Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Manhua; Wang, Xiang; Yeom, Younghoon

A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase is dispersed.

Preparation of TiO2/(TiO2-V2O5)/polypyrrole nanocomposites and a study on catalytic activities of the hybrid materials under UV/Visible light and in the dark

NASA Astrophysics Data System (ADS)

Piewnuan, C.; Wootthikanokkhan, J.; Ngaotrakanwiwat, P.; Meeyoo, V.; Chiarakorn, S.

2014-11-01

Hybrid metal oxides/polymer nanocomposites, namely TiO2/(TiO2-V2O5)/polypyrrole (PPy), were synthesized via in situ polymerization. Structures of the products were characterized by SEM-EDX, XRD, and FTIR techniques. The light absorbance and band gap energy values of the materials were evaluated by UV/Visible spectroscopy. The catalytic activity of the materials was determined from a degradation of methylene blue. It was found that, regardless of the polymerization time, the absorbance of TiO2/(TiO2-V2O5)/PPy was greater than those of TiO2/PPy and the neat TiO2, respectively. This was in accordance with the decrease in the band gap energy of the materials. The catalytic activity of TiO2/(TiO2-V2O5) was also observed in the dark. After polymerization, the catalytic activity of nanocomposite under UV/Visible light and in the dark was compromised. The above effects are discussed in the light of the energy storage ability of V2O5 and capability of the polymer in acting as a binder for the system.

Electro-catalytic degradation of sulfisoxazole by using graphene anode.

PubMed

Wang, Yanyan; Liu, Shuan; Li, Ruiping; Huang, Yingping; Chen, Chuncheng

2016-05-01

Graphite and graphene electrodes were prepared by using pure graphite as precursor. The electrode materials were characterized by a scanning electron microscope (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV) measurements. The electro-catalytic activity for degradation of sulfisoxazole (SIZ) was investigated by using prepared graphene or graphite anode. The results showed that the degradation of SIZ was much more rapid on the graphene than that on the graphite electrode. Moreover, the graphene electrode exhibited good stability and recyclability. The analysis on the intermediate products and the measurement of active species during the SIZ degradation demonstrated that indirect oxidation is the dominant mechanism, involving the electro-catalytic generation of OH and O2(-) as the main active oxygen species. This study implies that graphene is a promising potential electrode material for long-term application to electro-catalytic degradation of organic pollutants. Copyright © 2015. Published by Elsevier B.V.

Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts

DOE PAGES

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

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

Preparation of improved catalytic materials for water purification

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Paneva, D.; Tsvetkov, M.; Kunev, B.; Milanova, M.; Petrov, N.; Mitov, I.

2014-04-01

The aim of presented paper was to study preparation of catalytic materials for water purification. Iron oxide (Fe3O4) samples supported on activated carbon were prepared by wet impregnation method and low temperature heating in an inert atmosphere. The as-prepared, activated and samples after catalytic test were characterized by Mössbauer spectroscopy and X-ray diffraction. The obtained X-ray diffraction patterns of prepared samples show broad and low-intensity peaks of magnetite phase and the characteristic peaks of the activated carbon. The average crystallite size of magnetite particles was calculated below 20 nm. The registered Mössbauer spectra of prepared materials show a superposition of doublet lines or doublet and sextet components. The calculated hyperfine parameters after spectra evaluation reveal the presence of magnetite phase with nanosize particles. Relaxation phenomena were registered in both cases, i.e. superparamagnetism or collective magnetic excitation behavior, respectively. Low temperature Mössbauer spectra confirm this observation. Application of materials as photo-Fenton catalysts for organic pollutions degradation was studied. It was obtained high adsorption degree of dye, extremely high reaction rate and fast dye degradation. Photocatalytic behaviour of a more active sample was enhanced using mechanochemical activation (MCA). The nanometric size and high dispersion of photocatalyst particles influence both the adsorption and degradation mechanism of reaction. The results showed that all studied photocatalysts effectively decompose the organic pollutants under UV light irradiation. Partial oxidation of samples after catalytic tests was registered. Combination of magnetic particles with high photocatalytic activity meets both the requirements of photocatalytic degradation of water contaminants and that of recovery for cyclic utilization of material.

Self-assembling biomolecular catalysts for hydrogen production

NASA Astrophysics Data System (ADS)

Jordan, Paul C.; Patterson, Dustin P.; Saboda, Kendall N.; Edwards, Ethan J.; Miettinen, Heini M.; Basu, Gautam; Thielges, Megan C.; Douglas, Trevor

2016-02-01

The chemistry of highly evolved protein-based compartments has inspired the design of new catalytically active materials that self-assemble from biological components. A frontier of this biodesign is the potential to contribute new catalytic systems for the production of sustainable fuels, such as hydrogen. Here, we show the encapsulation and protection of an active hydrogen-producing and oxygen-tolerant [NiFe]-hydrogenase, sequestered within the capsid of the bacteriophage P22 through directed self-assembly. We co-opted Escherichia coli for biomolecular synthesis and assembly of this nanomaterial by expressing and maturing the EcHyd-1 hydrogenase prior to expression of the P22 coat protein, which subsequently self assembles. By probing the infrared spectroscopic signatures and catalytic activity of the engineered material, we demonstrate that the capsid provides stability and protection to the hydrogenase cargo. These results illustrate how combining biological function with directed supramolecular self-assembly can be used to create new materials for sustainable catalysis.

Electrocatalytic H2 production from seawater over Co, N-codoped nanocarbons.

PubMed

Gao, Shuang; Li, Guo-Dong; Liu, Yipu; Chen, Hui; Feng, Liang-Liang; Wang, Yun; Yang, Min; Wang, Dejun; Wang, Shan; Zou, Xiaoxin

2015-02-14

One of the main barriers blocking sustainable hydrogen production is the use of expensive platinum-based catalysts to produce hydrogen from water. Herein we report the cost-effective synthesis of catalytically active, nitrogen-doped, cobalt-encased carbon nanotubes using inexpensive starting materials-urea and cobalt chloride hexahydrate (CoCl2·6H2O). Moreover, we show that the as-obtained nanocarbon material exhibits a remarkable electrocatalytic activity toward the hydrogen evolution reaction (HER); and thus it can be deemed as a potential alternative to noble metal HER catalysts. In particular, the urea-derived carbon nanotubes synthesized at 900 °C (denoted as U-CNT-900) show a superior catalytic activity for HER with low overpotential and high current density in our study. Notably also, U-CNT-900 has the ability to operate stably at all pH values (pH 0-14), and even in buffered seawater (pH 7). The possible synergistic effects between carbon-coated cobalt nanoparticles and the nitrogen dopants can be proposed to account for the HER catalytic activity of U-CNT-900. Given the high natural abundance, ease of synthesis, and high catalytic activity and durability in seawater, this U-CNT-900 material is promising for hydrogen production from water in industrial applications.

Materials and Mechanisms of Photo-Assisted Chemical Reactions under Light and Dark Conditions: Can Day-Night Photocatalysis Be Achieved?

PubMed

Sakar, M; Nguyen, Chinh-Chien; Vu, Manh-Hiep; Do, Trong-On

2018-03-09

The photoassisted catalytic reaction, conventionally known as photocatalysis, is expanding into the field of energy and environmental applications. It is widely known that the discovery of TiO 2 -assisted photochemical reactions has led to several unique applications, such as degradation of pollutants in water and air, hydrogen production through water splitting, fuel conversion, cancer treatment, antibacterial activity, self-cleaning glasses, and concrete. These multifaceted applications of this phenomenon can be enriched and expanded further if this process is equipped with more tools and functions. The term "photoassisted" catalytic reactions clearly emphasizes that photons are required to activate the catalyst; this can be transcended even into the dark if electrons are stored in the material for the later use to continue the catalytic reactions in the absence of light. This can be achieved by equipping the photocatalyst with an electron-storage material to overcome current limitations in photoassisted catalytic reactions. In this context, this article sheds lights on the materials and mechanisms of photocatalytic reactions under light and dark conditions. The manifestation of such systems could be an unparalleled technology in the near future that could influence all spheres of the catalytic sciences. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

BIOTEMPLATING OF TITANIUM DIOXIDE NANOPARTICLES FOR THE GREEN PRODUCTION OF PHOTOCHEMICALLY ACTIVE CATALYSTS: SYNTHESIS, CHARACTERIZATION, AND PHOTOCATALYTIC EVALUATION

EPA Science Inventory

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...

Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

PubMed

Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

2014-08-01

The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable. Copyright © 2014. Published by Elsevier B.V.

Synthesis and characterization of a new porphyrin-polyoxometalate hybrid material and investigation of its catalytic activity.

PubMed

Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

2012-03-14

In the present work, the preparation of a new organic-inorganic hybrid material in which tetrakis(p-aminophenylporphyrin) is covalently linked to a Lindqvist structure of polyoxometalate, is reported. This new porphyrin-polyoxometalate hybrid material was characterized by (1)H NMR, FT-IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided spectral data of the synthesis of this compound. Cyclic voltammetry showed the influence of the porphyrin on the redox process of the polyoxometalate. The catalytic activity of this hybrid material was investigated in the alkene epoxidation with NaIO(4).

Catalytic, hollow, refractory spheres, conversions with them

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1989-01-01

Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Catalytic, hollow, refractory spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1987-01-01

Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Metal–organic framework supported cobalt catalysts for the oxidative dehydrogenation of propane at low temperature

DOE PAGES

Li, Zhanyong; Peters, Aaron W.; Bernales, Varinia; ...

2016-11-30

Here, Zr-based metal–organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr 6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in themore » two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O 2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.« less

Insight into the epitaxial encapsulation of Pd catalysts in an oriented metalloporphyrin network thin film for tandem catalysis.

PubMed

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.

Postassembly Transformation of a Catalytically Active Composite Material, Pt@ZIF-8, via Solvent-Assisted Linker Exchange.

PubMed

Stephenson, Casey J; Hupp, Joseph T; Farha, Omar K

2016-02-15

2-Methylimidazolate linkers of Pt@ZIF-8 are exchanged with imidazolate using solvent-assisted linker exchange (SALE) to expand the apertures of the parent material and create Pt@SALEM-2. Characterization of the material before and after SALE was performed. Both materials are active as catalysts for the hydrogenation of 1-octene, whereas the hydrogenation of cis-cyclohexene occurred only with Pt@SALEM-2, consistent with larger apertures for the daughter material. The largest substrate, β-pinene, proved to be unreactive with H2 when either material was employed as a candidate catalyst, supporting the contention that substrate molecules, for both composites, must traverse the metal-organic framework component in order to reach the catalytic nanoparticles.

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.

ZIF-67 incorporated with carbon derived from pomelo peels: A highly efficient bifunctional catalyst for oxygen reduction/evolution reactions

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

Novel application of thermally expanded graphite as the support of catalysts for direct synthesis of DMC from CH3OH and CO2.

PubMed

Bian, J; Xiao, M; Wang, S J; Lu, Y X; Meng, Y Z

2009-06-01

Novel Cu-Ni bimetallic catalysts supported on thermally expanded graphite (TEG) were prepared as an example to show the particular characteristics of TEG as a carbon support material. The structures of TEG and the synthesized Cu-Ni/TEG catalysts were characterized using BET, FTIR, TG, SEM, TEM, XRD and TPR techniques. The catalytic activities of the prepared catalysts were investigated by performing micro-reaction in the direct synthesis of dimethyl carbonate (DMC) from CH3OH and CO2. The experimental results indicated that the prepared Cu-Ni/TEG catalysts exhibited highly catalytic activity. Under the optimal catalytic conditions at 100 degrees C and under 1.2 MPa, the highest conversion of CH3OH of 4.97% and high selectivity of DMC of 89.3% can be achieved. The highly catalytic activity of Cu-Ni/TEG in DMC synthesis can be attributed to the synergetic effects of metal Cu, Ni and Cu-Ni alloy in the activation of CH3OH and CO2 and the particular characteristics of TEG as a carbon support material.

Atomic-Scale Principles of Combustion Nanocatalysis

DTIC Science & Technology

2014-05-19

of Combustion Nanocatalysts: Structures, Electronic Characteristics and Catalytic Pathways MURI FINAL REPORT Reporting Period: June 1, 2008 to...properties of nanoscale materials to be employed for catalytic combustion of fuels and propellants. Furthermore the research program seeks to establish... catalytic cycle. Both the carbon– hydrogen bond activation and the subsequent desorption of the ethylene product molecule require cooperative action

A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

DOE PAGES

Liu, Wen; Hu, Enyuan; Jiang, Hong; ...

2016-02-19

Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superiormore » activity for hydrogen evolution, achieving current densities of 10 mA cm –2 and 100 mA cm –2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.« less

Catalysts for lean burn engine exhaust abatement

DOEpatents

Ott, Kevin C.; Clark, Noline C.; Paffett, Mark T.

2006-08-01

The present invention provides a process for catalytically reducing nitrogen oxides in an exhaust gas stream containing nitrogen oxides and a reductant material by contacting the gas stream under conditions effective to catalytically reduce the nitrogen oxides with a catalyst comprising a aluminum-silicate type material and a minor amount of a metal, the catalyst characterized as having sufficient catalytic activity so as to reduce the nitrogen oxides by at least 60 percent under temperatures within the range of from about 200.degree. C. to about 400.degree. C.

Catalysts For Lean Burn Engine Exhaust Abatement

DOEpatents

Ott, Kevin C.; Clark, Noline C.; Paffett, Mark T.

2004-04-06

The present invention provides a process for catalytically reducing nitrogen oxides in an exhaust gas stream containing nitrogen oxides and a reductant material by contacting the gas stream under conditions effective to catalytically reduce the nitrogen oxides with a catalyst comprising a aluminum-silicate type material and a minor amount of a metal, the catalyst characterized as having sufficient catalytic activity so as to reduce the nitrogen oxides by at least 60 percent under temperatures within the range of from about 200.degree. C. to about 400.degree. C.

Catalysts for lean burn engine exhaust abatement

DOEpatents

Ott, Kevin C.; Clark, Noline C.; Paffett, Mark T.

2003-01-01

The present invention provides a process for catalytically reducing nitrogen oxides in an exhaust gas stream containing nitrogen oxides and a reductant material by contacting the gas stream under conditions effective to catalytically reduce the nitrogen oxides with a catalyst comprising a aluminum-silicate type material and a minor amount of a metal, the catalyst characterized as having sufficient catalytic activity so as to reduce the nitrogen oxides by at least 60 percent under temperatures within the range of from about 200.degree. C. to about 400.degree. C.

