe precursor. Fe impregnated on TiO2 exhibits markedly higher activity than its Al2O3 and SiO2 counterparts. The speciation of interfacial Fe is analyzed with diffuse reflectance UV-vis analysis and interpretation of the data in the context of benzoic oxidation rates suggests that the surface activity of the solids for ·OH generation correlates strongly with the isolated (i.e., mononuclear) Fe species. Therefore, iron dispersed on mineral colloids is a significant form of reactive iron surfaces in the aquatic environment.
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Chen, Chunmao; Yu, Ji; Yoza, Brandon A; Li, Qing X; Wang, Gang
2015-04-01
Catalytic ozonation is a promising wastewater treatment technology. However, the high cost of the catalyst hinders its application. A novel "wastes-treat-wastes" technology was developed to reuse spent fluid catalytic cracking catalysts (sFCCc) for the ozonation of petrochemical wastewater in this study. Multivalent vanadium (V(4+) and V(5+)), iron (Fe(2+) and Fe(3+)) and nickel (Ni(2+)) oxides that are distributed on the surface of sFCCc and poisoned FCC catalysts are the catalytic components for ozonation. The sFCCc assisted catalytic ozonation (sFCCc-O) of nitrobenzene indicated that the sFCCc significantly promoted hydroxyl radical mediated oxidation. The degradation rate constant of nitrobenzene in sFCCc-O (0.0794 min(-1) at 298 K) was approximately doubled in comparison with that in single ozonation (0.0362 min(-1) at 298 K). The sFCCc-O of petrochemical wastewater increased chemical oxygen demand removal efficiency by three-fold relative to single ozonation. The number of oxygen-containing (Ox) polar contaminants in the effluent (253) from sFCCc-O treatment decreased to about 70% of the initial wastewater (353). The increased oxygen/carbon atomic ratio and decreased number of Ox polar contaminants indicated a high degree of degradation. The present study showed the role and potential of sFCCc for catalytic ozonation of petrochemical wastewater, particularly in an advantage of the cost-effectiveness through "wastes-treat-wastes". Copyright © 2015 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Warju; Harto, S. P.; Soenarto
2018-01-01
One of the automotive technologies to reduce exhaust gas emissions from the spark-ignition engine (SIE) is by using a catalytic converter. The aims of this research are firstly to conduct a metallic catalytic converter, secondly to find out to what extend chrome-coated copper plate (Cu+Cr) as a catalyst is efficient. To measure the concentration of carbon monoxide (CO) and hydrocarbon (HC) on the frame there are two conditions required. First is when the standard condition, and second is when Cu+Cr metallic catalytic converter is applied using exhaust gas analyzer. Exhaust gas emissions from SIE are measured by using SNI 19-7118.1-2005. The testing of CO and HC emissions were conducted with variable speed to find the trend of exhaust gas emissions from idle speed to high speed. This experiment results in the fact that the use of Cu+Cr metallic catalytic converter can reduce the production of CO and HC of a four-stroke gasoline engine. The reduction of CO and HC emission are 95,35% and 79,28%. Using active metal catalyst in form of metallic catalytic converter, it is gained an optimum effective surface of a catalyst which finally is able to decrease the amount of CO and HC emission significantly in every spinning happened in the engine. Finally, this technology can be applied to the spark ignition engine both car and motorcycle to support blue sky program in Indonesia.
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[FeFe]-Hydrogenases: recent developments and future perspectives.
Wittkamp, F; Senger, M; Stripp, S T; Apfel, U-P
2018-06-08
[FeFe]-Hydrogenases are the most efficient enzymes for catalytic hydrogen turnover. Their H2 production efficiency is hitherto unrivalled. However, functional details of the catalytic machinery and possible modes of application are discussed controversially. The incorporation of synthetically modified cofactors and utilization of semi-artificial enzymes only recently allowed us to shed light on key steps of the catalytic cycle. Herein, we summarize the essential findings regarding the redox chemistry of [FeFe]-hydrogenases and discuss their catalytic hydrogen turnover. We furthermore will give an outlook on potential research activities and exploit the utilization of synthetic cofactor mimics.
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Effect of bath temperature on surface morphology and photocatalytic activity of ZnO nanorods
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sriharan, N.; Senthil, T. S., E-mail: tssenthi@gmail.com; Muthukumarasamy, N.
2016-05-06
ZnO nanorods were prepared by using simple hydrothermal method using four different bath temperatures. All the prepared ZnO nanorods are annealed at 450°C and are characterized by using various techniques such as X-ray diffraction, UV spectra and scanning electron microscopy. Photocatalytic activity of the prepared ZnO nanorods is analyzed. A novel photocatalytic reactor designed with ZnO nanorods prepared at 90°C shows enhanced catalytic efficiency. The role of light irradiation time, bath temperature and surface morphology of the ZnO nanorods on the performance of photocatalytic reaction is analyzed.
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Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A
2017-07-14
Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.
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Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films
Hong, Wesley T.; Stoerzinger, Kelsey; Crumlin, Ethan J.; ...
2016-02-11
Transition metal perovskite oxides are promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, but a lack of fundamental understanding of oxide surfaces impedes the rational design of novel catalysts with improved device efficiencies. In particular, understanding the surface chemistry of oxides is essential for controlling both catalytic activity and long-term stability. Thus, elucidating the physical nature of species on perovskite surfaces and their catalytic enhancement would generate new insights in developing oxide electrocatalysts. In this article, we perform near-ambient pressure XPS of model brownmillerite Sr 2Co 2O 5 (SCO) epitaxial thin films with different crystallographic orientations. Detailedmore » analysis of the Co 2p spectra suggests that the films lose oxygen as a function of temperature. Moreover, deconvolution of the O 1s spectra shows distinct behavior for (114)-oriented SCO films compared to (001)-oriented SCO films, where an additional bulk oxygen species is observed. These findings indicate a change to a perovskite-like oxygen chemistry that occurs more easily in (114) SCO than (001) SCO, likely due to the orientation of oxygen vacancy channels out-of-plane with respect to the film surface. This difference in surface chemistry is responsible for the anisotropy of the oxygen surface exchange coefficient of SCO and may contribute to the enhanced ORR kinetics of La 0.8Sr 0.2CoO 3-δ thin films by SCO surface particles observed previously.« less
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Wang, Hui-Fang; Liu, Zhi-Pan
2008-08-20
Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.
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Oxygen Activation and Photoelectrochemical Oxidation on Oxide Surfaces
2013-12-04
electrolysis followed by product determination from mass spectroscopy showed that acetophenone was produced with a 95% Faradaic efficiency. The H/D kinetic...vs. NHE) 10 electrode: scan rate, 100mV/s. (b) Plot of catalytic currents during electrolysis at −1.38 V, icat (background subtracted), vs...controlled potential electrolysis at 3.0 V at two boron doped diamond electrodes (~0.85 cm2). Red line: background current without added catalyst
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The role of surface generated radicals in catalytic combustion
NASA Technical Reports Server (NTRS)
Santavicca, D. A.; Stein, Y.; Royce, B. S. H.
1985-01-01
Experiments were conducted to better understand the role of catalytic surface reactions in determining the ignition characteristics of practical catalytic combustors. Hydrocarbon concentrations, carbon monoxide and carbon dioxide concentrations, hydroxyl radical concentrations, and gas temperature were measured at the exit of a platinum coated, stacked plate, catalytic combustor during the ignition of lean propane-air mixtures. The substrate temperature profile was also measured during the ignition transient. Ignition was initiated by suddenly turning on the fuel and the time to reach steady state was of the order of 10 minutes. The gas phase reaction, showed no pronounced effect due to the catalytic surface reactions, except the absence of a hydroxyl radical overshoot. It is found that the transient ignition measurements are valuable in understanding the steady state performance characteristics.
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Lu, Ping; Campbell, Charles T; Xia, Younan
2013-10-09
A triphasic catalytic system (Pt/TiO2-SiO2) with an "islands in the sea" configuration was fabricated by controlling the selectivity of SiO2 deposition onto the surface of TiO2 versus the surface of Pt nanoparticles. The Pt surface was exposed, while the nanoparticles were supported on TiO2 and isolated from each other by SiO2 to achieve both significantly improved sinter resistance up to 700 °C and outstanding activity after high-temperature calcination. This work not only demonstrates the feasibility of using a new triphasic system with uncovered catalyst to maximize the thermal stability and catalytic activity but also offers a general approach to the synthesis of high-performance catalytic systems with tunable compositions.
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Munirathinam, Rajesh; Ricciardi, Roberto; Egberink, Richard J M; Huskens, Jurriaan; Holtkamp, Michael; Wormeester, Herbert; Karst, Uwe; Verboom, Willem
2013-01-01
Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and X-ray photoelectron spectroscopy (XPS). XPS revealed the presence of one gallium per 2-3 styrene sulfonate groups of the polymer brushes. The catalytic activity of the Lewis acid-functionalized brushes in a microreactor was demonstrated for the dehydration of oximes, using cinnamaldehyde oxime as a model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3.
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Architecting Graphene Oxide Rolled-Up Micromotors: A Simple Paper-Based Manufacturing Technology.
Baptista-Pires, Luis; Orozco, Jahir; Guardia, Pablo; Merkoçi, Arben
2018-01-01
A graphene oxide rolled-up tube production process is reported using wax-printed membranes for the fabrication of on-demand engineered micromotors at different levels of oxidation, thickness, and lateral dimensions. The resultant graphene oxide rolled-up tubes can show magnetic and catalytic movement within the addition of magnetic nanoparticles or sputtered platinum in the surface of graphene-oxide-modified wax-printed membranes prior to the scrolling process. As a proof of concept, the as-prepared catalytic graphene oxide rolled-up micromotors are successfully exploited for oil removal from water. This micromotor production technology relies on an easy, operator-friendly, fast, and cost-efficient wax-printed paper-based method and may offer a myriad of hybrid devices and applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Mosaddegh, Elaheh
2013-11-01
The nano eggshell powder (NESP) has been prepared by ultrasound irradiation and used as a novel and biodegradable catalyst with high catalytic activity and reusability in green synthesis of 2-aminochromenes via condensation of α- or β-phathol, malononitrile and aromatic aldehydes at 120 °C under solvent-free conditions. The reaction proceeds to completion within 10-35 min in 91-98% yield. Nano eggshell catalyst was characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and X-ray fluorescence, thermal gravimetric, surface area and elemental analyses. In addition, the catalytic activity and chemical structure of nano-sized eggshell were compared with pure CaCO3. Copyright © 2013 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Huang, Aimin; Wei, Bangzhi; Mo, Junyong; Wang, Yajing; Ma, Lin
2018-01-01
Polyethyleneimine (PEI) has long been considered as "golden standard" for polymeric gene delivery carriers. However the molecular basis of the cytotoxicity of PEI is poorly understood. Little is known about the effects of PEI on the structure and functions of biomacromolecules. In this work, fluorescence, UV-vis absorption, circular dichroism spectroscopy were conducted to investigate the influence of PEI of average molecular weight 25, 10 and 1.8 kDa (denoted as PEI25k, PEI10k and PEI1.8k) on the conformation of horseradish peroxidase (HRP) and its catalytic efficiency. Zeta-potential measurement and isothermal titration calorimetry were used to reveal the mechanism of the interaction between PEIs and HRP. PEIs were found to bind onto the surface of HRP predominantly via hydrophobic interaction and hydrogen bond or van der Waals interaction. The complex formation between HRP and PEI induced a more compact conformation of the enzyme and an increased hydrophobicity of the microenvironment surrounding heme pocket. The conformational change of HRP had little impact on the affinity towards H2O2 and phenol. However, the increase in the non-planarity of porphyrin ring in the heme group led to an increase in the exposure degree of the active center and thus an enhancement of catalytic efficiency of HRP in the presence of high molecular weight PEIs (PEI25k and PEI10k). The polymer size played an important role in PEI-HRP interaction. PEI of low molecular weight (PEI1.8k) was less efficient to alter the conformation and catalytic activity of HRP in aqueous solutions.
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Kim, Jongwook; Kang, Jonghyun; Jeong, Uiyoung; Kim, Heesuk; Lee, Hyunjung
2013-04-24
We report a multifunctional platinium nanofiber (PtNF) web that can act as a catalyst layer in dye-sensitized solar cell (DSSC) to simultaneously function as a transparent counter electrode (CE), i.e., without the presence of an indium-doped tin oxide (ITO) or fluorine-doped tin oxide (FTO) glass. This PtNF web can be easily produced by electrospinning, which is highly cost-effective and suitable for large-area industrial-scale production. Electrospun PtNFs are straight and have a length of a few micrometers, with a common diameter of 40-70 nm. Each nanofiber is composed of compact, crystalline Pt grains and they are well-fused and highly interconnected, which should be helpful to provide an efficient conductive network for free electron transport and a large surface area for electrocatalytic behavior. A PtNF web is served as a counter electrode in DSSC and the photovoltaic performance increases up to a power efficiency of 6.0%. It reaches up to 83% of that in a conventional DSSC using a Pt-coated FTO glass as a counter electrode. Newly designed DSSCs containing PtNF webs display highly stable photoelectric conversion efficiencies, and excellent catalytic, conductive, and transparent properties, as well as long-term stability. Also, while the DSSC function is retained, the fabrication cost is reduced by eliminating the transparent conducting layer on the counter electrode. The presented method of fabricating DSSCs based on a PtNF web can be extended to other electrocatalytic optoelectronic devices that combine superior catalytic activity with high conductivity and transparency.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, Zeheng, E-mail: zehengyang@hfut.edu.cn; Wang, Kun; Shao, Zongming
Hierarchical array catalysts with micro/nano structures on substrates not only possess high reactivity from large surface area and suitable interface, but intensify mass transfer through shortening the diffusion paths of both reactants and products for high catalytic efficiency. Herein, we first demonstrate fabrication of Fe{sub 2}O{sub 3} hierarchical arrays grown on stainless-steel substrates via in-situ hydrothermal chemical oxidation followed by heat treatment in N{sub 2} atmosphere. As a Fenton-like catalyst, Fe{sub 2}O{sub 3} hierarchical arrays exhibit excellent catalytic activity and life cycle performance for methylene blue (MB) dye degradation in aqueous solution in the presence of H{sub 2}O{sub 2}. Themore » Fe{sub 2}O{sub 3} catalyst with unique hierarchical structures and efficient transport channels, effectively activates H{sub 2}O{sub 2} to generate large quantity of • OH radicals and highly promotes reaction kinetics between MB and • OH radicals. Immobilization of hierarchical array catalysts on stainless-steel can prevent particles agglomeration, facilitate the recovery and reuse of the catalysts, which is expected promising applications in wastewater remediation. - Graphical abstract: The in-situ synthesis of Fe{sub 2}O{sub 3} hierarchical arrays on stainless-steel substrates was reported for the first time, which exhibit excellent catalytic activity performance for methylene blue (MB) dye degradation in aqueous solution in the presence of H{sub 2}O{sub 2}. - Highlights: • Fe{sub 2}O{sub 3} hierarchical arrays was prepared by in-situ hydrothermal chemical oxidation. • F{sup −} ions play an important role in the formation of the Fe{sub 2}O{sub 3} hierarchical arrays. • Fe{sub 2}O{sub 3} hierarchical arrays show high catalytic activity to methylene blue degradation.« less
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Im, Hyeongwook; Kim, Taewoo; Song, Hyelynn; Choi, Jongho; Park, Jae Sung; Ovalle-Robles, Raquel; Yang, Hee Doo; Kihm, Kenneth D.; Baughman, Ray H.; Lee, Hong H.; Kang, Tae June; Kim, Yong Hyup
2016-01-01
Conversion of low-grade waste heat into electricity is an important energy harvesting strategy. However, abundant heat from these low-grade thermal streams cannot be harvested readily because of the absence of efficient, inexpensive devices that can convert the waste heat into electricity. Here we fabricate carbon nanotube aerogel-based thermo-electrochemical cells, which are potentially low-cost and relatively high-efficiency materials for this application. When normalized to the cell cross-sectional area, a maximum power output of 6.6 W m−2 is obtained for a 51 °C inter-electrode temperature difference, with a Carnot-relative efficiency of 3.95%. The importance of electrode purity, engineered porosity and catalytic surfaces in enhancing the thermocell performance is demonstrated. PMID:26837457
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Lee, Si Woo; Hong, Jong Wook; Lee, Hyunhwa; Wi, Dae Han; Kim, Sun Mi; Han, Sang Woo; Park, Jeong Young
2018-06-14
The intrinsic correlation between an enhancement of catalytic activity and the flow of hot electrons generated at metal-oxide interfaces suggests an intriguing way to control catalytic reactions and is a significant subject in heterogeneous catalysis. Here, we show surface plasmon-induced catalytic enhancement by the peculiar nanocatalyst design of hexoctahedral (HOH) Au nanocrystals (NCs) with Cu2O clusters. We found that this inverse catalyst comprising a reactive oxide for the catalytic portion and a metal as the source of electrons by localized surface plasmon resonance (localized SPR) exhibits a change in catalytic activity by direct hot electron transfer or plasmon-induced resonance energy transfer (PIRET) when exposed to light. We prepared two types of inverse catalysts, Cu2O at the vertex sites of HOH Au NCs (Cu2O/Au vertex site) and a HOH Au NC-Cu2O core-shell structure (HOH Au@Cu2O), to test the structural effect on surface plasmons. Under broadband light illumination, the Cu2O/Au vertex site catalyst showed 30-90% higher catalytic activity and the HOH Au@Cu2O catalyst showed 10-30% higher catalytic activity than when in the dark. Embedding thin SiO2 layers between the HOH Au NCs and the Cu2O verified that the dominant mechanism for the catalytic enhancement is direct hot electron transfer from the HOH Au to the Cu2O. Finite-difference time domain calculations show that a much stronger electric field was formed on the vertex sites after growing the Cu2O on the HOH Au NCs. These results imply that the catalytic activity is enhanced when hot electrons, created from photon absorption on the HOH Au metal and amplified by the presence of surface plasmons, are transferred to the reactive Cu2O.
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NASA Astrophysics Data System (ADS)
Yu, Ming'e.; Li, Caiting; Zeng, Guangming; Zhou, Yang; Zhang, Xunan; Xie, Yin'e.
2015-07-01
A series of novel catalysts (CexSny) for the selective catalytic reduction of NO by NH3 were prepared by the inverse co-precipitation method. The aim of this novel design was to improve the NO removal efficiency of CeTi by the introduction of SnO2. It was found that the Ce-Sn-Ti catalyst was much more active than Ce-Ti and the best Ce:Sn molar ratio was 2:1. Ce2Sn1 possessed a satisfied NO removal efficiency at low temperature (160-280 °C), while over 90% NO removal efficiency maintained in the temperature range of 280-400 °C at the gas hourly space velocity (GHSV) of 50,000 h-1. Besides, Ce2Sn1 kept a stable NO removal efficiency within a wide range of GHSV and a long period of reacting time. Meanwhile, Ce2Sn1 exhibited remarkable resistance to both respectively and simultaneously H2O and SO2 poisoning due to the introduction of SnO2. The promotional effect of SnO2 was studied by N2 adsorption-desorption, X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS) and H2 temperature programmed reduction (H2-TPR) for detail information. The characterization results revealed that the excellent catalytic performance of Ce2Sn1 was associated with the higher specific surface area, larger pore volume and poorer crystallization. Besides, the introduction of SnO2 could result in not only greater conversion of Ce4+ to Ce3+ but also the increase amount of chemisorbed oxygen, which are beneficial to improve the SCR activity. More importantly, a novel peak appearing at lower temperatures through the new redox equilibrium of 2Ce4+ + Sn2+ ↔ 2Ce3+ + Sn4+ and higher total H2 consumption can be obtained by the addition of SnO2. Finally, the possible reaction mechanism of the selective catalytic reduction over Ce2Sn1 was also proposed.
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NASA Astrophysics Data System (ADS)
Lang, Qingqing; Hu, Wenli; Zhou, Penghui; Huang, Tianlong; Zhong, Shuxian; Yang, Lining; Chen, Jianrong; Bai, Song
2017-12-01
Photocatalytic conversion of CO2 to value-added chemicals, a potential route to addressing the depletion of fossil fuels and anthropogenic climate change, is greatly limited by the low-efficient semiconductor photocatalyst. The integration of cocatalyst with light-harvesting semiconductor is a promising approach to enhancing the photocatalytic performance in CO2 reduction reaction. The enhancement is greatly determined by the catalytic active sites on the surface of cocatalyst. Herein, we demonstrate that the photocatalytic performance in the CO2 reduction reaction is greatly promoted by twin defects engineered Pd cocatalyst. In this work, Pd nanoicosahedrons with twin defects were in situ grown on C3N4 nanosheets, which effectively improve the photocatalytic performance in reduction of CO2 to CO and CH4 in comparison with Pd nanotetrahedrons without twin defects. It is proposed that the twin boundary (TB) terminations on the surface of Pd cocatalysts are highly catalytic active sites for CO2 reduction reaction. Based on the proposed mechanism, the photocatalytic activity and selectivity in CO2 reduction were further advanced through reducing the size of Pd icosahedral cocatalyst resulted from the increased surface density of TB terminations. The defect engineering on the surface of cocatalyst represents a novel route in realizing high-performance photocatalytic applications.
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Mohamad, Nur Royhaila; Marzuki, Nur Haziqah Che; Buang, Nor Aziah; Huyop, Fahrul; Wahab, Roswanira Abdul
2015-01-01
The current demands of sustainable green methodologies have increased the use of enzymatic technology in industrial processes. Employment of enzyme as biocatalysts offers the benefits of mild reaction conditions, biodegradability and catalytic efficiency. The harsh conditions of industrial processes, however, increase propensity of enzyme destabilization, shortening their industrial lifespan. Consequently, the technology of enzyme immobilization provides an effective means to circumvent these concerns by enhancing enzyme catalytic properties and also simplify downstream processing and improve operational stability. There are several techniques used to immobilize the enzymes onto supports which range from reversible physical adsorption and ionic linkages, to the irreversible stable covalent bonds. Such techniques produce immobilized enzymes of varying stability due to changes in the surface microenvironment and degree of multipoint attachment. Hence, it is mandatory to obtain information about the structure of the enzyme protein following interaction with the support surface as well as interactions of the enzymes with other proteins. Characterization technologies at the nanoscale level to study enzymes immobilized on surfaces are crucial to obtain valuable qualitative and quantitative information, including morphological visualization of the immobilized enzymes. These technologies are pertinent to assess efficacy of an immobilization technique and development of future enzyme immobilization strategies. PMID:26019635
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Lang, Qingqing; Hu, Wenli; Zhou, Penghui; Huang, Tianlong; Zhong, Shuxian; Yang, Lining; Chen, Jianrong; Bai, Song
2017-12-01
Photocatalytic conversion of CO 2 to value-added chemicals, a potential route to addressing the depletion of fossil fuels and anthropogenic climate change, is greatly limited by the low-efficient semiconductor photocatalyst. The integration of cocatalyst with light-harvesting semiconductor is a promising approach to enhancing the photocatalytic performance in CO 2 reduction reaction. The enhancement is greatly determined by the catalytic active sites on the surface of cocatalyst. Herein, we demonstrate that the photocatalytic performance in the CO 2 reduction reaction is greatly promoted by twin defects engineered Pd cocatalyst. In this work, Pd nanoicosahedrons with twin defects were in situ grown on C 3 N 4 nanosheets, which effectively improve the photocatalytic performance in reduction of CO 2 to CO and CH 4 in comparison with Pd nanotetrahedrons without twin defects. It is proposed that the twin boundary (TB) terminations on the surface of Pd cocatalysts are highly catalytic active sites for CO 2 reduction reaction. Based on the proposed mechanism, the photocatalytic activity and selectivity in CO 2 reduction were further advanced through reducing the size of Pd icosahedral cocatalyst resulted from the increased surface density of TB terminations. The defect engineering on the surface of cocatalyst represents a novel route in realizing high-performance photocatalytic applications.
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Li, Zhipeng; Liu, Feng; You, Hong; Ding, Yi; Yao, Jie; Jin, Chao
2018-04-01
This paper investigated the performance of the combined system of catalytic ozonation and the gas-liquid-solid internal circulating fluidized bed reactor for the advanced treatment of biologically pretreated coal chemical industry wastewater (CCIW). The results indicated that with ozonation alone for 60min, the removal efficiency of chemical oxygen demand (COD) could reach 34%. The introduction of activated carbon, pumice, γ-Al 2 O 3 carriers improved the removal performance of COD, and the removal efficiency was increased by 8.6%, 4.2%, 2%, respectively. Supported with Mn, the catalytic performance of activated carbon and γ-Al 2 O 3 were improved significantly with COD removal efficiencies of 46.5% and 41.3%, respectively; however, the promotion effect of pumice supported with Mn was insignificant. Activated carbon supported with Mn had the best catalytic performance. The catalytic ozonation combined system of MnO X /activated carbon could keep ozone concentration at a lower level in the liquid phase, and promote the transfer of ozone from the gas phase to the liquid phase to improve ozonation efficiency.
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Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation.
Mao, Junjie; Chen, Wenxing; He, Dongsheng; Wan, Jiawei; Pei, Jiajing; Dong, Juncai; Wang, Yu; An, Pengfei; Jin, Zhao; Xing, Wei; Tang, Haolin; Zhuang, Zhongbin; Liang, Xin; Huang, Yu; Zhou, Gang; Wang, Leyu; Wang, Dingsheng; Li, Yadong
2017-08-01
Developing cost-effective, active, and durable electrocatalysts is one of the most important issues for the commercialization of fuel cells. Ultrathin Pt-Mo-Ni nanowires (NWs) with a diameter of ~2.5 nm and lengths of up to several micrometers were synthesized via a H 2 -assisted solution route (HASR). This catalyst was designed on the basis of the following three points: (i) ultrathin NWs with high numbers of surface atoms can increase the atomic efficiency of Pt and thus decrease the catalyst cost; (ii) the incorporation of Ni can isolate Pt atoms on the surface and produce surface defects, leading to high catalytic activity (the unique structure and superior activity were confirmed by spherical aberration-corrected electron microscopy measurements and ethanol oxidation tests, respectively); and (iii) the incorporation of Mo can stabilize both Ni and Pt atoms, leading to high catalytic stability, which was confirmed by experiments and density functional theory calculations. Furthermore, the developed HASR strategy can be extended to synthesize a series of Pt-Mo-M (M = Fe, Co, Mn, Ru, etc.) NWs. These multimetallic NWs would open up new opportunities for practical fuel cell applications.
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Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation
Mao, Junjie; Chen, Wenxing; He, Dongsheng; Wan, Jiawei; Pei, Jiajing; Dong, Juncai; Wang, Yu; An, Pengfei; Jin, Zhao; Xing, Wei; Tang, Haolin; Zhuang, Zhongbin; Liang, Xin; Huang, Yu; Zhou, Gang; Wang, Leyu; Wang, Dingsheng; Li, Yadong
2017-01-01
Developing cost-effective, active, and durable electrocatalysts is one of the most important issues for the commercialization of fuel cells. Ultrathin Pt-Mo-Ni nanowires (NWs) with a diameter of ~2.5 nm and lengths of up to several micrometers were synthesized via a H2-assisted solution route (HASR). This catalyst was designed on the basis of the following three points: (i) ultrathin NWs with high numbers of surface atoms can increase the atomic efficiency of Pt and thus decrease the catalyst cost; (ii) the incorporation of Ni can isolate Pt atoms on the surface and produce surface defects, leading to high catalytic activity (the unique structure and superior activity were confirmed by spherical aberration–corrected electron microscopy measurements and ethanol oxidation tests, respectively); and (iii) the incorporation of Mo can stabilize both Ni and Pt atoms, leading to high catalytic stability, which was confirmed by experiments and density functional theory calculations. Furthermore, the developed HASR strategy can be extended to synthesize a series of Pt-Mo-M (M = Fe, Co, Mn, Ru, etc.) NWs. These multimetallic NWs would open up new opportunities for practical fuel cell applications. PMID:28875160
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A general method for the catalytic nazarov cyclization of heteroaromatic compounds.
Malona, John A; Colbourne, Jessica M; Frontier, Alison J
2006-11-23
A general, catalytic method for efficient Nazarov cyclization of systems containing heteroaromatic components has been developed. Scandium triflate was identified as the most reactive promoter, and it was found that addition of lithium perchlorate was necessary for synthetically useful catalytic cyclizations. The method was used to synthesize a range of cyclopentanone-fused heteroaromatic systems in 36-97% yield, and the reactivity trends observed demonstrate the impact of polarization on cyclization efficiency. [reaction: see text].
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Evaluation of the Catalytic Activity and Cytotoxicity of Palladium Nanocubes. The Role of Oxygen
Dahal, Eshan; Curtiss, Jessica; Subedi, Deepak; Chen, Gen; Houston, Jessica P.; Smirnov, Sergei
2015-01-01
Recently it has been reported that palladium nanocubes (PdNC) are capable of generating singlet oxygen without photo-excitation simply via chemisorption of molecular oxygen on its surface. Such a trait would make PdNC a highly versatile catalyst suitable in organic synthesis and a Reactive Oxygen Species (ROS) inducing cancer treatment reagent. Here we thoroughly investigated the catalytic activity of PdNC with respect to their ability to produce singlet oxygen and to oxidize 3,5,3′,5′-tetramethyl-benzidine (TMB), as well as, analyzed the cytotoxic properties of PdNC on HeLa cells. Our findings showed no evidence of singlet oxygen production by PdNC. The nanocubes’ activity is not necessarily linked to activation of oxygen. The oxidation of substrate on PdNC can be a first step followed by PdNC regeneration with oxygen or other oxidant. The catalytic activity of PdNC towards oxidation of TMB is very high and shows direct two-electrons oxidation when the surface of PdNC is clean and the ratio of TMB/PdNC is not very high. Sequential one electron oxidation is observed when the pristine quality of PdNC surface is compromised by serum or uncontrolled impurities and/or the ratio of TMB/PdNC is high. Clean PdNC in serum-free media efficiently induce apoptosis of HeLa cells. It is the primary route of cell death and is associated with hyperpolarization of mitochondria, contrary to a common mitochondrial depolarization initiated by ROS. Again, the effects are very sensitive to how well the pristine surface of PdNC is preserved, suggesting that PdNC can be used as an apoptosis inducing agent but only with appropriate drug delivery system. PMID:25886644
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Robust Catalysis on 2D Materials Encapsulating Metals: Concept, Application, and Perspective.
Deng, Jiao; Deng, Dehui; Bao, Xinhe
2017-11-01
Great endeavors are undertaken to search for low-cost, rich-reserve, and highly efficient alternatives to replace precious-metal catalysts, in order to cut costs and improve the efficiency of catalysts in industry. However, one major problem in metal catalysts, especially nonprecious-metal catalysts, is their poor stability in real catalytic processes. Recently, a novel and promising strategy to construct 2D materials encapsulating nonprecious-metal catalysts has exhibited inimitable advantages toward catalysis, especially under harsh conditions (e.g., strong acidity or alkalinity, high temperature, and high overpotential). The concept, which originates from unique electron penetration through the 2D crystal layer from the encapsulated metals to promote a catalytic reaction on the outermost surface of the 2D crystal, has been widely applied in a variety of reactions under harsh conditions. It has been vividly described as "chainmail for catalyst." Herein, recent progress concerning this chainmail catalyst is reviewed, particularly focusing on the structural design and control with the associated electronic properties of such heterostructure catalysts, and also on their extensive applications in fuel cells, water splitting, CO 2 conversion, solar cells, metal-air batteries, and heterogeneous catalysis. In addition, the current challenges that are faced in fundamental research and industrial application, and future opportunities for these fantastic catalytic materials are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Zhu, Wenjun; Jin, Jianhui; Chen, Xiao; Li, Chuang; Wang, Tonghua; Tsang, Chi-Wing; Liang, Changhai
2018-02-01
Effective utilization of coal bed methane is very significant for energy utilization and environment protection. Catalytic combustion of methane is a promising way to eliminate trace amounts of oxygen in the coal bed methane and the key to this technology is the development of high-efficiency catalysts. Herein, we report a series of Ce 1-x La x O 2-δ (x = 0-0.8) monolithic catalysts for the catalytic combustion of methane, which are prepared by citric acid method. The structural characterization shows that the substitution of La enhance the oxygen vacancy concentration and reducibility of the supports and promote the migration of the surface oxygen, as a result improve the catalytic activity of CeO 2 . M-Ce 0.8 La 0.2 O 2-δ (monolithic catalyst, Ce 0.8 La 0.2 O 2-δ coated on cordierite honeycomb) exhibits outstanding activity for methane combustion, and the temperature for 10 and 90% methane conversion are 495 and 580 °C, respectively. Additionally, Ce 0.8 La 0.2 O 2-δ monolithic catalyst presents excellent stability at high temperature. These Ce 1-x La x O 2-δ monolithic materials with a small amount of La incorporation therefore show promises as highly efficient solid solution catalysts for lean-oxygen methane combustion. Graphical abstract ᅟ.
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Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.
Gao, Zhenwei; Zhang, Yonggang; Li, Deyi; Werth, Charles J; Zhang, Yalei; Zhou, Xuefei
2015-04-09
The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate. Copyright © 2015 Elsevier B.V. All rights reserved.
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Li, Shangyi; Tang, Yiming; Chen, Weirui; Hu, Zhe; Li, Xukai; Li, Laisheng
2017-10-15
Three-dimensional mesoporous MCM-48 and Ce loaded MCM-48 (Ce/MCM-48) were synthesized by hydrothermal and impregnating methods, respectively. They were characterized by XRD, SEM, TEM, EDS, XPS, N 2 adsorption-desorption techniques, and the results showed that Ce/MCM-48 still retained a highly ordered cubic structure. A series of experiments were conducted to study the catalytic activity of Ce/MCM-48 and Ce/MCM-41 for ozonation of clofibric acid in aqueous solution. Total Organic Carbon (TOC) removal efficiency in Ce/MCM-48/O 3 can be improved to 64% at 120min reaction time, 54% by Ce/MCM-41/O 3 , only 24% by MCM-48/O 3 , 23% by single ozonation. Ce/MCM-48 did not show any adsorption capacity for CA. Effect of initial pH revealed that active sites were surface protonated hydroxyl groups. The restraint of phosphate and sodium hydrogen sulfite (NaHSO 3 ) on the mineralization of CA illustrated more hydroxyl radicals were generated by Ce/MCM-48 catalysts than Ce/MCM-41. The degradation pathway of CA was investigated by the alterations of pH under different conditions. Recycle tests of catalysts demonstrated that compared with Ce/MCM-41, Ce/MCM-48 exhibited more excellent catalytic efficiency and stability because of its unique pore systems. Copyright © 2017 Elsevier Inc. All rights reserved.
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Fuel cell with interdigitated porous flow-field
Wilson, Mahlon S.