Effects of Metal Composition and Ratio on Peptide-Templated Multimetallic PdPt Nanomaterials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merrill, Nicholas A.; Nitka, Tadeusz T.; McKee, Erik M.

It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bio-inspired approaches have become increasing popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a 3D template for the formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive towards a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Ptmore » ratio to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied using transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted which indicated a slight catalytic enhancement for the multicomponent materials. These results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.« less

Effects of metal composition and ratio on peptide-templated multimetallic PdPt nanomaterials

DOE PAGES

Merrill, Nicholas A.; Nitka, Tadeusz T.; McKee, Erik M.; ...

2017-02-03

It can be difficult to simultaneously control the size, composition, and morphology of metal nanomaterials under benign aqueous conditions. For this, bioinspired approaches have become increasingly popular due to their ability to stabilize a wide array of metal catalysts under ambient conditions. In this regard, we used the R5 peptide as a three-dimensional template for formation of PdPt bimetallic nanomaterials. Monometallic Pd and Pt nanomaterials have been shown to be highly reactive toward a variety of catalytic processes, but by forming bimetallic species, increased catalytic activity may be realized. The optimal metal-to-metal ratio was determined by varying the Pd:Pt ratiomore » to obtain the largest increase in catalytic activity. To better understand the morphology and the local atomic structure of the materials, the bimetallic PdPt nanomaterials were extensively studied by transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and pair distribution function analysis. The resulting PdPt materials were determined to form multicomponent nanostructures where the Pt component demonstrated varying degrees of oxidation based upon the Pd:Pt ratio. To test the catalytic reactivity of the materials, olefin hydrogenation was conducted, which indicated a slight catalytic enhancement for the multicomponent materials. Finally, these results suggest a strong correlation between the metal ratio and the stabilizing biotemplate in controlling the final materials morphology, composition, and the interactions between the two metal species.« less

Quantitative Phase Composition of TiO 2-Coated Nanoporous-Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic

DOE PAGES

Bagge-Hansen, Michael; Wichmann, Andre; Wittstock, Arne; ...

2014-02-03

Porous titania/metal composite materials have many potential applications in the fields of green catalysis, energy harvesting, and storage in which both the overall morphology of the nanoporous host material and the crystallographic phase of the titania (TiO 2) guest determine the material’s performance. New insights into the structure–function relationships of these materials were obtained by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy that, for example, provides quantitative crystallographic phase composition from ultrathin, nanostructured titania films, including sensitivity to amorphous components. We demonstrate that crystallographic phase, morphology, and catalytic activity of TiO 2-functionalized nanoporous gold (np-Au) can be controlled by amore » simple annealing procedure (T < 1300 K). The material was prepared by atomic layer deposition of ~2 nm thick TiO 2 on millimeter-sized samples of np-Au (40–50 nm mean ligament size) and catalytically investigated with respect to aerobic CO oxidation. Moreover, the annealing-induced changes in catalytic activity are correlated with concurrent morphology and phase changes as provided by cross-sectional scanning electron microscopy, transmission electron microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.« less

Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies

NASA Astrophysics Data System (ADS)

Kumar, Gaurav; Tibbitts, Luke; Newell, Jaclyn; Panthi, Basu; Mukhopadhyay, Ahana; Rioux, Robert M.; Pursell, Christopher J.; Janik, Michael; Chandler, Bert D.

2018-03-01

Supported metal catalysts, which are composed of metal nanoparticles dispersed on metal oxides or other high-surface-area materials, are ubiquitous in industrially catalysed reactions. Identifying and characterizing the catalytic active sites on these materials still remains a substantial challenge, even though it is required to guide rational design of practical heterogeneous catalysts. Metal-support interactions have an enormous impact on the chemistry of the catalytic active site and can determine the optimum support for a reaction; however, few direct probes of these interactions are available. Here we show how benzyl alcohol oxidation Hammett studies can be used to characterize differences in the catalytic activity of Au nanoparticles hosted on various metal-oxide supports. We combine reactivity analysis with density functional theory calculations to demonstrate that the slope of experimental Hammett plots is affected by electron donation from the underlying oxide support to the Au particles.

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.

Correlation between the microstructures of graphite oxides and their catalytic behaviors in air oxidation of benzyl alcohol.

PubMed

Geng, Longlong; Wu, Shujie; Zou, Yongcun; Jia, Mingjun; Zhang, Wenxiang; Yan, Wenfu; Liu, Gang

2014-05-01

A series of graphite oxide (GO) materials were obtained by thermal treatment of oxidized natural graphite powder at different temperatures (from 100 to 200 °C). The microstructure evolution (i.e., layer structure and surface functional groups) of the graphite oxide during the heating process is studied by various characterization means, including XRD, N2 adsorption, TG-DTA, in situ DRIFT, XPS, Raman, TEM and Boehm titration. The characterization results show that the structures of GO materials change gradually from multilayer sheets to a transparent ultrathin 2D structure of the carbon sheets. The concentration of surface COH and HOCO groups decrease significantly upon treating temperature increasing. Benzyl alcohol oxidation with air as oxidant source was carried out to detect the catalytic behaviors of different GO materials. The activities of GO materials decrease with the increase of treating temperatures. It shows that the structure properties, including ultrathin sheets and high specific surface area, are not crucial factors affecting the catalytic activity. The type and amount of surface oxygen-containing functional groups of GO materials tightly correlates with the catalytic performance. Carboxylic groups on the surface of GO should act as oxidative sites for benzyl alcohol and the reduced form could be reoxidized by molecular oxygen. Copyright © 2014 Elsevier Inc. All rights reserved.

Composite ceria-coated aerogels and methods of making the same

DOEpatents

Eyring, Edward M; Ernst, Richard D; Turpin, Gregory C; Dunn, Brian C

2013-05-07

Ceria-coated aerogels can include an aerogel support material having a stabilized ceria coating thereon. The ceria coating can be formed by solution or vapor deposition of alcogels or aerogels. Additional catalytic metal species can also be incorporated into the coating to form multi-metallic compounds having improved catalytic activity. Further, the ceria coated aerogels retain high surface areas at elevated temperatures. Thus, improvements in catalytic activity and thermal stability can be achieved using these ceria-coated composite aerogels.

Enhanced Hydrothermal Stability and Catalytic Performance of HKUST-1 by Incorporating Carboxyl-Functionalized Attapulgite.

PubMed

Yuan, Bo; Yin, Xiao-Qian; Liu, Xiao-Qin; Li, Xing-Yang; Sun, Lin-Bing

2016-06-29

Much attention has been paid to metal-organic frameworks (MOFs) due to their large surface areas, tunable functionality, and diverse structure. Nevertheless, most reported MOFs show poor hydrothermal stability, which seriously hinders their applications. Here a strategy is adopted to tailor the properties of MOFs by means of incorporating carboxyl-functionalized natural clay attapulgite (ATP) into HKUST-1, a well-known MOF. A new type of hybrid material was thus fabricated from the hybridization of HKUST-1 and ATP. Our results indicated that the hydrothermal stability of the MOFs as well as the catalytic performance was apparently improved. The frameworks of HKUST-1 were severely destroyed after hydrothermal treatment (hot water vapor, 60 °C), while that of the hybrid materials was maintained. For the hybrid materials containing 8.4 wt % of ATP, the surface area reached 1302 m(2)·g(-1) and was even higher than that of pristine HKUST-1 (1245 m(2)·g(-1)). In the ring-opening of styrene oxide, the conversion reached 98.9% at only 20 min under catalysis from the hybrid material, which was obviously higher than that over pristine HKUST-1 (80.9%). Moreover, the hybrid materials showed excellent reusability and the catalytic activity was recoverable without loss after six cycles. Our materials provide promising candidates for heterogeneous catalysis owing to the good catalytic activity and reusability.

Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

DOEpatents

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2011-02-01

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Design of Stratified Functional Nanoporous Materials for CO 2 Capture and Conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, J. Karl; Ye, Jingyun

The objective of this project is to develop novel nanoporous materials for CO 2 capture and conversion. The motivation of this work is that capture of CO 2 from flue gas or the atmosphere coupled with catalytic hydrogenation of CO 2 into valuable chemicals and fuels can reduce the net amount of CO 2 in the atmosphere while providing liquid transportation fuels and other commodity chemicals. One approach to increasing the economic viability of carbon capture and conversion is to design a single material that can be used for both the capture and catalytic conversion of CO 2, because suchmore » a material could increase efficiency through process intensification. We have used density functional theory (DFT) methods to design catalytic moieties that can be incorporated into various metal organic framework (MOF) materials. We chose to work with MOFs because they are highly tailorable, can be functionalized, and have been shown to selectively adsorb CO 2 over N 2, which is a requirement for CO 2 capture from flue gas. Moreover, the incorporation of molecular catalytic moieties into MOF, through covalent bonding, produces a heterogeneous catalytic material having activities and selectivities close to those of homogeneous catalysts, but without the draw-backs associated with homogeneous catalysis.« less

Indented Cu2MoS4 nanosheets with enhanced electrocatalytic and photocatalytic activities realized through edge engineering.

PubMed

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.

IFCC primary reference procedures for the measurement of catalytic activity concentrations of enzymes at 37 °C. Part 9: reference procedure for the measurement of catalytic concentration of alkaline phosphatase International Federation of Clinical Chemistry and Laboratory Medicine (IFCC) Scientific Division, Committee on Reference Systems of Enzymes (C-RSE) (1)).

PubMed

Schumann, Gerhard; Klauke, Rainer; Canalias, Francesca; Bossert-Reuther, Steffen; Franck, Paul F H; Gella, F-Javier; Jørgensen, Poul J; Kang, Dongchon; Lessinger, Jean-Marc; Panteghini, Mauro; Ceriotti, Ferruccio

2011-09-01

Abstract This paper is the ninth in a series dealing with reference procedures for the measurement of catalytic activity concentrations of enzymes at 37 °C and the certification of reference preparations. Other parts deal with: Part 1. The concept of reference procedures for the measurement of catalytic activity concentrations of enzymes; Part 2. Reference procedure for the measurement of catalytic concentration of creatine kinase; Part 3. Reference procedure for the measurement of catalytic concentration of lactate dehydrogenase; Part 4. Reference procedure for the measurement of catalytic concentration of alanine aminotransferase; Part 5. Reference procedure for the measurement of catalytic concentration of aspartate aminotransferase; Part 6. Reference procedure for the measurement of catalytic concentration of γ-glutamyltransferase; Part 7. Certification of four reference materials for the determination of enzymatic activity of γ-glutamyltransferase, lactate dehydrogenase, alanine aminotransferase and creatine kinase at 37 °C; Part 8. Reference procedure for the measurement of catalytic concentration of α-amylase. The procedure described here is derived from the previously described 30 °C IFCC reference method. Differences are tabulated and commented on in Appendix 1.

Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process

DOEpatents

Gardner, Timothy J.; Lott, Stephen E.; Lockwood, Steven J.; McLaughlin, Linda I.

1998-01-01

A catalytic material of activated hydrous metal oxide doped with platinum, palladium, or a combination of these, and optionally containing an alkali or alkaline earth metal, that is effective for NO.sub.X reduction in an oxidizing exhaust stream from a combustion process is disclosed. A device for reduction of nitrogen oxides in an exhaust stream, particularly an automotive exhaust stream, the device having a substrate coated with the activated noble-metal doped hydrous metal oxide of the invention is also provided.

Nano-Structured Bio-Inorganic Hybrid Material for High Performing Oxygen Reduction Catalyst.

PubMed

Jiang, Rongzhong; Tran, Dat T; McClure, Joshua P; Chu, Deryn

2015-08-26

In this study, we demonstrate a non-Pt nanostructured bioinorganic hybrid (BIH) catalyst for catalytic oxygen reduction in alkaline media. This catalyst was synthesized through biomaterial hemin, nanostructured Ag-Co alloy, and graphene nano platelets (GNP) by heat-treatment and ultrasonically processing. This hybrid catalyst has the advantages of the combined features of these bio and inorganic materials. A 10-fold improvement in catalytic activity (at 0.8 V vs RHE) is achieved in comparison of pure Ag nanoparticles (20-40 nm). The hybrid catalyst reaches 80% activity (at 0.8 V vs RHE) of the state-of-the-art catalyst (containing 40% Pt and 60% active carbon). Comparable catalytic stability for the hybrid catalyst with the Pt catalyst is observed by chronoamperometric experiment. The hybrid catalyst catalyzes 4-electron oxygen reduction to produce water with fast kinetic rate. The rate constant obtained from the hybrid catalyst (at 0.6 V vs RHE) is 4 times higher than that of pure Ag/GNP catalyst. A catalytic model is proposed to explain the oxygen reduction reaction at the BIH catalyst.

Lamellar zirconium phosphates to host metals for catalytic purposes.

PubMed

Ballesteros-Plata, Daniel; Infantes-Molina, Antonia; Rodríguez-Aguado, Elena; Braos-García, Pilar; Rodríguez-Castellón, Enrique

2018-02-27

In the present study a porous lamellar zirconium phosphate heterostructure (PPH) formed from zirconium(iv) phosphate expanded with silica galleries (P/Zr molar ratio equal to 2 and (Si + Zr)/P equal to 3) was prepared to host noble metals. Textural and structural characterization of PPH-noble metal materials was carried out in order to elucidate the location and dispersion of the metallic particles and the properties of the resulting material to be used in catalytic processes. In the present paper, their activity in the catalytic hydrodeoxygenation (HDO) reaction of dibenzofuran (DBF) was evaluated. X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) evidenced that the structure of the pillared zirconium phosphate material was not modified by the incorporation of Pt and Pd. Moreover, transmission electron microscopy (TEM) showed a different dispersion of the noble metal. The acidity of the resulting PPH-noble metal materials also changed, although in all cases the acidity was of weak nature, and the incorporation of noble metals affected Brønsted acid sites as observed from 31 P NMR spectra. In general, the textural, structural and acidic properties of the resulting materials suggest that PPH can be considered a good candidate to be used as a catalytic support. Thus, the catalytic results of the PPH-noble metal samples indicated that the Pd sample showed a stable behavior probably ascribed to a high dispersion of the active phase. However, the Pt sample suffered from fast deactivation. The selectivity to the reaction products was strongly dependent on the noble metal employed.

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.

Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

DOE PAGES

Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh; ...

2015-11-04

The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe 2) 4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe 2) n@MSN. Exhaustive characterization of Zr(NMe 2) n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe 2) 3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe 2) n@MSN material reacts with pinacolborane (HBpin) to provide Me 2NBpin and the material ZrH/Bpin@MSN thatmore » is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/ 2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D 2. The zirconium hydride material or the zirconium amide precursor Zr(NMe 2) n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.« less

Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh

The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe 2) 4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe 2) n@MSN. Exhaustive characterization of Zr(NMe 2) n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe 2) 3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe 2) n@MSN material reacts with pinacolborane (HBpin) to provide Me 2NBpin and the material ZrH/Bpin@MSN thatmore » is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/ 2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D 2. The zirconium hydride material or the zirconium amide precursor Zr(NMe 2) n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.« less

The doping effect on the catalytic activity of graphene for oxygen evolution reaction in a lithium-air battery: a first-principles study.

PubMed

Ren, Xiaodong; Wang, Beizhou; Zhu, Jinzhen; Liu, Jianjun; Zhang, Wenqing; Wen, Zhaoyin

2015-06-14

A lithium-air battery as an energy storage technology can be used in electric vehicles due to its large energy density. However, its poor rate capability, low power density and large overpotential problems limit its practical usage. In this paper, the first-principles thermodynamic calculations were performed to study the catalytic activity of X-doped graphene (X = B, N, Al, Si, and P) materials as potential cathodes to enhance charge reactions in a lithium-air battery. Among these materials, P-doped graphene exhibits the highest catalytic activity in reducing the charge voltage by 0.25 V, while B-doped graphene has the highest catalytic activity in decreasing the oxygen evolution barrier by 0.12 eV. By combining these two catalytic effects, B,P-codoped graphene was demonstrated to have an enhanced catalytic activity in reducing the O2 evolution barrier by 0.70 eV and the charge voltage by 0.13 V. B-doped graphene interacts with Li2O2 by Li-sited adsorption in which the electron-withdrawing center can enhance charge transfer from Li2O2 to the substrate, facilitating reduction of O2 evolution barrier. In contrast, X-doped graphene (X = N, Al, Si, and P) prefers O-sited adsorption toward Li2O2, forming a X-O2(2-)···Li(+) interface structure between X-O2(2-) and the rich Li(+) layer. The active structure of X-O2(2-) can weaken the surrounding Li-O2 bonds and significantly reduce Li(+) desorption energy at the interface. Our investigation is helpful in developing a novel catalyst to enhance oxygen evolution reaction (OER) in Li-air batteries.

Metal-organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations.

PubMed

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.

Encapsulation of nanoclusters in dried gel materials via an inverse micelle/sol gel synthesis

DOEpatents

Martino, Anthony; Yamanaka, Stacey A.; Kawola, Jeffrey S.; Showalter, Steven K.; Loy, Douglas A.

1998-01-01

A dried gel material sterically entrapping nanoclusters of a catalytically active material and a process to make the material via an inverse micelle/sol-gel synthesis. A surfactant is mixed with an apolar solvent to form an inverse micelle solution. A salt of a catalytically active material, such as gold chloride, is added along with a silica gel precursor to the solution to form a mixture. To the mixture are then added a reducing agent for the purpose of reducing the gold in the gold chloride to atomic gold to form the nanoclusters and a condensing agent to form the gel which sterically entraps the nanoclusters. The nanoclusters are normally in the average size range of from 5-10 nm in diameter with a monodisperse size distribution.

Direct Single-Enzyme Biomineralization of Catalytically Active Ceria and Ceria–Zirconia Nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curran, Christopher D.; Lu, Li; Jia, Yue

Biomineralization is an intriguing approach to the synthesis of functional inorganic materials for energy applications whereby biological systems are engineered to mineralize inorganic materials and control their structure over multiple length scales under mild reaction conditions. Herein we demonstrate a single-enzyme-mediated biomineralization route to synthesize crystalline, catalytically active, quantum-confined ceria (CeO2–x) and ceria–zirconia (Ce1–yZryO2–x) nanocrystals for application as environmental catalysts. In contrast to typical anthropogenic synthesis routes, the crystalline oxide nanoparticles are formed at room temperature from an otherwise inert aqueous solution without the addition of a precipitant or additional reactant. An engineered form of silicatein, rCeSi, as a singlemore » enzyme not only catalyzes the direct biomineralization of the nanocrystalline oxides but also serves as a templating agent to control their morphological structure. The biomineralized nanocrystals of less than 3 nm in diameter are catalytically active toward carbon monoxide oxidation following an oxidative annealing step to remove carbonaceous residue. The introduction of zirconia into the nanocrystals leads to an increase in Ce(III) concentration, associated catalytic activity, and the thermal stability of the nanocrystals.« less

Atomically Precise Growth of Catalytically Active Cobalt Sulfide on Flat Surfaces and within a Metal–Organic Framework via Atomic Layer Deposition

DOE PAGES

Peters, Aaron W.; Li, Zhanyong; Farha, Omar K.; ...

2015-08-04

Atomic layer deposition (ALD) has been employed as a new synthetic route to thin films of cobalt sulfide on silicon and fluorine-doped tin oxide platforms. The self-limiting nature of the stepwise synthesis is established through growth rate studies at different pulse times and temperatures. Additionally, characterization of the materials by X-ray diffraction and X-ray photoelectron spectroscopy indicates that the crystalline phase of these films has the composition Co 9S 8. The nodes of the metal–organic framework (MOF) NU-1000 were then selectively functionalized with cobalt sulfide via ALD in MOFs (AIM). Spectroscopic techniques confirm uniform deposition of cobalt sulfide throughout themore » crystallites, with no loss in crystallinity or porosity. The resulting material, CoS-AIM, is catalytically active for selective hydrogenation of m-nitrophenol to m-aminophenol, and outperforms the analogous oxide AIM material (CoO-AIM) as well as an amorphous CoS x reference material. Here, these results reveal AIM to be an effective method of incorporating high surface area and catalytically active cobalt sulfide in metal–organic frameworks.« less

Systems including catalysts in porous zeolite materials within a reactor for use in synthesizing hydrocarbons

DOEpatents

Rolllins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2012-07-24

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Fabrication and testing of low-temperature catalytically active washcoat materials for next-generation vehicle catalytic converters.

DOT National Transportation Integrated Search

2014-01-01

With funds from this grant, Youngstown State University has purchased a : Quantachrome iQ Chemisorption Analyzer and built a Chemical Reactor with Gas : Chromatographer for catalyst characterization. PI has been involved in the purchase and : install...

Development of novel catalytically active polymer-metal-nanocomposites based on activated foams and textile fibers.

PubMed

Domènech, Berta; Ziegler, Kharla K; Carrillo, Fernando; Muñoz, Maria; Muraviev, Dimitri N; Macanás, Jorge

2013-05-16

In this paper, we report the intermatrix synthesis of Ag nanoparticles in different polymeric matrices such as polyurethane foams and polyacrylonitrile or polyamide fibers. To apply this technique, the polymer must bear functional groups able to bind and retain the nanoparticle ion precursors while ions should diffuse through the matrix. Taking into account the nature of some of the chosen matrices, it was essential to try to activate the support material to obtain an acceptable value of ion exchange capacity. To evaluate the catalytic activity of the developed nanocomposites, a model catalytic reaction was carried out in batch experiments: the reduction of p-nitrophenol by sodium borohydride.

New porous titanium–niobium oxide for photocatalytic degradation of bromocresol green dye in aqueous solution

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

Cobalt- and iron-based nanoparticles hosted in SBA-15 mesoporous silica and activated carbon from biomass: Effect of modification procedure

NASA Astrophysics Data System (ADS)

Tsoncheva, Tanya; Genova, Izabela; Paneva, Daniela; Dimitrov, Momtchil; Tsyntsarski, Boyko; Velinov, Nicolay; Ivanova, Radostina; Issa, Gloria; Kovacheva, Daniela; Budinova, Temenujka; Mitov, Ivan; Petrov, Narzislav

2015-10-01

Ordered mesoporous silica of SBA-15 type and activated carbon, prepared from waste biomass (peach stones), are used as host matrix of nanosized iron and cobalt particles. The effect of preparation procedure on the state of loaded nanoparticles is in the focus of investigation. The obtained materials are characterized by Boehm method, low temperature physisorption of nitrogen, XRD, UV-Vis, FTIR, Mossbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic behaviour of the samples is tested in methanol decomposition. The dispersion, oxidative state and catalytic behaviour of loaded cobalt and iron nanoparticles are successfully tuned both by the nature of porous support and the metal precursor used during the samples preparation. Facile effect of active phase deposition from aqueous solution of nitrate precursors is assumed for activated carbon support. For the silica based materials the catalytic activity could be significantly improved when cobalt acetylacetonate is used during the modification. The complex effect of pore topology and surface functionality of different supports on the active phase formation is discussed.

Preparation of zeolite supported TiO{sub 2}, ZnO and ZrO{sub 2} and the study on their catalytic activity in NO{sub x} reduction and 1-pentanol dehydration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fatimah, Is

Preparation of zeolite supported TiO{sub 2}, ZnO and ZrO{sub 2} and their catalytic activity was studied. Activated natural zeolite from Indonesia was utilized for the preparation and catalytic activity test on NO{sub x} reduction by NH{sub 3} and also 1-pentanol dehydration were examined. Physicochemical characterization of materials was studied by x-ray diffraction (XRD) measurement, scanning electron microscope, solid acidity determination and also gas sorption analysis. The results confirmed that the preparation gives some improvements on physicochemical characters suitable for catalysis mechanism in those reactions. Solid acidity and specific surface area contributed significantly to the activity.

Fluorine-doped carbon nanotubes as an efficient metal-free catalyst for destruction of organic pollutants in catalytic ozonation.

PubMed

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.

Identifying the Atomic-Level Effects of Metal Composition on the Structure and Catalytic Activity of Peptide-Templated Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merrill, Nicholas A.; McKee, Erik M.; Merino, Kyle C.

2015-10-12

Bioinspired approaches for the formation of metallic nanomaterials have been extensively employed for a diverse range of applications including diagnostics and catalysis. These materials can often be used under sustainable conditions; however, it is challenging to control the material size, morphology, and composition simultaneously. Here we have employed the R5 peptide, which forms a 3D scaffold to direct the size and linear shape of bimetallic PdAu nanomaterials for catalysis. The materials were prepared at varying Pd:Au ratios to probe optimal compositions to achieve maximal catalytic efficiency. These materials were extensively characterized at the atomic level using transmission electron microscopy, extendedmore » X-ray absorption fine structure spectroscopy, and atomic pair distribution function analysis derived from high-energy X-ray diffraction patterns to provide highly resolved structural information. The results confirmed PdAu alloy formation, but also demonstrated that significant surface structural disorder was present. The catalytic activity of the materials was studied for olefin hydrogenation, which demonstrated enhanced reactivity from the bimetallic structures.These results present a pathway to the bioinspired production of multimetallic materials with enhanced properties, which can be assessed via a suite of characterization methods to fully ascertain structure/function relationships.« less

Encapsulation of nanoclusters in dried gel materials via an inverse micelle/sol gel synthesis

DOEpatents

Martino, A.; Yamanaka, S.A.; Kawola, J.S.; Showalter, S.K.; Loy, D.A.

1998-09-29

A dried gel material sterically entrapping nanoclusters of a catalytically active material and a process to make the material via an inverse micelle/sol-gel synthesis are disclosed. A surfactant is mixed with an apolar solvent to form an inverse micelle solution. A salt of a catalytically active material, such as gold chloride, is added along with a silica gel precursor to the solution to form a mixture. To the mixture are then added a reducing agent for the purpose of reducing the gold in the gold chloride to atomic gold to form the nanoclusters and a condensing agent to form the gel which sterically entraps the nanoclusters. The nanoclusters are normally in the average size range of from 5--10 nm in diameter with a monodisperse size distribution. 1 fig.

Bioinspired catalytic materials for energy-relevant conversions

NASA Astrophysics Data System (ADS)

Artero, Vincent

2017-09-01

The structure of active sites of enzymes involved in bioenergetic processes can inspire design of active, stable and cost-effective catalysts for renewable-energy technologies. For these materials to reach maturity, the benefits of bioinspired systems must be combined with practical technological requirements.

Facile synthesis of pristine graphene-palladium nanocomposites with extraordinary catalytic activities using swollen liquid crystals

NASA Astrophysics Data System (ADS)

Vats, T.; Dutt, S.; Kumar, R.; Siril, P. F.

2016-09-01

Amazing conductivity, perfect honeycomb sp2 arrangement and the high theoretical surface area make pristine graphene as one of the best materials suited for application as catalyst supports. Unfortunately, the low reactivity of the material makes the formation of nanocomposite with inorganic materials difficult. Here we report an easy approach to synthesize nanocomposites of pristine graphene with palladium (Pd-G) using swollen liquid crystals (SLCs) as a soft template. The SLC template gives the control to deposit very small Pd particles of uniform size on G as well as RGO. The synthesized nanocomposite (Pd-G) exhibited exceptionally better catalytic activity compared with Pd-RGO nanocomposite in the hydrogenation of nitrophenols and microwave assisted C-C coupling reactions. The catalytic activity of Pd-G nanocomposite during nitrophenol reduction reaction was sixteen times higher than Pd nanoparticles and more than double than Pd-RGO nanocomposite. The exceptionally high activity of pristine graphene supported catalysts in the organic reactions is explained on the basis of its better pi interacting property compared to partially reduced RGO. The Pd-G nanocomposite showed exceptional stability under the reaction conditions as it could be recycled upto a minimum of 15 cycles for the C-C coupling reactions without any loss in activity.

Clear microstructure-performance relationships in Mn-containing perovskite and hexaaluminate compounds prepared by activated reactive synthesis.

PubMed

Laassiri, Said; Bion, Nicolas; Duprez, Daniel; Royer, Sébastien; Alamdari, Houshang

2014-03-07

Microstructural properties of mixed oxides play essential roles in their oxygen mobility and consequently in their catalytic performances. Two families of mixed oxides (perovskite and hexaaluminate) with different microstructural features, such as crystal size and specific surface area, were prepared using the activated reactive synthesis (ARS) method. It was shown that ARS is a flexible route to synthesize both mixed oxides with nano-scale crystal size and high specific surface area. Redox properties and oxygen mobility were found to be strongly affected by the material microstructure. Catalytic activities of hexaaluminate and perovskite materials for methane oxidation were discussed in the light of structural, redox and oxygen mobility properties.

Preparation, Characterization, and Catalytic Activity of MoCo/USY Catalyst on Hydrodeoxygenation Reaction of Anisole

NASA Astrophysics Data System (ADS)

Nugrahaningtyas, K. D.; Suharbiansah, R. S. R.; Rahmawati, F.