1997-01-01
A polymer electrolyte membrane (PEM) fuel cell is formed with an improved system for distributing gaseous reactants to the membrane surface. A PEM fuel cell has an ionic transport membrane with opposed catalytic surfaces formed thereon and separates gaseous reactants that undergo reactions at the catalytic surfaces of the membrane. The fuel cell may also include a thin gas diffusion layer having first and second sides with a first side contacting at least one of the catalytic surfaces. A macroporous flow-field with interdigitated inlet and outlet reactant channels contacts the second side of the thin gas diffusion layer for distributing one of the gaseous reactants over the thin gas diffusion layer for transport to an adjacent one of the catalytic surfaces of the membrane. The porous flow field may be formed from a hydrophilic material and provides uniform support across the backside of the electrode assembly to facilitate the use of thin backing layers.
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Fuel cell with interdigitated porous flow-field
Wilson, M.S.
1997-06-24
A polymer electrolyte membrane (PEM) fuel cell is formed with an improved system for distributing gaseous reactants to the membrane surface. A PEM fuel cell has an ionic transport membrane with opposed catalytic surfaces formed thereon and separates gaseous reactants that undergo reactions at the catalytic surfaces of the membrane. The fuel cell may also include a thin gas diffusion layer having first and second sides with a first side contacting at least one of the catalytic surfaces. A macroporous flow-field with interdigitated inlet and outlet reactant channels contacts the second side of the thin gas diffusion layer for distributing one of the gaseous reactants over the thin gas diffusion layer for transport to an adjacent one of the catalytic surfaces of the membrane. The porous flow field may be formed from a hydrophilic material and provides uniform support across the backside of the electrode assembly to facilitate the use of thin backing layers. 9 figs.
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NASA Astrophysics Data System (ADS)
Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu
2014-12-01
Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.
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Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu
2014-12-19
Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.
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Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu
2014-01-01
Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276
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General Catalytic Enantioselective Access to Monohalomethyl and Trifluoromethyl Cyclopropanes.
Huang, Wei-Sheng; Schlinquer, Claire; Poisson, Thomas; Pannecoucke, Xavier; Charette, André B; Jubault, Philippe
2018-05-29
An efficient catalytic enantioselective access to chiral functionalized trifluoromethyl cyclopropanes from two classes of diazo compounds and alpha-trifluoromethyl styrenes using Rh2((S)-BTPCP)4 as a catalyst is described. This method provides an efficient and practical strategy for the synthesis of highly functionalized CF3-cyclopropanes with excellent diastereoselectivities (up to 20:1) and enantioselectivities (up to 99% ee). The depicted methodology represents up to date the most efficient catalytic enantioselective method to access highly decorated chiral CF3-cyclopropanes. Extension to chiral monohalomethyl cyclopropanes in high ee is also reported. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Active anatase (0 0 1)-like surface of hydrothermally synthesized titania nanotubes
NASA Astrophysics Data System (ADS)
Chen, Qiang; Mogilevsky, Gregory; Wagner, George W.; Forstater, Jacob; Kleinhammes, Alfred; Wu, Yue
2009-11-01
Using 31P and 13C NMR with DFT calculations we demonstrate the exposed surface of titania nanotubes (TiNTs) is a stable, unterminated anatase (0 0 1)-like surface and is catalytically active under ambient conditions. We find that methanol dissociatively adsorbs on the surface of TiNTs agreeing with the predicted activity of surface dissociation of organic molecules on the crystalline (0 0 1)-anatase surface. We further examined the catalytic activity of anatase power, TiNT, and nanosheets in catalytic hydrolysis of S-[2-(diisopropylamino)ethyl]- O-ethyl methylphosphonothioate (VX) via 31P NMR and demonstrate that titanate-like nanosheets are inactive in the reaction owing to their hydroxylated (0 0 1) surface.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Hao; Yin, Feng-Xiang; Chen, Biao-Hua
Developing carbon catalyst materials using natural, abundant and renewable resources as precursors plays an increasingly important role in clean energy generation and environmental protection. In this work, N-doped pomelo-peel-derived carbon (NPC) materials were prepared using a widely available food waste-pomelo peels and melamine. The synthetic NPC exhibits well-defined porosities and a highly doped-N content (e.g. 6.38 at% for NPC-2), therefore affords excellent oxygen reduction reaction (ORR) catalytic activities in alkaline electrolytes. NPC was further integrated with ZIF-67 to form ZIF-67@NPC hybrids through solvothermal reactions. The hybrid catalysts show substantially enhanced ORR catalytic activities comparable to that of commercial 20 wamore » Pt/C. Furthermore, the catalysts also exhibit excellent oxygen evolution reaction (OER) catalytic activities. Among all prepared ZIF-67@NPC hybrids, the optimal composition with ZIF-67 to NPC ratio of 2:1 exhibits the best ORR and OER bifunctional catalytic performance and the smallest Delta E (E-OER@10 mA cm(-2)-E-ORR@-1 mA cm(-2)) value of 0.79 V. The catalyst also demonstrated desirable 4-electron transfer pathways and superior catalytic stabilities. The Co-N-4 in ZIF-67, electrochemical active surface area, and the strong interactions between ZIF-67 and NPC are attributed as the main contributors to the bifunctional catalytic activities. These factors act synergistically, resulting in substantially enhanced bifunctional catalytic activities and stabilities; consequently, this hybrid catalyst is among the best of the reported bifunctional electrocatalysts and is promising for use in metal-air batteries and fuel cells. (C) 2016 Elsevier B.V. All rights reserved.« less
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NASA Astrophysics Data System (ADS)
Cavendish, Rio
As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO 2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.
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Rise of nano effects in electrode during electrocatalytic CO2 conversion.
Yang, Ki Dong; Lee, Chan Woo; Jang, Jun Ho; Ha, Tak Rae; Nam, Ki Tae
2017-09-01
The electrocatalytic conversion of CO 2 into value-added fuels has received increasing attention as a promising way to mitigate the atmospheric CO 2 concentration and close the broken carbon-cycle. Early studies, focused on polycrystalline metal electrodes, outlined in detail the overall trends in the catalytic activity and product selectivity of pure metals; however, several inherent limitations were found, such as low current density and high overpotential, which hindered electrocatalytic CO 2 reduction from practical application. Fortunately, the recent development of precisely synthesized nanocatalysts has led to several breakthroughs in catalytic CO 2 conversion. By carefully controlling the thermodynamic adsorption energies and flow dynamics of reaction intermediates, nanosized electrocatalysts afford more versatile and energetically efficient routes to convert CO 2 into desired chemicals. In this article, we review the state-of-the-art nanocatalysts applied for CO 2 conversion and discuss newly found phenomena at the local environment near the catalyst surface. The mechanistic understanding of these findings can provide insight into the future design of catalysts for the efficient and selective reduction of CO 2 .
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Guan, Yongxin; Feng, Yangyang; Wan, Jing; Yang, Xiaohui; Fang, Ling; Gu, Xiao; Liu, Ruirui; Huang, Zhengyong; Li, Jian; Luo, Jun; Li, Changming; Wang, Yu
2018-05-27
Herein, a unique ganoderma-like MoS 2 /NiS 2 hetero-nanostructure with isolated Pt atoms anchored is reported. This novel ganoderma-like heterostructure can not only efficiently disperse and confine the few-layer MoS 2 nanosheets to fully expose the edge sites of MoS 2 , and provide more opportunity to capture the Pt atoms, but also tune the electronic structure to modify the catalytic activity. Because of the favorable dispersibility and exposed large specific surface area, single Pt atoms can be easily anchored on MoS 2 nanosheets with ultrahigh loading of 1.8 at% (the highest is 1.3 at% to date). Owing to the ganoderma-like structure and platinum atoms doping, this catalyst shows Pt-like catalytic activity for the hydrogen evolution reaction with an ultralow overpotential of 34 mV and excellent durability of only 2% increase in overpotential for 72 h under the constant current density of 10 mA cm -2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Natural Magnetite: an efficient catalyst for the degradation of organic contaminant
NASA Astrophysics Data System (ADS)
He, Hongping; Zhong, Yuanhong; Liang, Xiaoliang; Tan, Wei; Zhu, Jianxi; Yan Wang, Christina
2015-05-01
Iron (hydr)oxides are ubiquitous earth materials that have high adsorption capacities for toxic elements and degradation ability towards organic contaminants. Many studies have investigated the reactivity of synthetic magnetite, while little is known about natural magnetite. Here, we first report the reactivity of natural magnetites with a variety of elemental impurities for catalyzing the decomposition of H2O2 to produce hydroxyl free radicals (•OH) and the consequent degradation of p-nitrophenol (p-NP). We observed that these natural magnetites show higher catalytic performance than that of the synthetic pure magnetite. The catalytic ability of natural magnetite with high phase purity depends on the surface site density while that for the magnetites with exsolutions relies on the mineralogical nature of the exsolved phases. The pleonaste exsolution can promote the generation of •OH and the consequent degradation of p-NP; the ilmenite exsolution has little effect on the decomposition of H2O2, but can increase the adsorption of p-NP on magnetite. Our results imply that natural magnetite is an efficient catalyst for the degradation of organic contaminants in nature.
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Wan, Zhong; Wang, Jianlong
2017-02-15
In this paper, Fe 3 O 4 -Mn 3 O 4 /reduced graphene oxide (RGO) hybrid was synthesized through polyol process and impregnation method and used as heterogeneous Fenton-like catalyst for degradation of sulfamethazine (SMT) in aqueous solution. The hybrid catalyst had higher catalytic efficiency compared with Fe 3 O 4 -Mn 3 O 4 and Mn 3 O 4 as catalyst for degradation of SMT . The effects of pH value, H 2 O 2 concentration, catalyst dosage, initial SMT concentration and temperature on SMT degradation were investigated. The removal efficiency of SMT was about 98% at following optimal conditions: pH=3, T=35°C, Fe 3 O 4 /Mn 3 O 4 -RGO composites=0.5g/L, H 2 O 2 =6mM. The inhibitor experiments indicated that the main active species was hydroxyl radicals (·OH) on catalyst surface. At last, the possible catalytic mechanism was proposed. Copyright © 2016 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Miao, Zongcheng; Yang, Fengxia; Luan, Yi; Shu, Xin; Ramella, Daniele
2017-12-01
In this work, a core-shell magnetic composite Fe3O4@P4VP@ZIF-8 microspheres were successfully designed and synthesized. A polymerization approach on the surface of pre-made Fe3O4 microspheres was employed for the synthesis of Fe3O4@P4VP. The zinc-derived Zeolite Imidazolate Framework (ZIF) shell was introduced through a layer-by-layer strategy. The obtained Fe3O4@P4VP@ZIF-8 core-shell structure was employed as an efficient Knoevenagel condensation catalyst for a variety of aldehydes. Furthermore, the inner P4VP layer also served as a basic additive in the condensation reaction process, while much less homogeneous basic additive was used. High catalytic reaction efficiency was achieved when the P4VP layer was utilized in combination with a Lewis acidity bearing ZIF-8 layer. The Fe3O4@P4VP@ZIF-8 catalyst was tested for recyclability and no drop in the catalytic activity was observed after more than five cycles.
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2011-12-01
8 C. Catalytic activity of evolved variants with GA ................................................................. 11 D...several variants of rePON1 with enhanced activity towards a racemic mixture of CMP-Coumarin by screening ‘neutral drift’ libraries of rePON1 (e.g. 1G3, 2G9...22. The most active variant was 3B3, which had ~250-fold higher catalytic efficiency (kcat/Km 20x106 M-1min-1) compared to the wild-type-like
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Chen, Zhao-Yang; Duan, Long-Fa; Sheng, Tian; Lin, Xiao; Chen, Ya-Feng; Chu, You-Qun; Sun, Shi-Gang; Lin, Wen-Feng
2017-06-21
Core-shell composites with strong phase-phase contact could provide an incentive for catalytic activity. A simple, yet efficient, H 2 O-mediated method has been developed to synthesize a mesoscopic core-shell W@WC architecture with a dodecahedral microstructure, via a one-pot reaction. The H 2 O plays an important role in the resistance of carbon diffusion, resulting in the formation of the W core and W-terminated WC shell. Density functional theory (DFT) calculations reveal that adding W as core reduced the oxygen adsorption energy and provided the W-terminated WC surface. The W@WC exhibits significant electrocatalytic activities toward hydrogen evolution and nitrobenzene electroreduction reactions, which are comparable to those found for commercial Pt/C, and substantially higher than those found for meso- and nano-WC materials. The experimental results were explained by DFT calculations based on the energy profiles in the hydrogen evolution reactions over WC, W@WC, and Pt model surfaces. The W@WC also shows a high thermal stability and thus may serve as a promising more economical alternative to Pt catalysts in these important energy conversion and environmental protection applications. The current approach can also be extended or adapted to various metals and carbides, allowing for the design and fabrication of a wide range of catalytic and other multifunctional composites.
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Xu, Huajie; Wang, Bingkai; Shan, Changfu; Xi, Pinxian; Liu, Weisheng; Tang, Yu
2018-02-21
Developing convenient doping to build highly active oxygen evolution reaction (OER) electrocatalysts is a practical process for solving the energy crisis. Herein, a facile and low-cost in situ self-assembly strategy for preparing a Ce-doped NiFe-LDH nanosheets/nanocarbon (denoted as NiFeCe-LDH/CNT, LDH = layered double hydroxide and CNT = carbon nanotube) hierarchical nanocomposite is established for enhanced OER, in which the novel material provides its overall advantageous structural features, including high intrinsic catalytic activity, rich redox properties, high, flexible coordination number of Ce 3+ , and strongly coupled interface. Further experimental results indicate that doped Ce into NiFe-LDH/CNT nanoarrays brings about the reinforced specific surface area, electrochemical surface area, lattice defects, and the electron transport between the LDH nanolayered structure and the framework of CNTs. The effective synergy prompts the NiFeCe-LDH/CNT nanocomposite to possess superior OER electrocatalytic activity with a low onset potential (227 mV) and Tafel slope (33 mV dec -1 ), better than the most non-noble metal-based OER electrocatalysts reported. Therefore, the combination of the remarkable catalytic ability and the facile normal temperature synthesis conditions endows the Ce-doped LDH nanocomposite as a promising catalyst to expand the field of lanthanide-doped layered materials for efficient water-splitting electrocatalysis with scale-up potential.
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Zhang, Nan; Zhao, He; Zhang, Guangming; Chong, Shan; Liu, Yucan; Sun, Liyan; Chang, Huazhen; Huang, Ting
2017-02-01
High efficiency and facile separation are desirable for catalysts used in water treatment. In this study, a magnetic catalyst (nitrogen doped iron/activated carbon) was prepared and used for pharmaceutical wastewater treatment. The catalyst was characterized using BET, SEM, XRD, VSM and XPS. Results showed that iron and nitrogen were successfully loaded and doped, magnetic Fe 2 N was formed, large amount of active surface oxygen and Fe(II) were detected, and the catalyst could be easily separated from water. Diclofenac was then degraded using the catalyst in ultrasound system. The catalyst showed high catalytic activity with 95% diclofenac removal. Analysis showed that ·OH attack of diclofenac was a main pathway, and then ·OH generation mechanism was clarified. The effects of catalyst dosage, sonication time, ultrasonic density, initial pH, and inorganic anions on diclofenac degradation were studied. Sulfate anion enhanced the degradation of diclofenac. Mechanism in the catalytic ultrasonic process was analyzed and reactions were clarified. Large quantity of oxidants was generated on the catalyst surface, including ·OH, O 2 - , O - and HO 2 ·, which degraded diclofenac efficiently. In the solution and interior of cavitation bubbles, ·OH and "hot spot" effects contributed to the degradation of diclofenac. Reuse of the catalyst was further investigated to enhance its economy, and the catalyst maintained activity after seven uses. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Roy, Mouni; Basak, Somjyoti; Naskar, Milan Kanti
2016-02-21
A simple soft bi-templating process was used for the synthesis of mesoporous manganese oxide nanostructures using KMnO4 as a precursor and polyethylene glycol and cetyltrimethylammonium bromide as templates in the presence of benzaldehyde as an organic additive in alkaline media, followed by calcination at 400 °C. X-ray diffraction and Raman spectroscopic analysis of the calcined products confirmed the existence of stoichiometric (MnO2 and Mn5O8) and non-stoichiometric mixed phases (MnO2 + Mn5O8) of Mn oxides obtained by tuning the concentration of the additive and the synthesis time. The surface properties of the prepared Mn oxides were determined by X-ray photoelectron spectroscopy. The mesoporosity of the samples was confirmed by N2 adsorption-desorption. Different synthetic conditions resulted in the formation of different morphologies of the Mn oxides (α-MnO2, Mn5O8, and α-MnO2 + Mn5O8), such as nanoparticles, nanorods, and nanowires. The synthesized mesoporous Mn oxide nanostructures were used for the catalytic oxidation of the harmful air pollutant carbon monoxide. The Mn5O8 nanoparticles with the highest Brunauer-Emmett-Teller surface area and the non-stoichiometric manganese oxide (α-MnO2 + Mn5O8) nanorods with a higher Mn(3+) concentration had the best catalytic efficiency.
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Zhang, Ri-Chao; Sun, Dan; Zhang, Ruirui; Lin, Wen-Feng; Macias-Montero, Manuel; Patel, Jenish; Askari, Sadegh; McDonald, Calum; Mariotti, Davide; Maguire, Paul
2017-01-01
Conductive polymers have been increasingly used as fuel cell catalyst support due to their electrical conductivity, large surface areas and stability. The incorporation of metal nanoparticles into a polymer matrix can effectively increase the specific surface area of these materials and hence improve the catalytic efficiency. In this work, a nanoparticle loaded conductive polymer nanocomposite was obtained by a one-step synthesis approach based on room temperature direct current plasma-liquid interaction. Gold nanoparticles were directly synthesized from HAuCl4 precursor in poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). The resulting AuNPs/PEDOT:PSS nanocomposites were subsequently characterized under a practical alkaline direct ethanol fuel cell operation condition for its potential application as an electrocatalyst. Results show that AuNPs sizes within the PEDOT:PSS matrix are dependent on the plasma treatment time and precursor concentration, which in turn affect the nanocomposites electrical conductivity and their catalytic performance. Under certain synthesis conditions, unique nanoscale AuNPs/PEDOT:PSS core-shell structures could also be produced, indicating the interaction at the AuNPs/polymer interface. The enhanced catalytic activity shown by AuNPs/PEDOT:PSS has been attributed to the effective electron transfer and reactive species diffusion through the porous polymer network, as well as the synergistic interfacial interaction at the metal/polymer and metal/metal interfaces. PMID:28436454
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Lin, Kun-Yi Andrew; Chen, Yu-Chien; Lin, Tien-Yu; Yang, Hongta
2017-07-01
Zirconia-supported LaCoO 3 perovskite (LaCoO 3 /ZrO 2 (LCZ)) is prepared and adopted for the first time as a heterogeneous catalyst for activating Oxone to degrade organic pollutants. The resulting LCZ exhibits a significantly higher surface area (i.e., 10 times) than bulk LaCoO 3 powder as nanoscale LaCoO 3 particles were easily afforded on the surface of ZrO 2 support. As Rhodamine B (RB) decolorization is selected as a model test to evaluate catalytic activity for activating Oxone, LCZ showed a much higher catalytic activity to activate Oxone than LaCoO 3 even though LCZ contained only 12.5wt% of LaCoO 3 . LCZ-activated Oxone also remained effective for RB decolorization even in the presence of salts and other organic contaminant. The mechanism of RB decolorization by LCZ-activated Oxone was revealed and involved sulfate radical and other reactive oxygen species. The mechanism of Oxone activation by LCZ could be owing to both La 3+ and Co 3+ of LCZ. LCZ was recycled to activate Oxone for RB decolorization over multiple times without loss of catalytic activity. These results demonstrate that LCZ is a promising LaCoO 3 -based nanocomposite as a heterogeneous catalyst for activating Oxone to degrade organic pollutants. Copyright © 2017 Elsevier Inc. All rights reserved.
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Bo, Longli; Quan, Xie; Wang, Xiaochang; Chen, Shuo
2008-08-30
Granular activated carbon-supported platinum (Pt/GAC) catalysts were prepared by microwave irradiation and characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). Pt particles dispersing onto the surface of GAC could be penetrated by microwave and acted as "reaction centre" in the degradations of p-nitrophenol (PNP) and pentachlorophenol (PCP) in aqueous solution by microwave-assisted catalytic oxidation. The reaction was carried out through a packed bed reactor under ambient pressure and continuous flow mode. Under the conditions of microwave power 400 W, influent flow 6.4 mL min(-1) and air flow 120 mL min(-1), phenolic solutions with high concentration (initial concentrations of PNP and PCP solutions were 1469 and 1,454 mg L(-1), respectively) were treated effectively by Pt/GAC, 86% PNP and 90% PCP were degraded and total organic carbon (TOC) removal reached 85% and 71%, respectively. Compared with GAC, loaded Pt apparently accelerated oxidative reaction so that Pt/GAC had a better degrading and mineralizing efficiencies for PNP. Hydraulic retention time was only 16 min in experiment, which was shortened greatly compared with catalytic wet air oxidation. Pyrolysis and oxidation of phenolic pollutants occurred simultaneously on the surface of Pt/GAC by microwave irradiation.
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NASA Astrophysics Data System (ADS)
Zhang, Ri-Chao; Sun, Dan; Zhang, Ruirui; Lin, Wen-Feng; Macias-Montero, Manuel; Patel, Jenish; Askari, Sadegh; McDonald, Calum; Mariotti, Davide; Maguire, Paul
2017-04-01
Conductive polymers have been increasingly used as fuel cell catalyst support due to their electrical conductivity, large surface areas and stability. The incorporation of metal nanoparticles into a polymer matrix can effectively increase the specific surface area of these materials and hence improve the catalytic efficiency. In this work, a nanoparticle loaded conductive polymer nanocomposite was obtained by a one-step synthesis approach based on room temperature direct current plasma-liquid interaction. Gold nanoparticles were directly synthesized from HAuCl4 precursor in poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). The resulting AuNPs/PEDOT:PSS nanocomposites were subsequently characterized under a practical alkaline direct ethanol fuel cell operation condition for its potential application as an electrocatalyst. Results show that AuNPs sizes within the PEDOT:PSS matrix are dependent on the plasma treatment time and precursor concentration, which in turn affect the nanocomposites electrical conductivity and their catalytic performance. Under certain synthesis conditions, unique nanoscale AuNPs/PEDOT:PSS core-shell structures could also be produced, indicating the interaction at the AuNPs/polymer interface. The enhanced catalytic activity shown by AuNPs/PEDOT:PSS has been attributed to the effective electron transfer and reactive species diffusion through the porous polymer network, as well as the synergistic interfacial interaction at the metal/polymer and metal/metal interfaces.
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Study of Pt-Rh/CeO2-ZrO2-MxOy (M = Y, La)/Al2O3 three-way catalysts
NASA Astrophysics Data System (ADS)
Jiaxiu, Guo; Zhonghua, Shi; Dongdong, Wu; Huaqiang, Yin; Maochu, Gong; Yaoqiang, Chen
2013-05-01
CeO2-ZrO2-MxOy (M = Y; La) mixed oxides, prepared by co-precipitation method and characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Raman spectra (RM) and oxygen pulse reaction, were comparatively investigated to elucidate the combinational effects of Y and/or La oxide promoters on the catalytic activity and anti-aging performance of monolithic cordierite honeycomb catalysts with low Pt and Rh content. The catalytic activities, water-gas shift (WGS) and steam reforming reaction (SR) were studied under a simulated gas mixture. The catalysts were also characterized by H2-temperature-programmed reduction (H2-TPR) and O2-temperature-programmed desorption (O2-TPD). The results showed that the prepared CeO2-ZrO2-MxOy oxides have a face-centered cubic fluorite structure and are nanosize. La3+ ions can significantly improve thermal stability and efficiently retard CeO2-ZrO2 crystal sintering and growth. Doped CeO2-ZrO2 with Y3+ and La3+ has 105 and 60 m2/g surface area and 460 and 390 μmol/g OSC before and after aging. The T50 of fresh Pt-Rh/CZYL/LA is 170 °C for CO, 222 °C for C3H8 and 189 °C for NO, and shift to 205, 262 and 228 °C after hydrothermal aging, which are better than those of Pt-Rh/CZY/LA or Pt-Rh/CZL/LA. WGS and SR are relate to the OSC of oxygen storage materials and absorbed oxygen species on the catalyst surface and affect the three-way catalytic activities of catalysts. The reductive property of noble metals and the dissociatively adsorbed O2 on the surface of catalysts are closely related to the catalytic activities.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hsieh, Yu-Chi; Senanayake, Sanjaya D.; Zhang, Yu
2015-09-04
Metallic silver (Ag) is known as an efficient electrocatalyst for the conversion of carbon dioxide (CO 2) to carbon monoxide (CO) in aqueous or nonaqueous electrolytes. However, polycrystalline silver electrocatalysts require significant overpotentials in order to achieve high selectivity toward CO 2 reduction, as compared to the side reaction of hydrogen evolution. Here we report a high-surface-area Ag nanocoral catalyst, fabricated by an oxidation–reduction method in the presence of chloride anions in an aqueous medium, for the electro-reduction of CO 2 to CO with a current efficiency of 95% at the low overpotential of 0.37 V and the current densitymore » of 2 mA cm –2. A lower limit of TOF of 0.4 s –1 and TON > 8.8 × 10 4 (over 72 h) was estimated for the Ag nanocoral catalyst at an overpotential of 0.49 V. The Ag nanocoral catalyst demonstrated a 32-fold enhancement in surface-area-normalized activity, at an overpotential of 0.49 V, as compared to Ag foil. We found that, in addition to the effect on nanomorphology, the adsorbed chloride anions play a critical role in the observed enhanced activity and selectivity of the Ag nanocoral electrocatalyst toward CO 2 reduction. Synchrotron X-ray photoelectron spectroscopy (XPS) studies along with a series of control experiments suggest that the chloride anions, remaining adsorbed on the catalyst surface under electrocatalytic conditions, can effectively inhibit the side reaction of hydrogen evolution and enhance the catalytic performance for CO 2 reduction.« less
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Sharma, R K; Sharma, Shivani
2014-01-21
The present work reports the fabrication of a novel and highly efficient silica nanospheres-based palladium catalyst (SiO2@APTES@Pd-FFR) via immobilization of a palladium complex onto silica nanospheres functionalized with 3-aminopropyltriethoxysilane (APTES), and its catalytic application for the oxidative amination of aldehydes to yield commercially important amides. The structure of the nano-catalyst was confirmed by Solid-state (13)C CPMAS and (29)Si CPMAS NMR spectroscopy, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectroscopy (FT-IR), Energy dispersive X-ray fluorescence spectroscopy (ED-XRF), Atomic absorption spectroscopy (AAS), Transmission electron microscopy (TEM) and elemental analysis. The nano-catalyst was found to be highly effective for the oxidative amination of aldehydes using hydrogen peroxide as an environmentally benign oxidant to give amides. The effect of various reaction parameters such as temperature, amount of catalyst, reaction time, type of solvent, oxidant used, substrate to oxidant ratio etc. have been demonstrated to achieve high catalytic efficacy. Moreover, this nanostructured catalyst could be recovered with simplicity and reused for several cycles without any significant loss in its catalytic activity. In addition, the stability of the reused nano-catalyst was proved by FT-IR and HRTEM techniques. It is worth noting that the features of mild reaction conditions, simple work-up procedure, high product yield, no use of toxic organic solvents, high turn-over frequency (TOF), and easy recovery and reusability of the present quasi-homogeneous nano-catalyst make this protocol an attractive alternative to the existing catalytic methods for the oxidative amination of aldehydes to furnish industrially important amides.
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Zheng, Guangchao; Kaefer, Katharina; Mourdikoudis, Stefanos; Polavarapu, Lakshminarayana; Vaz, Belén; Cartmell, Samantha E; Bouleghlimat, Azzedine; Buurma, Niklaas J; Yate, Luis; de Lera, Ángel R; Liz-Marzán, Luis M; Pastoriza-Santos, Isabel; Pérez-Juste, Jorge
2015-01-15
We present a novel strategy based on the immobilization of palladium nanoparticles (Pd NPs) on filter paper for development of a catalytic system with high efficiency and recyclability. Oleylamine-capped Pd nanoparticles, dispersed in an organic solvent, strongly adsorb on cellulose filter paper, which shows a great ability to wick fluids due to its microfiber structure. Strong van der Waals forces and hydrophobic interactions between the particles and the substrate lead to nanoparticle immobilization, with no desorption upon further immersion in any solvent. The prepared Pd NP-loaded paper substrates were tested for several model reactions such as the oxidative homocoupling of arylboronic acids, the Suzuki cross-coupling reaction, and nitro-to-amine reduction, and they display efficient catalytic activity and excellent recyclability and reusability. This approach of using NP-loaded paper substrates as reusable catalysts is expected to open doors for new types of catalytic support for practical applications.
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Nemoto, Tetsuhiro; Kakei, Hiroyuki; Gnanadesikan, Vijay; Tosaki, Shin-Ya; Ohshima, Takashi; Shibasaki, Masakatsu
2002-12-11
The catalytic asymmetric epoxidation of alpha,beta-unsaturated amides using Sm-BINOL-Ph3As=O complex was succeeded. Using 5-10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of beta-aryl alpha-hydroxy amides, including beta-aryllactyl-leucine methyl esters. Interestingly, it was found that beneficial modifications on the Pd catalyst were achieved by the constituents of the first epoxidation, producing a more suitable catalyst for the Pd-catalyzed epoxide opening reaction in terms of chemoselectivity.
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Quesada-Peñate, I; Julcour-Lebigue, C; Jáuregui-Haza, U J; Wilhelm, A M; Delmas, H
2012-06-30
The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties. Copyright © 2012 Elsevier B.V. All rights reserved.
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Wang, Yusen; Wang, Xiaoxia; Feng, Xiaolan; Ye, Xiao; Fu, Jie
2018-01-01
Layered double hydroxides (LDHs) have been widely used as an important subset of solid base catalysts. However, developing low-cost, small-sized LDH nanoparticles with enhanced surface catalytic sites remains a challenge. In this work, silica aerogel (SA)-supported, small-sized Mg–Al LDH nanosheets were successfully prepared by one-pot coprecipitation of Mg and Al ions in an alkaline suspension of crushed silica aerogel. The supported LDH nanosheets were uniformly dispersed in the SA substrate with the smallest average radial diameter of 19.2 nm and the thinnest average thickness of 3.2 nm, both dimensions being significantly less than those of the vast majority of LDH nanoparticles reported. The SA/LDH composites also showed large pore volume (up to 1.3 cm3·g) and pore diameter (>9 nm), and therefore allow efficient access of reactants to the edge catalytic sites of LDH nanosheets. In a base-catalyzed Henry reaction of benzaldehyde with nitromethane, the SA/LDH catalysts showed high reactant conversions and favorable stability in 6 successive cycles of reactions. The low cost of the SA carrier and LDH precursors, easy preparation method, and excellent catalytic properties make these SA/LDH composites a competitive example of solid-base catalysts. PMID:29462941
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Wang, Lijun; Wang, Yusen; Wang, Xiaoxia; Feng, Xiaolan; Ye, Xiao; Fu, Jie
2018-02-16
Layered double hydroxides (LDHs) have been widely used as an important subset of solid base catalysts. However, developing low-cost, small-sized LDH nanoparticles with enhanced surface catalytic sites remains a challenge. In this work, silica aerogel (SA)-supported, small-sized Mg-Al LDH nanosheets were successfully prepared by one-pot coprecipitation of Mg and Al ions in an alkaline suspension of crushed silica aerogel. The supported LDH nanosheets were uniformly dispersed in the SA substrate with the smallest average radial diameter of 19.2 nm and the thinnest average thickness of 3.2 nm, both dimensions being significantly less than those of the vast majority of LDH nanoparticles reported. The SA/LDH composites also showed large pore volume (up to 1.3 cm3·g) and pore diameter (>9 nm), and therefore allow efficient access of reactants to the edge catalytic sites of LDH nanosheets. In a base-catalyzed Henry reaction of benzaldehyde with nitromethane, the SA/LDH catalysts showed high reactant conversions and favorable stability in 6 successive cycles of reactions. The low cost of the SA carrier and LDH precursors, easy preparation method, and excellent catalytic properties make these SA/LDH composites a competitive example of solid-base catalysts.
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Molla, Rostam Ali; Iqubal, Md Asif; Ghosh, Kajari; Kamaluddin; Islam, Sk Manirul
2015-04-14
A new copper-grafted mesoporous poly-melamine-formaldehyde (Cu-mPMF) has been synthesized from melamine and paraformaldehyde in DMSO medium, followed by grafting of Cu(ii) at its surface. Cu-mPMF has been characterized by elemental analysis, powder XRD, HR TEM, FE-SEM, N2 adsorption study, FT-IR, UV-vis DRS, TGA-DTA, EPR spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The Cu-grafted mesoporous material showed very good catalytic activity in methyl esterification of benzylic alcohols and amidation of nitriles. Moreover, the catalyst is easily recoverable and can be reused seven times without appreciable loss of catalytic activity in the above reactions. The highly dispersed and strongly bound Cu(ii) sites in the Cu-grafted mesoporous polymer could be responsible for the observed high activities of the Cu-mPMF catalyst. Due to strong binding with the functional groups of the polymer, no evidence of leached copper from the catalyst during the course of reaction emerged, suggesting true heterogeneity in the catalytic process.
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Meng, Xianguang; Liu, Lequan; Ouyang, Shuxin; Xu, Hua; Wang, Defa; Zhao, Naiqin; Ye, Jinhua
2016-08-01
Nanometal materials play very important roles in solar-to-chemical energy conversion due to their unique catalytic and optical characteristics. They have found wide applications from semiconductor photocatalysis to rapidly growing surface plasmon-mediated heterogeneous catalysis. The recent research achievements of nanometals are reviewed here, with regard to applications in semiconductor photocatalysis, plasmonic photocatalysis, and plasmonic photo-thermocatalysis. As the first important topic discussed here, the latest progress in the design of nanometal cocatalysts and their applications in semiconductor photocatalysis are introduced. Then, plasmonic photocatalysis and plasmonic photo-thermocatalysis are discussed. A better understanding of electron-driven and temperature-driven catalytic behaviors over plasmonic nanometals is helpful to bridge the present gap between the communities of photocatalysis and conventional catalysis controlled by temperature. The objective here is to provide instructive information on how to take the advantages of the unique functions of nanometals in different types of catalytic processes to improve the efficiency of solar-energy utilization for more practical artificial photosynthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Li, Zhan Jun; Ali, Ghafar; Kim, Hyun Jin; Yoo, Seong Ho; Cho, Sung Oh
2014-01-01
We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed.