2018-03-01

This research aims to prepare, characterize, and study the catalytic activity of Molybdenum (Mo) and Cobalt (Co) metal with supporting material Ultra Stable Y-Zeolite (USY), to produce catalysts with activity in hydrotreatment reaction and in order to eliminate impurities compounds that containing unwanted groups heteroatoms. The bimetallic catalysts MoCo/USY were prepared by wet impregnation method with weight variation of Co metal 0%, 2%, 4%, 6%, 8%, and Mo metal 8% (w/w), respectively. Activation method of the catalyst included calcination, oxidation, reduction and the crystallinity was characterized using X-ray diffraction (XRD), the acidity of the catalyst was analyzed using Fourier Transform Infrared Spectroscopy (FT-IR) and gravimetry method, minerals present in the catalyst was analyzed using X-Ray Fluorescence (XRF), and surface of the catalyst was analyzed using Surface Area Analyzer (SAA). Catalytic activity test (benzene yield product) of MoCo/USY on hydrodeoxigenation reaction of anisole aimed to determine the effect of Mo-Co/USY for catalytic activity in the reaction hydrodeoxigenation (HDO) anisole. Based on characterization and test of catalytic activity, it is known that catalytic of MoCo/USY 2% (catalyst B) shows best activities with acidity of 10.209 mmol/g, specific area of catalyst of 426.295 m2/g, pore average of 14.135 Å, total pore volume 0.318 cc/g, and total yield of HDO products 6.06%.

Development and characterization of silica and titania based nano structured materials for the removal of indoor and outdoor air pollutants

NASA Astrophysics Data System (ADS)

Peiris, Thelge Manindu Nirasha

Solar energy driven catalytic systems have gained popularity in environmental remediation recently. Various photocatalytic systems have been reported in this regard and most of the photocatalysts are based on well-known semiconducting material, Titanium Dioxide, while some are based on other materials such as Silicon Dioxide and various Zeolites. However, in titania based photocatalysts, titania is actively involved in the catalytic mechanism by absorbing light and generating exitons. Because of this vast popularity of titania in the field of photocatalysis it is believed that photocatalysis mainly occurs via non-localized mechanisms and semiconductors are extremely important. Even though it is still rare, photocatalysis could be localized and possible without use of a semiconductor as well. Thus, to support localized photocatalytic systems, and to compare the activity to titania based systems, degradation of organic air pollutants by nanostructured silica, titania and mixed silica titania systems were studied. New materials were prepared using two different approaches, precipitation technique (xerogel) and aerogel preparation technique. The prepared xerogel samples were doped with both metal (silver) and non-metals (carbon and sulfur) and aerogel samples were loaded with Chromium, Cobalt and Vanadium separately, in order to achieve visible light photocatalytic activity. Characterization studies of the materials were carried out using Nova BET analysis, DR UV-vis spectrometry, powder X-ray diffraction, X-ray photoelectron Spectroscopy, FT-IR spectroscopy, Transmission Electron Microscopy, etc. Kinetics of the catalytic activities was studied using a Shimadzu GCMS-QP 5000 instrument using a closed glass reactor. All the experiments were carried out in gaseous phase using acetaldehyde as the model pollutant. Kinetic results suggest that chromium doped silica systems are good UV and visible light active photocatalysts. This is a good example for a localized photocatalytic activity. In contrast, our xerogel system shows comparatively high visible light photocatalytic activity for the titania based system, showing the importance of non-localized nature of photocatalysis. The Cobalt doped silica system shows interesting dark catalytic activity towards acetaldehyde and several other pollutants. Thus, in summary, based on the different activities we observed during our studies these materials could be successfully used to improve the quality of both indoor and outdoor air.

Functionality based detection of airborne engineered nanoparticles in quasi real time: a new type of detector and a new metric.

PubMed

Neubauer, Nicole; Seipenbusch, Martin; Kasper, Gerhard

2013-08-01

A new type of detector which we call the Catalytic Activity Aerosol Monitor (CAAM) was investigated towards its capability to detect traces of commonly used industrial catalysts in ambient air in quasi real time. Its metric is defined as the catalytic activity concentration (CAC) expressed per volume of sampled workplace air. We thus propose a new metric which expresses the presence of nanoparticles in terms of their functionality - in this case a functionality of potential relevance for damaging effects - rather than their number, surface, or mass concentration in workplace air. The CAAM samples a few micrograms of known or anticipated airborne catalyst material onto a filter first and then initiates a chemical reaction which is specific to that catalyst. The concentration of specific gases is recorded using an IR sensor, thereby giving the desired catalytic activity. Due to a miniaturization effort, the laboratory prototype is compact and portable. Sensitivity and linearity of the CAAM response were investigated with catalytically active palladium and nickel nano-aerosols of known mass concentration and precisely adjustable primary particle size in the range of 3-30 nm. With the miniature IR sensor, the smallest detectable particle mass was found to be in the range of a few micrograms, giving estimated sampling times on the order of minutes for workplace aerosol concentrations typically reported in the literature. Tests were also performed in the presence of inert background aerosols of SiO2, TiO2, and Al2O3. It was found that the active material is detectable via its catalytic activity even when the particles are attached to a non-active background aerosol.

A recyclable Au(I) catalyst for selective homocoupling of arylboronic acids: significant enhancement of nano-surface binding for stability and catalytic activity.

PubMed

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.

Method for recovering catalytic elements from fuel cell membrane electrode assemblies

DOEpatents

Shore, Lawrence [Edison, NJ; Matlin, Ramail [Berkeley Heights, NJ; Heinz, Robert [Ludwigshafen, DE

2012-06-26

A method for recovering catalytic elements from a fuel cell membrane electrode assembly is provided. The method includes converting the membrane electrode assembly into a particulate material, wetting the particulate material, forming a slurry comprising the wetted particulate material and an acid leachate adapted to dissolve at least one of the catalytic elements into a soluble catalytic element salt, separating the slurry into a depleted particulate material and a supernatant containing the catalytic element salt, and washing the depleted particulate material to remove any catalytic element salt retained within pores in the depleted particulate material.

A new V-doped Bi2(O,S)3 oxysulfide catalyst for highly efficient catalytic reduction of 2-nitroaniline and organic dyes.

PubMed

Abay, Angaw Kelemework; Kuo, Dong-Hau; Chen, Xiaoyun; Saragih, Albert Daniel

2017-12-01

A new type of convenient, and environmentally friendly, Vanadium (V)-doped Bi 2 (O,S) 3 oxysulfide catalyst with different V contents was successfully synthesized via a simple and facile method. The obtained V-doped Bi 2 (O,S) 3 solid solution catalysts were fully characterized by conventional methods. The catalytic performance of the samples was tested by using the reduction of 2-nitroaniline (2-NA) in aqueous solution. The reduction/decolorization of methylene blue (MB) and rhodamine B (RhB) was also chosen to evaluate the universality of catalysts. It was observed that the introduction of V can improve the catalytic performance, and 20%V-Bi 2 (O,S) 3 was found to be the optimal V doping concentration for the reduction of 2-NA, MB, and RhB dyes. For comparative purposes, a related V-free Bi 2 (O, S) 3 oxysulfide material was synthesized and tested as the catalyst. The superior activity of V-doped Bi 2 (O,S) 3 over pure Bi 2 (O,S) 3 was ascribed mainly to an increase in active sites of the material and also due to the presence of synergistic effects. The presence of V 5+ as found from XPS analysis may interact with Bi atoms and enhancing the catalytic activity of the sample. In the catalytic reduction of 2-NA, MB and RhB, the obtained V-doped Bi 2 (O,S) 3 oxysulfide catalyst exhibited excellent catalytic activity as compared with other reported catalysts. Furthermore this highly efficient, low-cost and easily reusable V-doped Bi 2 (O,S) 3 catalyst is anticipated to be of great potential in catalysis in the future. Copyright © 2017 Elsevier Ltd. All rights reserved.

MOF-derived magnetic carbonaceous nanocomposite as a heterogeneous catalyst to activate oxone for decolorization of Rhodamine B in water.

PubMed

Lin, Kun-Yi Andrew; Chang, Hsuan-Ang; Chen, Ru-Chieh

2015-07-01

Metal Organic Frameworks (MOFs) represents one of the most interesting and versatile materials nowadays. As interests to explore MOFs' functionality and potential continue to grow, using MOFs as a platform/template to develop other functional materials has received a great attention recently. Among these MOF-derived materials, MOF-derived carbonaceous materials are particularly attractive owing to its simple preparation and dual characteristics from carbon and metals. Herein, we propose to prepare a cobalt-based magnetic carbonaceous nanocomposite (MCN) by one-step carbonization of the cobalt-containing MOF, ZIF-67. Because of cobalt oxide (i.e., Co3O4) in MCN, MCN not only exhibits magnetic controllability but also catalytic activity to activate Oxone. To investigate and optimize this MCN-activated Oxone process, the decolorization of a cationic dye, Rhodamine B (Rh.B) in water is selected as a model reaction. This MCN-activated Oxone process was found to be the most effective when the ratio of Oxone/MCN was 5/1. While the high temperatures significantly improved the decolorization efficiency, the high initial pH was unfavorable for the Rh.B decolorization by this catalytic Oxone process. UV irradiation and ultrasonication were both found to enhance this MCN-activated Oxone process. The recyclability test revealed that MCN can be continuously used with constant and effective catalytic activity. These features enable MCN to be a promising and interesting catalyst for the wet chemical oxidation such as the Oxone oxidation process. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrochemical characterization of nano-sized Pd-based catalysts as cathode materials in direct methanol fuel cells.

PubMed

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

To improve the catalytic activity of palladium (Pd) as a cathode catalyst in direct methanol fuel cells (DMFCs), we prepared palladium-titanium oxide (Pd-TiO2) catalysts which the Pd and TiO2 nanoparticles were simultaneously impregnated on carbon. We selected Pd and TiO2 as catalytic materials because of their electrochemical stability in acid solution. The crystal structure and the loading amount of Pd and TiO2 on carbon were characterized by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis (EDX). The electrochemical characterization of Pd-TiO2/C catalysts for the oxygen reduction reaction was carried out in half and single cell systems. The catalytic activities of the Pd-TiO2 catalysts were strongly influenced by the TiO2 content. In the single cell test, the Pd-TiO2 catalysts showed very comparable performance to the Pt catalyst.

Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

DOEpatents

Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV; Haynes, Daniel [Morgantown, WV; Smith, Mark [Morgantown, WV; Spivey, James J [Baton Rouge, LA

2012-03-13

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A.sub.2-w-xA'.sub.wA''.sub.xB.sub.2-y-zB'.sub.yB''.sub.zO.sub.7-.DELTA.. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H.sub.2+CO) for fuel cells, among other uses.

Pyrochlore catalysts for hydrocarbon fuel reforming

DOEpatents

Berry, David A.; Shekhawat, Dushyant; Haynes, Daniel; Smith, Mark; Spivey, James J.

2012-08-14

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A₂B_2-y-zB'_yB"_zO_7-.DELTA., where y>0 and z.gtoreq.0. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H₂+CO) for fuel cells, among other uses.

Hydrous oxide ion-exchange compound catalysts

DOEpatents

Dosch, Robert G.; Stephens, Howard P.

1990-01-01

A catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchange with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

Influence of peracetic acid modification on the physicochemical properties of activated carbon and its performance in the ozone-catalytic oxidation of gaseous benzene

NASA Astrophysics Data System (ADS)

Fang, Ruimei; Huang, Haibao; Huang, Wenjun; Ji, Jian; Feng, Qiuyu; Shu, Yajie; Zhan, Yujie; Liu, Gaoyuan; Xie, Ruijie

2017-10-01

Coal based activated carbon (AC) was pretreated by peracetic acid solution and used for supporting Mn catalyst towards oxidation of gaseous benzene by catalytic ozonation. The as-obtained activated carbon was characterized by XPS, BET, SEM, and TG technologies. It indicates that peracetic acid solution modification not only raised the quantity of chemisorbed oxygen or water, and hydroxyl group on activated carbon material surface, but also increased the specific surface area and benzene adsorption capacity of activated carbon. Benzene could be completely removed in 300 min and CO2 selectivity reached to 61.9% over Mn/AC-modified catalyst. A possible catalytic ozonation mechanism of activated carbon which was treated by peracetic acid solution supported Mn catalyst for oxidation of benzene was proposed.

Electronic Structure and Reactivity of TM-Doped La1-xSrxCoO3 (TM = Ni, Fe) Catalysts

NASA Astrophysics Data System (ADS)

Grice, S. C.; Flavell, W. R.; Thomas, A. G.; Warren, S.; Marr, P. G.; Jewitt, D. E.; Khan, N.; Dunwoody, P. M.; Jones, S. A.

The catalytic properties of LaCoO3 in the oxidation of organic molecules in aqueous solution are explored as a function of doping with both Sr substitution for La and Fe and Ni substitution for Co. VUV photoemission is used to explore the surface reactivity of the ceramic catalysts in aqueous solution, using H2O as a probe molecule. These measurements are complemented by EXAFS and XANES measurements designed to probe the local defect structure and by GC measurements of catalytic activity in the aqueous epoxidation of crotyl alcohol. We relate the observed catalytic activity to the defect structure of the doped materials. In Ni-doped materials, oxygen vacancies appear to be the predominant defect, whereas in Fe-doped samples, electron holes are stabilised on Fe, leading to very different behaviour in oxidation. The surface reactivity to water is also influenced by the TM d electron count, with water binding more strongly to Fe-doped materials than to those containing Ni. The influence of these factors on the rate of the unwanted hydrogen peroxide decomposition reaction and hence on activity in epoxidation is discussed.

Cathodic electrochemical activation of Co3O4 nanoarrays: a smart strategy to significantly boost the hydrogen evolution activity.

PubMed

Yang, Li; Zhou, Huang; Qin, Xin; Guo, Xiaodong; Cui, Guanwei; Asiri, Abdullah M; Sun, Xuping

2018-02-22

Co(hydro)oxides show unsatisfactory catalytic activity for the hydrogen evolution reaction (HER) in alkaline media, and it is thus highly desirable but still remains a challenge to design and develop Co(hydro)oxide derived materials as superb hydrogen-evolving catalysts using a facile, rapid and less energy-intensive method. Here, we propose a cathodic electrochemical activation strategy toward greatly boosted HER activity of a Co 3 O 4 nanoarray via room-temperature cathodic polarization in sodium hypophosphite solution. After activation, the overpotential significantly decreases from 260 to 73 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 1.0 M KOH. Notably, this activated electrode also shows strong long-term electrochemical durability with the retention of its catalytic activity at 100 mA cm -2 for at least 40 h.

High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting.