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Gold Decorated Graphene for Rapid Dye Reduction and Efficient Electro Catalytic Oxidation of Ethanol
NASA Astrophysics Data System (ADS)
Siddhardha, R. S.; Kumar v, Lakshman; Kaniyoor, A.; Podila, R.; Kumar, V. S.; Venkataramaniah, K.; Ramaprabhu, S.; Rao, A.; Ramamurthy, S. S.; Clemson University Team; Sri Sathya Sai Institute of Higher Learning Team; IITMadras Team
2013-03-01
A well known disadvantage in fabrication of metal-graphene composite is the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. Here, we demonstrate a novel one pot synthesis of gold nanoparticles (AuNPs) by laser ablation of gold strip and simultaneous decoration of these on functionalized graphene derivatives. Not only the impregnation of AuNPs was linker free, but also the synthesis by itself was surfactant free. This resulted in in-situ decoration of pristine AuNPs on functionalized graphene derivatives. These materials were well characterized and tested for catalytic applications pertaining to dye reduction and electrooxidation. The catalytic reduction rates are 1.4 x 102 and 9.4x102 times faster for Rhodamine B and Methylene Blue dyes respectively, compared to earlier reports. The enhanced rate involves synergistic interplay of electronic relay between AuNPs and the dye, also charge transfer between the graphene system and dye. In addition, the onset potential for ethanol oxidation was found to be more negative ~ 100 mV, an indication of its promising application in direct ethanol fuel cells.
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Computational and Physical Analysis of Catalytic Compounds
NASA Astrophysics Data System (ADS)
Wu, Richard; Sohn, Jung Jae; Kyung, Richard
2015-03-01
Nanoparticles exhibit unique physical and chemical properties depending on their geometrical properties. For this reason, synthesis of nanoparticles with controlled shape and size is important to use their unique properties. Catalyst supports are usually made of high-surface-area porous oxides or carbon nanomaterials. These support materials stabilize metal catalysts against sintering at high reaction temperatures. Many studies have demonstrated large enhancements of catalytic behavior due to the role of the oxide-metal interface. In this paper, the catalyzing ability of supported nano metal oxides, such as silicon oxide and titanium oxide compounds as catalysts have been analyzed using computational chemistry method. Computational programs such as Gamess and Chemcraft has been used in an effort to compute the efficiencies of catalytic compounds, and bonding energy changes during the optimization convergence. The result illustrates how the metal oxides stabilize and the steps that it takes. The graph of the energy computation step(N) versus energy(kcal/mol) curve shows that the energy of the titania converges faster at the 7th iteration calculation, whereas the silica converges at the 9th iteration calculation.
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Pacardo, Dennis B; Slocik, Joseph M; Kirk, Kyle C; Naik, Rajesh R; Knecht, Marc R
2011-05-01
To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions. © The Royal Society of Chemistry 2011
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NASA Astrophysics Data System (ADS)
Pacardo, Dennis B.; Slocik, Joseph M.; Kirk, Kyle C.; Naik, Rajesh R.; Knecht, Marc R.
2011-05-01
To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions.
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Catalytic recombination of nitrogen and oxygen on high-temperature reusable surface insulation
NASA Technical Reports Server (NTRS)
Scott, C. D.
1980-01-01
The energy transfer catalytic recombination coefficient for nitrogen and oxygen recombination on the surface coating of high-temperature reusable surface insulation (HRSI) is inferred from stagnation point heat flux measurements in a high-temperature dissociated arc jet flow. The resulting catalytic recombination coefficients are correlated with an Arrhenius model for convenience, and these expressions may be used to account for catalytic recombination effects in predictions of the heat flux on the HRSI thermal protection system of the Space Shuttle Orbiter during reentry flight. Analysis of stagnation point pressure and total heat balance enthalpy measurements indicates that the arc heater reservoir conditions are not in chemical equilibrium. This is contrary to what is usually assumed for arc jet analysis and indicates the need for suitable diagnostics and analyses, especially when dealing with chemical reaction phenomena such as catalytic recombination heat transfer effects.
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Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.
Collins, Gillian; Holmes, Justin D
2016-07-01
Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Adzic, Radoslav R.; Gong, Kuanping; Cai, Yun
A method of synthesizing activated electrocatalyst, preferably having a morphology of a nanostructure, is disclosed. The method includes safely and efficiently removing surfactants and capping agents from the surface of the metal structures. With regard to metal nanoparticles, the method includes synthesis of nanoparticle(s) in polar or non-polar solution with surfactants or capping agents and subsequent activation by CO-adsorption-induced surfactant/capping agent desorption and electrochemical oxidation. The method produces activated macroparticle or nanoparticle electrocatalysts without damaging the surface of the electrocatalyst that includes breaking, increasing particle thickness or increasing the number of low coordination sites.
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Role of Exposed Surfaces on Zinc Oxide Nanostructures in the Catalytic Ethanol Transformation.
Morales, María V; Asedegbega-Nieto, Esther; Iglesias-Juez, Ana; Rodríguez-Ramos, Inmaculada; Guerrero-Ruiz, Antonio
2015-07-08
For a series of nanometric ZnO materials, the relationship between their morphological and surface functionalities and their catalytic properties in the selective decomposition of ethanol to yield acetaldehyde was explored. Six ZnO solids were prepared by a microemulsion-precipitation method and the thermal decomposition of different precursors and compared with a commercial sample. All these materials were characterized intensively by XRD and SEM to obtain their morphological specificities. Additionally, surface area determinations and IR spectroscopy were used to detect differences in the surface properties. The density of acid surface sites was determined quantitatively using an isopropanol dehydration test. Based on these characterization studies and on the results of the catalytic tests, it has been established that ZnO basal surfaces seem to be responsible for the production of ethylene as a minor product as well as for secondary reactions that yield acetyl acetate. Furthermore, one specific type of exposed hydroxyl groups appears to govern the surface catalytic properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Liu, Y Y; Guo, X L; Zhao, L; Zhu, L; Chen, Z T; Chen, J; Zhang, Y; Sun, L T; Zhao, Y H
2018-06-08
The application of Au nanoparticles (Au NPs) often requires surface modification with chemical surfactants, which dramatically reduce the surface activity and increase the chemical contamination and cost of Au NPs. In this research, we have developed a novel Au NPs/reduced graphene oxide/Ni foam hybrid (Au NPs/RGO/NiF) by in situ reduction through ascorbic acid and replacement reaction. This method is green, facile and efficient. The Au NPs are free of chemical surfactants and are homogeneously distributed on the surface of the RGO/NiF. The as-prepared Au NPs/RGO/NiF hybrid is uniform, stable and exhibits not only a high reduction efficiency for the reduction of 4-nitrophenol with a catalytic kinetic constant of up to 0.46 min -1 (0.15 cm 3 catalysis) but also a sensitive and selective detection of H 2 O 2 with a detection limit of ∼1.60 μM.
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Wang, Yanyong; Qiao, Man; Li, Yafei; Wang, Shuangyin
2018-04-01
Intrinsically inferior electrocatalytic activity of NiFe layered double hydroxides (LDHs) nanosheets is considered as a limiting factor to inhibit the electrocatalytic properties for oxygen evolution reaction (OER). Proper defect engineering to tune the surface electronic configuration of electrocatalysts may significantly improve the intrinsic activity. In this work, the selective formation of cation vacancies in NiFe LDHs nanosheets is successfully realized. The as-synthesized NiFe LDHs-V Fe and NiFe LDHs-V Ni electrocatalysts show excellent activity for OER, mainly attributed to the introduction of rich iron or nickel vacancies in NiFe LDHs nanosheets, which efficiently tune the surface electronic structure increasing the adsorbing capacity of OER intermediates. Density functional theory (DFT) computational results also further indicate that the OER catalytic performance of NiFe LDHs can be pronouncedly improved by introducing Fe or Ni vacancies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Liu, Y. Y.; Guo, X. L.; Zhao, L.; Zhu, L.; Chen, Z. T.; Chen, J.; Zhang, Y.; Sun, L. T.; Zhao, Y. H.
2018-06-01
The application of Au nanoparticles (Au NPs) often requires surface modification with chemical surfactants, which dramatically reduce the surface activity and increase the chemical contamination and cost of Au NPs. In this research, we have developed a novel Au NPs/reduced graphene oxide/Ni foam hybrid (Au NPs/RGO/NiF) by in situ reduction through ascorbic acid and replacement reaction. This method is green, facile and efficient. The Au NPs are free of chemical surfactants and are homogeneously distributed on the surface of the RGO/NiF. The as-prepared Au NPs/RGO/NiF hybrid is uniform, stable and exhibits not only a high reduction efficiency for the reduction of 4-nitrophenol with a catalytic kinetic constant of up to 0.46 min‑1 (0.15 cm3 catalysis) but also a sensitive and selective detection of H2O2 with a detection limit of ∼1.60 μM.
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Pt 3Re alloy nanoparticles as electrocatalysts for the oxygen reduction reaction
Raciti, David; Kubal, Joseph; Ma, Cheng; ...
2015-12-25
Development of renewable energy technologies requires advanced catalysts for efficient electrical-chemical energy conversion reactions. Here in this paper, we report the study of Pt-Re alloy nanoparticles as an electrocatalyst for the oxygen reduction reaction (ORR). An organic solution approach is developed to synthesize monodisperse and homogeneous Pt 3Re alloy nanoparticles. Electrochemical studies show that these nanoparticles exhibit an improvement factor of 4 in catalytic activity for the ORR compared to commercial Pt catalysts of similar particle sizes. Fundamental understanding of the structure-property relationship is established by combining material characterization using X-ray spectroscopy and atomically resolved electron microscopy, as well asmore » Density Functional Theory (DFT) calculations. Lastly, our work revealed that an electronic modification of the surface properties of Pt by subsurface Re (ligand effect) accounts for the catalytic enhancement.« less
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Munirathinam, Rajesh; Ricciardi, Roberto; Egberink, Richard J M; Huskens, Jurriaan; Holtkamp, Michael; Wormeester, Herbert; Karst, Uwe
2013-01-01
Summary Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and X-ray photoelectron spectroscopy (XPS). XPS revealed the presence of one gallium per 2–3 styrene sulfonate groups of the polymer brushes. The catalytic activity of the Lewis acid-functionalized brushes in a microreactor was demonstrated for the dehydration of oximes, using cinnamaldehyde oxime as a model substrate, and for the formation of oxazoles by ring closure of ortho-hydroxy oximes. The catalytic activity of the microreactor could be maintained by periodic reactivation by treatment with GaCl3. PMID:24062830
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Huang, Jianwen; Sun, Yinghui; Zhang, Yadong; Zou, Guifu; Yan, Chaoyi; Cong, Shan; Lei, Tianyu; Dai, Xiao; Guo, Jun; Lu, Ruifeng; Li, Yanrong; Xiong, Jie
2018-02-01
High-performance electrocatalysts are desired for electrochemical energy conversion, especially in the field of water splitting. Here, a new member of phosphate electrocatalysts, nickel metaphosphate (Ni 2 P 4 O 12 ) nanocrystals, is reported, exhibiting low overpotential of 270 mV to generate the current density of 10 mA cm -2 and a superior catalytic durability of 100 h. It is worth noting that Ni 2 P 4 O 12 electrocatalyst has remarkable oxygen evolution performance operating in basic media. Further experimental and theoretical analyses demonstrate that N dopant boosts the catalytic performance of Ni 2 P 4 O 12 due to optimizing the surface electronic structure for better charge transfer and decreasing the adsorption energy for the oxygenic intermediates. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Wu, Ganxue; Feng, Xi; Zhang, Hailong; Zhang, Yanhua; Wang, Jianli; Chen, Yaoqiang; Dan, Yi
2018-01-01
The promotional effect of nickel additive on the catalytic performance of the representative FeVO4/TiO2 for NH3-SCR reaction is systematically studied for the first time in the present work. The experimental results showed that NOx conversion at low temperature and N2 selectivity could be significantly improved by Ni doping and 0.4Ni-FeV-Ti exhibited the highest NOx removal efficiency. Analysis by XRD, SEM/HR-TEM, Raman, TPD, DRIFTS, TPR and XPS showed that nickel doping effectively promoted the interaction of FeVO4 nanoparticles with TiO2, consequently resulting in an enhanced acidity property, improved redox activity and giving rise to the formation of the surface oxygen vacancies and defect sites.
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Elementary photocatalytic chemistry on TiO2 surfaces.
Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming
2016-07-07
Photocatalytic hydrogen production and pollutant degradation provided both great opportunities and challenges in the field of sustainable energy and environmental science. Over the past few decades, we have witnessed fast growing interest and efforts in developing new photocatalysts, improving catalytic efficiency and exploring the reaction mechanism at the atomic and molecular levels. Owing to its relatively high efficiency, nontoxicity, low cost and high stability, TiO2 becomes one of the most extensively investigated metal oxides in semiconductor photocatalysis. Fundamental studies on well characterized single crystals using ultrahigh vacuum based surface science techniques could provide key microscopic insight into the underlying mechanism of photocatalysis. In this review, we have summarized recent progress in the photocatalytic chemistry of hydrogen, water, oxygen, carbon monoxide, alcohols, aldehydes, ketones and carboxylic acids on TiO2 surfaces. We focused this review mainly on the rutile TiO2(110) surface, but some results on the rutile TiO2(011), anatase TiO2(101) and (001) surfaces are also discussed. These studies provided fundamental insights into surface photocatalysis as well as stimulated new investigations in this exciting field. At the end of this review, we have discussed how these studies can help us to develop new photocatalysis models.
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Combined catalysts for the combustion of fuel in gas turbines
Anoshkina, Elvira V.; Laster, Walter R.
2012-11-13
A catalytic oxidation module for a catalytic combustor of a gas turbine engine is provided. The catalytic oxidation module comprises a plurality of spaced apart catalytic elements for receiving a fuel-air mixture over a surface of the catalytic elements. The plurality of catalytic elements includes at least one primary catalytic element comprising a monometallic catalyst and secondary catalytic elements adjacent the primary catalytic element comprising a multi-component catalyst. Ignition of the monometallic catalyst of the primary catalytic element is effective to rapidly increase a temperature within the catalytic oxidation module to a degree sufficient to ignite the multi-component catalyst.
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High-spatial-resolution mapping of catalytic reactions on single particles
Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan; ...
2017-01-26
We report the critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has beenmore » used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. Lastly, these observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles-which contain metal atoms with low coordination numbers-are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.« less
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Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design.
Greeley, Jeffrey
2016-06-07
Scaling relationships are theoretical constructs that relate the binding energies of a wide variety of catalytic intermediates across a range of catalyst surfaces. Such relationships are ultimately derived from bond order conservation principles that were first introduced several decades ago. Through the growing power of computational surface science and catalysis, these concepts and their applications have recently begun to have a major impact in studies of catalytic reactivity and heterogeneous catalyst design. In this review, the detailed theory behind scaling relationships is discussed, and the existence of these relationships for catalytic materials ranging from pure metal to oxide surfaces, for numerous classes of molecules, and for a variety of catalytic surface structures is described. The use of the relationships to understand and elucidate reactivity trends across wide classes of catalytic surfaces and, in some cases, to predict optimal catalysts for certain chemical reactions, is explored. Finally, the observation that, in spite of the tremendous power of scaling relationships, their very existence places limits on the maximum rates that may be obtained for the catalyst classes in question is discussed, and promising strategies are explored to overcome these limitations to usher in a new era of theory-driven catalyst design.
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Polyvinylpyrrolidone (PVP)-Capped Pt Nanocubes with Superior Peroxidase-Like Activity
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ye, Haihang; Liu, Yuzi; Chhabra, Ashima
2016-12-21
Peroxidase mimics of inorganic nanoparticles are expected to circumvent the inherent issues of natural peroxidases, providing enhanced performance in important applications such as diagnosis and imaging. Despite the report of a variety of peroxidase mimics in the past decade, very limited progress has been made on improving their catalytic efficiency. The catalytic efficiencies of most previously reported mimics are only up to one order of magnitude higher than those of natural peroxidases. In this work, we demonstrate a type of highly efficient peroxidase mimic – polyvinylpyrrolidone (PVP)-capped Pt nanocubes of sub-10 nm in size. These PVP-capped Pt cubes are ~200-foldmore » more active than the natural counterparts and exhibit a record-high specific catalytic efficiency. In addition to the superior efficiency, the new mimic shows several other promising features, including excellent stabilities, well-controlled uniformity in both size and shape, controllable sizes, and facile and scalable production.« less
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Zhao, Yingxuan; Lai, Qingxue; Zhu, Junjie; Zhong, Jia; Tang, Zeming; Luo, Yan; Liang, Yanyu
2018-05-01
Designing rational nanostructures of metal-organic frameworks based carbon materials to promote the bifunctional catalytic activity of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is highly desired but still remains a great challenge. Herein, an in situ growth method to achieve 1D structure-controllable zeolitic imidazolate frameworks (ZIFs)/polyacrylonitrile (PAN) core/shell fiber (PAN@ZIFs) is developed. Subsequent pyrolysis of this precursor can obtain a heteroatom-doped carbon nanofiber network as an efficient bifunctional oxygen electrocatalyst. The electrocatalytic performance of derived carbon nanofiber is dominated by the structures of PAN@ZIFs fiber, which is facilely regulated by efficiently controlling the nucleation and growth process of ZIFs on the surface of polymer fiber as well as optimizing the components of ZIFs. Benefiting from the core-shell structures with appropriate dopants and porosity, as-prepared catalysts show brilliant bifunctional ORR/OER catalytic activity and durability. Finally, the rechargeable Zn-air battery assembled from the optimized catalyst (CNF@Zn/CoNC) displays a peak power density of 140.1 mW cm -2 , energy density of 878.9 Wh kg Zn -1 , and excellent cyclic stability over 150 h, giving a promising performance in realistic application. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Near-Infrared Plasmonic-Enhanced Solar Energy Harvest for Highly Efficient Photocatalytic Reactions.
Cui, Jiabin; Li, Yongjia; Liu, Lei; Chen, Lin; Xu, Jun; Ma, Jingwen; Fang, Gang; Zhu, Enbo; Wu, Hao; Zhao, Lixia; Wang, Leyu; Huang, Yu
2015-10-14
We report a highly efficient photocatalyst comprised of Cu7S4@Pd heteronanostructures with plasmonic absorption in the near-infrared (NIR)-range. Our results indicated that the strong NIR plasmonic absorption of Cu7S4@Pd facilitated hot carrier transfer from Cu7S4 to Pd, which subsequently promoted the catalytic reactions on Pd metallic surface. We confirmed such enhancement mechanism could effectively boost the sunlight utilization in a wide range of photocatalytic reactions, including the Suzuki coupling reaction, hydrogenation of nitrobenzene, and oxidation of benzyl alcohol. Even under irradiation at 1500 nm with low power density (0.45 W/cm(2)), these heteronanostructures demonstrated excellent catalytic activities. Under solar illumination with power density as low as 40 mW/cm(2), nearly 80-100% of conversion was achieved within 2 h for all three types of organic reactions. Furthermore, recycling experiments showed the Cu7S4@Pd were stable and could retain their structures and high activity after five cycles. The reported synthetic protocol can be easily extended to other Cu7S4@M (M = Pt, Ag, Au) catalysts, offering a new solution to design and fabricate highly effective photocatalysts with broad material choices for efficient conversion of solar energy to chemical energy in an environmentally friendly manner.
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NASA Technical Reports Server (NTRS)
Thompson, John O.; Akse, James R.
1993-01-01
Thermally regenerable sorbent beds were demonstrated to be a highly efficient means for removal of toxic airborne trace organic contaminants aboard spacecraft. The utilization of the intrinsic weight savings available through this technology was not realized since many of the contaminants desorbed during thermal regeneration are poisons to the catalytic oxidizer or form highly toxic oxidation by-products in the Trace Contaminant Control System (TCCS). Included in this class of compounds are nitrogen, sulfur, silicon, and halogen containing organics. The catalytic reduction of these problematic contaminants using hydrogen at low temperatures (200-300 C) offers an attractive route for their destruction since the by-products of such reactions, hydrocarbons and inorganic gases, are easily removed by existing technology. In addition, the catalytic oxidizer can be operated more efficiently due to the absence of potential poisons, and any posttreatment beds can be reduced in size. The incorporation of the catalyst within the sorbent bed further improves the system's efficiency. The demonstration of this technology provides the basis for an efficient regenerable TCCS for future NASA missions and can be used in more conventional settings to efficiently remove environmental pollutants.
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Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading
Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.; ...
2017-11-24
Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less
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Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading
DOE Office of Scientific and Technical Information (OSTI.GOV)
Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.
Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less
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NASA Astrophysics Data System (ADS)
Wasey, A. H. M. Abdul; Das, G. P.; Majumder, C.
2017-05-01
Traditionally, h-BN is used as coating material to prevent corrosion on the metal surface. In sharp contrast to this, here we show catalytic behavior of h-BN monolayer deposited on Ni(111) surface, clearly demonstrating the influence of the support in modulation of h-BN electronic structure. Using first principles density functional theory we have studied the interaction of O2 molecules with the h-BN/Ni(111) surface. The activation of Osbnd O bond, which is the most important step for oxidative catalysis, showed dependence on the O2 coverage. Thus this study is extremely important to predict the optimum O2 pressure in reaction chamber for efficient catalysis.
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Gu, Jiali; Liu, Min; Guo, Fei; Xie, Wenping; Lu, Wenqiang; Ye, Lidan; Chen, Zhirong; Yuan, Shenfeng; Yu, Hongwei
2014-02-05
Mandelate racemase (MR) is a promising candidate for the dynamic kinetic resolution of racemates. However, the poor activity of MR towards most of its non-natural substrates limits its widespread application. In this work, a virtual screening method based on the binding energy in the transition state was established to assist in the screening of MR mutants with enhanced catalytic efficiency. Using R-3-chloromandelic acid as a model substrate, a total of 53 mutants were constructed based on rational design in the two rounds of screening. The number of mutants for experimental validation was brought down to 17 by the virtual screening method, among which 14 variants turned out to possess improved catalytic efficiency. The variant V26I/Y54V showed 5.2-fold higher catalytic efficiency (k(cat)/K(m)) towards R-3-chloromandelic acid than that observed for the wild-type enzyme. Using this strategy, mutants were successfully obtained for two other substrates, R-mandelamide and R-2-naphthylglycolate (V26I and V29L, respectively), both with a 2-fold improvement in catalytic efficiency. These results demonstrated that this method could effectively predict the trend of mutational effects on catalysis. Analysis from the energetic and structural assays indicated that the enhanced interactions between the active sites and the substrate in the transition state led to improved catalytic efficiency. It was concluded that this virtual screening method based on the binding energy in the transition state was beneficial in enzyme rational redesign and helped to better understand the catalytic properties of the enzyme. Copyright © 2013 Elsevier Inc. All rights reserved.
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Wang, Yu-Hsiang; Chen, Kuan-Chung
2014-09-10
The effects of synthetic goethite (α-FeOOH) used as the catalyst in catalytic ozonation for the degradation of disinfection by-product (DBP) precursors are investigated. A biofiltration column applied following the catalytic ozonation process is used to evaluate the efficiency of removing DBP precursors via biotreatment. Ozone can rapidly react with aromatic compounds and oxidize organic compounds, resulting in a decrease in the fluorescence intensity of dissolved organic matter (DOM). In addition, catalytic ozonation can break down large organic molecules, which causes a blue shift in the emission-excitation matrix spectra. Water treated with catalytic ozonation is composed of low-molecular structures, including soluble microbial products (SMPs) and other aromatic proteins (APs). The DOM in SMPs and APs is removed by subsequent biofiltration. Catalytic ozonation has a higher removal efficiency for dissolved organic carbon and higher ultraviolet absorbance at 254 nm compared to those of ozonation without a catalyst. The use of catalytic ozonation and subsequent biofiltration leads to a lower DBP formation potential during chlorination compared to that obtained using ozonation and catalytic ozonation alone. Regarding DBP species during chlorination, the bromine incorporation factor (BIF) of trihalomethanes and haloacetic acids increases with increasing catalyst dosage in catalytic ozonation. Moreover, the highest BIF is obtained for catalytic ozonation and subsequent biofiltration.
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Wang, Yu-Hsiang; Chen, Kuan-Chung
2014-01-01
The effects of synthetic goethite (α-FeOOH) used as the catalyst in catalytic ozonation for the degradation of disinfection by-product (DBP) precursors are investigated. A biofiltration column applied following the catalytic ozonation process is used to evaluate the efficiency of removing DBP precursors via biotreatment. Ozone can rapidly react with aromatic compounds and oxidize organic compounds, resulting in a decrease in the fluorescence intensity of dissolved organic matter (DOM). In addition, catalytic ozonation can break down large organic molecules, which causes a blue shift in the emission-excitation matrix spectra. Water treated with catalytic ozonation is composed of low-molecular structures, including soluble microbial products (SMPs) and other aromatic proteins (APs). The DOM in SMPs and APs is removed by subsequent biofiltration. Catalytic ozonation has a higher removal efficiency for dissolved organic carbon and higher ultraviolet absorbance at 254 nm compared to those of ozonation without a catalyst. The use of catalytic ozonation and subsequent biofiltration leads to a lower DBP formation potential during chlorination compared to that obtained using ozonation and catalytic ozonation alone. Regarding DBP species during chlorination, the bromine incorporation factor (BIF) of trihalomethanes and haloacetic acids increases with increasing catalyst dosage in catalytic ozonation. Moreover, the highest BIF is obtained for catalytic ozonation and subsequent biofiltration. PMID:25211774
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Adsorption of Vanadium (V) from SCR Catalyst Leaching Solution and Application in Methyl Orange.
Sha, Xuelong; Ma, Wei; Meng, Fanqing; Wang, Ren; Fuping, Tian; Wei, Linsen
2016-12-01
In this study, we explored an effective and low-cost catalyst and its adsorption capacity and catalytic capacity for Methyl Orange Fenton oxidation degradation were investigated. The catalyst was directly prepared by reuse of magnetic iron oxide (Fe3O4) after saturated adsorption of vanadium (V) from waste SCR (Selective Catalytic Reduction) catalyst. The obtained catalyst was characterized by FTIR, XPS and the results showed that vanadium (V) adsorption process of Fe3O4 nanoparticles was non-redox reaction. The effects of pH, adsorption kinetics and equilibrium isotherms of adsorption were assessed. Adsorption of vanadium (V) ions by Fe3O4 nanoparticles could be well described by the Sips isotherm model which controlled by the mixed surface reaction and diffusion (MSRDC) adsorption kinetic model. The results show that vanadium (V) was mainly adsorbed on external surface of the Fe3O4 nanoparticles. The separation-recovering tungsten (VI) and vanadium (V) from waste SCR catalyst alkaline solution through pH adjustment was also investigated in this study. The results obtained from the experiments indicated that tungsten (VI) was selectively adsorbed from vanadium (V)/tungsten (VI) mixed solution in certain acidic condition by Fe3O4 nanoparticle to realize their recovery. Tungsten (V) with some impurity can be obtained by releasing from adsorbent, which can be confirmed by ICP-AES. The Methyl Orange degradation catalytic performance illustrated that the catalyst could improve Fenton reaction effectively at pH = 3.0 compare to Fe3O4 nanoparticles alone. Therefore, Fe3O4 nanoparticle adsorbed vanadium (V) has a potential to be employed as a heterogeneous Fenton-like catalyst in the present contribution, and its catalytic activity was mainly evaluated in terms of the decoloration efficiency of Methyl Orange.
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NASA Astrophysics Data System (ADS)
Albers, Peter W.; Parker, Stewart F.
The attractiveness of neutron scattering techniques for the detailed characterization of materials of high degrees of dispersity and structural complexity as encountered in the chemical industry is discussed. Neutron scattering picks up where other analytical methods leave off because of the physico-chemical properties of finely divided products and materials whose absorption behavior toward electromagnetic radiation and electrical conductivity causes serious problems. This is demonstrated by presenting typical applications from large-scale production technology and industrial catalysis. These include the determination of the proton-related surface chemistry of advanced materials that are used as reinforcing fillers in the manufacture of tires, where interrelations between surface chemistry, rheological properties, improved safety, and significant reduction of fuel consumption are the focus of recent developments. Neutron scattering allows surface science studies of the dissociative adsorption of hydrogen on nanodispersed, supported precious metal particles of fuel cell catalysts under in situ loading at realistic gas pressures of about 1 bar. Insight into the occupation of catalytically relevant surface sites provides valuable information about the catalyst in the working state and supplies essential scientific input for tailoring better catalysts by technologists. The impact of deactivation phenomena on industrial catalysts by coke deposition, chemical transformation of carbonaceous deposits, and other processes in catalytic hydrogenation processes that result in significant shortening of the time of useful operation in large-scale plants can often be traced back in detail to surface or bulk properties of catalysts or materials of catalytic relevance. A better understanding of avoidable or unavoidable aspects of catalyst deactivation phenomena under certain in-process conditions and the development of effective means for reducing deactivation leads to more energy-efficient and, therefore, environmentally friendly processes and helps to save valuable resources. Even small or gradual improvements in all these fields are of considerable economic impact.
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NASA Astrophysics Data System (ADS)
El Majdoub, Lotfia; Shi, Yasai; Yuan, Yuan; Zhou, Annan; Abutartour, Abubaker; Xu, Qinghong
2015-10-01
Zirconocene catalyst supported on silica gel was prepared for olefin polymerization by surface modification of calcined silica with SiCl4, and the reaction between the modified silica and cyclopentadienyl sodium and ZrCl4. The catalyst was characterized by using Fourier-transform infrared (FT-IR) spectrometer, thermogravimetric (TG), and differential scanning calorimetric (DSC) analytic spectrometer. It was found that the metallocene structure could be formed and connected on silica surface by chemical bond. Initial catalytic tests showed that the supported metallocene was catalytically active (methylaluminoxane as a cocatalyst), producing polymer with higher molecular weight than the metallocene just immobilized on the surface of silica gel.
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Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures
NASA Astrophysics Data System (ADS)
Hashemian, Mohammad Amin
Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional Pt/TiO2(por) transducers were unusual in many regards. Addition of various H2 amounts to the initial 160 Torr O2 atmosphere over the sample led to well repeatable chemicurrents of both transient and steady-state characters, depending on a specific H2 addition procedure. It is suggested that adsorption of hydrogen on Pt/TiO2 structures leads to dissociation of hydrogen molecules on Pt surface followed by "spillover" of hydrogen atoms from Pt toward TiO2 support. In contrast to oxygen, hydrogen manifests donor properties by giving electrons to the TiO2 conductance band and adsorbing as H+ ions. This effect is well illustrated with the I-V curves, showing highly conductive Ohmic characteristics of the samples in H2 atmosphere. Two versions of the spillover process leading eventually to H+ ion adsorption on TiO2 will be considered: H-atom and proton (pre-ionized H-atom) spillover. This research work is a pioneering effort to challenge the direct utility of the non-adiabatic electronic processes in catalytic nanomaterial systems, paving the road toward novel energy conversion devices, solid-state chemical sensors and signal transducers.
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Liu, Tao; Mai, Xianmin; Chen, Haijun; Ren, Jing; Liu, Zheting; Li, Yingxiang; Gao, Lina; Wang, Ning; Zhang, Jiaoxia; He, Hongcai; Guo, Zhanhu
2018-03-01
The carbon nanotube aerogel (CNA) with an ultra-low density, three-dimensional network nanostructure, superior electronic conductivity and large surface area is being widely employed as a catalytic electrode and catalytic support. Impressively, dye-sensitized solar cells (DSSCs) assembled with a CNA counter electrode (CE) achieved a maximum power conversion efficiency (PCE) of 8.28%, which exceeded that of the conventional platinum (Pt)-based DSSC (7.20%) under the same conditions. Furthermore, highly dispersed CoS 2 nanoparticles endowed with excellent intrinsic catalytic activity were hydrothermally incorporated to form a CNA-supported CoS 2 (CNA-CoS 2 ) CE, which was due to the large number of catalytically active sites and sufficient connections between CoS 2 and the CNA. The electrocatalytic ability and stability were systematically evaluated by cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and Tafel polarization, which confirmed that the resultant CNA-CoS 2 hybrid CE exhibited a remarkably higher electrocatalytic activity toward I 3 - reduction, and faster ion diffusion and electron transfer than the pure CNA CE. Such cost-effective DSSCs assembled with an optimized CNA-CoS 2 CE yielded an enhanced PCE of 8.92%, comparable to that of the cell fabricated with the CNA-Pt hybrid CE reported in our published literature (9.04%). These results indicate that the CNA-CoS 2 CE can be considered as a promising candidate for Pt-free CEs used in low-cost and high-performance DSSCs.
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Wang, Sibo; Ren, Zheng; Song, Wenqiao; ...
2015-04-24
Here, a hydrothermal strategy combined with colloidal deposition synthesis was successfully used to grow ZnO/perovskite (LaBO 3, B=Mn, Co, Ni) core-shell nanorod arrays within three dimensional (3-D) honeycomb cordierite substrates. A facile sonication assisted colloidal wash coating process is able to coat a uniformly dispersed perovskite nanoparticles onto the large scale ZnO nanorod arrays rooted on the channel surfaces of the 3D cordierite substrate achieved by hydrothermal synthesis. Compared to traditional wash-coated perovskite catalysts, an enhanced catalytic performance was observed for propane oxidation with 25°C lower light-off temperature than wash-coated perovskite catalyst of similar LaMnO 3 loading (4.3mg). Temperature programmedmore » reduction and desorption under H 2 and O 2 atmosphere, respectively, were used to study the reducibility and oxygen activity of these core-shell nanorod arrays based monolithic catalysts, revealing a catalytic activity sequence of LaCoO 3>LaMnO 3>La 2NiO 4 at the initial stage of catalytic reaction. The good dispersion and size control in La-based perovskite nanoparticles and their interfaces to ZnO nanorod arrays support may contribute to the enhancement of catalytic performance. Lastly, this work may provide a new type of Pt-group metals (PGM) free catalysts with improved catalytic performance for hydrocarbon oxidations at low temperatures.« less
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Salari, M; Aboutalebi, S H; Aghassi, A; Wagner, P; Mozer, A J; Wallace, G G
2015-02-28
The trade-off between performance and complexity of the device manufacturing process should be balanced to enable the economic harvest of solar energy. Here, we demonstrate a conceptual, yet practical and well-regulated strategy to achieve efficient solar photocatalytic activity in TiO2 through controlled phase transformation and disorder engineering in the surface layers of TiO2 nanotubes. This approach enabled us to fine-tune the bandgap structure of undoped TiO2 according to our needs while simultaneously obtaining robust separation of photo-excited charge carriers. Introduction of specific surface defects also assisted in utilization of the visible part of sunlight to split water molecules for the production of oxygen. The strategy proposed here can serve as a guideline to overcome the practical limitation in the realization of efficient, non-toxic, chemically stable photoelectrochemical systems with high catalytic activity at neutral pH under visible illumination conditions. We also successfully incorporated TiO2 nanotube arrays (TNTAs) with free-based porphyrin affording a pathway with an overall 140% enhanced efficiency, an oxygen evolution rate of 436 μL h(-1) and faradic efficiencies over 100%.
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Aratani, Yusuke; Yamada, Yusuke; Fukuzumi, Shunichi
2015-03-18
Selective hydroxylation of benzene derivatives and alkanes to the corresponding phenol and alcohol derivatives with hydrogen peroxide was efficiently catalysed by a manganese tris(2-pyridylmethyl)amine (tpa) complex ([(tpa)Mn(II)](2+)) incorporated into mesoporous silica-alumina with highly acidic surfaces in contrast to the reactions in a homogeneous solution where [(tpa)Mn(II)](2+) was converted catalytically to a much less active bis(μ-oxo)dimanganese(III,IV) complex.