PubMed

Feng, Liang-Liang; Yu, Guangtao; Wu, Yuanyuan; Li, Guo-Dong; Li, Hui; Sun, Yuanhui; Asefa, Tewodros; Chen, Wei; Zou, Xiaoxin

2015-11-11

Elaborate design of highly active and stable catalysts from Earth-abundant elements has great potential to produce materials that can replace the noble-metal-based catalysts commonly used in a range of useful (electro)chemical processes. Here we report, for the first time, a synthetic method that leads to in situ growth of {2̅10} high-index faceted Ni3S2 nanosheet arrays on nickel foam (NF). We show that the resulting material, denoted Ni3S2/NF, can serve as a highly active, binder-free, bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Ni3S2/NF is found to give ∼100% Faradaic yield toward both HER and OER and to show remarkable catalytic stability (for >200 h). Experimental results and theoretical calculations indicate that Ni3S2/NF's excellent catalytic activity is mainly due to the synergistic catalytic effects produced in it by its nanosheet arrays and exposed {2̅10} high-index facets.

Enhancement of the catalytic activity of Pt nanoparticles toward methanol electro-oxidation using doped-SnO2 supporting materials

NASA Astrophysics Data System (ADS)

Merati, Zohreh; Basiri Parsa, Jalal

2018-03-01

Catalyst supports play important role in governing overall catalyst activity and durability. In this study metal oxides (SnO2, Sb and Nb doped SnO2) were electrochemically deposited on titanium substrate (Ti) as a new support material for Pt catalyst in order to electro-oxidation of methanol. Afterward platinum nanoparticles were deposited on metal oxide film via electro reduction of platinum salt in an acidic solution. The surface morphology of modified electrodes were evaluated by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX) techniques. The electro-catalytic activities of prepared electrodes for methanol oxidation reaction (MOR) and oxidation of carbon monoxide (CO) absorbed on Pt was considered with cyclic voltammetry. The results showed high catalytic activity for Pt/Nb-SnO2/Ti electrode. The electrochemical surface area (ECSA) of a platinum electro-catalyst was determined by hydrogen adsorption. Pt/Nb-SnO2/Ti electrode has highest ECSA compared to other electrode resulting in high activity toward methanol electro-oxidation and CO stripping experiments. The doping of SnO2 with Sb and Nb improved ECSA and MOR activity, which act as electronic donors to increase electronic conductivity.

Method to produce catalytically active nanocomposite coatings

DOEpatents

Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

2016-02-09

A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

A virus-based biocatalyst

NASA Astrophysics Data System (ADS)

Carette, Noëlle; Engelkamp, Hans; Akpa, Eric; Pierre, Sebastien J.; Cameron, Neil R.; Christianen, Peter C. M.; Maan, Jan C.; Thies, Jens C.; Weberskirch, Ralf; Rowan, Alan E.; Nolte, Roeland J. M.; Michon, Thierry; van Hest, Jan C. M.

2007-04-01

Virus particles are probably the most precisely defined nanometre-sized objects that can be formed by protein self-assembly. Although their natural function is the storage and transport of genetic material, they have more recently been applied as scaffolds for mineralization and as containers for the encapsulation of inorganic compounds. The reproductive power of viruses has been used to develop versatile analytical methods, such as phage display, for the selection and identification of (bio)active compounds. To date, the combined use of self-assembly and reproduction has not been used for the construction of catalytic systems. Here we describe a self-assembled system based on a plant virus that has its coat protein genetically modified to provide it with a lipase enzyme. Using single-object and bulk catalytic studies, we prove that the virus-anchored lipase molecules are catalytically active. This anchored biocatalyst, unlike man-made supported catalysts, has the capability to reproduce itself in vivo, generating many independent catalytically active copies.

Role of non-metallic atoms in enhancing the catalytic activity of nickel-based compounds for hydrogen evolution reaction† †Electronic supplementary information (ESI) available: Experimental details, structure and morphology characterization, electrochemical characterizations, supplementary figures and data. See DOI: 10.1039/c7sc04851c

PubMed Central

Zheng, Xingqun; Peng, Lishan; Yang, Na; Yang, Yanjun; Li, Jing; Wang, Jianchuan

2018-01-01

The transition-metal compounds (MX) have gained wide attention as hydrogen evolution reaction (HER) electrocatalysts; however, the interaction between the non-metallic atom (X) and the metal atom (M) in MX, and the role of X in the enhanced catalytic activity of MX, are still ambiguous. In this work, we constructed a simple model [X/Ni(100)] to decipher the contribution of X towards enhancing the catalytic activity of NiX, which allows us to accurately predict the trend in HER catalytic activity of NiX based on the easily accessible physico-chemical characteristics of X. Theoretical calculations showed that the electronegativity (χX) and the principle quantum number (nX) of X are two important descriptors for evaluating and predicting the HER catalytic activity of NiX catalysts effectively. X atoms in the VIA group can enhance the HER activity of X/Ni(100) more significantly than those in the second period due to the large χX or nX. At a relatively low X coverage, the S/Ni(100) possesses the best HER activity among all of the discussed X/Ni(100) models, and the optimum surface S : Ni atomic ratio is about 22–33%. Further experiments demonstrated that the Ni–Ni3S2 catalyst with a surface S : Ni atomic ratio of 28.9% exhibits the best catalytic activity and lowest charge transfer resistance. The trend in catalytic activity of NiX with differing X offers a new possible strategy to exploit MX materials and design new active catalysts rationally. PMID:29675227

Tapered bed bioreactor

DOEpatents

Scott, Charles D.; Hancher, Charles W.

1977-01-01

A vertically oriented conically shaped column is used as a fluidized bed bioreactor wherein biologically catalyzed reactions are conducted in a continuous manner. The column utilizes a packing material a support having attached thereto a biologically active catalytic material.

Catalyst design with atomic layer deposition

DOE PAGES

O'Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan; ...

2015-02-06

Atomic layer deposition (ALD) has emerged as an interesting tool for the atomically precise design and synthesis of catalytic materials. Herein, we discuss examples in which the atomic precision has been used to elucidate reaction mechanisms and catalyst structure-property relationships by creating materials with a controlled distribution of size, composition, and active site. We highlight ways ALD has been utilized to design catalysts with improved activity, selectivity, and stability under a variety of conditions (e.g., high temperature, gas and liquid phase, and corrosive environments). In addition, due to the flexibility and control of structure and composition, ALD can create myriadmore » catalytic structures (e.g., high surface area oxides, metal nanoparticles, bimetallic nanoparticles, bifunctional catalysts, controlled microenvironments, etc.) that consequently possess applicability for a wide range of chemical reactions (e.g., CO 2 conversion, electrocatalysis, photocatalytic and thermal water splitting, methane conversion, ethane and propane dehydrogenation, and biomass conversion). Lastly, the outlook for ALD-derived catalytic materials is discussed, with emphasis on the pending challenges as well as areas of significant potential for building scientific insight and achieving practical impacts.« less

Catalyst design with atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan

Atomic layer deposition (ALD) has emerged as an interesting tool for the atomically precise design and synthesis of catalytic materials. Herein, we discuss examples in which the atomic precision has been used to elucidate reaction mechanisms and catalyst structure-property relationships by creating materials with a controlled distribution of size, composition, and active site. We highlight ways ALD has been utilized to design catalysts with improved activity, selectivity, and stability under a variety of conditions (e.g., high temperature, gas and liquid phase, and corrosive environments). In addition, due to the flexibility and control of structure and composition, ALD can create myriadmore » catalytic structures (e.g., high surface area oxides, metal nanoparticles, bimetallic nanoparticles, bifunctional catalysts, controlled microenvironments, etc.) that consequently possess applicability for a wide range of chemical reactions (e.g., CO 2 conversion, electrocatalysis, photocatalytic and thermal water splitting, methane conversion, ethane and propane dehydrogenation, and biomass conversion). Lastly, the outlook for ALD-derived catalytic materials is discussed, with emphasis on the pending challenges as well as areas of significant potential for building scientific insight and achieving practical impacts.« less

Catalytic conversion of methane to methanol using Cu-zeolites.

PubMed

Alayon, Evalyn Mae C; Nachtegaal, Maarten; Ranocchiari, Marco; van Bokhoven, Jeroen A

2012-01-01

The conversion of methane to value-added liquid chemicals is a promising answer to the imminent demand for fuels and chemical synthesis materials in the advent of a dwindling petroleum supply. Current technology requires high energy input for the synthesis gas production, and is characterized by low overall selectivity, which calls for alternative reaction routes. The limitation to achieve high selectivity is the high C-H bond strength of methane. High-temperature reaction systems favor gas-phase radical reactions and total oxidation. This suggests that the catalysts for methane activation should be active at low temperatures. The enzymatic-inspired metal-exchanged zeolite systems apparently fulfill this need, however, methanol yield is low and a catalytic process cannot yet be established. Homogeneous and heterogeneous catalytic systems have been described which stabilize the intermediate formed after the first C-H activation. The understanding of the reaction mechanism and the determination of the active metal sites are important for formulating strategies for the upgrade of methane conversion catalytic technologies.

Direct 3D Printing of Catalytically Active Structures

DOE PAGES

Manzano, J. Sebastian; Weinstein, Zachary B.; Sadow, Aaron D.; ...

2017-09-22

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. And as proof of principle, chemically activemore » cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azide-alkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints.« less

Direct 3D Printing of Catalytically Active Structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manzano, J. Sebastian; Weinstein, Zachary B.; Sadow, Aaron D.

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. And as proof of principle, chemically activemore » cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azide-alkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints.« less

New porphyrin-polyoxometalate hybrid materials: synthesis, characterization and investigation of catalytic activity in acetylation reactions.

PubMed

Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

2012-10-14

New hybrid complexes based on covalent interaction between 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatozinc(II) and 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatotin(IV) chloride, and a Lindqvist-type polyoxometalate, Mo(6)O(19)(2-), were prepared. These new porphyrin-polyoxometalate hybrid materials were characterized by (1)H NMR, FT IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided several spectral data for synthesis of these compounds. Cyclic voltammetry showed the influence of the polyoxometalate on the redox process of the porphyrin ring. The catalytic activity of tin(IV)porphyrin-hexamolybdate hybrid material was investigated in the acetylation of alcohols and phenols with acetic anhydride. The reusability of this catalyst was also investigated.

A green surfactant-assisted synthesis of hierarchical TS-1 zeolites with excellent catalytic properties for oxidative desulfurization.

PubMed

Du, Shuting; Li, Fen; Sun, Qiming; Wang, Ning; Jia, Mingjun; Yu, Jihong

2016-02-25

Hierarchical TS-1 zeolites with uniform intracrystalline mesopores have been successfully synthesized through the hydrothermal method by using the green and cheap surfactant Triton X-100 as the mesoporous template. The resultant materials exhibit remarkably enhanced catalytic activity in oxidative desulfurization reactions compared to the conventional TS-1 zeolite.

Improved hydrous oxide ion-exchange compound catalysts

DOEpatents

Dosch, R.G.; Stephens, H.P.

1986-04-09

Disclosed is a catalytic material of improved activity which comprises a hydrous, alkali metal or alkaline earth metal or quaternary ammonium titanate, zirconate, niobate, or tantalate, in which the metal or ammonium cations have been exchanged with a catalytically effective quantity of a catalyst metal, and which has been subsequently treated with a solution of a Bronsted acid.

I. Synthesis, characterization, and base catalysis of novel zeolite supported super-basic materials II. Oxidative dehydrogenation of ethane over reduced heteropolyanion catalysts

NASA Astrophysics Data System (ADS)

Galownia, Jonathan M.

This thesis is composed of two separate and unrelated projects. The first part of this thesis outlines an investigation into the synthesis and characterization of a novel zeolite supported super-base capable of carbon-carbon olefin addition to alkyl aromatics. A zeolite supported basic material capable of such reactions would benefit many fine chemical syntheses, as well as vastly improve the economics associated with production of the high performance thermoplastic polyester polyethylene naphthalate. The thermal decomposition of alkali---metal azides impregnated in zeolite X is investigated as a novel route to the synthesis of a zeolite supported super-base. Impregnation of the alkali---metal azide precursor is shown to result in azide species occluded within the pores of the zeolite support by using high speed, solid-state 23Na MAS and 2D MQMAS NMR, FTIR, and TGA characterization methods. Addition of alkali---metal azides to the zeolite results in redistribution of the extra-lattice cations in the zeolite framework. Thermal decomposition of impregnated azide species produces further cation redistribution, but no neutral metallic clusters are detected by high speed, solid-state 23Na MAS NMR following thermal activation of the materials. Instead, it is possible that inactive ionic clusters are formed. The thermally activated materials do not promote base catalysis for the isomerization of 1-butene, the ethylation of toluene and o-xylene, and the alkenylation of o-xylene with 1,3-butadiene to produce 5-ortho-tolyl-pent-2-ene (5-OTP). The lack of catalytic activity in the materials is attributed to failure of the materials to form neutral metallic clusters during thermal treatment, possibly due to preferential formation of NMR silent ionic clusters. The formation of neutral metallic clusters is found to be insensitive to synthesis technique and activation procedure. It is concluded that the impregnation of alkali---metal azides in zeolite X does not provide a reliable precursor for the formation of zeolite supported super-basic materials. The second part of this thesis describes the oxidative dehydrogenation of ethane over partially reduced heteropolyanions. Niobium and pyridine exchanged salts of phosphomolybdic (NbPMo12Pyr) and phosphovanadomolybdic (NbPMo11VPyr) acids are investigated as catalyst precursors to prepare materials for catalyzing the oxidative dehydrogenation of ethane to ethylene and acetic acid at atmospheric pressure. The effects of feed composition, steam flow, temperature, and precursor composition on catalytic activity and selectivity are presented for both ethane and ethylene oxidation. Production of ethylene and acetic acid from ethane using the catalytic materials exceeds that reported in the literature for Mo-V-Nb-Ox systems under atmospheric or elevated pressure. Production of acetic acid from ethylene is also greater than that observed for Mo-V-Nb-Ox systems. Addition of vanadium reduces catalytic activity and selectivity to both ethylene and acetic acid while niobium is essential for the formation of acetic acid from ethane. Other metals such as antimony, iron, and gallium do not provide the same beneficial effect as niobium. Molybdenum in close proximity to niobium is the active site for ethane activation while niobium is directly involved in the transformation of ethylene to acetic acid. A balance of niobium and protonated pyridine is required to produce an active catalyst. Water is found to aid in desorption of acetic acid, thereby limiting deep oxidation to carbon oxides. A reaction scheme is proposed for the production of acetic acid from ethane over the catalytic materials.