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Simple Preparation of Novel Metal-Containing Mesoporous Starches †
Ojeda, Manuel; Budarin, Vitaliy; Shuttleworth, Peter S.; Clark, James H.; Pineda, Antonio; Balu, Alina M.; Romero, Antonio A.; Luque, Rafael
2013-01-01
Metal-containing mesoporous starches have been synthesized using a simple and efficient microwave-assisted methodology followed by metal impregnation in the porous gel network. Final materials exhibited surface areas >60 m2 g−1, being essentially mesoporous with pore sizes in the 10–15 nm range with some developed inter-particular mesoporosity. These materials characterized by several techniques including XRD, SEM, TG/DTA and DRIFTs may find promising catalytic applications due to the presence of (hydr)oxides in their composition. PMID:28809249
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Mallampati, Srinivasa Reddy; Lee, Byoung Ho; Mitoma, Yoshiharu; Simion, Cristian
2017-02-01
One method of weakening the inherently hydrophobic surface of plastics relevant to flotation separation is heterogeneous nano-Fe/Ca/CaO catalytic ozonation. Nano-Fe/Ca/CaO-catalyzed ozonation for 15 min efficiently decreases the surface hydrophobicity of brominated and chlorinated flame retardant (B/CFR)-containing plastics (such as acrylonitrile-butadienestyrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) in automobile shredder residue (ASR) to such an extent that their flotation ability is entirely depressed. Such a hydrophilization treatment also stimulates the ABS, HIPS, and PVC surface roughness, wetting of the surface, and the thermodynamic equilibrium conditions at the surface and ultimately changes surface polarity. SEM-EDS, AFM, and XPS analyses of the PVC and ABS surfaces demonstrated a marked decrease in [Cl/Br] and a significant increase in the number of hydrophilic groups, such as C-O, C=O, and (C=O)-O. Under froth flotation conditions at 50 rpm, about 99.5 % of ABS and 99.5 % of HIPS in ASR samples settled out, resulting in a purity of 98 and 98.5 % for ABS and HIPS in ASR samples, respectively. Furthermore, at 150 rpm, we also obtained 100 % PVC separation in the settled fraction, with 98 % purity in ASR. Total recovery of non-B/CFR-containing plastics reached nearly 100 % in the floating fraction. The amount of nano-Fe/Ca/CaO reagent employed during ozonation is very small, and additional removal of surface contaminants from the recycled ASR plastic surfaces by ozonation makes the developed process simpler, greener, and more effective.
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NASA Astrophysics Data System (ADS)
Khoobi, Mehdi; Delshad, Tayebeh Modiri; Vosooghi, Mohsen; Alipour, Masoumeh; Hamadi, Hosein; Alipour, Eskandar; Hamedani, Majid Pirali; Sadat ebrahimi, Seyed Esmaeil; Safaei, Zahra; Foroumadi, Alireza; Shafiee, Abbas
2015-02-01
A novel magnetically separable catalyst was prepared based on surface modification of Fe3O4 magnetic nanoparticle (MNPs) with polyethyleneimine (PEI) via covalent bonding. [3-(2,3-Epoxypropoxy)propyl]trimethoxysilane (EPO) was used as cross linker to bond PEI on the surface of MNPs with permanent stability in contrast to PEI coating via electrostatic interactions. The synthesized catalyst was characterized by Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM). The catalyst show high efficiency for one-pot synthesis of 2-amino-3-cyano-4H-pyran derivatives via multi-component reaction (MCR). This procedure offers the advantages of green reaction media, high yield, short reaction time, easy purification of the products and simple recovery and reuse of the catalyst by simple magnetic decantation without significant loss of catalytic activity.
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Oxygen evolution reaction in nanoconfined carbon nanotubes
NASA Astrophysics Data System (ADS)
Li, Ying; Lu, Xuefeng; Li, Yunfang; Zhang, Xueqing
2018-05-01
Improving oxygen electrochemistry through nanoscopic confinement has recently been highlighted as a promising strategy. In-depth understanding the role of confinement is therefore required. In this study, we simulate the oxygen evolution reaction (OER) on iron oxide nanoclusters under confinement of (7,7) and (8,8) armchair carbon nanotubes (CNTs). The free energies of the four proton coupled electron transfer (PCET) steps and the OER overpotentials are calculated. The Fe4O6 nanocluster confined in (7,7) CNT is found to be the most active for OER among the systems considered in this work. This leads to an increase in catalytic efficiency of OER compared to the hematite (110) surface, which was reported recently as an active surface towards OER. The calculated results show that the OER overpotential depends strongly on the magnetic properties of the iron oxide nanocluster. These findings are helpful for experimental design of efficient catalyst for water splitting applications.
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Clay Minerals as Solid Acids and Their Catalytic Properties.
ERIC Educational Resources Information Center
Helsen, J.
1982-01-01
Discusses catalytic properties of clays, attributed to acidity of the clay surface. The formation of carbonium ions on montmorillonite is used as a demonstration of the presence of surface acidity, the enhanced dissociation of water molecules when polarized by cations, and the way the surface can interact with organic substances. (Author/JN)
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Chughtai, Adeel H; Ahmad, Nazir; Younus, Hussein A; Laypkov, A; Verpoort, Francis
2015-10-07
Novel catalytic materials are highly demanded to perform a variety of catalytic organic reactions. MOFs combine the benefits of heterogeneous catalysis like easy post reaction separation, catalyst reusability, high stability and homogeneous catalysis such as high efficiency, selectivity, controllability and mild reaction conditions. The possible organization of active centers like metallic nodes, organic linkers, and their chemical synthetic functionalization on the nanoscale shows potential to build up MOFs particularly modified for catalytic challenges. In this review, we have summarized the recent research progress in heterogeneous catalysis by MOFs and their catalytic behavior in various organic reactions, highlighting the key features of MOFs as catalysts based on the active sites in the framework. Examples of their post functionalization, inclusion of active guest species and metal nanoparticles have been discussed. Finally, the use of MOFs as catalysts for asymmetric heterogeneous catalysis and stability of MOFs has been presented as separate sections.
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Zhuang, Haifeng; Han, Hongjun; Jia, Shengyong; Hou, Baolin; Zhao, Qian
2014-08-01
Advanced treatment of biologically pretreated coal gasification wastewater (CGW) was investigated employing heterogeneous catalytic ozonation integrated with anoxic moving bed biofilm reactor (ANMBBR) and biological aerated filter (BAF) process. The results indicated that catalytic ozonation with the prepared catalyst (i.e. MnOx/SBAC, sewage sludge was converted into sludge based activated carbon (SBAC) which loaded manganese oxides) significantly enhanced performance of pollutants removal by generated hydroxyl radicals. The effluent of catalytic ozonation process was more biodegradable and less toxic than that in ozonation alone. Meanwhile, ANMBBR-BAF showed efficient capacity of pollutants removal in treatment of the effluent of catalytic ozonation at a shorter reaction time, allowing the discharge limits to be met. Therefore, the integrated process with efficient, economical and sustainable advantages was suitable for advanced treatment of real biologically pretreated CGW. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Intercalated layered clay composites and their applications
NASA Astrophysics Data System (ADS)
Phukan, Anjali
Supported inorganic reagents are rapidly emerging as new and environmentally acceptable reagents and catalysts. The smectite group of layered clay minerals, such as, Montmorillonite, provides promising character for adsorption, catalytic activity, supports etc. for their large surface area, swelling behavior and ion exchange properties. Aromatic compounds intercalated in layered clays are useful in optical molecular devices. Clay is a unique material for adsorption of heavy metals and various toxic substances. Clay surfaces are known to be catalytically active due to their surface acidity. Acid activated clays possess much improved surface areas and acidities and have higher pore volumes so that can absorb large molecules in the pores. The exchangeable cations in clay minerals play a key role in controlling surface acidity and catalytic activity. Recently, optically active metal-complex-Montmorillonite composites are reported to be active in antiracemization purposes. In view of the above, a research work, relating to the preparation of different modified clay composites and their catalytic applications were carried out. The different aspects and results of the present work have been reported in four major chapters. Chapter I: This is an introductory chapter, which contains a review of the literature regarding clay-based materials. Clay minerals are phyllosilicates with layer structure. Montmorillonite, a member of smectite group of clay, is 2:1 phyllosilicate, where a layer is composed of an octahedral sheet sandwiched by two tetrahedral sheets. Such clay shows cation exchange capacity (CEC) and is expressed in milli-equivalents per 100 gm of dry clay. Clays can be modified by interaction with metal ion, metal complexes, metal cluster and organic cations for various applications. Clays are also modified by treating with acid followed by impregnation with metal salts or ions. Montmorillonite can intercalate suitable metal complexes in excess of CEC to form double or pseudo-trilayer composites. Metal ion and metal ion metal salts intercalated on Montmorillonite are efficient catalysts for Friedel-Crafts (FC) reactions, such as benzylation of benzene, synthesis of Raspberry ketone [4-(4'-hydroxyphenyl)butan-2-one] etc. Montmorillonite clay can be used as a good support for controlled release of pesticides and medicinal drugs, adsorbent for cationic dyes, toxic substances and heavy metals effective adsorbent for radioactive and toxic industrial wastes,...
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NASA Astrophysics Data System (ADS)
MacLean, M.; Holden, M.
2009-01-01
The effect of gas/surface interaction in making CFD predictions of convective heating has been considered with application to ground tests performed in high enthalpy shock tunnels where additional heating augmentation attributable to surface recombination has been observed for nitrogen, air and carbon dioxide flows. For test articles constructed of stainless steel and aluminum, measurements have been made with several types of heat transfer instrumentation including thin- film, calorimeter, and coaxial thermocouple sensors. These experiments have been modeled by computations made with the high quality, chemically reacting, Navier- Stokes solver, DPLR and the heating results compared. Some typical cases considered include results on an axisymmetric sphere-cone, axisymmetric spherical capsule, spherical capsule at angle of attack, and two- dimensional cylinder. In nitrogen flows, cases considered show a recombination probability on the order of 10-3, which agrees with published data. In many cases in air and CO2, measurements exceeding the predicted level of convective heating have been observed which are consistent with approximately complete recombination (to O2/N2 or CO2) on the surface of the model (sometimes called a super-catalytic wall). It has been recognized that the conclusion that this behavior is tied to an excessively high degree of catalytic efficiency is dependent on the current understanding of the freestream and shock-layer state of the gas.
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Chemically-modified cellulose paper as a microstructured catalytic reactor.
Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira
2015-01-15
We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.
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Su, Yanping; Chen, Chun; Zhu, Xiaoguang; Zhang, Yong; Gong, Wanbing; Zhang, Haimin; Zhao, Huijun; Wang, Guozhong
2017-05-16
We report a fast and simple method for the synthesis of Ni-based metal-organic-frameworks (Ni-MOFs). Due to the existence of nickel ions and an organic ligand, the MOFs are employed as a sacrificial template for the facile preparation of carbon-embedded Ni (Ni/C) catalysts by a direct thermal decomposition method. The obtained Ni/C catalysts exhibit excellent catalytic activity for selectively transforming furfural (FAL) to tetrahydrofurfuryl alcohol (THFOL) due to the Ni nanoparticles (NPs) embedded uniformly in the ligand-derived carbon. The exemplified results illustrate that the catalytic performance of the Ni/C catalyst is greatly affected by the calcination conditions (temperature and time), composition of the Ni-MOF precursor and the catalysis conditions. The conversion of FAL and selectivity of THFOL both reached 100% under the conditions of 120 °C, 1 MPa H 2 pressure and 120 min of hydrogenation over the Ni/C-500 catalyst, derived from the pyrolysis of Ni-MOFs (Ni : BTC mole ratio of 1.0) at 500 °C for 120 min, which exhibits an average nanoparticle size of ∼14 nm and uniform dispersion, and the highest BET surface area (∼92 m 2 g -1 ) among all investigated Ni/C catalysts. This facilely prepared heterogeneous catalyst would be very promising for the replacement of noble metal catalysts for the efficient catalytic conversion of biomass-derived feedstocks into value-added chemicals.
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NASA Astrophysics Data System (ADS)
Wang, Wenxia; He, Qi; Xiao, Kaijun; Zhu, Liang
2018-03-01
In the study, a two-major step involving a hydrothermal method and an electrostatic self-assembly method was adopted to synthesis Fe3O4/GO nanocomposites. The Fe3O4 nanoparticles were successfully modified with the 3-aminopropyltrimethoxy-silane and homogeneously deposited onto the surface of GO. They were used as Fenton-like catalyst to degrade Rhodamine B and displayed a higher activity compared with the pristine Fe3O4 nanoparticles, H2O2, Fe3O4/GO nanocomposite and Fe3O4/H2O2 system, demonstrating the synergistic effect between the superior adsorption properties of GO and the excellent catalytic activity of Fe3O4/H2O2 system. Besides, the possible catalytic mechanism and degradation pathway for RhB molecules by Fe3O4/GO nanocomposites and H2O2 was proposed based on the liquid chromatography-mass spectrometry (LC-MS) analysis. The result reveals that the •OH radicals should be the main actives species during catalytic degradation of RhB by the Fe3O4/GO/H2O2 system. In addition, the catalyst is reusable and shows efficiency up to 5 cycles. We believe the strategy in our work can provide insight into designing the novel catalysts for large-scale degradation of organic pollutants in the wastewater.
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Selvaraj, M; Park, D-W; Kim, I; Kawi, S; Ha, C S
2012-08-28
Well hexagonally ordered NbSBA-15 catalysts synthesized by an efficient hydrothermal method were used, for the first time, for the selective synthesis of vitamin K(3) by liquid-phase oxidation of 2-methyl-1-naphthol (2MN1-OH) under various reaction conditions. The recyclable NbSBA-15 catalysts were also reused to find their catalytic activities. To investigate the leaching of non-framework niobium species on the surface of silica networks, the results of original and recyclable NbSBA-15 catalysts were correlated and compared. To find an optimum condition for the selective synthesis of vitamin K(3), the washed NbSBA-15(2.2pH) was extensively used in this reaction with various reaction parameters such as temperature, time and ratios of reactant (2M1N-OH to H(2)O(2)), and the obtained results were also demonstrated. Additionally, the liquid-phase oxidation of 2M1N-OH was carried out with different solvents to find the best solvent with a good catalytic activity. Based on the all catalytic studies, the vitamin K(3) selectivity (97.3%) is higher in NbSBA-15(2.2pH) than that of other NbSBA-15 catalysts, and the NbSBA-15(2.2pH) is found to be a highly active and eco-friendly heterogeneous catalyst for the selective synthesis of vitamin K(3).
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Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction
NASA Astrophysics Data System (ADS)
Ge, Zhijun; Wang, Ling; He, Zhangxing; Li, Yuehua; Jiang, Yingqiao; Meng, Wei; Dai, Lei
2018-04-01
A novel strategy for improving the electro-catalytic properties of graphite felt (GF) electrode in vanadium redox flow battery (VRFB) is designed by depositing cobalt phosphide (CoP) onto GF surface. The CoP powder is synthesized by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Cyclic voltammetry results confirm that the CoP-modified graphite felt (GF-CoP) electrode has excellent reversibility and electro-catalytic activity to the VO2+/VO2+ cathodic reaction compared with the pristine GF electrode. The cell using GF-CoP electrode shows apparently higher discharge capacity over that based on GF electrode. The cell using GF-CoP electrode has the capacity of 67.2 mA h at 100 mA cm-2, 32.7 mA h larger than that using GF electrode. Compared with cell using GF electrode, the voltage efficiency of the cell based on GF-CoP electrode increases by 5.9% and energy efficiency by 5.4% at a current density of 100 mA cm-2. The cell using GF-CoP electrode can reach 94.31% capacity retention after 50 cycles at a current density of 30 mA cm-2. The results show that the CoP can effectively promote the VO2+/VO2+ redox reaction, implying that metal phosphides are a new kind of potential catalytic materials for VRFB.
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NASA Astrophysics Data System (ADS)
Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie; Guo, Mond F.; Derewinski, Miroslaw A.; Xu, Zhijie; Gray, Michel J.; Prodinger, Sebastian; Ramasamy, Karthikeyan K.
2016-11-01
The formation of carbonaceous deposits (coke) in zeolite pores during catalysis leads to temporary deactivation of catalyst, necessitating regeneration steps, affecting throughput, and resulting in partial permanent loss of catalytic efficiency. Yet, even to date, the coke molecule distribution is quite challenging to study with high spatial resolution from surface to bulk of the catalyst particles at a single particle level. To address this challenge we investigated the coke molecules in HZSM-5 catalyst after ethanol conversion treatment by a combination of C K-edge X-ray absorption spectroscopy (XAS), 13C Cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR) spectroscopy, and atom probe tomography (APT). XAS and NMR highlighted the aromatic character of coke molecules. APT permitted the imaging of the spatial distribution of hydrocarbon molecules located within the pores of spent HZSM-5 catalyst from surface to bulk at a single particle level. 27Al NMR results and APT results indicated association of coke molecules with Al enriched regions within the spent HZSM-5 catalyst particles. The experimental results were additionally validated by a level-set-based APT field evaporation model. These results provide a new approach to investigate catalytic deactivation due to hydrocarbon coking or poisoning of zeolites at an unprecedented spatial resolution.
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Xia, Tianyu; Liu, Jialong; Wang, Shouguo; Wang, Chao; Sun, Young; Gu, Lin; Wang, Rongming
2016-05-04
The high cost and poor durability of Pt nanoparticles (NPs) are great limits for the proton exchange membrane fuel cells (PEMFCs) from being scaled-up for commercial applications. Pt-based bimetallic NPs together with a uniform distribution can effectively reduce the usage of expensive Pt while increasing poison resistance of intermediates. In this work, a simple one-pot method was used to successfully synthesize ultrafine (about 7.5 nm) uniform NiPt truncated octahedral nanoparticles (TONPs) in dimethylformamid (DMF) without any seeds or templates. The as-prepared NiPt TONPs with Pt-rich surfaces exhibit greatly improved catalytic activities together with good tolerance and better stability for ethylene glycol oxidation reaction (EGOR) and oxygen reduction reaction (ORR) in comparison with NiPt NPs and commercial Pt/C catalysts in alkaline electrolyte. For example, the value of mass and specific activities for EGOR are 23.2 and 17.6 times higher comparing with those of commercial Pt/C, respectively. Our results demonstrate that the dramatic enhancement is mainly attributed to Pt-rich surface, larger specific surface area, together with coupling between Ni and Pt atoms. This developed method provides a promising pathway for simple preparation of highly efficient electrocatalysts for PEMFCs in the near future.
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Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie; Guo, Mond F.; Derewinski, Miroslaw A.; Xu, Zhijie; Gray, Michel J.; Prodinger, Sebastian; Ramasamy, Karthikeyan K.
2016-01-01
The formation of carbonaceous deposits (coke) in zeolite pores during catalysis leads to temporary deactivation of catalyst, necessitating regeneration steps, affecting throughput, and resulting in partial permanent loss of catalytic efficiency. Yet, even to date, the coke molecule distribution is quite challenging to study with high spatial resolution from surface to bulk of the catalyst particles at a single particle level. To address this challenge we investigated the coke molecules in HZSM-5 catalyst after ethanol conversion treatment by a combination of C K-edge X-ray absorption spectroscopy (XAS), 13C Cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR) spectroscopy, and atom probe tomography (APT). XAS and NMR highlighted the aromatic character of coke molecules. APT permitted the imaging of the spatial distribution of hydrocarbon molecules located within the pores of spent HZSM-5 catalyst from surface to bulk at a single particle level. 27Al NMR results and APT results indicated association of coke molecules with Al enriched regions within the spent HZSM-5 catalyst particles. The experimental results were additionally validated by a level-set–based APT field evaporation model. These results provide a new approach to investigate catalytic deactivation due to hydrocarbon coking or poisoning of zeolites at an unprecedented spatial resolution. PMID:27876869
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Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming
2015-01-01
Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity. PMID:26333629
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NASA Astrophysics Data System (ADS)
Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming
2015-09-01
Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity.
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Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming
2015-09-03
Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity.
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Efficient process for previous metal recovery from cell membrane electrode assemblies
Shore, Lawrence; Matlin, Ramail; Heinz, Robert
2010-05-04
A method is provided for recovering a catalytic element from a fuel cell membrane electrode assembly. The method includes grinding the membrane electrode assembly into a powder, extracting the catalytic element by forming a slurry comprising the powder and an acid leachate adapted to dissolve the catalytic element into a soluble salt, and separating the slurry into a depleted powder and a supernatant containing the catalytic element salt. The depleted powder is washed to remove any catalytic element salt retained within pores in the depleted powder and the catalytic element is purified from the salt.
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Polymer network/carbon layer on monolith support and monolith catalytic reactor
Nordquist, Andrew Francis; Wilhelm, Frederick Carl; Waller, Francis Joseph; Machado, Reinaldo Mario
2003-08-26
The present invention relates to an improved monolith catalytic reactor and a monolith support. The improvement in the support resides in a polymer network/carbon coating applied to the surface of a porous substrate and a catalytic metal, preferably a transition metal catalyst applied to the surface of the polymer network/carbon coating. The monolith support has from 100 to 800 cells per square inch and a polymer network/carbon coating with surface area of from 0.1 to 15 m.sup.2 /gram as measured by adsorption of N.sub.2 or Kr using the BET method.
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Ye, Weichun; Shi, Xuezhao; Zhang, Yane; Hong, Chenghui; Wang, Chunming; Budzianowski, Wojciech M; Xue, Desheng
2016-02-10
Palladium-cobalt alloy nanoparticles were synthesized and dispersed on carbon black support, aiming to have a less expensive catalyst. Catalytic behaviors of PdCo/C catalyst for the oxidation of hydroquinone (HQ) with H2O2 in aqueous solution were evaluated using high-performance liquid chromatography (HPLC). The results revealed that PdCo/C catalyst had better catalytic activity than an equal amount of commercial Pd/C and Co/C catalysts because of the d-band hybridization between Pd and Co. The effects of pH value, solvent, and various interferents including inorganic and organic compounds on the efficiency of HQ oxidation were further investigated. Furthermore, on the basis of mixed potential theory, comprehensive electrochemical measurements such as the open-circuit potential-time (OCP-t) technique and Tafel plot were efficient to assess the catalytic activity of the catalyst, and the results obtained were consistent with those of HPLC measurements. The efficient HQ oxidation was closely associated with the catalytic activity of PdCo nanoparticles because they accelerated the electron-transfer process and facilitated the generation of OH radicals.
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Ferroelectrics: A pathway to switchable surface chemistry and catalysis
NASA Astrophysics Data System (ADS)
Kakekhani, Arvin; Ismail-Beigi, Sohrab; Altman, Eric I.
2016-08-01
It has been known for more than six decades that ferroelectricity can affect a material's surface physics and chemistry thereby potentially enhancing its catalytic properties. Ferroelectrics are a class of materials with a switchable electrical polarization that can affect surface stoichiometry and electronic structure and thus adsorption energies and modes; e.g., molecular versus dissociative. Therefore, ferroelectrics may be utilized to achieve switchable surface chemistry whereby surface properties are not fixed but can be dynamically controlled by, for example, applying an external electric field or modulating the temperature. Several important examples of applications of ferroelectric and polar materials in photocatalysis and heterogeneous catalysis are discussed. In photocatalysis, the polarization direction can control band bending at water/ferroelectric and ferroelectric/semiconductor interfaces, thereby facilitating charge separation and transfer to the electrolyte and enhancing photocatalytic activity. For gas-surface interactions, available results suggest that using ferroelectrics to support catalytically active transition metals and oxides is another way to enhance catalytic activity. Finally, the possibility of incorporating ferroelectric switching into the catalytic cycle itself is described. In this scenario, a dynamic collaboration of two polarization states can be used to drive reactions that have been historically challenging to achieve on surfaces with fixed chemical properties (e.g., direct NOx decomposition and the selective partial oxidation of methane). These predictions show that dynamic modulation of the polarization can help overcome some of the fundamental limitations on catalytic activity imposed by the Sabatier principle.
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Ferrari, Alessandro R; Lee, Misun; Fraaije, Marco W
2015-06-01
Chitooligosaccharide oxidase from Fusarium graminearum (ChitO) oxidizes N-acetyl-D-glucosamine (GlcNAc) and its oligomers with high efficiency at the C1-hydroxyl moiety while it shows poor or no activity with other carbohydrates. By sequence and structural comparison with other known carbohydrate oxidases (glucooligosaccharide oxidase from Acremonium strictum and lactose oxidase from Microdochium nivale) eleven mutants were designed to redirect the catalytic scope of ChitO for improved oxidation of lactose, cellobiose and maltose. The catalytic properties of the most interesting mutants were further improved by combining single mutations. This has resulted in the creation of a set of ChitO variants that display totally different substrate tolerances. One ChitO variant shows a dramatic improvement in catalytic efficiency towards oxidation of glucose, cellobiose, lactose, and maltose. We also describe a ChitO variant with the highest catalytic efficiency in GlcNAc oxidation so far reported in the literature. © 2015 Wiley Periodicals, Inc.
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NASA Astrophysics Data System (ADS)
Zuo, Yong; Song, Ji-Ming; Niu, He-Lin; Mao, Chang-Jie; Zhang, Sheng-Yi; Shen, Yu-Hua
2016-04-01
P-nitrophenol (4-NP) and hydrazine hydrate are considered to be highly toxic pollutants in wastewater, and it is of great importance to remove them. Herein, TiO2-loaded Co0.85Se thin films with heterostructure were successfully synthesized by a hydrothermal route. The as-synthesized samples were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy and selective-area electron diffraction. The results demonstrate that TiO2 nanoparticles with a size of about 10 nm are easily loaded on the surface of graphene-like Co0.85Se nanofilms, and the NH3 · H2O plays an important role in the generation and crystallization of TiO2 nanoparticles. Brunauer-Emmett-Teller measurement shows that the obtained nanocomposites have a larger specific surface area (199.3 m2 g-1) than that of Co0.85Se nanofilms (55.17 m2 g-1) and TiO2 nanoparticles (19.49 m2 g-1). The catalytic tests indicate Co0.85Se-TiO2 nanofilms have the highest activity for 4-NP reduction and hydrazine hydrate decomposition within 10 min and 8 min, respectively, compared with the corresponding precursor Co0.85Se nanofilms and TiO2 nanoparticles. The enhanced catalytic performance can be attributed to the larger specific surface area and higher rate of interfacial charge transfer in the heterojunction than that of the single components. In addition, recycling tests show that the as-synthesized sample presents stable conversion efficiency for 4-NP reduction.
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Zuo, Yong; Song, Ji-Ming; Niu, He-Lin; Mao, Chang-Jie; Zhang, Sheng-Yi; Shen, Yu-Hua
2016-04-08
P-nitrophenol (4-NP) and hydrazine hydrate are considered to be highly toxic pollutants in wastewater, and it is of great importance to remove them. Herein, TiO2-loaded Co0.85Se thin films with heterostructure were successfully synthesized by a hydrothermal route. The as-synthesized samples were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy and selective-area electron diffraction. The results demonstrate that TiO2 nanoparticles with a size of about 10 nm are easily loaded on the surface of graphene-like Co0.85Se nanofilms, and the NH3 · H2O plays an important role in the generation and crystallization of TiO2 nanoparticles. Brunauer-Emmett-Teller measurement shows that the obtained nanocomposites have a larger specific surface area (199.3 m(2) g(-1)) than that of Co0.85Se nanofilms (55.17 m(2) g(-1)) and TiO2 nanoparticles (19.49 m(2) g(-1)). The catalytic tests indicate Co0.85Se-TiO2 nanofilms have the highest activity for 4-NP reduction and hydrazine hydrate decomposition within 10 min and 8 min, respectively, compared with the corresponding precursor Co0.85Se nanofilms and TiO2 nanoparticles. The enhanced catalytic performance can be attributed to the larger specific surface area and higher rate of interfacial charge transfer in the heterojunction than that of the single components. In addition, recycling tests show that the as-synthesized sample presents stable conversion efficiency for 4-NP reduction.
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Zheng, Fei; Huang, Huoqing; Wang, Xiaoyu; Tu, Tao; Liu, Qiong; Meng, Kun; Wang, Yuan; Su, Xiaoyun; Xie, Xiangming; Luo, Huiying
2016-10-01
The aim of this work was to study the contribution of the N-terminal structure to cellulase catalytic performance. A wild-type cellulase (BaCel5) of glycosyl hydrolase (GH) family 5 from Bispora antennata and two hybrid enzymes (BaCel5(127) and BaCel5(167)) with replacement of the N-terminal (βα)3 (127 residues) or (βα)4 (167 residues)-barrel with the corresponding sequences of TeEgl5A from Talaromyces emersonii were produced in Pichia pastoris and biochemically characterized. BaCel5 exhibited optimal activity at pH 5.0 and 50°C but had low catalytic efficiency (25.4±0.8mLs(-1)mg(-1)). In contrast, BaCel5(127) and BaCel5(167) showed similar enzymatic properties but improved catalytic performance. When using CMC-Na, barley β-glucan, lichenan, and cellooligosaccharides as substrates, BaCel5(127) and BaCel5(167) had increased specific activities and catalytic efficiencies by ∼1.8-6.7-fold and ∼1.0-4.7-fold, respectively. The catalytic efficiency of BaCel5(167) was even higher than that of parental proteins. The underlying mechanism was analyzed by molecular docking and molecular dynamic simulation. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Improving the engine power of a catalytic Janus-sphere micromotor by roughening its surface.
Longbottom, Brooke W; Bon, Stefan A F
2018-03-15
Microspheres with catalytic caps have become a popular model system for studying self-propelled colloids. Existing experimental studies involve predominantly "smooth" particle surfaces. In this study we determine the effect of irregular surface deformations on the propulsive mechanism with a particular focus on speed. The particle surfaces of polymer microspheres were deformed prior to depositing a layer of platinum which resulted in the formation of nanoscopic pillars of catalyst. Self-propulsion was induced upon exposure of the micromotors to hydrogen peroxide, whilst they were dispersed in water. The topological surface features were shown to boost speed (~2×) when the underlying deformations are small (nanoscale), whilst large deformations afforded little difference despite a substantial apparent catalytic surface area. Colloids with deformed surfaces were more likely to display a mixture of rotational and translational propulsion than their "smooth" counterparts.
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Ma, Fangwei; Ma, Di; Wu, Guang; Geng, Weidan; Shao, Jinqiu; Song, Shijiao; Wan, Jiafeng; Qiu, Jieshan
2016-05-10
A smart and sustainable strategy based on charge-induced self-assembly and nanocrystal-assisted catalytic graphitization is explored for the efficient construction of 3D nanostructure hierarchical porous graphitic carbons from the pectin biopolymer. The electrostatic interaction between the negatively charged pectin chains and magnesium ions plays a crucial role in the formation of 3D architectures. The 3D HPGCs possess a three-dimensional carbon framework with a hierarchical porous structure, flake-like graphitic carbon walls and high surface area (1320 m(2) g(-1)). The 3D HPGCs show an outstanding specific capacitance of 274 F g(-1) and excellent rate capability with a high capacitance retention of 85% at a high current density of 50 A g(-1) for supercapacitor electrodes. This strategy provided a novel approach to effectively construct 3D porous carbon nanostructures from biopolymers.
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Liao, Weisheng; Liu, Hsin-Wang; Chen, Hsing-Jung; Chang, Wen-Yen; Chiu, Kong-Hwa; Wai, Chien M
2011-01-01
Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO₂ containing 1 MPa of H₂ at 40-50°C. Kinetic studies based on in situ UV/Vis spectra of the CO₂ phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces. Copyright © 2010 Elsevier Ltd. All rights reserved.
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Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution
Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala; ...
2017-09-05
Here, we report a facile synthetic protocol to pre-pare mesoporous FeS 2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS 2 materials with high surface area were successfully prepared by a sol-gel method follow-ing a sulfurization treatment in an H 2S atmosphere. A re-markable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm 2 and a Tafel slope of 78 mV per decade under alka-line conditions (pH 13). These theoretical calculations indicate that the excellent catalytic activity of mesoporous FeSmore » 2 is attributed to the exposed (210) facets. The mesoporous FeS 2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.« less
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kmos: A lattice kinetic Monte Carlo framework
NASA Astrophysics Data System (ADS)
Hoffmann, Max J.; Matera, Sebastian; Reuter, Karsten
2014-07-01
Kinetic Monte Carlo (kMC) simulations have emerged as a key tool for microkinetic modeling in heterogeneous catalysis and other materials applications. Systems, where site-specificity of all elementary reactions allows a mapping onto a lattice of discrete active sites, can be addressed within the particularly efficient lattice kMC approach. To this end we describe the versatile kmos software package, which offers a most user-friendly implementation, execution, and evaluation of lattice kMC models of arbitrary complexity in one- to three-dimensional lattice systems, involving multiple active sites in periodic or aperiodic arrangements, as well as site-resolved pairwise and higher-order lateral interactions. Conceptually, kmos achieves a maximum runtime performance which is essentially independent of lattice size by generating code for the efficiency-determining local update of available events that is optimized for a defined kMC model. For this model definition and the control of all runtime and evaluation aspects kmos offers a high-level application programming interface. Usage proceeds interactively, via scripts, or a graphical user interface, which visualizes the model geometry, the lattice occupations and rates of selected elementary reactions, while allowing on-the-fly changes of simulation parameters. We demonstrate the performance and scaling of kmos with the application to kMC models for surface catalytic processes, where for given operation conditions (temperature and partial pressures of all reactants) central simulation outcomes are catalytic activity and selectivities, surface composition, and mechanistic insight into the occurrence of individual elementary processes in the reaction network.
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NASA Astrophysics Data System (ADS)
Kumar, Aniket; Rout, Lipeeka; Achary, Lakkoji Satish Kumar; Dhaka, Rajendra. S.; Dash, Priyabrat
2017-02-01
A facile, efficient and environmentally-friendly protocol for the synthesis of xanthenes by graphene oxide based nanocomposite (GO-CuFe2O4) has been developed by one-pot condensation route. The nanocomposite was designed by decorating copper ferrite nanoparticles on graphene oxide (GO) surface via a solution combustion route without the use of template. The as-synthesized GO-CuFe2O4 composite was comprehensively characterized by XRD, FTIR, Raman, SEM, EDX, HRTEM with EDS mapping, XPS, N2 adsorption-desorption and ICP-OES techniques. This nanocomposite was then used in an operationally simple, cost effective, efficient and environmentally benign synthesis of 14H-dibenzo xanthene under solvent free condition. The present approach offers several advantages such as short reaction times, high yields, easy purification, a cleaner reaction, ease of recovery and reusability of the catalyst by a magnetic field. Based upon various controlled reaction results, a possible mechanism for xanthene synthesis over GO-CuFe2O4 catalyst was proposed. The superior catalytic activity of the GO-CuFe2O4 nanocomposite can be attributed to the synergistic interaction between GO and CuFe2O4 nanoparticles, high surface area and presence of small sized CuFe2O4 NPs. This versatile GO-CuFe2O4 nanocomposite synthesized via combustion method holds great promise for applications in wide range of industrially important catalytic reactions.
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NASA Astrophysics Data System (ADS)
Kim, Yu-jin; Ma, Rory; Reddy, D. Amaranatha; Kim, Tae Kyu
2015-12-01
Graphitized carbon-encapsulated palladium (Pd) core-shell nanospheres were produced via pulsed laser ablation of a solid Pd foil target submerged in acetonitrile. The microstructural features and optical properties of these nanospheres were characterized via high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. Microstructural analysis indicated that the core-shell nanostructures consisted of single-crystalline cubic metallic Pd spheres that serve as the core material, over which graphitized carbon was anchored as a heterogeneous shell. The absorbance spectrum of the synthesized nanostructures exhibited a broad (absorption) band at ∼264 nm; this band corresponded to the typical inter-band transition of a metallic system and resulted possibly from the absorbance of the ionic Pd2+. The catalytic properties of the Pd and Pd@C core-shell nanostructures were investigated using the reduction of nitrobenzene to aniline by an excess amount of NaBH4 in an aqueous solution at room temperature, as a model reaction. Owing to the graphitized carbon-layered structure and the high specific surface area, the resulting Pd@C nanostructures exhibited higher conversion efficiencies than their bare Pd counterparts. In fact, the layered structure provided access to the surface of the Pd nanostructures for the hydrogenation reaction, owing to the synergistic effect between graphitized carbon and the nanostructures. Their unique structure and excellent catalytic performance render Pd@C core-shell nanostructures highly promising candidates for catalysis applications.
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Shen, Wenli; Qu, Yuanyuan; Pei, Xiaofang; Li, Shuzhen; You, Shengnan; Wang, Jingwei; Zhang, Zhaojing; Zhou, Jiti
2017-01-05
A facile one-pot eco-friendly process for synthesis of gold nanoparticles (AuNPs) with high catalytic activity was achieved using cell-free extracts of Aspergillus sp. WL-Au as reducing, capping and stabilizing agents. The surface plasmon resonance band of UV-vis spectrum at 532nm confirmed the presence of AuNPs. Transmission electron microscopy images showed that quite uniform spherical AuNPs were synthesized and the average size of nanoparticles increased from 4nm to 29nm with reaction time. X-ray diffraction analysis verified the formation of nano-crystalline gold particles. Fourier transform infrared spectra showed the presence of functional groups on the surface of biosynthesized AuNPs, such as OH, NH, CO, CH, COH and COC groups, which increased the stability of AuNPs. The biogenic AuNPs could serve as a highly efficient catalyst for 4-nitrophenol reduction. The reaction rate constant was linearly correlated with the concentration of AuNPs, which increased from 0.59min -1 to 1.51min -1 with the amount of AuNPs increasing form 1.46×10 -6 to 17.47×10 -6 mmol. Moreover, the as-synthesized AuNPs exhibited a remarkable normalized catalytic activity (4.04×10 5 min -1 mol -1 ), which was much higher than that observed for AuNPs synthesized by other biological and conventional chemical methods. Copyright © 2016 Elsevier B.V. All rights reserved.
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Catalytic oxidation of waste materials
NASA Technical Reports Server (NTRS)
Jagow, R. B.
1977-01-01
Aqueous stream of human waste is mixed with soluble ruthenium salts and is introduced into reactor at temperature where ruthenium black catalyst forms on internal surfaces of reactor. This provides catalytically active surface to convert oxidizable wastes into breakdown products such as water and carbon dioxide.
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Kulyk, Kostiantyn; Palianytsia, Borys; Alexander, John D; Azizova, Liana; Borysenko, Mykola; Kartel, Mykola; Larsson, Mats; Kulik, Tetiana
2017-07-19
Valeric acid is an important renewable platform chemical that can be produced efficiently from lignocellulosic biomass. Upgrading of valeric acid by catalytic pyrolysis has the potential to produce value added biofuels and chemicals on an industrial scale. Understanding the different mechanisms involved in the thermal transformations of valeric acid on the surface of nanometer-sized oxides is important for the development of efficient heterogeneously catalyzed pyrolytic conversion techniques. In this work, the thermal decomposition of valeric acid on the surface of nanoscale SiO 2 , γ-Al 2 O 3 , CeO 2 /SiO 2 , Al 2 O 3 /SiO 2 and TiO 2 /SiO 2 has been investigated by temperature-programmed desorption mass spectrometry (TPD MS). Fourier transform infrared spectroscopy (FTIR) has also been used to investigate the structure of valeric acid complexes on the oxide surfaces. Two main products of pyrolytic conversion were observed to be formed depending on the nano-catalyst used-dibutylketone and propylketene. Mechanisms of ketene and ketone formation from chemisorbed fragments of valeric acid are proposed and the kinetic parameters of the corresponding reactions were calculated. It was found that the activation energy of ketenization decreases in the order SiO 2 >γ-Al 2 O 3 >TiO 2 /SiO 2 >Al 2 O 3 /SiO 2 , and the activation energy of ketonization decreases in the order γ-Al 2 O 3 >CeO 2 /SiO 2 . Nano-oxide CeO 2 /SiO 2 was found to selectively catalyze the ketonization reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Zhang, Xin; Zhao, Haitao; Wang, Jianhui
2010-08-01
Au nanoparticles stabilized by polystyrene-co-polymethacrylic acid microspheres (PS-co-PMAA) were prepared and characterized via X-ray diffraction (XRD), and transmission electron microscope (TEM). The Au nanoparticles supported on the microspheres showed highly selective catalytic activity for homo-coupling reactions of arylboronic acids in a system of aryl-halides and arylboronic acids. X-ray photoelectron spectroscopy (XPS) spectra of the catalyst shows large amounts of Au(I) complexes band to the surface of the Au nanoparticles, which contributes to the selective homocoupling of the arylboronic acids. More importantly, this supported Au complex is a highly recyclable catalyst. The supported Au catalyst can be recycled and reused at least 6 times for a phenylboronic acid reactant, whereas the parent complex shows very low catalytic activity for this compound. The high catalytic activity of this material is attributed to: (1) the high surface to volume ratio which leads to more active sites being exposed to reactants; (2) the strong surface binding of the Au nanoparticle to the Au(I) complexes, which enhances both the stability and the catalytic activity of these complexes.
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NASA Astrophysics Data System (ADS)
Choi, Sukwon
Sulfur in transportation fuels remains a leading source of SOx emissions from vehicle engines and is a major source of air pollution. The very low levels of sulfur globally mandated for transportation fuels in the near future cannot be achieved by current practices of hydrodesulfurization (HDS) for sulfur removal, which operate under severe conditions (high T, P) and use valuable H2. Novel vapor-phase catalytic oxidesulfurization (ODS) processes of selectively oxidizing various organosulfur compounds (carbonyl sulfide, carbon disulfide, methanethiol, dimethyl sulfide (DMS), dimethyl disulfide (DMDS), thiophene, 2,5-dimenthylthiophene) typically found in various industrial streams (e.g., petroleum refining, pulp and paper) into valuable chemical intermediates (H 2CO, CO, H2, maleic anhydride and concentrated SO2) has been extensively studied. This research has primarily focused on establishing the fundamental kinetics and mechanisms of these selective oxidation reactions over well-defined supported metal oxide catalysts. The selective oxidation reactions of COS + O2 → CO + SO2; 2CS2 + 5O2 → 2CO + 4SO2; CH3SH + 2O 2 → H2CO + SO2 + H2O; C4 H4S + 3O2 → C4H2O 3 + H2O + SO2; were studied. Raman spectroscopy revealed that the supported metal oxide phases were 100% dispersed on the oxide substrate. All the catalysts were highly active and selective for the oxidesulfurization of carbonyl sulfide, carbon disulfide, methanethiol, and thiophene between 290--330°C, 230--270°C, 350--400°C, and 250--400°C, respectively and did not deactivate. The TOFs (turnover frequency, normalized activity per active catalytic site) for all ODS reactions over supported vanadia catalysts, only containing molecularly dispersed surface vanadia species, varied within one order of magnitude and revealed the V-O-Support bridging bond was involved in the critical rate-determining kinetic steps. The surface reaction mechanism for each reaction was revealed by in situ IR (infrared) and temperature programmed surface reaction-mass spectroscopy (TPSR-MS). The systematic investigation of vapor-phase oxidesulfurization (ODS) reactions of organosulfur compounds over catalytic supported metal oxides revealed the facile S-O exchange mechanisms allow for the efficient removal of sulfur while producing value-added chemicals and represents the discovery of a new series of catalytic reactions.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Buckpitt, Alan, E-mail: arbuckpitt@ucdavis.edu; Morin, Dexter; Murphy, Shannon
Naphthalene produces species and cell selective injury to respiratory tract epithelial cells of rodents. In these studies we determined the apparent K{sub m}, V{sub max}, and catalytic efficiency (V{sub max}/K{sub m}) for naphthalene metabolism in microsomal preparations from subcompartments of the respiratory tract of rodents and non-human primates. In tissues with high substrate turnover, major metabolites were derived directly from naphthalene oxide with smaller amounts from conjugates of diol epoxide, diepoxide, and 1,2- and 1,4-naphthoquinones. In some tissues, different enzymes with dissimilar K{sub m} and V{sub max} appeared to metabolize naphthalene. The rank order of V{sub max} (rat olfactory epitheliummore » > mouse olfactory epithelium > murine airways ≫ rat airways) correlated well with tissue susceptibility to naphthalene. The V{sub max} in monkey alveolar subcompartment was 2% that in rat nasal olfactory epithelium. Rates of metabolism in nasal compartments of the monkey were low. The catalytic efficiencies of microsomes from known susceptible tissues/subcompartments are 10 and 250 fold higher than in rat airway and monkey alveolar subcompartments, respectively. Although the strong correlations between catalytic efficiencies and tissue susceptibility suggest that non-human primate tissues are unlikely to generate metabolites at a rate sufficient to produce cellular injury, other studies showing high levels of formation of protein adducts support the need for additional studies. - Highlights: • Naphthalene is metabolized with high catalytic efficiency in susceptible tissue. • Naphthalene is metabolized at low catalytic efficiency in non-susceptible tissue. • Respiratory tissues of the non human primate metabolize naphthalene slowly.« less
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Magnetic nanoparticles entrapped in siliceous mesocellular foam: a new catalyst support.
Lee, Su Seong; Riduan, Siti Nurhanna; Erathodiyil, Nandanan; Lim, Jaehong; Cheong, Jian Liang; Cha, Junhoe; Han, Yu; Ying, Jackie Y
2012-06-11
γ-Fe(2)O(3) nanoparticles were formed inside the cage-like pores of mesocellular foam (MCF). These magnetic nanoparticles showed a uniform size distribution that could be easily controlled by the MCF pore size, as well as by the hydrocarbon chain length used for MCF surface modification. Throughout the entrapment process, the pore structure and surface area of the MCF remained intact. The resulting magnetic MCF facilitated the immobilization of biocatalysts, homogeneous catalysts, and nanoclusters. Moreover, the MCF allowed for facile catalyst recovery by using a simple magnet. The supported catalysts exhibited excellent catalytic efficiencies that were comparable to their homogeneous counterparts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Catalytic Chemistry of Hydrocarbon Conversion Reactions on Metallic Single Crystals
NASA Astrophysics Data System (ADS)
Tysoe, Wilfred T.
The ability to be able to follow the chemistry of adsorbates on model catalyst surfaces has, in principle, allowed us to peer inside the “black box” of a catalytic reaction and understand the pathway. Such a strategy is most simply implemented for well-ordered single crystal model catalysts for which the catalytic reaction proceeds in ultrahigh vacuum. Thus, in order to be a good model for the supported catalyst, the single crystal should catalyze the reactions with kinetics identical to those for the supported system. This chapter focuses on catalytic systems that fulfill these criteria, namely alkene and alkyne hydrogenation and acetylene cyclotrimerization on Pd(111). The surface chemistry and geometries of the reactants in ultrahigh vacuum are explored in detail allowing fundamental insights into the catalytic reaction pathways to be obtained.
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NASA Astrophysics Data System (ADS)
Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang
2018-04-01
Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.
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Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer
NASA Astrophysics Data System (ADS)
Pan, Hui
2016-02-01
Water electrolysis is an efficient way for hydrogen production. Finding efficient, cheap, and eco-friendly electrocatalysts is essential to the development of this technology. In the work, we present a first-principles study on the effects of tension on the hydrogen evolution reaction of a novel electrocatalyst, vanadium disulfide (VS2) monolayer. Two electrocatalytic processes, individual and collective processes, are investigated. We show that the catalytic ability of VS2 monolayer at higher hydrogen coverage can be efficiently improved by escalating tension. We find that the individual process is easier to occur in a wide range of hydrogen coverage and the collective process is possible at a certain hydrogen coverage under the same tension. The best hydrogen evolution reaction with near-zero Gibbs free energy can be achieved by tuning tension. We further show that the change of catalytic activity with tension and hydrogen coverage is induced by the change of free carrier density around the Fermi level, that is, higher carrier density, better catalytic performance. It is expected that tension can be a simple way to improve the catalytic activity, leading to the design of novel electrocatalysts for efficient hydrogen production from water electrolysis.
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NASA Astrophysics Data System (ADS)
Ding, Shuaishuai; Zhang, Chunhua; Liu, Yefei; Jiang, Hong; Chen, Rizhi
2017-12-01
Highly efficient Pd@CN catalysts for selective hydrogenation of phenol to cyclohexanone in water were successfully fabricated by loading Pd nanoparticles (NPs) in N-doped carbons (CN) derived from ZIF-67 with dicyandiamide (DICY) as the additional nitrogen source. For comparison, polyvinylpyrrolidone (PVP) was also used as the additional nitrogen source during the ZIF-67 synthesis. The results showed that the PVP and DICY had significantly different impacts on the microstructures of as-obtained CN materials and the catalytic performance of Pd@CN catalysts in the phenol hydrogenation. The addition of DICY had the positive promotion effect on the surface area of the obtained CN materials. Moreover, the introduction of DICY could increase the nitrogen content of CN and then prevent the re-oxidation of Pd NPs during air contact, resulting in higher Pd0 ratio. In comparison with PVP, the DICY was more suitable as the additional nitrogen source for the formation of CN and Pd@CN (Pd@CND, Pd@CNP). The Pd@CND exhibited superior catalytic activity as compared to Pd@CNP (phenol conversion 96.9% vs. 67.4%). More importantly, the as-prepared Pd@CND catalyst could be reused for four times without catalytic performance reduction. The work would aid the development of Pd@CN catalysts with superior catalytic properties.
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Structural, optical and photo-catalytic activity of nanocrystalline NiO thin films
DOE Office of Scientific and Technical Information (OSTI.GOV)
Al-Ghamdi, Attieh A.; Abdel-wahab, M. Sh., E-mail: mshabaan90@yahoo.com; Materials Science and Nanotechnology Department, Faculty of Postgraduate Studies for Advanced Sciences, Beni-Suef University, Beni-Suef
2016-03-15
Highlights: • Synthesis of nanocrystalline NiO thin films with different thicknesses using DC magnetron sputtering technique. • Effect of film thickness and particle size on photo-catalytic degradation of methyl green dye under UV light was studied. • The deposited NiO thin films are efficient, stable and possess high photo-catalytic activity upon reuse. - Abstract: Physical deposition of nanocrystalline nickel oxide (NiO) thin films with different thickness 30, 50 and 80 nm have been done on glass substrate by DC magnetron sputtering technique and varying the deposition time from 600, 900 to 1200 s. The results of surface morphology and opticalmore » characterization of these films obtained using different characterization techniques such as X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), photoluminescence (PL) and UV–vis spectrophotometry provide important information like formation of distinct nanostructures in different films and its effect on their optical band gap which has decreased from 3.74 to 3.37 eV as the film thickness increases. Most importantly these films have shown very high stability and a specialty to be recycled without much loss of their photo-catalytic activity, when tested as photo-catalysts for the degradation of methyl green dye (MG) from the wastewater under the exposure of 18 W energy of UV lamp.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Xiao, Xiao; Yang, Hanjing; Arutiunian, Vagan
The catalytic activity of human cytidine deaminase APOBEC3B (A3B) has been correlated with kataegic mutational patterns within multiple cancer types. The molecular basis of how the N-terminal non-catalytic CD1 regulates the catalytic activity and consequently, biological function of A3B remains relatively unknown. Here, we report the crystal structure of a soluble human A3B-CD1 variant and delineate several structural elements of CD1 involved in molecular assembly, nucleic acid interactions and catalytic regulation of A3B. We show that (i) A3B expressed in human cells exists in hypoactive high-molecular-weight (HMW) complexes, which can be activated without apparent dissociation into low-molecular-weight (LMW) species aftermore » RNase A treatment. (ii) Multiple surface hydrophobic residues of CD1 mediate the HMW complex assembly and affect the catalytic activity, including one tryptophan residue W127 that likely acts through regulating nucleic acid binding. (iii) One of the highly positively charged surfaces on CD1 is involved in RNA-dependent attenuation of A3B catalysis. (iv) Surface hydrophobic residues of CD1 are involved in heterogeneous nuclear ribonucleoproteins (hnRNPs) binding to A3B. The structural and biochemical insights described here suggest that unique structural features on CD1 regulate the molecular assembly and catalytic activity of A3B through distinct mechanisms.« less
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NASA Technical Reports Server (NTRS)
Miller, Christopher J.; Shyam, Vikram; Rigby, David L.
2013-01-01
This work studied the feasibility of using Helmholtz resonator cavities embedded in low-pressure-turbine (LPT) airfoils to (1) reduce core noise by damping acoustic modes; (2) use the synthetic jets produced by the liner hole acoustic oscillations to improve engine efficiency by maintaining turbulent attached flow in the LPT at low-Reynolds-number cruise conditions; and (3) reduce engine nitrogen oxide emissions by lining the internal cavities with materials capable of catalytic conversion. Flat plates with embedded Helmholtz resonators, designed to resonate at either 3000 or at 400 Hz, were simulated using computational fluid dynamics. The simulations were conducted for two inlet Mach numbers, 0.25 and 0.5, corresponding to Reynolds numbers of 90 000 and 164 000 based on the effective chordwise distance to the resonator orifice. The results of this study are (1) the region of acoustic treatment may be large enough to have a benefit; (2) the jets may not possess sufficient strength to reduce flow separation (based on prior work by researchers in the flow control area); and (3) the additional catalytic surface area is not exposed to a high velocity, so it probably does not have any benefit.
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NASA Astrophysics Data System (ADS)
Labhane, P. K.; Sonawane, S. H.; Sonawane, G. H.; Patil, S. P.; Huse, V. R.
2018-03-01
Mg doped ZnO nanoparticles decorated on graphene oxide (GO) sheets were synthesized by a wet impregnation method. The effect of Mg doping on ZnO and ZnO-GO composite has been evaluated by using x-ray diffraction (XRD), Williamson-Hall Plot (Wsbnd H Plot), field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM) and energy dispersive x-ray spectroscopy (EDX). The physical parameters of as-prepared samples were estimated by XRD data. FESEM and HR-TEM images showed the uniform distribution of nanoparticles on GO crumpled paper like sheet. Solar light photocatalytic activities of samples were evaluated spectrophotometrically by the degradation of p-nitrophenol (PNP) and indigo carmine (IC) solution. Mgsbnd ZnO decorated on GO sheets exhibit excellent catalytic efficiency compared to all other prepared samples under identical conditions, degrading PNP and IC nearly 99% within 60 min under sunlight. The effective degradation by Mgsbnd ZnO decorated on GO sheet would be due to extended solar light absorption, enhanced adsorptivity on the composite catalyst surface and efficient charge separation of photo-induced electrons. Finally, plausible mechanism was suggested with the help of scavengers study.
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Liu, Y Y; Zhao, Y H; Zhou, Y; Guo, X L; Chen, Z T; Zhang, W J; Zhang, Y; Chen, J; Wang, Z M; Sun, L T; Zhang, T
2018-08-03
Noble metal nanoparticles (NPs) such as Au and Ag have shown many applications in the field of catalysis, sensing etc. due to their excellent photoelectric properties. But agglomeration and a low recovery rate are big problems for their applications. In this research, a novel Ag NPs/graphene (reduced graphene oxide)-loading loofah sponge (Ag NPs/RGO-LS) was synthesized through a one-step reduction method. Where the RGO is used as a nano-support with the high specific surface area and the high conductivity to prevent the agglomeration of Ag NPs and provide a conductive layer. The natural, green, low-cost and high-yield LS is designed as a macro-support to reduce the loss of Ag NPs during recycling. The as-prepared Ag NPs/RGO-LS is stable, uniform, and exhibits high efficiency and reusability in the catalytic reduction of 4-nitrophenol (4-NP) with a high rate constant of 1.893 min -1 as well as an average conversion of 98% in 6 min during five cycles. The results have not only paved the way for the wide application of Ag NPs but also provide a new road for the application of other metal NPs.
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NASA Astrophysics Data System (ADS)
Lee, Jungkuk; Park, Min-Sik; Kim, Ki Jae
2017-02-01
Nitrogen-doped carbon nanotubes (NCNTs) are directly grown on the surface of a three-dimensional (3D) Ni foam substrate by floating catalytic chemical vapor deposition (FCCVD). The electrochemical properties of the 3D NCNT-Ni foam are thoroughly examined as a potential electrode for non-aqueous redox flow batteries (RFBs). During synthesis, nitrogen atoms can be successfully doped onto the carbon nanotube (CNT) lattices by forming an abundance of nitrogen-based functional groups. The 3D NCNT-Ni foam electrode exhibits excellent electrochemical activities toward the redox reactions of [Fe (bpy)3]2+/3+ (in anolyte) and [Co(bpy)3]+/2+ (in catholyte), which are mainly attributed to the hierarchical 3D structure of the NCNT-Ni foam electrode and the catalytic effect of nitrogen atoms doped onto the CNTs; this leads to faster mass transfer and charge transfer during operation. As a result, the RFB cell assembled with 3D NCNT-Ni foam electrodes exhibits a high energy efficiency of 80.4% in the first cycle; this performance is maintained up to the 50th cycle without efficiency loss.
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Feng, Ningning; Mu, Xiaowei; Zhang, Xueping; He, Ping; Zhou, Haoshen
2017-02-01
Aprotic Li-O 2 batteries have attracted worldwide interest owing to their ultrahigh theoretical energy density. However, the practical Li-O 2 batteries still suffer from high charge overpotential and low energy efficiency resulting from the sluggish kinetics in electrochemically oxidizing the insulating lithium peroxide (Li 2 O 2 ). Recently, dissolved redox mediators in the electrolyte have enabled the effective catalytic oxidation of Li 2 O 2 at the liquid-solid interface. Here, we report that the incorporation of N-methylphenothiazine (MPT), as a redox shuttle in Li-O 2 batteries, provides a dramatic reduction in charge overpotential to 0.67 V and an improved round-trip efficiency close to 76%. Moreover, the efficacy of MPT in Li-O 2 cells was further investigated by various characterizations. On charging, MPT + cations are first generated electrochemically at the cathode surface and subsequently oxidize the solid discharge products Li 2 O 2 through a chemical reaction. Furthermore, the presence of MPT has been demonstrated to improve the cycling stability of the cells and suppress side reactions arising from carbon and electrolytes at high potentials.
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Wang, Haitao; Wang, Wei; Asif, Muhammad; Yu, Yang; Wang, Zhengyun; Wang, Junlei; Liu, Hongfang; Xiao, Junwu
2017-10-19
The design and synthesis of a promising porous carbon-based electrocatalyst with an ordered and uninterrupted porous structure for oxygen reduction reaction (ORR) is still a significant challenge. Herein, an efficient catalyst based on cobalt-embedded nitrogen-doped ordered mesoporous carbon nanosheets (Co/N-OMCNS) is successfully prepared through a two-step procedure (cobalt ion-coordinated self-assembly and carbonization process) using 3-aminophenol as a nitrogen source, cobalt acetate as a cobalt source and Pluronic F127 as a mesoporous template. This work indicates that the formation of a two dimensional nanosheet structure is directly related to the extent of the cobalt ion coordination interaction. Moreover, the critical roles of pyrolysis temperature in nitrogen doping and ORR catalytic activity are also investigated. Benefiting from the high surface area and graphitic degree, high contents of graphitic N and pyridinic N, ordered interconnected mesoporous carbon framework, as well as synergetic interaction between the cobalt nanoparticles and protective nitrogen doped graphitic carbon layer, the resultant optimal catalyst Co/N-OMCNS-800 (pyrolyzed at 800 °C) exhibits comparable ORR catalytic activity to Pt/C, superior tolerance to methanol crossover and stability.
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Jin, Mingjie; Long, Mingce; Su, Hanrui; Pan, Yue; Zhang, Qiuzhuo; Wang, Juan; Zhou, Baoxue; Zhang, Yanwu
2017-01-01
To develop highly efficient and conveniently separable iron containing catalysts is crucial to remove recalcitrant organic pollutants in wastewater through a heterogeneous Fenton-like reaction. A maghemite/montmorillonite composite was synthesized by a coprecipitation and calcination method. The physiochemical properties of catalysts were characterized by XRD, TEM, nitrogen physisorption, thermogravimetric analysis/differential scanning calorimetry (TG/DSC), zeta potential, and magnetite susceptibility measurements. The influence of calcination temperatures and reaction parameters was investigated. The calcined composites retain magnetism because the presence of montmorillonite inhibited the growth of γ-Fe 2 O 3 nanoparticles, as well as their phase transition. The catalytic activities for phenol degradation were significantly enhanced by calcinations, which strengthen the interaction between iron oxides and aluminosilicate framework and result in more negatively charged surface. The composite (73 m 2 /g) calcined at 350 °C had the highest catalytic activities, with more than 99 % phenol reduction after only 35 min reaction at pH 3.6. Simultaneously, this catalyst exhibited high stability, low iron leaching, and magnetically separable ability for consecutive usage, making it promising for the removal of recalcitrant organic pollutants in wastewater.
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Heterogeneous Catalysts for VOC Oxidation from Red Mud and Bagasse Ash Carbon
NASA Astrophysics Data System (ADS)
Pande, Gaurav
A range of VOC oxidation catalysts have been prepared in this study from agricultural and industrial waste as the starting point. The aim is to prepare catalysts with non-noble metal oxides as the active catalytic component (iron in red mud). The same active component was also supported on activated carbon obtained from unburned carbon in bagasse ash. Red mud which is an aluminum industry waste and rich in different phases of iron as oxide and hydroxide is used as the source for the catalytically active species. It is our aim to enhance the catalytic performance of red mud which though high in iron concentration has a low surface area and may not have the properties of an ideal catalyst by itself. In one of the attempts to enhance the catalytic performance, we have tried to leach red mud for which we have explored a range of leaching acids for effecting the leaching most efficiently and then precipitated the iron from the leachate as its hydroxide by precipitating with alkali solution followed by drying and calcination to give high surface area metal oxide material. Extensive surface characterization and VOC oxidation catalytic testing were performed for these solids. In a step to further enhance the catalytic activity towards oxidation, copper was introduced by taking another industrial waste from the copper tubing industry viz. the pickling acid. Copper has a more favourable redox potential making it catalytically more effective than iron. To make the mixed metal oxide, red mud leachate was mixed with the pickling acid in a pre-decided ratio before precipitating with alkali solution followed by drying and calcination as was done with the red mud leachate. The results from these experiments are encouraging. The temperature programmed reduction (TPR) of the solids show that the precipitate of red mud leachates show hydrogen uptake peak at a lower temperature than for just the calcined red mud. This could be due to the greatly enhanced surface area of the prepared solids. The highest surface area of 311 m2/g was for the sample prepared from oxalic acid and l-ascorbic acid as the leaching acid; as received red mud has a surface area of 11.5 m2/g. This sample showed better catalytic performance than the ones made from hydrochloric acid as the leaching acid in spite of a similar increase in surface area. High temperature XRD shows the reason for this difference in catalytic properties could be due to both the solids reducing in a different way to give different phases though they are both derived from red mud as the starting material. Also, the sample prepared with oxalic acid leachate had higher surface iron concentration. For the best catalyst (oxalic acid derived) the light off temperature is about 300 °C for toluene oxidation. For solids prepared from red mud leachate for iron source and pickling acid for copper source, it was seen that the TPR gave hydrogen absorption at temperatures even lower than that for red mud leachate precipitates. In another set of experiments, iron oxide impregnated on activated carbon supports were prepared. Activated carbon is known for its adsorption properties which could give a better access of the impregnated metal oxide catalyst to perform the catalytic oxidation on the adsorbed substrate. Unburned carbon in bagasse ash which is a sugar industry agricultural waste was used to get the activated carbon. This material was separated from the ash and further modified to enhance the activity and increase the porosity. To this effect steam activation was performed. To impart thermal stability for oxidation reaction, the carbon was impregnated by phosphoric acid at activated at high temperatures in inert atmosphere. These carbons were thermally stable due to the surface C--O--P groups. Toluene adsorption studies were also performed for both the steam activated as well as phosphoric acid activated carbon and it was found that the steam activated carbons with less surface oxygen had reasonable adsorption attributes. For iron impregnation onto the prepared bagasse ash carbons, two different methods of impregnation viz. incipient wetness method as well as impregnation by precipitation of the red mud leachate by adding alkali to a slurry of carbon and leachate (Pratt method) was used. It was found that impregnation by precipitation led to better butanol oxidation performing catalyst than the one prepared by impregnating by incipient wetness method. The best performing catalyst amongst the iron impregnated on carbon types was found to give 100% butanol conversion at 200 °C. It was also observed that red mud leachate precipitated catalyst performed well for toluene oxidation and not for butanol oxidation while carbon supported iron oxide catalysts worked better for butanol oxidation than for toluene oxidation.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Shan, Junjun; Zhang, Shiran; Choksi, Tej
2016-12-05
Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis weremore » explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.« less
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Maggi, Maristella; Chiarelli, Laurent R; Valentini, Giovanna; Scotti, Claudia
2015-01-01
Bacterial L-asparaginases have been used as anti-cancer drugs for over 4 decades though presenting, along with their therapeutic efficacy, several side effects due to their bacterial origin and, seemingly, to their secondary glutaminase activity. Helicobacter pylori type II L-asparaginase possesses interesting features, among which a reduced catalytic efficiency for L-GLN, compared to the drugs presently used in therapy. In the present study, we describe some enzyme variants with catalytic and in vitro cytotoxic activities different from the wild type enzyme. Particularly, replacements on catalytic threonines (T16D and T95E) deplete the enzyme of both its catalytic activities, once more underlining the essential role of such residues. One serendipitous mutant, M121C/T169M, had a preserved efficiency vs L-asparagine but was completely unable to carry out L-glutamine hydrolysis. Interestingly, this variant did not exert any cytotoxic effect on HL-60 cells. The M121C and T169M single mutants had reduced catalytic activities (nearly 2.5- to 4-fold vs wild type enzyme, respectively). Mutant Q63E, endowed with a similar catalytic efficiency versus asparagine and halved glutaminase efficiency with respect to the wild type enzyme, was able to exert a cytotoxic effect comparable to, or higher than, the one of the wild type enzyme when similar asparaginase units were used. These findings may be relevant to determine the role of glutaminase activity of L-asparaginase in the anti-proliferative effect of the drug and to shed light on how to engineer the best asparaginase/glutaminase combination for an ever improved, patients-tailored therapy.
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Maggi, Maristella; Chiarelli, Laurent R.; Valentini, Giovanna; Scotti, Claudia
2015-01-01
Bacterial L-asparaginases have been used as anti-cancer drugs for over 4 decades though presenting, along with their therapeutic efficacy, several side effects due to their bacterial origin and, seemingly, to their secondary glutaminase activity. Helicobacter pylori type II L-asparaginase possesses interesting features, among which a reduced catalytic efficiency for L-GLN, compared to the drugs presently used in therapy. In the present study, we describe some enzyme variants with catalytic and in vitro cytotoxic activities different from the wild type enzyme. Particularly, replacements on catalytic threonines (T16D and T95E) deplete the enzyme of both its catalytic activities, once more underlining the essential role of such residues. One serendipitous mutant, M121C/T169M, had a preserved efficiency vs L-asparagine but was completely unable to carry out L-glutamine hydrolysis. Interestingly, this variant did not exert any cytotoxic effect on HL-60 cells. The M121C and T169M single mutants had reduced catalytic activities (nearly 2.5- to 4-fold vs wild type enzyme, respectively). Mutant Q63E, endowed with a similar catalytic efficiency versus asparagine and halved glutaminase efficiency with respect to the wild type enzyme, was able to exert a cytotoxic effect comparable to, or higher than, the one of the wild type enzyme when similar asparaginase units were used. These findings may be relevant to determine the role of glutaminase activity of L-asparaginase in the anti-proliferative effect of the drug and to shed light on how to engineer the best asparaginase/glutaminase combination for an ever improved, patients-tailored therapy. PMID:25664771
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Murphy, John R.
2011-01-01
Research on diphtheria and anthrax toxins over the past three decades has culminated in a detailed understanding of their structure function relationships (e.g., catalytic (C), transmembrane (T), and receptor binding (R) domains), as well as the identification of their eukaryotic cell surface receptor, an understanding of the molecular events leading to the receptor-mediated internalization of the toxin into an endosomal compartment, and the pH triggered conformational changes required for pore formation in the vesicle membrane. Recently, a major research effort has been focused on the development of a detailed understanding of the molecular interactions between each of these toxins and eukaryotic cell factors that play an essential role in the efficient translocation of their respective catalytic domains through the trans-endosomal vesicle membrane pore and delivery into the cell cytosol. In this review, I shall focus on recent findings that have led to a more detailed understanding of the mechanism by which the diphtheria toxin catalytic domain is delivered to the eukaryotic cell cytosol. While much work remains, it is becoming increasingly clear that the entry process is facilitated by specific interactions with a number of cellular factors in an ordered sequential fashion. In addition, since diphtheria, anthrax lethal factor and anthrax edema factor all carry multiple coatomer I complex binding motifs and COPI complex has been shown to play an essential role in entry process, it is likely that the initial steps in catalytic domain entry of these divergent toxins follow a common mechanism. PMID:22069710
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Molecular system identification for enzyme directed evolution and design
NASA Astrophysics Data System (ADS)
Guan, Xiangying; Chakrabarti, Raj
2017-09-01
The rational design of chemical catalysts requires methods for the measurement of free energy differences in the catalytic mechanism for any given catalyst Hamiltonian. The scope of experimental learning algorithms that can be applied to catalyst design would also be expanded by the availability of such methods. Methods for catalyst characterization typically either estimate apparent kinetic parameters that do not necessarily correspond to free energy differences in the catalytic mechanism or measure individual free energy differences that are not sufficient for establishing the relationship between the potential energy surface and catalytic activity. Moreover, in order to enhance the duty cycle of catalyst design, statistically efficient methods for the estimation of the complete set of free energy differences relevant to the catalytic activity based on high-throughput measurements are preferred. In this paper, we present a theoretical and algorithmic system identification framework for the optimal estimation of free energy differences in solution phase catalysts, with a focus on one- and two-substrate enzymes. This framework, which can be automated using programmable logic, prescribes a choice of feasible experimental measurements and manipulated input variables that identify the complete set of free energy differences relevant to the catalytic activity and minimize the uncertainty in these free energy estimates for each successive Hamiltonian design. The framework also employs decision-theoretic logic to determine when model reduction can be applied to improve the duty cycle of high-throughput catalyst design. Automation of the algorithm using fluidic control systems is proposed, and applications of the framework to the problem of enzyme design are discussed.