Method of making a layered composite electrode/electrolyte

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2005-01-25

An electrode/electrolyte structure is prepared by a plurality of methods. An unsintered (possibly bisque fired) moderately catalytic electronically-conductive or homogeneous mixed ionic electronic conductive electrode material is deposited on a layer composed of a sintered or unsintered ionically-conductive electrolyte material prior to being sintered. A layer of particulate electrode material is deposited on an unsintered ("green") layer of electrolyte material and the electrode and electrolyte layers are sintered simultaneously, sometimes referred to as "co-firing," under conditions suitable to fully densify the electrolyte while the electrode retains porosity. Or, the layer of particulate electrode material is deposited on a previously sintered layer of electrolyte, and then sintered. Subsequently, a catalytic material is added to the electrode structure by infiltration of an electrolcatalyst precursor (e.g., a metal salt such as a transition metal nitrate). This may be followed by low temperature firing to convert the precursor to catalyst. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in an ionic (electrochemical) device such as fuel cells and electrolytic gas separation systems.

In situ formation of coal gasification catalysts from low cost alkali metal salts

DOEpatents

Wood, Bernard J.; Brittain, Robert D.; Sancier, Kenneth M.

1985-01-01

A carbonaceous material, such as crushed coal, is admixed or impregnated with an inexpensive alkali metal compound, such as sodium chloride, and then pretreated with a stream containing steam at a temperature of 350.degree. to 650.degree. C. to enhance the catalytic activity of the mixture in a subsequent gasification of the mixture. The treatment may result in the transformation of the alkali metal compound into another, more catalytically active, form.

Size-dependent ROS production by palladium and nickel nanoparticles in cellular and acellular environments - An indication for the catalytic nature of their interactions.

PubMed

Neubauer, Nicole; Palomaeki, Jaana; Karisola, Piia; Alenius, Harri; Kasper, Gerhard

2015-01-01

Palladium and nickel nanoparticles with variable but narrowly defined primary particle sizes in the range of 4-27 nm were investigated toward their catalytic activity and their ability to produce reactive oxygen species (ROS). The agglomerate size in the gas phase was between 50 and 150 nm, after transfer into solution probably larger. The catalytic activity was measured on the basis of CO oxidation to CO2. The formation of ROS was determined after transferring the particles into phosphate buffered saline (PBS), via the 2',7'-dichlorofluorescein method in a cell-free environment and with THP-1 cells. Activities were normalized with regard to catalyst surface area to enable a meaningful comparison of size effects. The solubility was measured for both materials and found to be 2 µg/ml for Ni and below the detection limit of 0.8 µg/ml for Pd. In the concentration range of about 4-250 µg/ml both materials induced a significant production of ROS in both acellular and cellular environments, with palladium being more active than nickel by several orders of magnitude. On an equal surface area concentration basis, both acellular and cellular ROS production showed a pronounced dependence on the primary particle size, with a maximum in the vicinity of 12 nm. The surface-specific catalytic activity also had a maximum at that size range. The correlation of these size effects is both surprising and - in combination with the poor solubility of palladium and nickel in PBS solution - a strong argument in favor of a particulate, catalytic mechanism for ROS production.

Lewis Acid Pairs for the Activation of Biomass-derived Oxygenates in Aqueous Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roman, Yuriy

2015-09-14

The objective of this project is to understand the mechanistic aspects behind the cooperative activation of oxygenates by catalytic pairs in aqueous media. Specifically, we will investigate how the reactivity of a solid Lewis acid can be modulated by pairing the active site with other catalytic sites at the molecular level, with the ultimate goal of enhancing activation of targeted functional groups. Although unusual catalytic properties have been attributed to the cooperative effects promoted by such catalytic pairs, virtually no studies exist detailing the use heterogeneous water-tolerant Lewis pairs. A main goal of this work is to devise rational pathwaysmore » for the synthesis of porous heterogeneous catalysts featuring isolated Lewis pairs that are active in the transformation of biomass-derived oxygenates in the presence of bulk water. Achieving this technical goal will require closely linking advanced synthesis techniques; detailed kinetic and mechanistic investigations; strict thermodynamic arguments; and comprehensive characterization studies of both materials and reaction intermediates. For the last performance period (2014-2015), two technical aims were pursued: 1) C-C coupling using Lewis acid and base pairs in Lewis acidic zeolites. Tin-, zirconium-, and hafnium containing zeolites (e.g., Sn-, Zr-, and Hf-Beta) are versatile solid Lewis acids that selectively activate carbonyl functional groups. In this aim, we demonstrate that these zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions. 2) One-pot synthesis of MWW zeolite nanosheets for activation of bulky substrates. Through post-synthetic modifications, layered zeolite precursors can be transformed into 2-dimensional (2D), zeolites with open architectures. These novel hierarchical microporous/mesoporous materials with exposed active sites can facilitate the conversion of bulky substrates while maintaining higher stability than amorphous mesoporous materials. However, post-synthetic exfoliation techniques are energy intensive, multi-step and require highly alkaline conditions that result in low silica yields and a partially amorphous product. In this aim, we demonstrate an effective one-pot synthesis method to generate exfoliated single-unit-cell thick MWW nanosheets. The new material, named MIT-1, is synthesized using a rationally-designed OSDA and results in a material with high crystallinity, surface area, and acidity that does not require post-synthetic treatments other than calcination. A parametric study of Al, Na, and water content reveals that MIT-1 crystallizes over a wide synthetic window. Characterization data show that MIT-1 has high mesoporosity with an external surface area exceeding 500 m2g-1 and a high external acid site density of 21 x 10-5 mol g-1. Catalytic tests demonstrate that MIT-1 has three-fold higher catalytic activity for the Friedel-Crafts alkylation of benzene with benzyl alcohol as compared to that of other 3D MWW topology zeolites.« less

Impregnated active carbons to control atmospheric emissions: influence of impregnation methodology and raw material on the catalytic activity.

PubMed

Alvim-Ferraz, Maria C M; Gaspar, Carla M T B

2005-08-15

Previous studies have reported the influence of raw material on the catalytic activity of metal oxides impregnated in activated carbons. However, knowledge was as yet quite scarce for impregnation performed before activation. The main objective of the study here reported was the development of such knowledge. Olive stones, pinewood sawdust, nutshells, and almond shells were recycled to prepare the activated carbons. Transition metal oxides (CoO, Co3O4, and CrO3) were impregnated aiming to prepare activated carbons to be used for the complete catalytic oxidation of benzene. When impregnation was performed after activation the impregnated species were deposited on the internal surface, blocking part of the initial porous texture. When impregnation was performed before activation, the metal species acted as catalysts during the activation step, allowing better catalyst distribution on a more well-developed mesoporous texture. Co3O4 was the best catalyst and almond shells were the best support. With this catalyst/support pair a conversion of 90% was possible at 404 K, the lowest temperature of all the carbons studied. Good conversions were obtained at temperatures that guarantee carbon stability (lower than 575 K). It was concluded that activated carbon was a suitable support for metal oxide catalysts aiming for the complete oxidation of benzene, especially when a suitable porous texture is induced, by performing the impregnation step before activation.

DNA hydrogel as a template for synthesis of ultrasmall gold nanoparticles for catalytic applications.

PubMed

Zinchenko, Anatoly; Miwa, Yasuyuki; Lopatina, Larisa I; Sergeyev, Vladimir G; Murata, Shizuaki

2014-03-12

DNA cross-linked hydrogel was used as a matrix for synthesis of gold nanoparticles. DNA possesses a strong affinity to transition metals such as gold, which allows for the concentration of Au precursor inside a hydrogel. Further reduction of HAuCl4 inside DNA hydrogel yields well dispersed, non-aggregated spherical Au nanoparticles of 2-3 nm size. The average size of these Au nanoparticles synthesized in DNA hydrogel is the smallest reported so far for in-gel metal nanoparticles synthesis. DNA hybrid hydrogel containing gold nanoparticles showed high catalytic activity in the hydrogenation reaction of nitrophenol to aminophenol. The proposed soft hybrid material is promising as environmentally friendly and sustainable material for catalytic applications.

Fabrication of CuO-doped catalytic material containing zeolite synthesized from red mud and rice husk ash for CO oxidation

NASA Astrophysics Data System (ADS)

Hieu Do Thi, Minh; Thinh Tran, Quoc; Nguyen, Tri; Van Nguyen Thi, Thuy; Huynh, Ky Phuong Ha

2018-06-01

In this study a series of the CuO-doped materials containing zeolite with varying CuO contents were synthesized from red mud (RM) and rice husk ash (RHA). The rice husk ash/red mud with the molar ratio of , and being 1.8, 2.5 and 60, respectively, were maintained during the synthetic process of materials. The characteristic structure samples were analyzed by x-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), Brunauer–Emmett–Teller (BET) surface area and H2 temperature program reduction (H2-TPR). The catalytic activity of samples was evaluated in CO oxidation reaction in a microflow reactor at temperature range 200 °C–350 °C. The obtained results showed that all synthetic samples there exist the A-type zeolites with the average crystal size of 15–20 nm, the specific surface area of , and pore volume of . The material synthesized from RM and RHA with the zeolite structure (ZRM, undoped CuO) could also oxidize CO completely at 350 °C, and its activity was increase significantly when doped with CuO. CuO-doped materials with the zeolite structure exhibited excellent catalytic activity in CO oxidation. The ZRM sample loading 5 wt% CuO with particle nanosize about 10–30 nm was the best one for CO oxidation with complete conversion temperature at 275 °C.

Comprehensive Utilization of Biomass Process Residues Rich in Cellulose

NASA Astrophysics Data System (ADS)

Zhong, Mei; Li, Qiang; Yu, Jian; Dong, Li; Wang, Yin; Xu, Guangwen

2010-11-01

This article investigated the method preparing porous material (PM) with VL and SL. Applications of the prepared material was tested in removal aqueous phenol and COD in tarry water and as the catalyst support for selective catalytic reduction (SCR) of NO in flue gas. The results showed that the optimal activation condition in CO2 for the carbonized VL at 800° C was at 875° C for 1 h, which provided large BET surface area and micropore volume. This material exhibited the highest adsorption to aqueous phenol among all the tested materials including a commercial activated carbon made from coconut shell, showing the potential application of the VL-base porous material in wastewater treatment. The study demonstrated also that the vanadium-base selective catalytic reduction (SCR) catalyst supported on the VL-base porous material (V2O5/VL-PM) provided fairly good activity as well SO2 resistance at temperatures round 200° C for SCR of NO. The activation of the carbonized SL material in H2O was better than that in CO2 for developing the pore structure of the porous material. Steam can improve the formation of mesopore than CO2. This was confirmed by the conclusion that higher COD removal rate was occurred on the PM-1 from SL when H2O was used as an activator.

Graphene incorporated, N doped activated carbon as catalytic electrode in redox active electrolyte mediated supercapacitor

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.

Additive Manufacturing of Catalytically Active Living Materials.

PubMed

Saha, Abhijit; Johnston, Trevor G; Shafranek, Ryan T; Goodman, Cassandra J; Zalatan, Jesse G; Storti, Duane W; Ganter, Mark A; Nelson, Alshakim

2018-04-25

Living materials, which are composites of living cells residing in a polymeric matrix, are designed to utilize the innate functionalities of the cells to address a broad range of applications such as fermentation and biosensing. Herein, we demonstrate the additive manufacturing of catalytically active living materials (AMCALM) for continuous fermentation. A multi-stimuli-responsive yeast-laden hydrogel ink, based on F127-dimethacrylate, was developed and printed using a direct-write 3D printer. The reversible stimuli-responsive behaviors of the polymer hydrogel inks to temperature and pressure are critical, as they enabled the facile incorporation of yeast cells and subsequent fabrication of 3D lattice constructs. Subsequent photo-cross-linking of the printed polymer hydrogel afforded a robust elastic material. These yeast-laden living materials were metabolically active in the fermentation of glucose into ethanol for 2 weeks in a continuous batch process without significant reduction in efficiency (∼90% yield of ethanol). This cell immobilization platform may potentially be applicable toward other genetically modified yeast strains to produce other high-value chemicals in a continuous biofermentation process.

Nitrogen enriched mesoporous organic polymer anchored copper(II) material: an efficient and reusable catalyst for the synthesis of esters and amides from aromatic systems.

PubMed

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.

Role of oil derived carbonaceous phase in the performance of sewage sludge-based materials as media for desulfurizaton of digester gas

NASA Astrophysics Data System (ADS)

Kante, Karifala; Qiu, Jieshan; Zhao, Zongbin; Chang, Yu; Bandosz, Teresa J.

2008-02-01

Desulfurization adsorbents for purification of digester gas were prepared by pyrolysis of sewage sludge impregnated with spent mineral oil. To evaluate the changes in the structural and chemical properties the pyrolysis time and temperature varied. The materials were characterized using adsorption of nitrogen, FTIR, XRD, ICP, SEM and thermal analysis. Their catalytic activity was tested in the removal of hydrogen sulfide from simulated mixture of digester gas. The results indicated the importance of new carbon phase from the oil precursor. It provided mesoporosity, which increased the dispersion of catalytic phase and space for storage of surface reaction products. The results indicated that the adsorbents obtained at 950 °C are much more active in the process of hydrogen sulfide oxidation than those obtained at 650 °C. Moreover, longer heat treatment is also beneficial for the development of surface catalytic properties. Extensive pyrolysis stabilizes carbon phase via increasing its degree of aromatization and provides activation agents for this phase coming from decomposition and rearrangement of inorganic phase.

Method of fabricating electrode catalyst layers with directionally oriented carbon support for proton exchange membrane fuel cell

DOEpatents

Liu, Di-Jia; Yang, Junbing

2010-07-20

A method of making a membrane electrode assembly (MEA) having an anode and a cathode and a proton conductive membrane there between. A bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated in the nanotubes forms at least one portion of the MEA and is in contact with the membrane. A combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into a first reaction zone maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is transmitted to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes. The nanotubes are in contact with a portion of the MEA at production or being positioned in contact thereafter. Methods of forming a PEMFC are also disclosed.

Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

PubMed Central

2015-01-01

Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

Imidazolium- and Triazine-Based Porous Organic Polymers for Heterogeneous Catalytic Conversion of CO2 into Cyclic Carbonates.