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Chen, Bang-Bao; Ma, De-Kun; Ke, Qing-Ping; Chen, Wei; Huang, Shao-Ming
2016-03-07
Edges often play a role as active centers for catalytic reactions in some nanomaterials. Therefore it is highly desirable to enhance catalytic activity of a material through modulating the microstructure of the edges. However, the study associated with edge engineering is less investigated and still at its preliminary stage. Here we report that Cu2MoS4 nanosheets with indented edges can be fabricated through a simple chemical etching route at room temperature, using Cu2MoS4 nanosheets with flat ones as sacrifice templates. Taking the electrocatalytic hydrogen evolution reaction (HER), photocatalytic degradation of rhodamine B (RhB) and conversion of benzyl alcohol as examples, the catalytic activity of Cu2MoS4 indented nanosheets (INSs) obtained through edge engineering was comparatively studied with those of Cu2MoS4 flat nanosheets (FNSs) without any modification. The photocatalytic tests revealed that the catalytic active sites of Cu2MoS4 nanosheets were associated with their edges rather than basal planes. Cu2MoS4 INSs were endowed with larger electrochemically active surface area (ECSA), more active edges and better hydrophilicity through the edge engineering. As a result, the as-fabricated Cu2MoS4 INSs exhibited an excellent HER activity with a small Tafel slope of 77 mV dec(-1), which is among the best records for Cu2MoS4 catalysts. The present work demonstrated the validity of adjusting catalytic activity of the material through edge engineering and provided a new strategy for designing and developing highly efficient catalysts.
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Theoretical evidence of PtSn alloy efficiency for CO oxidation.
Dupont, Céline; Jugnet, Yvette; Loffreda, David
2006-07-19
The efficiency of PtSn alloy surfaces toward CO oxidation is demonstrated from first-principles theory. Oxidation kinetics based on atomistic density-functional theory calculations shows that the Pt3Sn surface alloy exhibits a promising catalytic activity for fuel cells. At room temperature, the corresponding rate outstrips the activity of Pt(111) by several orders of magnitude. According to the oxidation pathways, the activation barriers are actually lower on Pt3Sn(111) and Pt3Sn/Pt(111) surfaces than on Pt(111). A generalization of Hammer's model is proposed to elucidate the key role of tin on the lowering of the barriers. Among the energy contributions, a correlation is evidenced between the decrease of the barrier and the strengthening of the attractive interaction energy between CO and O moieties. The presence of tin modifies also the symmetry of the transition states which are composed of a CO adsorbate on a Pt near-top position and an atomic O adsorption on an asymmetric mixed PtSn bridge site. Along the reaction pathways, a CO2 chemisorbed surface intermediate is obtained on all the surfaces. These results are supported by a thorough vibrational analysis including the coupling with the surface phonons which reveals the existence of a stretching frequency between the metal substrate and the CO2 molecule.
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Li, Shuirong; Gong, Jinlong
2014-11-07
Owing to the considerable publicity that has been given to petroleum related economic, environmental, and political problems, renewed attention has been focused on the development of highly efficient and stable catalytic materials for the production of chemical/fuel from renewable resources. Supported nickel nanoclusters are widely used for catalytic reforming reactions, which are key processes for generating synthetic gas and/or hydrogen. New challenges were brought out by the extension of feedstock from hydrocarbons to oxygenates derivable from biomass, which could minimize the environmental impact of carbonaceous fuels and allow a smooth transition from fossil fuels to a sustainable energy economy. This tutorial review describes the recent efforts made toward the development of nickel-based catalysts for the production of hydrogen from oxygenated hydrocarbons via steam reforming reactions. In general, three challenges facing the design of Ni catalysts should be addressed. Nickel nanoclusters are apt to sinter under catalytic reforming conditions of high temperatures and in the presence of steam. Severe carbon deposition could also be observed on the catalyst if the surface carbon species adsorbed on metal surface are not removed in time. Additionally, the production of hydrogen rich gas with a low concentration of CO is a challenge using nickel catalysts, which are not so active in the water gas shift reaction. Accordingly, three strategies were presented to address these challenges. First, the methodologies for the preparation of highly dispersed nickel catalysts with strong metal-support interaction were discussed. A second approach-the promotion in the mobility of the surface oxygen-is favored for the yield of desired products while promoting the removal of surface carbon deposition. Finally, the process intensification via the in situ absorption of CO2 could produce a hydrogen rich gas with low CO concentration. These approaches could also guide the design of other types of heterogeneous base-metal catalysts for high temperature processes including methanation, dry reforming, and hydrocarbon combustion.
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The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.
Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M
2011-01-07
Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully understanding the activity of gold are considered.
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Golkhatmi, Faezeh Mahdinejad; Bahramian, Bahram; Mamarabadi, Mojtaba
2017-09-01
Newly, magnetic nanoparticles have extensively been used as alternative catalyst supports, in the view of their high surface area which results in high catalyst loading capacity, high dispersion, low toxicity, environmental preservation, distinguished stability, and suitable catalyst reusing. In the present study, the magnetite nanoparticles, NiFe 2 O 4 @Ag and NiFe 2 O 4 @Mo, were synthesized and characterized. The antimicrobial activities and catalytic properties of synthesized nanoparticles were tested afterwards. For synthetizing the nanoparticle NiFe 2 O 4 @Ag, silver ions were loaded onto the surface of the modified NiFe 2 O 4 and reduced to silver crystal by adding NaBH 4 . The antibacterial effects of NiFe 2 O 4 @Ag were examined against two species of soil and plant related bacteria named Bacillus subtilis (gram positive) and Pseudomonas syringae (gram negative), respectively. The antifungal activity of this nanoparticle was evaluated against two species of plant pathogenic fungi called Alternaria solani and Fusarium oxysporum. Biological results indicated that the synthesized material has shown an excellent antibacterial and antifungal activity against all examined bacteria and fungi so that, their growth were completely inhibited 24h after treatment with NiFe 2 O 4 @Ag. For the synthesis of a heterogeneous catalyst NiFe 2 O 4 @Mo, complex Mo(CO) 6 was loaded onto the surface of the modified NiFe 2 O 4 nanoparticle. This catalyst was found as an efficient catalyst for epoxidation of cis-cyclooctene and a wide variety of alkenes, including aromatic and aliphatic terminal ones using tert-butyl hydroperoxide as oxidant. This new heterogenized catalyst could easily be recovered by using a magnetic separator and reused four consecutive and loss only 13% of its catalytic activity. Copyright © 2017 Elsevier B.V. All rights reserved.
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Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics
DOE Office of Scientific and Technical Information (OSTI.GOV)
Klier, Kamil; Herman, Richard G
2005-11-30
This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. Themore » latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with blending octane No. of 105, and can replace aromatics in liquid fuels.« less
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NASA Astrophysics Data System (ADS)
Atribak, Idriss; Guillén-Hurtado, Noelia; Bueno-López, Agustín; García-García, Avelina
2010-10-01
Commercial and home-made Ce-Zr catalysts prepared by co-precipitation were characterised by XRD, Raman spectroscopy, N 2 adsorption at -196 °C and XPS, and were tested for NO oxidation to NO 2. Among the different physico-chemical properties characterised, the surface composition seems to be the most relevant one in order to explain the NO oxidation capacity of these Ce-Zr catalysts. As a general trend, Ce-Zr catalysts with a cerium-rich surface, that is, high XPS-measured Ce/Zr atomic surface ratios, are more active than those with a Zr-enriched surface. The decrease in catalytic activity of the Ce-Zr mixed oxided upon calcinations at 800 °C with regard to 500 °C is mainly attributed to the decrease in Ce/Zr surface ratio, that is, to the surface segregation of Zr. The phase composition (cubic or t'' for Ce-rich compositions) seems not to be a direct effect on the catalytic activity for NO oxidation in the range of compositions tested. However, the formation of a proper solid solution prevents important surface segregation of Zr upon calcinations at high temperature. The effect of the BET surface area in the catalytic activity for NO oxidation of Ce-Zr mixed oxides is minor in comparison with the effect of the Ce/Zr surface ratio.
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Atkinson, Nicky; Leitão, Nuno; Orr, Douglas J; Meyer, Moritz T; Carmo-Silva, Elizabete; Griffiths, Howard; Smith, Alison M; McCormick, Alistair J
2017-04-01
Introducing components of algal carbon concentrating mechanisms (CCMs) into higher plant chloroplasts could increase photosynthetic productivity. A key component is the Rubisco-containing pyrenoid that is needed to minimise CO 2 retro-diffusion for CCM operating efficiency. Rubisco in Arabidopsis was re-engineered to incorporate sequence elements that are thought to be essential for recruitment of Rubisco to the pyrenoid, namely the algal Rubisco small subunit (SSU, encoded by rbcS) or only the surface-exposed algal SSU α-helices. Leaves of Arabidopsis rbcs mutants expressing 'pyrenoid-competent' chimeric Arabidopsis SSUs containing the SSU α-helices from Chlamydomonas reinhardtii can form hybrid Rubisco complexes with catalytic properties similar to those of native Rubisco, suggesting that the α-helices are catalytically neutral. The growth and photosynthetic performance of complemented Arabidopsis rbcs mutants producing near wild-type levels of the hybrid Rubisco were similar to those of wild-type controls. Arabidopsis rbcs mutants expressing a Chlamydomonas SSU differed from wild-type plants with respect to Rubisco catalysis, photosynthesis and growth. This confirms a role for the SSU in influencing Rubisco catalytic properties. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.
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Antioxidant Cerium Oxide Nanoparticles in Biology and Medicine
Nelson, Bryant C.; Johnson, Monique E.; Walker, Marlon L.; Riley, Kathryn R.; Sims, Christopher M.
2016-01-01
Previously, catalytic cerium oxide nanoparticles (CNPs, nanoceria, CeO2-x NPs) have been widely utilized for chemical mechanical planarization in the semiconductor industry and for reducing harmful emissions and improving fuel combustion efficiency in the automobile industry. Researchers are now harnessing the catalytic repertoire of CNPs to develop potential new treatment modalities for both oxidative- and nitrosative-stress induced disorders and diseases. In order to reach the point where our experimental understanding of the antioxidant activity of CNPs can be translated into useful therapeutics in the clinic, it is necessary to evaluate the most current evidence that supports CNP antioxidant activity in biological systems. Accordingly, the aims of this review are three-fold: (1) To describe the putative reaction mechanisms and physicochemical surface properties that enable CNPs to both scavenge reactive oxygen species (ROS) and to act as antioxidant enzyme-like mimetics in solution; (2) To provide an overview, with commentary, regarding the most robust design and synthesis pathways for preparing CNPs with catalytic antioxidant activity; (3) To provide the reader with the most up-to-date in vitro and in vivo experimental evidence supporting the ROS-scavenging potential of CNPs in biology and medicine. PMID:27196936
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Efficient low-temperature soot combustion by bimetallic Ag-Cu/SBA-15 catalysts.
Wen, Zhaojun; Duan, Xinping; Hu, Menglin; Cao, Yanning; Ye, Linmin; Jiang, Lilong; Yuan, Youzhu
2018-02-01
In this study, the effects of copper (Cu) additive on the catalytic performance of Ag/SBA-15 in complete soot combustion were investigated. The soot combustion performance of bimetallic Ag-Cu/SBA-15 catalysts was higher than that of monometallic Ag and Cu catalysts. The optimum catalytic performance was acquired with the 5Ag 1 -Cu 0.1 /SBA-15 catalyst, on which the soot combustion starts at T ig =225°C with a T 50 =285°C. The temperature for 50% of soot combustion was lower than that of conventional Ag-based catalysts to more than 50°C (Aneggi et al., 2009). Physicochemical characterizations of the catalysts indicated that addition of Cu into Ag could form smaller bimetallic Ag-Cu nanolloy particles, downsizing the mean particle size from 3.7nm in monometallic catalyst to 2.6nm in bimetallic Ag-Cu catalyst. Further experiments revealed that Ag and Cu species elicited synergistic effects, subsequently increasing the content of surface active oxygen species. As a result, the structure modifications of Ag by the addition of Cu strongly intensified the catalytic performance. Copyright © 2017. Published by Elsevier B.V.
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NASA Astrophysics Data System (ADS)
Hu, Shuo; Yang, Guangxin; Jiang, Hong; Liu, Yefei; Chen, Rizhi
2018-03-01
Selective phenol hydrogenation is a green and sustainable technology to produce cyclohexanone. The work focused on investigating the role of catalyst reduction method in the liquid-phase phenol hydrogenation to cyclohexanone over Pd@CN (N-doped porous carbon). A series of reduction methods including flowing hydrogen reduction, in-situ reaction reduction and liquid-phase reduction were designed and performed. The results highlighted that the reduction method significantly affected the catalytic performance of Pd@CN in the liquid-phase hydrogenation of phenol to cyclohexanone, and the liquid-phase reduction with the addition of appropriate amount of phenol was highly efficient to improve the catalytic activity of Pd@CN. The influence mechanism was explored by a series of characterizations. The results of TEM, XPS and CO chemisorption confirmed that the reduction method mainly affected the size, surface composition and dispersion of Pd in the CN material. The addition of phenol during the liquid-phase reduction could inhibit the aggregation of Pd NPs and promote the reduction of Pd (2+), and then improved the catalytic activity of Pd@CN. The work would aid the development of high-performance Pd@CN catalysts for selective phenol hydrogenation.
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Esposito, Daniel V; Levin, Igor; Moffat, Thomas P; Talin, A Alec
2013-06-01
Photoelectrochemical (PEC) water splitting represents a promising route for renewable production of hydrogen, but trade-offs between photoelectrode stability and efficiency have greatly limited the performance of PEC devices. In this work, we employ a metal-insulator-semiconductor (MIS) photoelectrode architecture that allows for stable and efficient water splitting using narrow bandgap semiconductors. Substantial improvement in the performance of Si-based MIS photocathodes is demonstrated through a combination of a high-quality thermal SiO2 layer and the use of bilayer metal catalysts. Scanning probe techniques were used to simultaneously map the photovoltaic and catalytic properties of the MIS surface and reveal the spillover-assisted evolution of hydrogen off the SiO2 surface and lateral photovoltage driven minority carrier transport over distances that can exceed 2 cm. The latter finding is explained by the photo- and electrolyte-induced formation of an inversion channel immediately beneath the SiO2/Si interface. These findings have important implications for further development of MIS photoelectrodes and offer the possibility of highly efficient PEC water splitting.
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NASA Astrophysics Data System (ADS)
Yang, Shuting; Mao, Xinxin; Cao, Zhaoxia; Yin, Yanhong; Wang, Zhichao; Shi, Mengjiao; Dong, Hongyu
2018-01-01
Onion-derived nitrogen, sulfur self-doped nanoporous carbon spheres (NSC) as efficient metal-free electrocatalyst were synthesized via a facile hydrothermal and subsequent pyrolysis process. The typical NSC with a high BET specific surface area of 1558 m2 g-1, contains 6.23 at.% N and 0.36 at.% S, and possesses high concentration of pyridinic and graphitic nitrogen species. Experimentally, the best performance was the NSC-A2 which showed excellent catalytic activity to oxygen reduction reaction via a 4 electron mechanism with an onset potential of 0.88 V (vs. RHE), and a superior stability comparable to commercial Pt/C catalyst. The high electrocatalytic activity is attributed to not only the synergistic effect of N and S dual doping in carbon and the sufficient active sites, but also its high BET specific surface area and suitable microporous structure. The results demonstrate that it is a simple and scalable approach for preparing efficient and low-cost carbon-based electrocatalysts for oxygen reduction reaction.
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Catalytic degradation of picric acid by heterogeneous Fenton-based processes.
Dulova, Niina; Trapido, Marina; Dulov, Aleksandr
2011-01-01
The efficiency of goethite, magnetite and iron powder (Fe0) in catalysing the Fenton-based oxidation of picric acid (PA) in aqueous solution was studied. The effect of pH, hydrogen peroxide concentration, and catalyst type and dosage on treatment efficacy was investigated. The adsorption of PA from aqueous solution by heterogeneous catalysts was also examined. The results demonstrated negligible PA removal in H2O2/alpha-FeOOH and H2O2/Fe3O4 systems independent of process pH, and hydrogen peroxide and catalyst dosage. The PA adsorption effects of both iron oxides turned out to be insignificant for all studied pH values and catalyst dosages. The H2O2/Fe0 system proved efficient at degrading PA, but only under acidic conditions (pH 3). The results indicated that, due to rather fast leaching of ferrous ions from the iron powder surface, PA degradation was carried out mainly by the classic Fenton oxidation mechanism in the bulk solution. The adsorption of PA onto the iron powder surface may also contribute to the overall efficiency of PA degradation.
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Dong, Haifeng; Liu, Conghui; Ye, Haitao; Hu, Linping; Fugetsu, Bunshi; Dai, Wenhao; Cao, Yu; Qi, Xueqiang; Lu, Huiting; Zhang, Xueji
2015-01-01
An efficient three-dimensional (3D) hybrid material of nitrogen-doped graphene sheets (N-RGO) supporting molybdenum disulfide (MoS2) nanoparticles with high-performance electrocatalytic activity for hydrogen evolution reaction (HER) is fabricated by using a facile hydrothermal route. Comprehensive microscopic and spectroscopic characterizations confirm the resulting hybrid material possesses a 3D crumpled few-layered graphene network structure decorated with MoS2 nanoparticles. Electrochemical characterization analysis reveals that the resulting hybrid material exhibits efficient electrocatalytic activity toward HER under acidic conditions with a low onset potential of 112 mV and a small Tafel slope of 44 mV per decade. The enhanced mechanism of electrocatalytic activity has been investigated in detail by controlling the elemental composition, electrical conductance and surface morphology of the 3D hybrid as well as Density Functional Theory (DFT) calculations. This demonstrates that the abundance of exposed active sulfur edge sites in the MoS2 and nitrogen active functional moieties in N-RGO are synergistically responsible for the catalytic activity, whilst the distinguished and coherent interface in MoS2/N-RGO facilitates the electron transfer during electrocatalysis. Our study gives insights into the physical/chemical mechanism of enhanced HER performance in MoS2/N-RGO hybrids and illustrates how to design and construct a 3D hybrid to maximize the catalytic efficiency. PMID:26639026
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Liu, Wanting; Su, Qing; Ju, Pengyao; Guo, Bixuan; Zhou, Hui; Li, Guanghua; Wu, Qiaolin
2017-02-22
A hydrazone-based covalent organic framework (COF) was synthesized by condensation of 2,5-dimethoxyterephthalohydrazide with 1,3,5-triformylbenzene under solvothermal conditions. The COF material exhibits excellent porosity with a BET surface area of up to 1501 m 2 g -1 , high crystallinity, and good thermal and chemical stability. Moreover, it showed efficient photocatalytic activity towards cross-dehydrogenative coupling (CDC) reactions between tetrahydroisoquinolines and nucleophiles such as nitromethane, acetone, and phenylethyl ketone. The metal-free catalytic system also offers attractive advantages including simplicity of operation, wide substrate adaptability, ambient reaction conditions, and robust recycling capability of the catalyst, thus providing a promising platform for highly efficient and reusable photocatalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Ren, Miao; Liu, Haiyang; Qu, Jiao; Zhang, Yanan; Ma, Ying; Yuan, Xing
2018-03-07
The graphene (GR)/TiO 2 membrane was prepared by the sol-gel method and coated on the indium tin oxide (ITO) conductive glass, which showed high and stable photo(-electro)-catalytic activities to rhodamine B (Rh-B) in water. Characterization results showed that the GR was dispersed and wrapped in the needle-like TiO 2 . With GR/TiO 2 membrane and simulated sunlight irradiation, the removal efficiency of Rh-B (10 mg l -1 and pH at 5.4) arrived at 87.6% within 300 min. However, the higher removal efficiency for Rh-B reached to 97.8% by the photo-electro-catalytic degradation with the applied voltage 4 v for 30 min. The ·OH that generated in the photo-catalytic degradation process were responsible for Rh-B decomposition. The ·O 2 - played the significant role in the photo-electro-catalytic degradation of Rh-B. Furthermore, the decarboxylation was also occurred in the photo-electro-catalytic degradation for the Rh-B in water except for the deethylation and hydroxylation in the photo-catalytic degradation. In addition, the toxicities of the intermediates were calculated using the ECOSAR program and the EPIWIN software. The results indicated that the toxicities of intermediates from photo-electro-catalytic degradation for the Rh-B were higher than photo-catalytic degradation, due to the generation of decarboxylate.
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Influence of active site location on catalytic activity in de novo-designed zinc metalloenzymes.
Zastrow, Melissa L; Pecoraro, Vincent L
2013-04-17
While metalloprotein design has now yielded a number of successful metal-bound and even catalytically active constructs, the question of where to put a metal site along a linear, repetitive sequence has not been thoroughly addressed. Often several possibilities in a given sequence may exist that would appear equivalent but may in fact differ for metal affinity, substrate access, or protein dynamics. We present a systematic variation of active site location for a hydrolytically active ZnHis3O site contained within a de novo-designed three-stranded coiled coil. We find that the maximal rate, substrate access, and metal-binding affinity are dependent on the selected position, while catalytic efficiency for p-nitrophenyl acetate hydrolysis can be retained regardless of the location of the active site. This achievement demonstrates how efficient, tailor-made enzymes which control rate, pKa, substrate and solvent access (and selectivity), and metal-binding affinity may be realized. These findings may be applied to the more advanced de novo design of constructs containing secondary interactions, such as hydrogen-bonding channels. We are now confident that changes to location for accommodating such channels can be achieved without location-dependent loss of catalytic efficiency. These findings bring us closer to our ultimate goal of incorporating the secondary interactions we believe will be necessary in order to improve both active site properties and the catalytic efficiency to be competitive with the native enzyme, carbonic anhydrase.
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Surface Protonics Promotes Catalysis
Manabe, R.; Okada, S.; Inagaki, R.; Oshima, K.; Ogo, S.; Sekine, Y.
2016-01-01
Catalytic steam reforming of methane for hydrogen production proceeds even at 473 K over 1 wt% Pd/CeO2 catalyst in an electric field, thanks to the surface protonics. Kinetic analyses demonstrated the synergetic effect between catalytic reaction and electric field, revealing strengthened water pressure dependence of the reaction rate when applying an electric field, with one-third the apparent activation energy at the lower reaction temperature range. Operando–IR measurements revealed that proton conduction via adsorbed water on the catalyst surface occurred during electric field application. Methane was activated by proton collision at the Pd–CeO2 interface, based on the inverse kinetic isotope effect. Proton conduction on the catalyst surface plays an important role in methane activation at low temperature. This report is the first describing promotion of the catalytic reaction by surface protonics. PMID:27905505
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Enhanced catalyst activity by decorating of Au on Ag@Cu2O nanoshell
NASA Astrophysics Data System (ADS)
Chen, Lei; Liu, Maomao; Zhao, Yue; Kou, Qiangwei; Wang, Yaxin; Liu, Yang; Zhang, Yongjun; Yang, Jinghai; Jung, Young Mee
2018-03-01
We successfully synthesized Au-decorated Ag@Cu2O heterostructures via a simple galvanic replacement method. As the Au precursor concentration increased, the density of the Au nanoparticles (NPs) on the Ag@Cu2O surface increased, which changed the catalytic activity of the Ag@Cu2O-Au structure. The combination of Au, Ag, and Cu2O exhibited excellent catalytic properties, which can further effect on the catalyst activity of the Ag@Cu2O-Au structure. In addition, the proposed Ag@Cu2O-Au nanocomposite was used to transform the organic, toxic pollutant, 4-nitrophenol (4-NP), into its nontoxic and medicinally important amino derivative via a catalytic reduction to optimize the material performance. The proposed Au-decorated Ag@Cu2O exhibited excellent catalytic activity, and the catalytic reduction time greatly decreased (5 min). Thus, three novel properties of Ag@Cu2O-Au, i.e., charge redistribution and transfer, adsorption, and catalytic reduction of organic pollutants, were ascertained for water remediation. The proposed catalytic properties have potential applications for photocatalysis and localized surface plasmon resonance (LSPR)- and peroxidase-like catalysis.
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Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.
Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian
2016-05-11
Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction.
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NASA Astrophysics Data System (ADS)
Coppage, Ryan
Bio-inspired nanoparticle catalysis offers the opportunity to improve on current catalytic standards with respect to turnover efficiency, organic solvent use, and thermal activation. Unfortunately, projected energy demands will soon outweigh our fuel supplies. The task of creating multifunctional catalysts that both lower thermal activation and possess a number of functions in aqueous conditions is daunting. Similar to these needs, nature has evolved to create a wide range of highly specialized catalytic processes, which incorporate inorganic materials, take place in ambient temperatures, and in an aqueous environment. These specialized biological systems provide inspiration, but are not applicable to current needs. Exploitation of these biotic-abiotic systems could allow for green, multifunctional catalysts. In the resulting works, a peptide sequence has been isolated via phage display with affinity for Pd surfaces, that forms stable, peptide-capped nanoparticles. Substitution of residues results in the tuning of both nanocatalyst activity and nanoparticle size, such that a peptide surface-controlling effect can be noted. These characteristics can be exploited to ultimately understand the binding interactions among bio-inorganic interfaces, such that a rational design of biomolecules can be realized for the synthesis of highly active, green, multifunctional nanomaterials.
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NASA Astrophysics Data System (ADS)
Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong
2016-09-01
Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C-O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface.
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Zhang, Shuangshuang; Yu, Jun; Li, Huiying; Mao, Dongsen; Lu, Guanzhong
2016-01-01
Developing the high-efficient and green synthetic method for chiral amino alcohols is an intriguing target. We have developed the Mg2+-doped Cu/ZnO/Al2O3 catalyst for hydrogenation of L-phenylalanine methyl ester to chiral L-phenylalaninol without racemization. The effect of different L-phenylalanine esters on this title reaction was studied, verifying that Cu/ZnO/Al2O3 is an excellent catalyst for the hydrogenation of amino acid esters to chiral amino alcohols. DFT calculation was used to study the adsorption of substrate on the catalyst, and showed that the substrate adsorbs on the surface active sites mainly by amino group (-NH2) absorbed on Al2O3, and carbonyl (C=O) and alkoxy (RO-) group oxygen absorbed on the boundary of Cu and Al2O3. This catalytic hydrogenation undergoes the formation of a hemiacetal intermediate and the cleavage of the C–O bond (rate-determining step) by reacting with dissociated H to obtain amino aldehyde and methanol ad-species. The former is further hydrogenated to amino alcohols, and the latter desorbs from the catalyst surface. PMID:27619990
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Catalyst material and method of making
Matson, Dean W.; Fulton, John L.; Linehan, John C.; Bean, Roger M.; Brewer, Thomas D.; Werpy, Todd A.; Darab, John G.
1997-01-01
The material of the present invention is a mixture of catalytically active material and carrier materials, which may be catalytically active themselves. Hence, the material of the present invention provides a catalyst particle that has catalytically active material throughout its bulk volume as well as on its surface. The presence of the catalytically active material throughout the bulk volume is achieved by chemical combination of catalytically active materials with carrier materials prior to or simultaneously with crystallite formation.
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Catalyst material and method of making
Matson, D.W.; Fulton, J.L.; Linehan, J.C.; Bean, R.M.; Brewer, T.D.; Werpy, T.A.; Darab, J.G.
1997-07-29
The material of the present invention is a mixture of catalytically active material and carrier materials, which may be catalytically active themselves. Hence, the material of the present invention provides a catalyst particle that has catalytically active material throughout its bulk volume as well as on its surface. The presence of the catalytically active material throughout the bulk volume is achieved by chemical combination of catalytically active materials with carrier materials prior to or simultaneously with crystallite formation. 7 figs.
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Guo, Dingyi; Qi, Jing; Zhang, Wei; Cao, Rui
2017-01-20
The slow kinetics of water oxidation greatly jeopardizes the efficiency of water electrolysis for H 2 production. Developing highly active water oxidation electrodes with affordable fabrication costs is thus of great importance. Herein, a Ni II Fe III surface species on Ni metal substrate was generated by electrochemical modification of Ni in a ferrous solution by a fast, simple, and cost-effective procedure. In the prepared Ni II Fe III catalyst film, Fe III was incorporated uniformly through controlled oxidation of Fe II cations on the electrode surface. The catalytically active Ni II originated from the Ni foam substrate, which ensured the close contact between the catalyst and the support toward improved charge-transfer efficiency. The as-prepared electrode exhibited high activity and long-term stability for electrocatalytic water oxidation. The overpotentials required to reach water oxidation current densities of 50, 100, and 500 mA cm -2 are 276, 290, and 329 mV, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Liu, Yongxin; Zhang, Jiali; Song, Lingxiao; Xu, Wenyuan; Guo, Zanru; Yang, Xiaomin; Wu, Xiaoxin; Chen, Xi
2016-09-07
A novel coordination replication of Cu2O redox-template strategy is reported to efficiently fabricate Au-HKUST-1 composite nanocapsule, with a HKUST-1 sandwich shell and an embedded Au nanoparticles layer. The novel synthesis procedure involves forming Au nanoparticles on the surface of Cu2O, transforming partial Cu2O into HKUST-1 shell via coordination replication, and removing the residual Cu2O by acid. The as-prepared Au-HKUST-1 composite nanocapsules displayed high catalytic activity on CO oxidation.
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Reactivating Catalytic Surface: Insights into the Role of Hot Holes in Plasmonic Catalysis.
Peng, Tianhuan; Miao, Junjian; Gao, Zhaoshuai; Zhang, Linjuan; Gao, Yi; Fan, Chunhai; Li, Di
2018-03-01
Surface plasmon resonance of coinage metal nanoparticles is extensively exploited to promote catalytic reactions via harvesting solar energy. Previous efforts on elucidating the mechanisms of enhanced catalysis are devoted to hot electron-induced photothermal conversion and direct charge transfer to the adsorbed reactants. However, little attention is paid to roles of hot holes that are generated concomitantly with hot electrons. In this work, 13 nm spherical Au nanoparticles with small absorption cross-section are employed to catalyze a well-studied glucose oxidation reaction. Density functional theory calculation and X-ray absorption spectrum analysis reveal that hot holes energetically favor transferring catalytic intermediates to product molecules and then desorbing from the surface of plasmonic catalysts, resulting in the recovery of their catalytic activities. The studies shed new light on the use of the synergy of hot holes and hot electrons for plasmon-promoted catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Effect of Surface Preparation and Gas Flow on Nitrogen Atom Surface Recombination
NASA Technical Reports Server (NTRS)
Prok, George M.
1961-01-01
The effects of surface preparation and gas flow on the recombination of nitrogen atoms at copper and platinum surfaces were determined. Atoms were generated by an electrodeless 2450-megacycle-per-second discharge, and their concentration was measured by gas-phase titration with nitric oxide. Test surfaces were either vacuum-evaporated films or spheres machined from bulk metal and cemented around small glass-bead thermistors. Heat released by recombination was measured as the difference in electrical energy required to maintain a given thermistor temperature with and without a catalytic surface exposed. Recombination coefficients measured at flow velocities of 1120, 1790, 2250, and 3460 centimeters per second and at pressures of 0.42 and 0.59 millimeter of mercury showed that flow conditions had no effect. The results were also independent of atom concentration. A rough indication of the temperature dependence was obtained; it was greater for copper than for platinum. Platinum films deposited on platinum or on glass had the same activity - about 3 percent of the atoms impinging recombined. With copper, however, the glass substrate greatly reduced the percent of atoms recombining over that of a bulk copper substrate where 4 percent of the impinging atoms recombined. This effect could be overcome by depositing a second film on top of the first. Bulk metal samples were subjected to various surface treatments including polishing, degreasing with a chlorinated hydrocarbon, washing with nitric acid, and rinsing with water. Polished, degreased platinum had low activity compared to an evaporated film, but nitric acid treatment made it equivalent. Polished, degreased copper was only slightly less active than a copper film; nitric acid etching decreased the activity still further, probably by preferentially exposing facets of low catalytic efficiency.
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Methods and apparatuses for preparing a surface to have catalytic activity
Cooks, Robert G [West Lafayette, IN; Peng, Wen-Ping [West Lafayette, IN; Ouyang, Zheng [West Lafayette, IN; Goodwin, Michael P [West Lafayette, IN
2011-03-22
The invention provides methods and apparatuses that utilize mass spectrometry for preparation of a surface to have catalytic activity through molecular soft-landing of mass selected ions. Mass spectrometry is used to generate combinations of atoms in a particular geometrical arrangement, and ion soft-landing selects this molecular entity or combination of entities and gently deposits the entity or combination intact onto a surface.
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The ability of different nano-sized materials (NSM) to effectively act as active photo-catalytic surfaces has been described for the mineralization/inactivation of many different aqueous pollutants. The reason for their enhanced ability over larger catalytic surfaces owes muc...
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Nanoniobia modification of CdS photoanode for an efficient and stable photoelectrochemical cell.
Pareek, Alka; Paik, Pradip; Borse, Pramod H
2014-12-30
Herein we report the surface modification of a CdS film by niobia nanoparticles via thioglycerol as an organic linker and thus fabricate an efficient and a stable photoanode for a photoelectrochemical (PEC) cell. We have synthesized three differenly sized (∼3, ∼6 ,and ∼9 nm) niobia nanoparticles by a hydrothermal synthesis approach and have further investigated the particle-size-dependent PEC performance of the nanoparticle-modified CdS photoanode. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirm the formation of Nb2O5 nanoparticles that are prepared via decomposition of the niobium peroxo complex during the hydrothermal reaction and reveal the presence of surface OH(-) groups over niobia nanoparticles that impart a high catalytic property to a material. The nano-Nb2O5-modified photoanode displayed a 23-fold higher power conversion efficiency compared to that of CdS. This modified structure increases the open circuit voltage (OCV) from 0.65 to 0.77 V, which is attributed to the nano-Nb2O5-induced surface passivation effect over bare CdS. Linking of nanoparticles on the CdS surface improves the photocorrosion stability of the CdS photoanode for even longer than 4 h in contrast to the tens of minutes for the base CdS surface. The uniform coverage of the CdS photoanode surface by niobia nanoparticles is thus found to be the controlling parameter for achieving a higher PEC performance and stability of the photoanode. This finding directed us to design an improved CdS photoanode for efficient and prolonged PEC hydrogen generation from a PEC cell.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Tao, Franklin
Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co 3O 4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with differentmore » binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few important catalytic reactions, and essentially fundamentally understand catalytic mechanism. Furthermore, this correlation will guide the design of catalysts with high activity and selectivity.« less
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NASA Astrophysics Data System (ADS)
Chen, Tao
Promising new technologies for biomass conversion into fuels and chemical feedstocks rely on the production of bio-oils, which need to be upgraded in order to remove oxygen-containing hydrocarbons and water. A high oxygen concentration makes bio-oils acidic and corrosive, unstable during storage, and less energetically valuable per unit weight than petroleum-derived hydrocarbons. Although there are efficient processes for the production of bio-oils, there are no efficient technologies for their upgrading. Current technologies utilize traditional petroleum refining catalysts, which are not optimized for biomass processing. New upgrading technologies are, therefore, urgently needed for development of sustainable energy resources. Development of such new technologies, however, is severely hindered by a lack of fundamental understanding of how oxygen and oxygen-containing hydrocarbons derived from biomass interact with promising noble-metal catalysts. In this study, kinetic reaction measurements, catalyst characterization and quantum chemical calculations using density functional theory were combined for determining adsorption modes and reaction mechanisms of hydrocarbons in the presence of oxygen on surfaces of catalytic noble-metal nanoparticles. The results were used for developing improved catalyst formulations and optimization of reaction conditions. The addition of molybdenum to platinum catalysts was shown to improve catalytic activity, stability, and selectivity in hydrodeoxygenation of acetic acid, which served as a model biomass compound. The fundamental results that describe interactions of oxygen and hydrocarbons with noble-metal catalysts were extended to other reactions and fields of study: evaluation of the reaction mechanism for hydrogen peroxide decomposition, development of improved hydrogenation catalysts and determination of adsorption modes of a spectroscopic probe molecule.
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Chen, Weirui; Li, Xukai; Tang, Yiming; Zhou, Jialu; Wu, Dan; Wu, Yin; Li, Laisheng
2018-03-15
A flexible catalyst, Fe-Cu-MCM-41, was employed to enhance diclofenac (DCF) mineralization and inhibit bromate formation in catalytic ozonation process. Greater TOC removal was achieved in Fe-Cu-MCM-41/O 3 process (78%) than those in Fe-MCM-41/O 3 (65%), Cu-MCM-41/O 3 (73%) and sole ozonation (42%). But it was interesting that both Cu-MCM-41/O 3 and Fe-MCM-41/O 3 achieved 93% bromate inhibition efficiency, only 71% inhibition efficiency was observed in Fe-Cu-MCM-41/O 3 . Influence of pH, TBA/NaHSO 3 and detection of by-products were conducted to explore the mechanism. By Pyridine adsorption-IR and XPS, a relationship was found among activity of catalysts, Lewis acid sites and electron transfer effect between Fe (II/III) and Cu (I/II). Fe-Cu-MCM-41 promoted ozone decomposition to generate OH, which accounted for enhanced DCF mineralization. The consumption of aqueous O 3 also suppressed the oxidative of Br - and HBrO/Br - . More HBrO/BrO - accumulated in catalytic ozonation process and less bromate generated. Bromate formation in Fe-Cu-MCM-41/O 3 process was sensitive with pH value, the acidic condition was not favor for bromate formation. Both DCF mineralization and bromate inhibition were influenced by surface reaction. Moreover, Fe-Cu-MCM-41 showed excellent catalytic performance in suppressing the accumulation of carboxylic acid, especially for oxalic acid. Nearly no oxalic acid was detected during Fe-Cu-MCM-41/O 3 process. Copyright © 2017 Elsevier B.V. All rights reserved.
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Poisoning of bubble propelled catalytic micromotors: the chemical environment matters
Zhao, Guanjia; Sanchez, Samuel; Schmidt, Oliver G.
2013-01-01
Self-propelled catalytic microjets have attracted considerable attention in recent years and these devices have exhibited the ability to move in complex media. The mechanism of propulsion is via the Pt catalysed decomposition of H2O2 and it is understood that the Pt surface is highly susceptible to poisoning by sulphur-containing molecules. Here, we show that important extracellular thiols as well as basic organic molecules can significantly hamper the motion of catalytic microjet engines. This is due to two different mechanisms: (i) molecules such as dimethyl sulfoxide can quench the hydroxyl radicals produced at Pt surfaces and reduce the amount of oxygen gas generated and (ii) molecules containing –SH, –SSR, and –SCH3 moieties can poison the catalytically active platinum surface, inhibiting the motion of the jet engines. It is essential that the presence of such molecules in the environment be taken into consideration for future design and operation of catalytic microjet engines. We show this effect on catalytic micromotors prepared by both rolled-up and electrodeposition approaches, demonstrating that such poisoning is universal for Pt catalyzed micromotors. We believe that our findings will contribute significantly to this field to develop alternative systems or catalysts for self-propulsion when practical applications in the real environment are considered. PMID:23450281
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Li, Feng; Li, Jing; Zhang, Jie; Gao, Lili; Long, Xuefeng; Hu, Yiping; Li, Shuwen; Jin, Jun; Ma, Jiantai
2018-05-16
The photoelectrochemical (PEC) water splitting efficiency of hematite-based photoanode is still far from the theoretical value due to its poor surface reaction kinetics and high density of surface trapping states. To solve these drawbacks, a photoanode consisting of NiO nanoparticles anchored on a gradient P-doped α-Fe2O3 nanorod (NR) array (NiO/P-α-Fe2O3) was fabricated to achieve optimal light absorption and charge separation, and rapid surface reaction kinetic. Specifically, the photoanode with the NR arrays structure allowed high mass transport rate to be achieved while the P-doping effectively decreased surface trapping sites and improved the electrical conductivity of α-Fe2O3. Furthermore, the p-n junction formed between the NiO and P-α-Fe2O3 can further improve the PEC performance due to the efficient hole extraction property and water oxidization catalytic activity of NiO. Consequently, the NiO/P-α-Fe2O3 NR photoanode produced a high photocurrent density of 2.08 mA cm-2 at 1.23V vs. RHE and a 110 mV cathodic shift of the onset potential. This rational design of structure offers a new perspective in exploring high performance PEC photoanodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Mori, Kohsuke; Sano, Taiki; Kobayashi, Hisayoshi; Yamashita, Hiromi
2018-06-22
The hydrogenation of carbon dioxide (CO 2 ) to formic acid (FA; HCOOH), a renewable hydrogen storage material, is a promising means of realizing an economical CO 2 -mediated hydrogen energy cycle. The development of reliable heter-ogeneous catalysts is an urgent yet challenging task associated with such systems, although precise catalytic site design protocols are still lacking. In the present study, we demonstrate that PdAg alloy nanoparticles (NPs) supported on TiO 2 promote the efficient selective hydrogenation of CO 2 to give FA even under mild reaction conditions (2.0 MPa, 100 °C). Specimens made using surface engineering with atomic precision reveal a strong correlation between increased cata-lytic activity and decreased electron density of active Pd atoms resulting from a synergistic effect of alloying with Ag atoms. The isolated and electronically promoted surface-exposed Pd atoms in Pd@Ag alloy NPs exhibit a maximum turnover number of 14,839 based on the quantity of surface Pd atoms, which represents a more than ten-fold increase compared to the activity of monometallic Pd/TiO 2 . Kinetic and density functional theory (DFT) calculations show that the attack on the C atom in HCO 3 - by a dissociated H atom over an active Pd site is the rate-determining step during this reaction, and this step is boosted by PdAg alloy NPs having a low Pd/Ag ratio.
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Direct organocatalytic enantioselective functionalization of SiOx surfaces.
Parkin, John David; Chisholm, Ross; Frost, Aileen B; Bailey, Richard G; Smith, Andrew David; Hähner, Georg
2018-06-05
Traditional methods to prepare chiral surfaces involve either the adsorption of a chiral molecule onto an achiral surface, or adsorption of a species that forms a chiral template creating lattices with long range order. To date only limited alternative strategies to prepare chiral surfaces have been studied. In this manuscript a "bottom up" approach is developed that allows the preparation of chiral surfaces by direct enantioselective organocatalysis on a functionalized Si-oxide supported self-assembled monolayer (SAM). The efficient catalytic generation of enantiomerically enriched organic surfaces is achieved using a commercially available homogeneous isothiourea catalyst (HyperBTM) that promotes an enantioselective Michael-lactonization process upon a Si-oxide supported self-assembled monolayer functionalized with a reactive trifluoroenone group. Chiral atomic force microscopy (chi-AFM) is used to probe the enantiomeric enrichment of the organic films by measurement of the force distributions arising from interaction of D- or L-cysteine modified AFM tips and the organic films. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Wang, Jing; Chen, Shuo; Quan, Xie; Yu, Hongtao
2018-01-01
Metal-free carbon materials have been presented to be potential alternatives to metal-based catalysts for heterogeneous catalytic ozonation, yet the catalytic performance still needs to be enhanced. Doping carbon with non-metallic heteroatoms (e.g., N, B, and F) could alter the electronic structure and electrochemical properties of original carbon materials, has been considered to be an effective method for improving the catalytic activity of carbon materials. Herein, fluorine-doped carbon nanotubes (F-CNTs) were synthesized via a facile method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The as-synthesized F-CNTs exhibited notably enhanced catalytic activity towards catalytic ozonation for the degradation of organic pollutants. The oxalic acid removal efficiency of optimized F-CNTs was approximately two times as much as that of pristine CNTs, and even exceeded those of four conventional metal-based catalysts (ZnO, Al 2 O 3 , Fe 2 O 3 , and MnO 2 ). The XPS and Raman studies confirmed that the covalent CF bonds were formed at the sp 3 C sites instead of sp 2 C sites on CNTs, not only resulting in high positive charge density of C atoms adjacent to F atoms, but remaining the delocalized π-system with intact carbon structure of F-CNTs, which then favored the conversion of ozone molecules (O 3 ) into reactive oxygen species (ROS) and contributed to the high oxalic acid removal efficiency. Furthermore, electron spin resonance (ESR) studies revealed that superoxide radicals (O 2 - ) and singlet oxygen ( 1 O 2 ) might be the dominant ROS that responsible for the degradation of oxalic acid in these catalytic systems. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Fukuzumi, Shunichi; Mandal, Sukanta; Mase, Kentaro; Ohkubo, Kei; Park, Hyejin; Benet-Buchholz, Jordi; Nam, Wonwoo; Llobet, Antoni
2012-06-20
Four-electron reduction of O(2) by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-μ-1,2-peroxo complex, 1, in the presence of trifluoroacetic acid in acetonitrile. Kinetic investigations of the overall catalytic reaction and each step in the catalytic cycle showed that proton-coupled electron transfer from Me(8)Fc to 1 is the rate-determining step in the catalytic cycle.
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Nie, Jing; Zhu, Hong-Wei; Cui, Han-Feng; Hua, Ming-Qing; Ma, Jun-An
2007-08-02
A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, Zhili; Chen, Shihua; Li, Yonghe
2014-09-15
Sodium ions of TNWs were exchanged with hydrogen ions, and this protocol was very suitable for capturing high density of cobalt ions. Meanwhile, the fabricated Co{sub 3}O{sub 4}/TNWs nano-material presented a highly catalytic and stable activity for dye degradation. - Highlights: • Co{sub 3}O{sub 4} nanoparticles were deposited on the pretreated TNWs surface. • The TNWs treated by hydrogen ions captures higher density of cobalt ions. • The Co{sub 3}O{sub 4}/TNWs catalyst possesses highly efficiency for dyes degradation with oxone. - Abstract: In this paper, we reported a recyclable and highly active porous catalyst of titanate nanowires (TNWs) coated withmore » well-distributed Co{sub 3}O{sub 4} nanoparticles (NPs) (Co{sub 3}O{sub 4}/TNWs). Sodium ions of TNWs were exchanged with hydrogen ions in the dilute nitric acid, and this protocol was very suitable for capturing cobalt ions. X-ray diffraction (XRD) demonstrated the existence of Co{sub 3}O{sub 4} phase with unique lattice planes, such as (2 2 0), (3 1 1) and (5 1 1). Electron microscopes (FE-SEM and TEM) indicated that the Co{sub 3}O{sub 4} NPs with an average diameter of 22 ± 3 nm were coated uniformly on TNWs surface (average diameter: 37 ± 5.5 nm), and the Co{sub 3}O{sub 4} NPs mainly exposed their (2 2 0) and (2 2 2) active planes. XPS analysis confirms the formation of Co{sub 3}O{sub 4} phase by the presence of Co 2p peaks at 780.1 eV (2p 3/2) and 795.5 eV (2p 1/2). Methylene blue (MB) and other organic dyes (rhodamine B (RhB) and methyl orange (MO)) were chosen as target compounds for catalytic degradation under indoor scattering light. Compared to the original Co{sub 3}O{sub 4}/TNWs catalyst, the catalytic efficiency of nanoscaled catalyst with oxone for MB was about 15 times higher, and the MB solution (10 mg L{sup −1}) was completely degraded within 8 min. The catalytic activity of recycled catalyst used in the sixth run still remained very active, and the degradation time for MB was only 16 min. The nanosized catalyst also had a high activity for dyes of RhB (10 mg L{sup −1}) and MO (10 mg L{sup −1}), as the degradation efficiencies of RhB and MO after 10 min of contact time were about 90.2% and 92.6%, respectively.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Klein, Stefanie; Sommer, Anja; Distel, Luitpold V.R.
Highlights: Black-Right-Pointing-Pointer Ultrasmall citrate-coated SPIONs with {gamma}Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} structure were prepared. Black-Right-Pointing-Pointer SPIONs uptaken by MCF-7 cells increase the ROS production for about 240%. Black-Right-Pointing-Pointer The SPION induced ROS production is due to released iron ions and catalytically active surfaces. Black-Right-Pointing-Pointer Released iron ions and SPION surfaces initiate the Fenton and Haber-Weiss reaction. Black-Right-Pointing-Pointer X-ray irradiation of internalized SPIONs leads to an increase of catalytically active surfaces. -- Abstract: Internalization of citrate-coated and uncoated superparamagnetic iron oxide nanoparticles by human breast cancer (MCF-7) cells was verified by transmission electron microscopy imaging. Cytotoxicity studies employing metabolicmore » and trypan blue assays manifested their excellent biocompatibility. The production of reactive oxygen species in iron oxide nanoparticle loaded MCF-7 cells was explained to originate from both, the release of iron ions and their catalytically active surfaces. Both initiate the Fenton and Haber-Weiss reaction. Additional oxidative stress caused by X-ray irradiation of MCF-7 cells was attributed to the increase of catalytically active iron oxide nanoparticle surfaces.« less
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An efficient system for selectively altering genetic information within mRNAs
Montiel-González, Maria Fernanda; Vallecillo-Viejo, Isabel C.; Rosenthal, Joshua J. C.
2016-01-01
Site-directed RNA editing (SDRE) is a strategy to precisely alter genetic information within mRNAs. By linking the catalytic domain of the RNA editing enzyme ADAR to an antisense guide RNA, specific adenosines can be converted to inosines, biological mimics for guanosine. Previously, we showed that a genetically encoded iteration of SDRE could target adenosines expressed in human cells, but not efficiently. Here we developed a reporter assay to quantify editing, and used it to improve our strategy. By enhancing the linkage between ADAR's catalytic domain and the guide RNA, and by introducing a mutation in the catalytic domain, the efficiency of converting a UAG premature termination codon (PTC) to tryptophan (UGG) was improved from ∼11 % to ∼70 %. Other PTCs were edited, but less efficiently. Numerous off-target edits were identified in the targeted mRNA, but not in randomly selected endogenous messages. Off-target edits could be eliminated by reducing the amount of guide RNA with a reduction in on-target editing. The catalytic rate of SDRE was compared with those for human ADARs on various substrates and found to be within an order of magnitude of most. These data underscore the promise of site-directed RNA editing as a therapeutic or experimental tool. PMID:27557710
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Chang, Yan; Szybist, James P.; Pihl, Josh A.
This is the second part of a two-part investigation of on-board catalytic fuel reforming to increase the brake efficiency of a multicylinder, stoichiometric spark-ignited (SI) engine. In Part 1 of the investigation, we analytically and experimentally characterized the energetics and kinetics of a candidate reforming catalyst over a range of reforming equivalence ratios and oxygen concentration conditions to identify the best conditions for efficient reforming. In the present part of our investigation, we studied an engine strategy that combined exhaust gas recirculation (EGR)–loop reforming with dilution limit extension of the combustion. In our experiments, we found that, under an enginemore » operating condition of 2000 rpm and brake mean effective pressure (4 bar), catalytic EGR reforming made it possible to sustain stable combustion with a volumetric equivalent of 45%–55% EGR. Under this same operating condition with stoichiometric engine exhaust (and no reforming), we were only able to sustain stable combustion with EGR under 25%. In conclusion, these results indicate that multicylinder gasoline engine efficiency can be increased substantially with catalytic reforming combined with and higher EGR operation, resulting in a decrease of more than 8% in fuel consumption, compared to baseline operation.« less
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Chang, Yan; Szybist, James P.; Pihl, Josh A.; ...
2018-01-17
This is the second part of a two-part investigation of on-board catalytic fuel reforming to increase the brake efficiency of a multicylinder, stoichiometric spark-ignited (SI) engine. In Part 1 of the investigation, we analytically and experimentally characterized the energetics and kinetics of a candidate reforming catalyst over a range of reforming equivalence ratios and oxygen concentration conditions to identify the best conditions for efficient reforming. In the present part of our investigation, we studied an engine strategy that combined exhaust gas recirculation (EGR)–loop reforming with dilution limit extension of the combustion. In our experiments, we found that, under an enginemore » operating condition of 2000 rpm and brake mean effective pressure (4 bar), catalytic EGR reforming made it possible to sustain stable combustion with a volumetric equivalent of 45%–55% EGR. Under this same operating condition with stoichiometric engine exhaust (and no reforming), we were only able to sustain stable combustion with EGR under 25%. In conclusion, these results indicate that multicylinder gasoline engine efficiency can be increased substantially with catalytic reforming combined with and higher EGR operation, resulting in a decrease of more than 8% in fuel consumption, compared to baseline operation.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan
We report the critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has beenmore » used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. Lastly, these observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles-which contain metal atoms with low coordination numbers-are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.« less
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NASA Astrophysics Data System (ADS)
Liu, Baocang; Wang, Qin; Yu, Shengli; Jing, Peng; Liu, Lixia; Xu, Guangran; Zhang, Jun
2014-09-01
Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd2+ ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus greatly accelerating the reaction speed. Owing to its structural features, yolk-double-shell Pd@TiO2/Pd@TiO2 architecture exhibits extremely high catalytic performance on the Suzuki-Miyaura coupling reaction. The synthetic methodologies are robust for fabricating double-shell architectures with various configurations for applications such as in catalysis, drug delivery, and medicine release. The obtained double-shell architectures may be used as novel catalyst systems with highly efficient catalytic performance for other catalytic reactions.Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd2+ ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus greatly accelerating the reaction speed. Owing to its structural features, yolk-double-shell Pd@TiO2/Pd@TiO2 architecture exhibits extremely high catalytic performance on the Suzuki-Miyaura coupling reaction. The synthetic methodologies are robust for fabricating double-shell architectures with various configurations for applications such as in catalysis, drug delivery, and medicine release. The obtained double-shell architectures may be used as novel catalyst systems with highly efficient catalytic performance for other catalytic reactions. Electronic supplementary information (ESI) available: Synthetic schemes, TEM, SEM, XRD, FTIR, UV-DRS spectra, TPR, and catalytic data. See DOI: 10.1039/c4nr02692f
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About complex refractive index of black Si
NASA Astrophysics Data System (ADS)
Pinčík, Emil; Brunner, Robert; Kobayashi, Hikaru; Mikula, Milan
2017-12-01
The paper deals with the complex refractive index in the IR light region of two types of samples (i) as prepared black silicon, and (ii) thermally oxidized black silicon (BSi) nano-crystalline specimens produced both by the surface structure chemical transfer method using catalytic Ag evaporated spots (as prepared sample) and by the catalytic Pt catalytic mesh (thermally oxidized sample). We present, compare, and discuss the values of the IR complex refractive index obtained by calculation using the Kramers-Krönig transformation. Results indicate that small differences between optical properties of as prepared black Si and thermally oxidized BSi are given by: (i) - oxidation procedure, (ii) - thickness of the formed black Si layer, mainly, not by utilization of different catalytic metals, and by iii) the different thickness. Contamination of the surface by different catalytic metals contributes almost equally to the calculated values of the corresponding complex refractive index.
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Zhang, Hao; Xu, Xiaobin; Lin, Haifeng; Ud Din, Muhammad Aizaz; Wang, Haiqing; Wang, Xun
2017-09-14
Ultrathin nanocrystals generally provide a remarkable catalytic performance due to their high specific surface area and exposure of certain active sites. However, deactivation caused by growth and gathering limits the catalytic application of ultrathin nanocrystals. Here we report Ag nanocrystal-decorated polyoxometalate (Ag-POM) single-walled nanotubes assembled via a concise, surfactant-free soaking method as a new kind of well-defined core-sheath nanoreactor. The diameter of Ag nanocrystals inside polyoxometalate nanotubes can be controlled via simply adjusting the reactant concentration. Ag-POM provided outstanding oxidative desulfurization (ODS) catalytic performance for aromatic sulfocompounds at room temperature. It was suggested that Ag nanocrystals decorated on the inner surface played a key role in adjusting the electronic distribution and enhancing the catalytic activity. The as-prepared Ag-POM nanotubes are promising candidate catalysts with enhanced performance for practical catalytic applications in the gasoline desulfurization industry.
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Acid–base catalysis over perovskites: a review
DOE Office of Scientific and Technical Information (OSTI.GOV)
Polo-Garzon, Felipe; Wu, Zili
We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studiedmore » by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to achieve desired selectivities and enhanced rates.« less
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Acid–base catalysis over perovskites: a review
Polo-Garzon, Felipe; Wu, Zili
2018-01-15
We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studiedmore » by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to achieve desired selectivities and enhanced rates.« less
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Operando Positron Annihilation Gamma Spectrometer (OPAGS)
NASA Astrophysics Data System (ADS)
Satyal, S.; Shastry, K.; Mukherjee, S.; Weiss, A. H.
2009-03-01
Surface properties measured under UHV conditions cannot be extended to surfaces interacting with gases under realistic pressures due to surface reconstruction and other strong perturbations of the surface. Surface probing techniques require UHV conditions to perform efficiently and avoid data loss due to scattering of outgoing particles. This poster describes the design of an Operando Positron Annihilation Gamma Spectrometer (OPAGS) currently under construction at the University of Texas at Arlington. The new system will be capable of obtaining surface and defect specific chemical and charge state information from surfaces under realistic pressures. Differential pumping will be used to maintain the sample in a gas environment while the rest of the beam is under UHV. Elemental content of the surface interacting with the gas environment will be determined from the Doppler broadened gamma spectra. This system will also include a time of flight (TOF) Auger spectrometer which correlates with the results of the Doppler measurements at lower pressures. By employing the unique capabilities of OPAGS together with those of the TOF PAES spectroscopy the charge transfer mechanisms at the surface in catalytic systems can be understood.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Barroo, Cedric; Janvelyan, Nare; Zugic, Branko
To improve the understanding of catalytic processes, the surface structure and composition of the active materials need to be determined before and after reaction. Morphological changes may occur under reaction conditions and can dramatically influence the reactivity and/or selectivity of a catalyst. Goldbased catalysts with different architectures are currently being developed for selective oxidation reactions at low temperatures. Specifically, nanoporous Au (npAu) with a composition of Au 97-Ag 3 is obtained by dealloying a Ag 70-Au 30 bulk alloy. Recent studies highlight the efficiency of npAu catalysts for methanol oxidation using ozone to activate the catalysts before methanol oxidation. Inmore » this paper, we studied the morphological and compositional changes occurring at the surface of Au-based catalysts in certain conditions.« less
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Carbohydrates as efficient catalysts for the hydration of α-amino nitriles.
Chitale, Sampada; Derasp, Joshua S; Hussain, Bashir; Tanveer, Kashif; Beauchemin, André M
2016-11-01
Directed hydration of α-amino nitriles was achieved under mild conditions using simple carbohydrates as catalysts exploiting temporary intramolecularity. A broadly applicable procedure using both formaldehyde and NaOH as catalysts efficiently hydrated a variety of primary and secondary susbtrates, and allowed the hydration of enantiopure substrates to proceed without racemization. This work also provides a rare comparison of the catalytic activity of carbohydrates, and shows that the simple aldehydes at the basis of chemical evolution are efficient organocatalysts mimicking the function of hydratase enzymes. Optimal catalytic efficiency was observed with destabilized aldehydes, and with difficult substrates only simple carbohydrates such as formaldehyde and glycolaldehyde proved reliable.
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The DUSP–Ubl domain of USP4 enhances its catalytic efficiency by promoting ubiquitin exchange
Clerici, Marcello; Luna-Vargas, Mark P. A.; Faesen, Alex C.; Sixma, Titia K.
2014-01-01
Ubiquitin-specific protease USP4 is emerging as an important regulator of cellular pathways, including the TGF-β response, NF-κB signalling and splicing, with possible roles in cancer. Here we show that USP4 has its catalytic triad arranged in a productive conformation. Nevertheless, it requires its N-terminal DUSP–Ubl domain to achieve full catalytic turnover. Pre-steady-state kinetics measurements reveal that USP4 catalytic domain activity is strongly inhibited by slow dissociation of ubiquitin after substrate hydrolysis. The DUSP–Ubl domain is able to enhance ubiquitin dissociation, hence promoting efficient turnover. In a mechanism that requires all USP4 domains, binding of the DUSP–Ubl domain promotes a change of a switching loop near the active site. This ‘allosteric regulation of product discharge’ provides a novel way of regulating deubiquitinating enzymes that may have relevance for other enzyme classes. PMID:25404403
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Fan, Shuqin; Hou, Chuantao; Liang, Bo; Feng, Ruirui; Liu, Aihua
2015-09-01
In this work, a bacterial surface displaying enzyme based two-compartment biofuel cell for the direct electrical energy conversion from degradation products of lignocellulosic biomass is reported. Considering that the main degradation products of the lignocellulose are glucose and xylose, xylose dehydrogenase (XDH) displayed bacteria (XDH-bacteria) and glucose dehydrogenase (GDH) displayed bacteria (GDH-bacteria) were used as anode catalysts in anode chamber with methylene blue as electron transfer mediator. While the cathode chamber was constructed with laccase/multi-walled-carbon nanotube/glassy-carbon-electrode. XDH-bacteria exhibited 1.75 times higher catalytic efficiency than GDH-bacteria. This assembled enzymatic fuel cell exhibited a high open-circuit potential of 0.80 V, acceptable stability and energy conversion efficiency. Moreover, the maximum power density of the cell could reach 53 μW cm(-2) when fueled with degradation products of corn stalk. Thus, this finding holds great potential to directly convert degradation products of biomass into electrical energy. Copyright © 2015 Elsevier Ltd. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander
Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulkmore » of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction.« less
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Lu, Jun-Bo; Ma, Xue-Lu; Wang, Jia-Qi; Liu, Jin-Cheng; Xiao, Hai; Li, Jun
2018-05-10
Model systems of the FeMo cofactor of nitrogenase have been explored extensively in catalysis to gain insights into their ability for nitrogen fixation that is of vital importance to the human society. Here we investigate the trigonal pyramidal borane-ligand Fe complex by first-principles calculations, and find that the variation of oxidation state of Fe along the reaction path correlates with that of the reverse-dative Fe → B bonding. The redox-flexibility of the reverse-dative Fe → B bonding helps to provide an electron reservoir that buffers and stabilizes the evolution of Fe oxidation state, which is essential for forming the key intermediates of N 2 activation. Our work provides insights for understanding and optimizing homogeneous and surface single-atom catalysts with reverse-dative donating ligands for efficient dinitrogen fixation. The extension of this kind of molecular catalytic active center to heterogeneous catalysts with surface single-clusters is also discussed.
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Lee, Hochun; Jung, Yongju; Kim, Seok
2012-02-01
In the present work, we had studied the graphite nanofibers as catalyst supports after a plasma treatment for studying the effect of surface modification. By controlling the plasma intensity, a surface functional group concentration was changed. The nanoparticle size, loading efficiency, and catalytic activity were studied, after Pt-Ru deposition by a chemical reduction. Pt-Ru catalysts deposited on the plasma-treated GNFs showed the smaller size, 3.58 nm than the pristine GNFs. The catalyst loading contents were enhanced with plasma power and duration time increase, meaning an enhanced catalyst deposition efficiency. Accordingly, cyclic voltammetry result showed that the specific current density was increased proportionally till 200 W and then the value was decreased. Enhanced activity of 40 (mA mg(-1)-catalyst) was accomplished at 200 W and 180 sec duration time. Consequently, it was found that the improved electroactivity was originated from the change of size or morphology of catalysts by controlling the plasma intensity.
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Wu, Yishang; Liu, Xiaojing; Han, Dongdong; Song, Xianyin; Shi, Lei; Song, Yao; Niu, Shuwen; Xie, Yufang; Cai, Jinyan; Wu, Shaoyang; Kang, Jian; Zhou, Jianbin; Chen, Zhiyan; Zheng, Xusheng; Xiao, Xiangheng; Wang, Gongming
2018-04-12
Metal sulfides for hydrogen evolution catalysis typically suffer from unfavorable hydrogen desorption properties due to the strong interaction between the adsorbed H and the intensely electronegative sulfur. Here, we demonstrate a general strategy to improve the hydrogen evolution catalysis of metal sulfides by modulating the surface electron densities. The N modulated NiCo 2 S 4 nanowire arrays exhibit an overpotential of 41 mV at 10 mA cm -2 and a Tafel slope of 37 mV dec -1 , which are very close to the performance of the benchmark Pt/C in alkaline condition. X-ray photoelectron spectroscopy, synchrotron-based X-ray absorption spectroscopy, and density functional theory studies consistently confirm the surface electron densities of NiCo 2 S 4 have been effectively manipulated by N doping. The capability to modulate the electron densities of the catalytic sites could provide valuable insights for the rational design of highly efficient catalysts for hydrogen evolution and beyond.
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Nanocrystalline ZnO as a Visible Active Photocatalyst for the Degradation of Benzene-1,4-diol
NASA Astrophysics Data System (ADS)
Ramachandran, Saranya; Sivasamy, A.
We have synthesized nanocrystalline ZnO by a simple precipitation method. The prepared ZnO was found to be highly phase pure and nanocrystalline hexagonal wurtzite structure. UV-Visible-DRS spectroscopy showed the material to have bandgap energy of 3.22eV. HR-SEM image revealed the material to be made up of distinct hexagonal particles with a highly porous surface. AFM analysis was employed to confirm the high surface roughness and porosity of the material. The photocatalytic activity of the prepared ZnO was evaluated by the degradation of benzene-1,4-diol (hydroquinone), under visible light irradiation. Preliminary experiments showed the catalyst to be effective at neutral pH with an optimum catalyst dosage of 4g/L. Kinetic studies showed the degradation reaction to follow pseudo-first-order kinetics. In the presence of commonly used industrial electrolytes, the catalyst exhibited a decrease in efficiency. Reusability studies showed the catalytic efficiency of ZnO to diminish marginally after the third cycle of reuse.
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Mistry, Hemma; Choi, Yong-Wook; Bagger, Alexander; ...
2017-07-14
Efficient, stable catalysts with high selectivity for a single product are essential if electroreduction of CO 2 is to become a viable route to the synthesis of industrial feedstocks and fuels. A plasma oxidation pre-treatment of silver foil enhances the number of low-coordinated catalytically active sites, which dramatically lowers the overpotential and increases the activity of CO 2 electroreduction to CO. At -0.6 V versus RHE more than 90 % Faradaic efficiency towards CO was achieved on a pre-oxidized silver foil. While transmission electron microscopy (TEM) and operando X-ray absorption spectroscopy showed that oxygen species can survive in the bulkmore » of the catalyst during the reaction, quasi in situ X-ray photoelectron spectroscopy showed that the surface is metallic under reaction conditions. Finally, DFT calculations reveal that the defect-rich surface of the plasma-oxidized silver foils in the presence of local electric fields drastically decrease the overpotential of CO 2 electroreduction.« less
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NASA Astrophysics Data System (ADS)
Hassan, N.; Ismail, K. N.; Hamid, K. H. Ku; Hadi, Abdul
2018-05-01
Depletion of fossil fuel sources in a few decades due to industrialization and motorization has led to a keen interest in the production of alternative fuels like biodiesel. Research on the development and improvement of more efficient transesterification process for biodiesel production has attain great attention in the last decade. The using of low cost catalyst is one of the main focuses on the biodiesel production. As a basic heterogeneous catalyst, CaO has been examined in the transesterification of vegetable oils for biodiesel production. In this research, calcium oxide (CaO-X) catalysts were prepared by sol-gel method at different Ca2+ precursor concentration (X = 1.0, 1.5, 2.0 M). The crystalline structure and morphology of the synthesized catalysts were characterized by means of x-ray diffraction (XRD) and N2 adsorption-desorption analysis. All the synthesized catalysts were then applied to transesterification reaction of palm oil to produce biodiesel. The characterization by x-ray diffraction demonstrate CaO-1.0 was partially hydrated due to the incomplete reaction during synthesis. As a matter of fact, formation of H2O on the surface of CaO causes lower basic strength of the catalysts, thus responsible in lowering the catalytic activity. It is demonstrated that CaO-2.0 exhibits mesoporous structure with least chemisorb amount of H2O on the catalysts surface has a very active catalytic activity. It was found that 2.0M of calcium precursor has high catalytic activity and 81% FAME yield was obtained within 3h reaction.
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NASA Astrophysics Data System (ADS)
Pretzer, Lori A.
Transition metal nanomaterials are used to catalyze many chemical reactions, including those key to environmental, medicinal, and petrochemical fields. Improving their catalytic properties and lifetime would have significant economic and environmental rewards. Potentially expedient options to make such advancements are to alter the shape, size, or composition of transition metal nanocatalysts. This work investigates the relationships between structure and catalytic properties of synthesized Au, Pd-on-Au, and Au-enzyme model transition metal nanocatalysts. Au and Pd-on-Au nanomaterials were studied due to their wide-spread application and structure-dependent electronic and geometric properties. The goal of this thesis is to contribute design procedures and synthesis methods that enable the preparation of more efficient transition metal nanocatalysts. The influence of the size and composition of Pd-on-Au nanoparticles (NPs) was systematically investigated and each was found to affect the catalyst's surface structure and catalytic properties. The catalytic hydrodechlorination of trichloroethene and reduction of 4-nitrophenol by Pd-on-Au nanoparticles were investigated as these reactions are useful for environmental and pharmaceutical synthesis applications, respectively. Structural characterization revealed that the dispersion and oxidation state of surface Pd atoms are controlled by the Au particle size and concentration of Pd. These structural changes are correlated with observed Pd-on-Au NP activities for both probe reactions, providing new insight into the structure-activity relationships of bimetallic nanocatalysts. Using the structure-dependent electronic properties of Au NPs, a new type of light-triggered biocatalyst was prepared and used to remotely control a model biochemical reaction. This biocatalyst consists of a model thermophilic glucokinase enzyme covalently attached to the surface of Au nanorods. The rod-like shape of the Au nanoparticles made the thermophilic-enzyme complexes responsive to near infrared electromagnetic radiation, which is absorbed minimally by biological tissues. When enzyme-Au nanorod complexes are illuminated with a near-infrared laser, thermal energy is generated which activates the thermophilic enzyme. Enzyme-Au nanorod complexes encapsulated in calcium alginate are reusable and stable for several days, making them viable for industrial applications. Lastly, highly versatile Au nanoparticles with diameters of ~3-12 nm were prepared using carbon monoxide (CO) to reduce a Au salt precursor onto preformed catalytic Au particles. Compared to other reducing agents used to generate metallic NPs, CO can be used at room temperature and its oxidized form does not interfere with the colloidal stability of NPs suspended in water. Controlled synthesis of different sized particles was verified through detailed ultraviolet-visible spectroscopy, small angle X-ray scattering, and transmission electron microscopy measurements. This synthesis method should be extendable to other monometallic and multimetallic compositions and shapes, and can be improved by using preformed particles with a narrower size distribution.