PubMed

Zhong, Hong; Su, Yanqing; Chen, Xingwei; Li, Xiaoju; Wang, Ruihu

2017-12-22

CO 2 adsorption and concomitant catalytic conversion into useful chemicals are promising approaches to alleviate the energy crisis and effects of global warming. This is highly desirable for developing new types of heterogeneous catalytic materials containing CO 2 -philic groups and catalytic active sites for CO 2 chemical transformation. Here, we present an imidazolium- and triazine-based porous organic polymer with counter chloride anion (IT-POP-1). The porosity and CO 2 affinity of IT-POP-1 may be modulated at the molecular level through a facile anion-exchange strategy. Compared with the post-modified polymers with iodide and hexafluorophosphate anions, IT-POP-1 possesses the highest surface area and the best CO 2 uptake capacity with excellent adsorption selectivity over N 2 . The roles of the task-specific components such as triazine, imidazolium, hydroxyl, and counter anions in CO 2 absorption and catalytic performance were illustrated. IT-POP-1 exhibits the highest catalytic activity and excellent recyclability in solvent- and additive-free cycloaddition reaction of CO 2 with epoxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A non-chemically selective top-down approach towards the preparation of hierarchical TS-1 zeolites with improved oxidative desulfurization catalytic performance.

PubMed

Du, Shuting; Chen, Xiaoxin; Sun, Qiming; Wang, Ning; Jia, Mingjun; Valtchev, Valentin; Yu, Jihong

2016-02-28

Hierarchical TS-1 zeolites with secondary macropores have been successfully prepared by using two different fluoride-containing chemical etching post-treated routes. Hierarchical TS-1 zeolites exhibited a chemical composition similar to that of the parent material and showed remarkably enhanced catalytic activity in oxidative desulfurization reaction.

Synthesis, characterization, and catalytic activity of type 2 crystalline titanates prepared with supercritical drying

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.

Remarkable photo-catalytic degradation of malachite green by nickel doped bismuth selenide under visible light irradiation

NASA Astrophysics Data System (ADS)

Kulsi, Chiranjit; Ghosh, Amrita; Mondal, Anup; Kargupta, Kajari; Ganguly, Saibal; Banerjee, Dipali

2017-01-01

Bismuth selenide (Bi2Se3) and nickel (Ni) doped Bi2Se3 were prepared by a solvothermal approach to explore the photo-catalytic performance of the materials in degradation of malachite green (MG). The presence of nickel was confirmed by X-ray photoelectron spectroscopy (XPS) measurement in doped Bi2Se3. The results showed that the nickel doping played an important role in microstructure and photo-catalytic activity of the samples. Nickel doped Bi2Se3 sample exhibited higher photo-catalytic activity than that of the pure Bi2Se3 sample under visible-light irradiation. The photo-catalytic degradation followed first-order reaction kinetics. Fast degradation kinetics and complete (100% in 5 min of visible light irradiation) removal of MG was achieved by nickel doped Bi2Se3 in presence of hydrogen peroxide (H2O2) due to modification of band gap energies leading to suppression of photo-generated electron-hole recombination.

PA-Tb-Cu MOF as luminescent nanoenzyme for catalytic assay of hydrogen peroxide.

PubMed

Qi, Zewan; Wang, Li; You, Qi; Chen, Yang

2017-10-15

Metal organic frameworks (MOFs) with flexible structures and components have aroused great interest in designing functional materials. In this work, we designed and made a kind of PA-Tb-Cu MOF nanoenzyme capable of emitting fluorescence for the catalytic reaction of hydrogen peroxide (H 2 O 2 ). Luminescent Tb 3+ , catalytic Cu 2+ and bridging ligand were assembled and integrated into a single material nanoenzyme. This PA-Tb-Cu MOF nanoenzyme not only possessed excellent catalytic activity comparable to horseradish peroxidase but also can real-time fluorescently indicate the concentration of H 2 O 2 as low as 0.2µM during catalysis. Luminescent PA-Tb-Cu MOF nanoenzyme did not need a common combined use of natural/artificial enzymes and chromogenic reactions for the quantification of H 2 O 2 in widely-used enzyme-catalytic reactions. The present strategy assembled directly from functional ions/molecules provides a new way for the design and development of smart, multifunctional artificial enzymes for wide applications in biocatalysis, bioassays and nano-biomedicine. Copyright © 2017 Elsevier B.V. All rights reserved.

Al-doped TiO{sub 2} mesoporous material supported Pd with enhanced catalytic activity for complete oxidation of ethanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jing, E-mail: mlczjsls123@163.com; Mu, Wentao, E-mail: mwt15035687833@163.com; Su, Liqing, E-mail: suliqing0163@163.com

Pd catalysts supported on Al-doped TiO{sub 2} mesoporous materials were evaluated in complete oxidation of ethanol. The catalysts synthesized by wet impregnation based on evaporation-induced self-assembly were characterized by X-ray diffraction, measurement of pore structure, XPS, FT-IR, temperature programmed reduction and TEM. Characteristic results showed that the aluminium was doped into the lattice of mesoporous anatase TiO{sub 2} to form Al-O-Ti defect structure. Catalytic results revealed that Al-doped catalysts were much more active than the pristine one, especially at low temperature (≤200 °C). This should be ascribed to the introduction of aluminium ions that suppressed the strong metal-support interaction andmore » increased the active sites of Pd oxides, enhanced the stabilized anatase TiO{sub 2}, improved well dispersed high valence palladium species with high reducibility and enriched chemisorption oxygen. - Graphical abstract: Al-doped Pd/TiO{sub 2} exhibited optimal catalytic performance for ethanol oxidation and CO{sub 2} yield by the suppression of SMSI. - Highlights: • Palladium catalysts supported on Al-doped TiO{sub 2} mesoporous materials were studied. • The introduction of Al can enhance anatase stabilization and increase defect TiO{sub 2}. • The Pd/Al-TiO{sub 2} catalysts show higher ethanol conversion and CO{sub 2} yield than Pd/TiO{sub 2}. • The influence of Al on SMSI and catalytic performance were evaluated by TPR and XPS.« less

Catalytic performance of strong acid catalyst: Methyl modified SBA-15 loaded perfluorinated sulfonic acid obtained by the waste perfluorinated sulfonic acid ion exchange membrane

NASA Astrophysics Data System (ADS)

Jiang, Tingshun; Huang, Qiuyan; Li, Yingying; Fang, Minglan; Zhao, Qian

2018-02-01

Mesoporous molecular sieve (SBA-15) was modified using the trimethylchlorosilane as functional agent and the silylation SBA-15 mesoporous material was prepared in this work. The alcohol solution of perfluorinated sulfonic acid dissolved from the waste perfluorinated sulfonic acid ion exchange membrane (PFSIEM) was loaded onto the resulting mesoporous material by the impregnation method and their physicochemical properties were characterized by FT-IR, N2-physisorption, XRD, TG-DSC and TEM. The catalytic activities of these synthesized solid acid catalysts were evaluated by alkylation of phenol with tert-butyl alcohol. The influence of reaction temperature, weight hour space velocity (WHSV) and reaction time on the phenol conversion and product selectivity were assessed by means of a series of experiments. The results showed that with the increase of the active component of the catalyst, these catalysts still remained good mesoporous structure, but the mesoporous ordering decreased to some extent. These catalysts exhibited good catalytic performance for the alkylation of phenol with tert-butanol. The maximum phenol conversion of 89.3% with 70.9% selectivity to 4-t-butyl phenol (4-TBP) was achieved at 120 °C and the WHSV is 4 h-1. The methyl group was loaded on the surface of the catalyst by trimethylchlorosilane. This is beneficial to retard the deactivation of the catalyst. In this work, the alkylation of phenol with tert-butyl alcohol were carried out using the methyl modified SBA-15 mesoporous materials loaded perfluorinated sulfonic acid as catalysts. The results show that the resulting catalyst exhibited high catalytic activity.

On the dynamical nature of the active center in a single-site photocatalyst visualized by 4D ultrafast electron microscopy

PubMed Central

Yoo, Byung-Kuk; Su, Zixue; Thomas, John Meurig; Zewail, Ahmed H.

2016-01-01

Understanding the dynamical nature of the catalytic active site embedded in complex systems at the atomic level is critical to developing efficient photocatalytic materials. Here, we report, using 4D ultrafast electron microscopy, the spatiotemporal behaviors of titanium and oxygen in a titanosilicate catalytic material. The observed changes in Bragg diffraction intensity with time at the specific lattice planes, and with a tilted geometry, provide the relaxation pathway: the Ti4+=O2− double bond transformation to a Ti3+−O1− single bond via the individual atomic displacements of the titanium and the apical oxygen. The dilation of the double bond is up to 0.8 Å and occurs on the femtosecond time scale. These findings suggest the direct catalytic involvement of the Ti3+−O1− local structure, the significance of nonthermal processes at the reactive site, and the efficient photo-induced electron transfer that plays a pivotal role in many photocatalytic reactions. PMID:26729878

Functionalized multi-walled carbon nanotubes in an aldol reaction

NASA Astrophysics Data System (ADS)

Chronopoulos, D. D.; Kokotos, C. G.; Karousis, N.; Kokotos, G.; Tagmatarchis, N.

2015-01-01

The covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with a proline-based derivative is reported. Initially, MWCNTs were oxidized in order to introduce a large number of carboxylic units on their tips followed by N-tert-butoxycarbonyl-2,2'(ethylenedioxy)bis-(ethylamine) conjugation through an amide bond. Then, a proline derivative bearing a carboxylic terminal moiety at the 4-position was coupled furnishing proline-modified MWCNTs. This new hybrid material was fully characterized by spectroscopic and microscopy means and its catalytic activity in the asymmetric aldol reaction between acetone and 4-nitrobenzaldehyde was evaluated for the first time, showing to proceed almost quantitatively in aqueous media. Furthermore, several amino-modified MWCNTs were prepared and examined in the particular aldol reaction. These new hybrid materials exhibited an enhanced catalytic activity in water, contrasting with the pristine MWCNTs as well as the parent organic molecule, which failed to catalyze the reaction efficiently. Furthermore, the modified MWCNTs proved to catalyze the aldol reaction even after three repetitive cycles. Overall, a green approach for the aldol reaction is presented, where water can be employed as the solvent and modified MWCNTs can be used as catalysts, which can be successfully recovered and reused, while their catalytic activity is retained.The covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with a proline-based derivative is reported. Initially, MWCNTs were oxidized in order to introduce a large number of carboxylic units on their tips followed by N-tert-butoxycarbonyl-2,2'(ethylenedioxy)bis-(ethylamine) conjugation through an amide bond. Then, a proline derivative bearing a carboxylic terminal moiety at the 4-position was coupled furnishing proline-modified MWCNTs. This new hybrid material was fully characterized by spectroscopic and microscopy means and its catalytic activity in the asymmetric aldol reaction between acetone and 4-nitrobenzaldehyde was evaluated for the first time, showing to proceed almost quantitatively in aqueous media. Furthermore, several amino-modified MWCNTs were prepared and examined in the particular aldol reaction. These new hybrid materials exhibited an enhanced catalytic activity in water, contrasting with the pristine MWCNTs as well as the parent organic molecule, which failed to catalyze the reaction efficiently. Furthermore, the modified MWCNTs proved to catalyze the aldol reaction even after three repetitive cycles. Overall, a green approach for the aldol reaction is presented, where water can be employed as the solvent and modified MWCNTs can be used as catalysts, which can be successfully recovered and reused, while their catalytic activity is retained. Electronic supplementary information (ESI) available: Experimental details for the synthesis of 5, 8 and 11; 1H & 13C NMR of compounds 8 and 11; ATR-IR spectra, thermographs and TEM imaging of hybrids 10 and 13. See DOI: 10.1039/c4nr06543c

PdHx entrapped in covalent triazine framework modulates selectivity in glycerol oxidation [Modulation of palladium activity and stability by a covalent triazine framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chan-Thaw, Carine E.; Villa, Alberto; Wang, Di

The confinement of a Pd nanoparticle within a nitrogen-containing covalent triazine framework (CTF) material was investigated to understand if the highly tunable CTF chemistry mediates the Pd catalytic properties through an ensemble effect with the CTF nitrogen atoms or a confinement effect within the CTF pores. The results surprisingly demonstrate that the CTF stabilizes the formation of 2.6 nm PdHx particles within the pores. These PdHx particles are very active for the liquid phase oxidation of glycerol due to the in situ formation of H2O2 which catalytically promotes the initial C-C cleavage. In addition the confined particles are stable overmore » many catalytic cycles whereas nanoparticles trapped outside of the pores loose activity rapidly. These results indicate that there is the potential to tune the CTF chemistry to significantly modify the chemistry of the catalytic metals.« less

PdHx entrapped in covalent triazine framework modulates selectivity in glycerol oxidation [Modulation of palladium activity and stability by a covalent triazine framework

DOE PAGES

Chan-Thaw, Carine E.; Villa, Alberto; Wang, Di; ...

2015-06-25

The confinement of a Pd nanoparticle within a nitrogen-containing covalent triazine framework (CTF) material was investigated to understand if the highly tunable CTF chemistry mediates the Pd catalytic properties through an ensemble effect with the CTF nitrogen atoms or a confinement effect within the CTF pores. The results surprisingly demonstrate that the CTF stabilizes the formation of 2.6 nm PdHx particles within the pores. These PdHx particles are very active for the liquid phase oxidation of glycerol due to the in situ formation of H2O2 which catalytically promotes the initial C-C cleavage. In addition the confined particles are stable overmore » many catalytic cycles whereas nanoparticles trapped outside of the pores loose activity rapidly. These results indicate that there is the potential to tune the CTF chemistry to significantly modify the chemistry of the catalytic metals.« less

CuNi NPs supported on MIL-101 as highly active catalysts for the hydrolysis of ammonia borane

NASA Astrophysics Data System (ADS)

Gao, Doudou; Zhang, Yuhong; Zhou, Liqun; Yang, Kunzhou

2018-01-01

The catalysts containing Cu, Ni bi-metallic nanoparticles were successfully synthesized by in-situ reduction of Cu2+ and Ni2+ salts into the highly porous and hydrothermally stable metal-organic framework MIL-101 via a simple liquid impregnation method. When the total amount of loading metal is 3 × 10-4 mol, Cu2Ni1@MIL-101 catalyst shows higher catalytic activity comparing to CuxNiy@MIL-101 with different molar ratio of Cu and Ni (x, y = 0, 0.5, 1.5, 2, 2.5, 3). Cu2Ni1@MIL-101 catalyst has the highest catalytic activity comparing to mono-metallic Cu and Ni counterparts and pure bi-metallic CuNi nanoparticles in hydrolytic dehydrogeneration of ammonia borane (AB) at room temperature. Additionally, in the hydrolysis reaction, the Cu2Ni1@MIL- 101 catalyst possesses excellent catalytic performances, which exhibit highly catalytic activity with turn over frequency (TOF) value of 20.9 mol H2 min-1 Cu mol-1 and a very low activation energy value of 32.2 kJ mol-1. The excellent catalytic activity has been successfully achieved thanks to the strong bi-metallic synergistic effects, uniform distribution of nanoparticles and the bi-functional effects between CuNi nanoparticles and the host of MIL-101. Moreover, the catalyst also displays satisfied durable stability after five cycles for the hydrolytically releasing H2 from AB. The non-noble metal catalysts have broad prospects for commercial applications in the field of hydrogen-stored materials due to the low prices and excellent catalytic activity.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stair, Peter C.