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Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar
2012-01-01
A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.
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Remarkable support effect on the reactivity of Pt/In2O3/MOx catalysts for methanol steam reforming
NASA Astrophysics Data System (ADS)
Liu, Xin; Men, Yong; Wang, Jinguo; He, Rong; Wang, Yuanqiang
2017-10-01
Effects of supports over Pt/In2O3/MOx catalysts with extremely low loading of Pt (1 wt%) and In2O3 loadings (3 wt%) are investigated for the hydrogen production of methanol steam reforming (MSR) in the temperature range of 250-400 °C. Under practical conditions without the pre-reduction, the 1Pt/3In2O3/CeO2 catalyst shows the highly efficient catalytic performance, achieving almost complete methanol conversion (98.7%) and very low CO selectivity of 2.6% at 325 °C. The supported Pt/In2O3 catalysts are characterized by means of Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), high-resolution transmission microscopy (HRTEM), temperature programmed reduction with hydrogen (H2-TPR), CO pulse chemisorption, temperature programmed desorption of methanol and water (CH3OH-TPD and H2O-TPD). These demonstrate that the nature of catalyst support of Pt/In2O3/MOx plays crucial roles in the Pt dispersion associated by the strong interaction among Pt, In2O3 and supporting materials and the surface redox properties at low temperature, and thus affects their capability to activate the reactants and determines the catalytic activity of methanol steam reforming. The superior 1Pt/3In2O3/CeO2 catalyst, exhibiting a remarkable reactivity and stability for 32 h on stream, demonstrates its potential for efficient hydrogen production of methanol steam reforming in mobile and de-centralized H2-fueled PEMFC systems.
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NASA Astrophysics Data System (ADS)
Sun, Lan; Wang, Tao; Zhang, Long; Sun, Yunjin; Xu, Kewei; Dai, Zhengfei; Ma, Fei
2018-02-01
The rational design and preparation of earth-abundant, stable and efficient electrocatalysts for hydrogen production is currently the subject in extensive scientific and technological researches toward the future of a clean-energy society. Herein, a mace-like MoS2/NiCo2S4 hierarchical structure is designed and synthesized on carbon fiber paper via a facile hydrothermal method, and evaluated as electrocatalyst for hydrogen evolution reaction. In the MoS2/NiCo2S4/carbon fiber paper hierarchical structures, MoS2 nanosheets are dispersively distributed on the surface of NiCo2S4 nanowires, which provides an enlarged surface area, abundant interfaces and catalytic active sites. As for hydrogen evolution reaction, such MoS2/NiCo2S4/carbon fiber paper heterostructures give rise to a hydrogen evolution reaction catalytic current density of 10 mA cm-2 with a lower overpotential of 139 mV and a smaller Tafel slope of 37 mV·dec-1 than those of MoS2/carbon fiber paper and NiCo2S4/carbon fiber paper counterparts, exhibiting a prominent electrocatalytic performance. Moreover, the electrocatalytic properties change little after 5000 CV cycles and continual electrolysis for 12 h without obvious decay, respectively, demonstrating high durability and stability. The excellent hydrogen evolution reaction performances endow the hierarchical configuration MoS2/NiCo2S4/carbon fiber paper with promising alternative in HER and other related renewable energy fields.
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Engineering New Catalysts for In-Process Elimination of Tars
DOE Office of Scientific and Technical Information (OSTI.GOV)
Felix, Larry G.
2012-09-30
The key objective of this project was to develop a new and more efficient methodology for engineering and economically producing optimized robust catalysts for the reduction or elimination of tars in biomass gasification. Whereas current catalyst technology typically disposes thin layers of catalytically-active material onto rigid supports via wet chemistry-based methods, this project investigated novel thermal methods for directly incorporating catalytically active materials onto robust supports as well as novel approaches for incorporating catalytically active materials on and/or within an otherwise inert refractory support material which is then subsequently formed and processed to create a catalytically-active material on all exposedmore » surfaces. Specifically, the focus of this engineered catalyst development was on materials which were derived from, or otherwise related to, olivine-like minerals, due to the inherent attrition resistance and moderate catalytic properties exhibited by natural olivine when used in a fluidized bed biomass gasifier. Task 1 of this project successfully demonstrated the direct thermal impregnation of catalytically-active materials onto an olivine substrate, with the production of a Ni-olivine catalyst. Nickel and nickel oxide were thermally impregnated onto an olivine substrate and when reduced were shown to demonstrate improved catalytic activity over the baseline olivine material and equal the tar-decomposing performance of Ni-olivine catalysts prepared by conventional wet impregnation. Task 2 involved coordination with our subcontracted project partners to further develop and characterize catalyst formulations and to optimize activity and production methods. Within this task, several significant new materials were developed. NexTech Materials developed a sintered ceramic nickel-magnesium-silicate catalyst that demonstrated superb catalytic activity and high resistance to deactivation by H2S. Alfred University developed both supported and integrated (bulk) catalysts via a glass-ceramic processing route which were shown to exhibit excellent catalytic activity and superior resistance to attrition deactivation. With the discovery of these active, robust, glass-based catalysts, and with the permission of the project officer, the investigation of waste-based materials as originally proposed for Task 3 and pilot-scale testing proposed in Task 5 were deferred indefinitely in favor of further investigation of the glass-ceramic based catalyst materials. This choice was justified in part because during FY 2006 and through FY 2007, funding restrictions imposed by congressional budget choices significantly reduced funding for DOE biomass-related projects. Funding for this project was limited to what had been authorized which slowed the pace of project work at GTI so that our project partners could continue in their work. Thereafter, project work was allowed to resume and with restored funding, the project continued and concentrated on the development and testing of glass-ceramic catalysts in bulk or supported formats. Work concluded with a final development devoted to increasing the surface area of glass-ceramic catalysts in the form of microspheres. Following that development, project reporting was completed and the project was concluded.« less
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Liu, Guoxue; Chen, Hongbin; Xia, Lu; Wang, Suqing; Ding, Liang-Xin; Li, Dongdong; Xiao, Kang; Dai, Sheng; Wang, Haihui
2015-10-14
Perovskites show excellent specific catalytic activity toward both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline solutions; however, small surface areas of the perovskites synthesized by traditional sol-gel methods lead to low utilization of catalytic sites, which gives rise to poor Li-O2 batteries performance and restricts their application. Herein, a hierarchical mesporous/macroporous perovskite La0.5Sr0.5CoO3-x (HPN-LSC) nanotube is developed to promote its application in Li-O2 batteries. The HPN-LSC nanotubes were synthesized via electrospinning technique followed by postannealing. The as-prepared HPN-LSC catalyst exhibits outstanding intrinsic ORR and OER catalytic activity. The HPN-LSC/KB electrode displays excellent performance toward both discharge and charge processes for Li-O2 batteries, which enhances the reversibility, the round-trip efficiency, and the capacity of resultant batteries. The synergy of high catalytic activity and hierarchical mesoporous/macroporous nanotubular structure results in the Li-O2 batteries with good rate capability and excellent cycle stability of sustaining 50 cycles at a current density of 0.1 mA cm(-2) with an upper-limit capacity of 500 mAh g(-1). The results will benefit for the future development of high-performance Li-O2 batteries using hierarchical mesoporous/macroporous nanostructured perovskite-type catalysts.
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Sun, Qi; Jin, Yingyin; Aguila, Briana; Meng, Xiangju; Ma, Shengqian; Xiao, Feng-Shou
2017-03-22
Direct use of atmospheric CO 2 as a C 1 source to synthesize high-value chemicals through environmentally benign processes is of great interest, yet challenging. Porous heterogeneous catalysts that are capable of simultaneously capturing and converting CO 2 are promising candidates for such applications. Herein, a family of organic ionic polymers with nanoporous structure, large surface area, strong affinity for CO 2 , and very high density of catalytic active sites (halide ions) was synthesized through the free-radical polymerization of vinylfunctionalized quaternary phosphonium salts. The resultant porous ionic polymers (PIPs) exhibit excellent activities in the cycloaddition of epoxides with atmospheric CO 2 , outperforming the corresponding soluble phosphonium salt analogues and ranking among the highest of known metal-free catalytic systems. The high CO 2 uptake capacity of the PIPs facilitates the enrichment of CO 2 molecules around the catalytic centers, thereby benefiting its conversion. We have demonstrated for the first time that atmospheric CO 2 can be directly converted to cyclic carbonates at room temperature using a heterogeneous catalytic system under metal-solvent free conditions. Moreover, the catalysts proved to be robust and fully recyclable, demonstrating promising potential for practical utilization for the chemical fixation of CO 2 . Our work thereby paves a way to the advance of PIPs as a new type of platform for capture and conversion of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.
2018-03-01
Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.
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NASA Astrophysics Data System (ADS)
Nan, Hui; Han, Jianhua; Luo, Qiang; Yin, Xuewen; Zhou, Yu; Yao, Zhibo; Zhao, Xiaochong; Li, Xin; Lin, Hong
2018-04-01
Exploiting efficient Pt-free counter-electrode materials with low cost and highly catalytic property is a hot topic in the field of Dye-sensitized solar cells (DSCs). Here, NiCo2S4/reduced graphene oxide (RGO) was prepared via an economical synthesis route, and the as-prepared composite exhibited comparable electrocatalytic property with the conventional Pt electrode as the counter-electrode. Notably, the introduction of RGO into the NiCo2S4 counter-electrode induces a significantly promoted electrocatalytic rate towards the triiodide reduction than that of pristine NiCo2S4 by increasing surface area in the composite electrode, as revealed by electrochemical impedance spectroscopic measurement and Tafel polarization measurement. The easy synthesis, low cost and excellent electrochemical performance of the NiCo2S4/RGO composites enable themselves to serve as promising counter-electrode candidates for efficient DSCs.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kong, Aiguo, E-mail: agkong@chem.ecnu.edu.cn; Fan, Xiaohong; Chen, Aoling
An in-situ MgO-templating synthesis route was introduced to obtain the mesoporous nitrogen-doped carbon microfibers by thermal conversion of new Mg-2,2′-biquinoline 4,4-dicarboxy acid coordination compound (Mg-DCA) microfibers. The investigated crystal structure of Mg-DCA testified that the assembling of Mg{sup 2+} and DCA through Mg-O coordination bond and hydrogen bond contributed to the formation of one-dimensional (1D) crystalline Mg-DCA microfibers. The nitrogen-doped carbons derived from the pyrolysis of Mg-DCA showed the well-defined microfiber morphology with high mesopore-surface area. Such mesoporous microfibers exhibited the efficient catalytic activity for oxygen reduction reaction (ORR) in alkaline solutions with better stability and methanol-tolerance performance. - Graphicalmore » abstract: Mesoporous nitrogen-doped carbon microfibers with efficient oxygen electroreduction activity were prepared by thermal conversion of new Mg-biquinoline-based coordination compound microfibers.« less
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Bedford, Nicholas M; Hughes, Zak E; Tang, Zhenghua; Li, Yue; Briggs, Beverly D; Ren, Yang; Swihart, Mark T; Petkov, Valeri G; Naik, Rajesh R; Knecht, Marc R; Walsh, Tiffany R
2016-01-20
Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction data and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.
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Synthesis and activity of histidine-containing catalytic peptide dendrimers.
Delort, Estelle; Nguyen-Trung, Nhat-Quang; Darbre, Tamis; Reymond, Jean-Louis
2006-06-09
Peptide dendrimers built by iteration of the diamino acid dendron Dap-His-Ser (His = histidine, Ser = Serine, Dap = diamino propionic acid) display a strong positive dendritic effect for the catalytic hydrolysis of 8-acyloxypyrene 1,3,6-trisulfonates, which proceeds with enzyme-like kinetics in aqueous medium (Delort, E.; Darbre, T.; Reymond, J.-L. J. Am. Chem. Soc. 2004, 126, 15642-3). Thirty-two mutants of the original third generation dendrimer A3 ((Ac-His-Ser)8(Dap-His-Ser)4(Dap-His-Ser)2Dap-His-Ser-NH2) were prepared by manual synthesis or by automated synthesis with use of a Chemspeed PSW1100 peptide synthesizer. Dendrimer catalysis was specific for 8-acyloxypyrene 1,3,6-trisulfonates, and there was no activity with other types of esters. While dendrimers with hydrophobic residues at the core and histidine residues at the surface only showed weak activity, exchanging serine residues in dendrimer A3 against alanine (A3A), beta-alanine (A3B), or threonine (A3C) improved catalytic efficiency. Substrate binding was correlated with the total number of histidines per dendrimer, with an average of three histidines per substrate binding site. The catalytic rate constant kcat depended on the placement of histidines within the dendrimers and the nature of the other amino acid residues. The fastest catalyst was the threonine mutant A3C ((Ac-His-Thr)8(Dap-His-Thr)4(Dap-His-Thr)2Dap-His-Thr-NH2), with kcat = 1.3 min(-1), kcat/k(uncat) = 90'000, KM = 160 microM for 8-bytyryloxypyrene 1,3,6-trisulfonate, corresponding to a rate acceleration of 18'000 per catalytic site and a 5-fold improvement over the original sequence A3.
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Yoshida, Hiromi; Yoshihara, Akihide; Ishii, Tomohiko; Izumori, Ken; Kamitori, Shigehiro
2016-12-01
Pseudomonas cichorii D-tagatose 3-epimerase (PcDTE), which has a broad substrate specificity, efficiently catalyzes the epimerization of not only D-tagatose to D-sorbose but also D-fructose to D-psicose (D-allulose) and also recognizes the deoxy sugars as substrates. In an attempt to elucidate the substrate recognition and catalytic reaction mechanisms of PcDTE for deoxy sugars, the X-ray structures of the PcDTE mutant form with the replacement of Cys66 by Ser (PcDTE_C66S) in complexes with deoxy sugars were determined. These X-ray structures showed that substrate recognition by the enzyme at the 1-, 2-, and 3-positions is responsible for enzymatic activity and that substrate-enzyme interactions at the 4-, 5-, and 6-positions are not essential for the catalytic reaction of the enzyme leading to the broad substrate specificity of PcDTE. They also showed that the epimerization site of 1-deoxy 3-keto D-galactitol is shifted from C3 to C4 and that 1-deoxy sugars may bind to the catalytic site in the inhibitor-binding mode. The hydrophobic groove that acts as an accessible surface for substrate binding is formed through the dimerization of PcDTE. In PcDTE_C66S/deoxy sugar complex structures, bound ligand molecules in both the linear and ring forms were detected in the hydrophobic groove, while bound ligand molecules in the catalytic site were in the linear form. This result suggests that the sugar-ring opening of a substrate may occur in the hydrophobic groove and also that the narrow channel of the passageway to the catalytic site allows a substrate in the linear form to pass through.
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Pan, Yuxiang; Wan, Zijian; Zhong, Longjie; Li, Xueqin; Wu, Qi; Wang, Jun; Wang, Ping
2017-06-01
Okadaic acid (OA) is a marine toxin ingested by shellfish. In this work, a simple, sensitive and label-free gap-based electrical competitive bioassay has been developed for this biotoxin detection. The gap-electrical biosensor is constructed by modifying interdigitated microelectrodes with gold nanoparticles (AuNPs) and using the self-catalytic growth of AuNPs as conductive bridges. In this development, the AuNPs growth is realized in the solution of glucose and chloroauric acid, with glucose oxidation used as the catalysis for growth of the AuNPs. The catalytic reaction product H 2 O 2 in turn reduces chloroauric acid to make the AuNPs grow. The conductance signal amplification is directly determined by the growth efficiency of AuNPs and closely related to the catalytic activity of AuNPs upon their interaction with OA molecule and OA aptamer. In the absence of OA molecule, the OA aptamer can absorb onto the surfaces of AuNPs due to electrostatic interaction, and the catalytically active sites of AuNPs are fully blocked. Thus the AuNPs growth would not happen. In contrast, the presence of OA molecule can hinder the interaction of OA aptamer and AuNPs. Then the AuNPs sites are exposed and the catalytic growth induces the conductance signal change. The results demonstrated that developed biosensor was able to specifically respond to OA ranging from 5 ppb to 80 ppb, providing limit of detection of 1 ppb. The strategy is confirmed to be effective for OA detection, which indicates the label-free OA biosensor has great potential to offer promising alternatives to the traditional analytical and immunological methods for OA detection.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Dong, Xinbo; Wang, Danjun; College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an 716000
2014-09-15
Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalystmore » is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.« less
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Patterned structures of graphene and graphitic carbon and methods for their manufacture
Polsky, Ronen; Xiao, Xiaoyin; Burckel, David Bruce; Wheeler, David R.; Brozik, Susan M.; Beechem, Thomas Edwin
2017-01-03
A patterned graphene or graphitic body is produced by providing a three-dimensionally patterned carbonaceous body; coating the body with a catalytic metal whereby is formed a coating having an inner surface proximal the body and an outer surface distal the body; and annealing the coated body under time and temperature conditions effective to form a graphene or graphitic layer on the outer surface of the catalytic metal coating.
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Patterned structures of graphene and graphitic carbon and methods for their manufacture
DOE Office of Scientific and Technical Information (OSTI.GOV)
Polsky, Ronen; Xiao, Xiaoyin; Burckel, David Bruce
A patterned graphene or graphitic body is produced by providing a three-dimensionally patterned carbonaceous body; coating the body with a catalytic metal whereby is formed a coating having an inner surface proximal the body and an outer surface distal the body; and annealing the coated body under time and temperature conditions effective to form a graphene or graphitic layer on the outer surface of the catalytic metal coating.
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Inhibition of human papillomavirus expression using DNAzymes.
Benítez-Hess, María Luisa; Reyes-Gutiérrez, Pablo; Alvarez-Salas, Luis Marat
2011-01-01
Deoxyribozymes (DXZs) are catalytic oligodeoxynucleotides capable of performing diverse functions including the specific cleavage of a target RNA. These molecules represent a new type of therapeutic oligonucleotides combining the efficiency of ribozymes and the intracellular endurance and simplicity of modified antisense oligonucleotides. Commonly used DXZs include the 8-17 and 10-23 motifs, which have been engineered to destroy disease-associated genes with remarkable efficiency. Targeting DXZs to disease-associated transcripts requires extensive biochemical testing to establish target RNA accessibility, catalytic efficiency, and nuclease sensibility. The usage of modified nucleotides to render nuclease-resistance DXZs must be counterweighted against deleterious consequences on catalytic activity. Further intracellular testing is required to establish the effect of microenvironmental conditions on DXZ activity and off-target issues. Application of modified DXZs to cervical cancer results in specific growth inhibition, cell death, and apoptosis. Thus, DXZs represent a highly effective antisense moiety with minimal secondary effects.
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NASA Astrophysics Data System (ADS)
Li, Shuo; Zhang, Guangshan; Zheng, Heshan; Zheng, Yongjie; Wang, Peng
2018-05-01
In this study, BiFeO3 (BFO) powders decorated on nickel foam (NF) with a high catalytic activity are prepared via a one-step microwave-assisted hydrothermal method. The factors that influence the degradation of bisphenol A (BPA) with BFO/NFs as catalysts are optimized to improve the catalytic activity in a microwave-enhanced Fenton-like process. BFO/NF exhibit a superior catalytic activity with a high BPA removal ratio (98.4%) and TOC removal ratio (69.5%) within 5 min. Results indicate that NF significantly affect the improvement of the catalytic activity of BFO because it served as a source of hydroxyl radicals (•OH) during degradation. The amount of •OH generated by BFO/NF is approximately 1.65-fold higher than that by pure BFO. After six reaction cycles, the stability and reusability of •OH remain high. These findings provide new insights into the synthesis of composites on heterogeneous catalysts with high efficiency and easy recyclability for water treatment applications.
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Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun
2015-03-21
Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method. Copyright © 2014 Elsevier B.V. All rights reserved.
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Design, integration and preliminary results of the IXV Catalysis experiment
NASA Astrophysics Data System (ADS)
Viladegut, Alan; Panerai, F.; Chazot, O.; Pichon, T.; Bertrand, P.; Verdy, C.; Coddet, C.
2017-06-01
The CATalytic Experiment (CATE) is an in-flight demonstration of catalysis effects at the surface of thermal protection materials. A high-catalytic coating was applied over the baseline ceramic material on the windward side of the intermediate experimental vehicle (IXV). The temperature jump due to different catalytic activities was detected during re-entry through measurements made with near-surface thermocouples on the windward side of the vehicle. The experiment aimed at contributing to the development and validation of gas/surface interaction models for re-entry applications. The present paper summarizes the design of CATE and its integration on the windward side of the IXV. Results of a qualification campaign at the Plasmatron facility of the von Karman Institute for Fluid Dynamics are presented. They provided an experimental evidence of the temperature jump at the low-to-high catalytic interface of the heat shield under aerothermal conditions relevant to the actual IXV flight. These tests also gave confidence so that the high-catalytic patch would not endanger the integrity of the vehicle and the safety of the mission. A preliminary assessment of flight data from the thermocouple measurements shows consistency with results of the qualification tests.
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Yu, Yaoguang; Yang, Xu; Zhao, Yanling; Zhang, Xiangbin; An, Liang; Huang, Miaoyan; Chen, Gang; Zhang, Ruiqin
2018-04-19
Introducing band gap states to TiO 2 photocatalysts is an efficient strategy for expanding the range of accessible energy available in the solar spectrum. However, few approaches are able to introduce band gap states and improve photocatalytic performance simultaneously. Introducing band gap states by creating surface disorder can incapacitate reactivity where unambiguous adsorption sites are a prerequisite. An alternative method for introduction of band gap states is demonstrated in which selected heteroatoms are implanted at preferred surface sites. Theoretical prediction and experimental verification reveal that the implanted heteroatoms not only introduce band gap states without creating surface disorder, but also function as active sites for the Cr VI reduction reaction. This promising approach may be applicable to the surfaces of other solar harvesting materials where engineered band gap states could be used to tune photophysical and -catalytic properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
McManus, Jesse R.; Yu, Weiting; Salciccioli, Michael; Vlachos, Dionisios G.; Chen, Jingguang G.; Vohs, John M.
2012-12-01
Molecules derived from cellulosic biomass, such as glucose, represent an important renewable feedstock for the production of hydrogen and hydrocarbon-based fuels and chemicals. Development of efficient catalysts for their reformation into useful products is needed; however, this requires a detailed understanding of their adsorption and reaction on catalytically active transition metal surfaces. In this paper we demonstrate that the standard surface science techniques routinely used to characterize the reaction of small molecules on metals are also amenable for use in studying the adsorption and reaction of complex biomass-derivatives on single crystal metal surfaces. In particular, Temperature Programmed Desorption (TPD) and High Resolution Electron Energy Loss Spectroscopy (HREELS) combined with Density Functional Theory (DFT) calculations were used to elucidate the adsorption configuration of D-glucose and glycolaldehye on Pt(111). Both molecules were found to adsorb in an η1 aldehyde configuration partially validating the use of simple, functionally-equivalent model compounds for surface studies of cellulosic oxygenates.
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Zhou, Xuemei; Shen, Xuetao; Xia, Zhaoming; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan
2015-09-16
Nano-/micrometer multiscale hierarchical structures not only provide large surface areas for surface redox reactions but also ensure efficient charge conductivity, which is of benefit for utilization in areas of electrochemical energy conversion and storage. Herein, hollow fluffy cages (HFC) of Co3O4, constructed of ultrathin nanosheets, were synthesized by the formation of Co(OH)2 hollow cages and subsequent calcination at 250 °C. The large surface area (245.5 m2 g(-1)) of HFC Co3O4 annealed at 250 °C ensures the efficient interaction between electrolytes and electroactive components and provides more active sites for the surface redox reactions. The hierarchical structures minimize amount of the grain boundaries and facilitate the charge transfer process. Thin thickness of nanosheets (2-3 nm) ensures the highly active sites for the surface redox reactions. As a consequence, HFC Co3O4 as the supercapacitor electrode exhibits a superior rate capability, shows an excellent cycliability of 10,000 cycles at 10 A g(-1), and delivers large specific capacitances of 948.9 and 536.8 F g(-1) at 1 and 40 A g(-1), respectively. Catalytic studies of HFC Co3O4 for oxygen evolution reaction display a much higher turnover frequency of 1.67×10(-2) s(-1) in pH 14.0 KOH electrolyte at 400 mV overpotential and a lower Tafel slope of 70 mV dec(-1). HFC Co3O4 with the efficient electrochemical activity and good stability can remain a promising candidate for the electrochemical energy conversion and storage.
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Apparatus and method for the electrolysis of water
Greenbaum, Elias
2015-04-21
An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen, the apparatus comprising: (i) at least one lithographically-patternable substrate having a surface; (ii) a plurality of microscaled catalytic electrodes embedded in said surface; (iii) at least one counter electrode in proximity to but not on said surface; (iv) means for collecting evolved hydrogen and/or oxygen gas; (v) electrical powering means for applying a voltage across said plurality of microscaled catalytic electrodes and said at least one counter electrode; and (vi) a container for holding an aqueous electrolyte and housing said plurality of microscaled catalytic electrodes and said at least one counter electrode. Electrolytic processes using the above electrolytic apparatus or functional mimics thereof are also described.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Mihaela Grigore; Richard Sakurovs; David French
Gasification of coke contributes to its degradation in the blast furnace. In this study, the effect of gasification on the inherent catalytic minerals in cokes and their reciprocal influence on gasification are investigated. The catalytic mineral phases identified in the cokes used in this study were metallic iron, iron sulfides, and iron oxides. Metallic iron and pyrrhotite were rapidly oxidized during gasification to iron oxide. The catalysts had a strong influence on the apparent rates at the initial stages of reaction. As gasification proceeds, their effect on the reaction rate diminishes as a result of reducing the surface contact betweenmore » catalyst and carbon matrix because of carbon consumption around the catalyst particles; with extended burnout the reactivity of the coke becomes increasingly dependent on surface area. The reaction rate in the initial stages was also influenced by the particle size of the catalytic minerals; for a given catalytic iron level, the cokes whose catalytic minerals were more finely dispersed had a higher apparent reaction rate than cokes containing larger catalytic particles. Iron, sodium, and potassium in the amorphous phase did not appear to affect the reaction rate. 40 refs., 16 figs., 6 tabs.« less
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Catalytic nanoporous membranes
Pellin, Michael J; Hryn, John N; Elam, Jeffrey W
2013-08-27
A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.
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Vohra, M Ismail; Li, De-Jing; Gu, Zhi-Gang; Zhang, Jian
2017-06-14
A palladium catalyst (Pd-Cs) encapsulated metalloporphyrin network PIZA-1 thin film with bifunctional properties has been developed through a modified epitaxial layer-by-layer encapsulation approach. Combining the oxidation activity of Pd-Cs and the acetalization activity of the Lewis acidic sites in the PIZA-1 thin film, this bifunctional catalyst of the Pd-Cs@PIZA-1 thin film exhibits a good catalytic activity in a one-pot tandem oxidation-acetalization reaction. Furthermore, the surface components can be controlled by ending the top layer with different precursors in the thin film preparation procedures. The catalytic performances of these thin films with different surface composites were studied under the same conditions, which showed different reaction conversions. The result revealed that the surface component can influence the catalytic performance of the thin films. This epitaxial encapsulation offers a good understanding of the tandem catalysis for thin film materials and provides useful guidance to develop new thin film materials with catalytic properties.
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In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.
Stefanidis, S D; Kalogiannis, K G; Iliopoulou, E F; Lappas, A A; Pilavachi, P A
2011-09-01
In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields. Copyright © 2011 Elsevier Ltd. All rights reserved.
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Yang, Dong; Ortuño, Manuel A; Bernales, Varinia; Cramer, Christopher J; Gagliardi, Laura; Gates, Bruce C
2018-03-14
Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr 6 O 8 . Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr 6 O 8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an S N 2 mechanism.
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Reversible Regulation of Catalytic Activity of Gold Nanoparticles with DNA Nanomachines
NASA Astrophysics Data System (ADS)
Zhou, Peipei; Jia, Sisi; Pan, Dun; Wang, Lihua; Gao, Jimin; Lu, Jianxin; Shi, Jiye; Tang, Zisheng; Liu, Huajie
2015-09-01
Reversible catalysis regulation has gained much attention and traditional strategies utilized reversible ligand coordination for switching catalyst’s conformations. However, it remains challenging to regulate the catalytic activity of metal nanoparticle-based catalysts. Herein, we report a new DNA nanomachine-driven reversible nano-shield strategy for circumventing this problem. The basic idea is based on the fact that the conformational change of surface-attached DNA nanomachines will cause the variation of the exposed surface active area on metal nanoparticles. As a proof-of-concept study, we immobilized G-rich DNA strands on gold nanoparticles (AuNPs) which have glucose oxidase (GOx) like activity. Through the reversible conformational change of the G-rich DNA between a flexible single-stranded form and a compact G-quadruplex form, the catalytic activity of AuNPs has been regulated reversibly for several cycles. This strategy is reliable and robust, which demonstrated the possibility of reversibly adjusting catalytic activity with external surface coverage switching, rather than coordination interactions.
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Shen, Lijuan; Xia, Yuzhou; Lin, Sen; Liang, Shijing; Wu, Ling
2017-10-05
Creating two-dimensional (2D) crystal-metal heterostructures with an ultrathin thickness has spurred increasing research endeavors in catalysis because of its fascinating opportunities in tuning the electronic state at the surface and enhancing the chemical reactivity. Here we report a novel and facile Nb 4+ -assisted strategy for the in situ growth of highly dispersed Pd nanoparticles (NPs) on monolayer HNb 3 O 8 nanosheets (HNb 3 O 8 NS) constituting a 2D Pd/HNb 3 O 8 NS heterostructure composite without using extra reducing agents and stabilizing agents. The Pd NP formation is directed via a redox reaction between an oxidative Pd salt precursor (H 2 PdCl 4 ) and reductive unsaturated surface metal (Nb 4+ ) sites induced by light irradiation on monolayer HNb 3 O 8 NS. The periodic arrangement of metal Nb nodes on HNb 3 O 8 NS leads to a homogeneous distribution of Pd NPs. Density functional theory (DFT) calculations reveal that the direct redox reaction between the Nb 4+ and Pd 2+ ions leads to a strong chemical interaction between the formed Pd metal NPs and the monolayer HNb 3 O 8 support. Consequently, the as-obtained Pd/HNb 3 O 8 composite serves as a highly efficient bifunctional catalyst in both heterogeneous thermocatalytic and photocatalytic selective reduction of aromatic nitro compounds in water under ambient conditions. The achieved high activity originates from the unique 2D nanosheet configuration and in situ Pd incorporation, which leads to a large active surface area, strong metal-support interaction and enhanced charge transport capability. Moreover, this facile Nb 4+ -assisted synthetic route has demonstrated to be general, which can be applied to load other metals such as Au and Pt on monolayer HNb 3 O 8 NS. It is anticipated that this work can extend the facile preparation of noble metal/nanosheet 2D heterostructures, as well as promote the simultaneous capture of duple renewable thermal and photon energy sources to drive an energy efficient catalytic process.
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NASA Astrophysics Data System (ADS)
Subramanian, Shyamala
This thesis explores two applications of self-assembled monolayers (SAMs) (a) for developing novel molecular assembly based nanolithography techniques and (b) for tailoring zeta-potential of surfaces towards achieving directional control of catalytically induced fluid flow. The first half of the thesis develops the process of molecular ruler lithography using sacrificial host structures. This is a novel hybrid nanolithography technique which combines chemical self-assembly with conventional fabrication methods for improving the resolution of existing lithography tools to sub-50 nm. Previous work related to molecular ruler lithography have shown the use of thiol-SAMs, placed one on top of the other like a molecular resist, for scaling down feature sizes. In this thesis various engineering solutions for improving the reproducibility, yield, nanoscale roughness and overall manufacturability of the process are introduced. This is achieved by introducing a sacrificial inert layer underneath the gold parent structure. This bilayer sacrificial host allows for preferential, easy and quick removal of the parent structures, isolates the parent metal from the underlying substrate and improves reproducibility of the lift-off process. Also it opens avenues for fabrication of high aspect ratio features. Also molecular layer vapor deposition method is developed for building the multilayer molecular resist via vapor phase to reduce contaminations and yield issues associated with solution phase deposition. The smallest isolated metal features produced using this process were 40 nm in width. The second half of the thesis describes application of thiol-SAMs to tailor surface properties of gold, specifically the surface charge or zeta potential. Previous work has demonstrated that the direction of movement of fluid in the vicinity of a catalytically active bimetallic junction placed in a solution of dilute hydrogen peroxide depends on the charge of the gold surface. SAMs with different end-group functionality impart different surface zeta potential to the gold surface. Zeta-potential engineering via patterning various end-group functionalized SAMs on gold surface to control direction of catalytically induced electroosmotic fluid flow is demonstrated for the first time. This work also describes the application of catalytic power to produce controlled rotational motion. Gold gears-like structures made using conventional microfabrication techniques and propelled by catalytic power are shown to rotate at speeds of 1 rotation/sec in a dilute solution of hydrogen peroxide. Fabrication of a force sensor for detection and measurement of catalytic forces is also introduced. The force sensor, with sensitivity in the piconewton range, consists of a microcantilever with a catalytically active silver post patterned on the tip. Changes in cantilever displacement and resonance frequency due to the catalytic force were monitored as a function of concentration of hydrogen peroxide. Overall, this thesis integrates SAM deposition and patterning techniques with conventional fabrication methods to engineer and control nanoscale structures and devices. Possible future device designs are described including CMOS devices having channel width defined using molecular ruler lithography with sacrificial hosts, drug delivery device based on AFM force sensor and channeless pumps powered by catalytic reactions with SAM controlled electroosmotic fluid flow.
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Liu, Baocang; Wang, Qin; Yu, Shengli; Jing, Peng; Liu, Lixia; Xu, Guangran; Zhang, Jun
2014-10-21
Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd(2+) ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus greatly accelerating the reaction speed. Owing to its structural features, yolk-double-shell Pd@TiO2/Pd@TiO2 architecture exhibits extremely high catalytic performance on the Suzuki-Miyaura coupling reaction. The synthetic methodologies are robust for fabricating double-shell architectures with various configurations for applications such as in catalysis, drug delivery, and medicine release. The obtained double-shell architectures may be used as novel catalyst systems with highly efficient catalytic performance for other catalytic reactions.