The research took advantage of our capabilities to perform in-situ and operando Raman spectroscopy on complex systems along with our developing expertise in the synthesis of uniform, supported metal oxide materials to investigate relationships between the catalytically active oxide composition, atomic structure, and support and the corresponding chemical and catalytic properties. The project was organized into two efforts: 1) Synthesis of novel catalyst materials by atomic layer deposition (ALD). 2) Spectroscopic and chemical investigations of coke formation and catalyst deactivation. ALD synthesis was combined with conventional physical characterization, Raman spectroscopy, and probe molecule chemisorption to study the effect of supportedmore » metal oxide composition and atomic structure on acid-base and catalytic properties. Operando Raman spectroscopy studies of olefin polymerization leading to coke formation and catalyst deactivation clarified the mechanism of coke formation by acid catalysts.« less

A review of catalyst-enhanced magnesium hydride as a hydrogen storage material

NASA Astrophysics Data System (ADS)

Webb, C. J.

2015-09-01

Magnesium hydride remains an attractive hydrogen storage material due to the high hydrogen capacity and low cost of production. A high activation energy and poor kinetics at practical temperatures for the pure material have driven research into different additives to improve the sorption properties. This review details the development of catalytic additives and their effect on the activation energy, kinetics and thermodynamic properties of magnesium hydride.

Amine-functionalized Zn(ii) MOF as an efficient multifunctional catalyst for CO2 utilization and sulfoxidation reaction.

PubMed

Patel, Parth; Parmar, Bhavesh; Kureshy, Rukhsana I; Khan, Noor-Ul H; Suresh, Eringathodi

2018-06-19

Herein, a zinc(ii)-based 3D mixed ligand metal organic framework (MOF) was synthesized via versatile routes including green mechanochemical synthesis. The MOF {[Zn(ATA)(L)·H2O]}n (ZnMOF-1-NH2) has been characterized by various physico-chemical techniques, including SCXRD, and composed of the bipyridyl-based Schiff base (E)-N'-(pyridin-4-ylmethylene)isonicotinohydrazide (L) and 2-aminoterephthalic acid (H2ATA) ligands as linkers. The MOF material has been explored as a multifunctional heterogeneous catalyst for the cycloaddition of alkyl and aryl epoxides with CO2 and sulfoxidation reactions of aryl sulfides. The influence of various reaction parameters is examined to optimize the performance of the catalytic reactions. It is found that solvent-free catalytic reaction conditions offer good catalytic conversion in the case of cyclic carbonates, and for sulfoxide, good conversion and selectivity are achieved in the presence of DCM as a solvent medium under ambient reaction conditions. The chemical and thermal stability of the catalyst are excellent and it is active for up to four catalytic cycles without significant loss in activity. Furthermore, based on the catalytic activity and structural evidence, a plausible mechanism for both catalytic reactions is proposed.

Catalytic hydrolysis of ammonia borane via cobalt palladium nanoparticles.

PubMed

Sun, Daohua; Mazumder, Vismadeb; Metin, Önder; Sun, Shouheng

2011-08-23

Monodisperse 8 nm CoPd nanoparticles (NPs) with controlled compositions were synthesized by the reduction of cobalt acetylacetonate and palladium bromide in the presence of oleylamine and trioctylphosphine. These NPs were active catalysts for hydrogen generation from the hydrolysis of ammonia borane (AB), and their activities were composition dependent. Among the 8 nm CoPd catalysts tested for the hydrolysis of AB, the Co(35)Pd(65) NPs exhibited the highest catalytic activity and durability. Their hydrolysis completion time and activation energy were 5.5 min and 27.5 kJ mol(-1), respectively, which were comparable to the best Pt-based catalyst reported. The catalytic performance of the CoPd/C could be further enhanced by a preannealing treatment at 300 °C under air for 15 h with the hydrolysis completion time reduced to 3.5 min. This high catalytic performance of Co(35)Pd(65) NP catalyst makes it an exciting alternative in pursuit of practical implementation of AB as a hydrogen storage material for fuel cell applications. © 2011 American Chemical Society

Spatial decoupling of light absorption and catalytic activity of Ni-Mo-loaded high-aspect-ratio silicon microwire photocathodes

NASA Astrophysics Data System (ADS)

Vijselaar, Wouter; Westerik, Pieter; Veerbeek, Janneke; Tiggelaar, Roald M.; Berenschot, Erwin; Tas, Niels R.; Gardeniers, Han; Huskens, Jurriaan

2018-03-01

A solar-driven photoelectrochemical cell provides a promising approach to enable the large-scale conversion and storage of solar energy, but requires the use of Earth-abundant materials. Earth-abundant catalysts for the hydrogen evolution reaction, for example nickel-molybdenum (Ni-Mo), are generally opaque and require high mass loading to obtain high catalytic activity, which in turn leads to parasitic light absorption for the underlying photoabsorber (for example silicon), thus limiting production of hydrogen. Here, we show the fabrication of a highly efficient photocathode by spatially and functionally decoupling light absorption and catalytic activity. Varying the fraction of catalyst coverage over the microwires, and the pitch between the microwires, makes it possible to deconvolute the contributions of catalytic activity and light absorption to the overall device performance. This approach provided a silicon microwire photocathode that exhibited a near-ideal short-circuit photocurrent density of 35.5 mA cm-2, a photovoltage of 495 mV and a fill factor of 62% under AM 1.5G illumination, resulting in an ideal regenerative cell efficiency of 10.8%.

Immobilization of chloroperoxidase on mesoporous materials for the oxidation of 4,6-dimethyldibenzothiophene, a recalcitrant organic sulfur compound present in petroleum fractions.

PubMed

Terrés, Eduardo; Montiel, Mayra; Le Borgne, Sylvie; Torres, Eduardo

2008-01-01

The catalytic potential of chloroperoxidase (CPO) immobilized on mesoporous materials was evaluated for the oxidation of 4,6-dimethyldibenzothiophene in water/acetonitrile mixtures. Two different types of materials were used for the immobilization: a metal containing Al-MCM-41 material with a pore size of 26 A and SBA-16 materials with three different pore sizes: 40, 90 and 117 A. The SBA-16 40 A did not retain any CPO. The nature and the pore size of the material affected the catalytic activity of the enzyme as well as its stability. Compared to the free enzyme, the thermal stability of CPO at 45 degrees C was two and three times higher than when immobilized on Al-MCM-41 and SBA-16 90 A, respectively.

An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

NASA Astrophysics Data System (ADS)

Almeida, T. S.; Palma, L. M.; Leonello, P. H.; Morais, C.; Kokoh, K. B.; De Andrade, A. R.

2012-10-01

The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved.

Impact of active phase chemical composition and dispersity on catalytic behavior in PROX reaction

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Paneva, D.; Todorova, S.; Kolev, H.; Shopska, M.; Yordanova, I.; Mitov, I.

2014-04-01

Iron and iron-platinum catalysts supported on activated carbon have been successfully synthesized by wet impregnation method and low-temperature treatment in inert atmosphere. The content of the supported phases corresponds to 10 wt % Fe and 0.5 wt % Pt. Four catalytic samples were synthesized: Sample A—activated carbon impregnated with Fe nitrate; Sample B—activated carbon impregnated with Pt salt; Sample C—activated carbon impregnated consequently with Fe and Pt salts; Sample D—activated carbon impregnated simultaneously with Fe and Pt salts. The as-prepared materials were characterized by Mössbauer spectroscopy, X-ray diffraction, infrared and X-ray photoelectron spectroscopy. The spectra show that the activated carbon support and the preparation procedure give rise to the synthesis of isolated metal Pt ions and ultradispersed Fe and Pt oxide species. Probably the presence of different functional groups of activated carbon gives rise to registered very high dispersion of loaded species on support. The catalytic tests were carried out in PROX reaction. A lower activity of bimetallic Pt-Fe samples was explained with the increase in surface oxygen species as a result of predomination of iron oxide on the support leading to the increase in selectivity to the H2 oxidation. Partial agglomeration of supported iron oxide phase was registered after catalytic tests.

Size and Electronic Modulation of Iridium Nanoparticles on Nitrogen Functionalized Carbon toward Advanced Electrocatalysts for Alkaline Water Splitting.

PubMed

Wang, Hua; Ming, Mei; Hu, Min; Xu, Caili; Wang, Yi; Zhang, Yun; Gao, Daojiang; Bi, Jian; Fan, Guangyin; Hu, Jin-Song

2018-06-14

Developing efficient catalytic materials for electrochemical water splitting is important. Herein, uniformly dispersed and size-controllable iridium (Ir) nanoparticles (NPs) were prepared using a nitrogen-functionalized carbon (Ir/CN) as the support. We found that nitrogen function can simultaneously modulate the size of Ir NPs to substantially enhance the catalytically active sites and adjust the electronic structure of Ir, thereby promoting electrocatalytic activity for water splitting. Consequently, the as-synthesized Ir/CN shows excellent electrocatalytic performance with overpotentials of 12 and 265 mV for hydrogen and oxygen evolution reactions in basic medium, respectively. These findings may pave a way for designing and synthesizing other similar materials as efficient catalysts for electrochemical water splitting.

Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges

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.

Mimicking Heme Enzymes in the Solid State: Metal-Organic Materials with Selectively Encapsulated Heme

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larsen, Randy W; Wojtas, Lukasz; Perman, Jason

2011-06-13

To carry out essential life processes, nature has had to evolve heme enzymes capable of synthesizing and manipulating complex molecules. These proteins perform a plethora of chemical reactions utilizing a single iron porphyrin active site embedded within an evolutionarily designed protein pocket. We herein report the first class of metal–organic materials (MOMs) that mimic heme enzymes in terms of both structure and reactivity. The MOMzyme-1 class is based upon a prototypal MOM, HKUST-1, into which catalytically active metalloporphyrins are selectively encapsulated in a “ship-in-a-bottle” fashion within one of the three nanoscale cages that exist in HKUST-1. MOMs offer unparalleled levelsmore » of permanent porosity and their modular nature affords enormous diversity of structures and properties. The MOMzyme-1 class could therefore represent a new paradigm for heme biomimetic catalysis since it combines the activity of a homogeneous catalyst with the stability and recyclability of heterogeneous catalytic systems within a single material.« less

Mimicking heme enzymes in the solid state: metal-organic materials with selectively encapsulated heme.

PubMed

Larsen, Randy W; Wojtas, Lukasz; Perman, Jason; Musselman, Ronald L; Zaworotko, Michael J; Vetromile, Carissa M

2011-07-13

To carry out essential life processes, nature has had to evolve heme enzymes capable of synthesizing and manipulating complex molecules. These proteins perform a plethora of chemical reactions utilizing a single iron porphyrin active site embedded within an evolutionarily designed protein pocket. We herein report the first class of metal-organic materials (MOMs) that mimic heme enzymes in terms of both structure and reactivity. The MOMzyme-1 class is based upon a prototypal MOM, HKUST-1, into which catalytically active metalloporphyrins are selectively encapsulated in a "ship-in-a-bottle" fashion within one of the three nanoscale cages that exist in HKUST-1. MOMs offer unparalleled levels of permanent porosity and their modular nature affords enormous diversity of structures and properties. The MOMzyme-1 class could therefore represent a new paradigm for heme biomimetic catalysis since it combines the activity of a homogeneous catalyst with the stability and recyclability of heterogeneous catalytic systems within a single material.

Peptide-Directed PdAu Nanoscale Surface Segregation: Toward Controlled Bimetallic Architecture for Catalytic Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bedford, Nicholas M.; Showalter, Allison R.; Woehl, Taylor J.

Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when mixing two different metallic species at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesizedmore » with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods were then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence-dependence in both surface structure and surface composition. Replica exchange solute tempering molecular dynamic simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Finally, taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged for rational bimetallic nanoparticle design using peptide-enabled approaches.« less

Peptide-Directed PdAu Nanoscale Surface Segregation: Toward Controlled Bimetallic Architecture for Catalytic Materials

DOE PAGES

Bedford, Nicholas M.; Showalter, Allison R.; Woehl, Taylor J.; ...

2016-09-01

Bimetallic nanoparticles are of immense scientific and technological interest given the synergistic properties observed when mixing two different metallic species at the nanoscale. This is particularly prevalent in catalysis, where bimetallic nanoparticles often exhibit improved catalytic activity and durability over their monometallic counterparts. Yet despite intense research efforts, little is understood regarding how to optimize bimetallic surface composition and structure synthetically using rational design principles. Recently, it has been demonstrated that peptide-enabled routes for nanoparticle synthesis result in materials with sequence-dependent catalytic properties, providing an opportunity for rational design through sequence manipulation. In this study, bimetallic PdAu nanoparticles are synthesizedmore » with a small set of peptides containing known Pd and Au binding motifs. The resulting nanoparticles were extensively characterized using high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy and high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Structural information obtained from synchrotron radiation methods were then used to generate model nanoparticle configurations using reverse Monte Carlo simulations, which illustrate sequence-dependence in both surface structure and surface composition. Replica exchange solute tempering molecular dynamic simulations were also used to predict the modes of peptide binding on monometallic surfaces, indicating that different sequences bind to the metal interfaces via different mechanisms. As a testbed reaction, electrocatalytic methanol oxidation experiments were performed, wherein differences in catalytic activity are clearly observed in materials with identical bimetallic composition. Finally, taken together, this study indicates that peptides could be used to arrive at bimetallic surfaces with enhanced catalytic properties, which could be leveraged for rational bimetallic nanoparticle design using peptide-enabled approaches.« less

Outstanding catalytic activity of ultra-pure platinum nanoparticles.

PubMed

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.

Electrocatalysis paradigm for protection of cathode materials in high-voltage lithium-ion batteries

DOE PAGES

Shkrob, Ilya A.; Abraham, Daniel P.

2016-07-06

A new mechanistic framework is suggested to account for the protective action of certain electrolyte additives on high-voltage positive electrode (cathode) materials. The mechanism involves inactivation of catalytically active centers on the electrode active materials through fragmentation reactions involving molecules at its surface. The cathode protection additives oxidize before the solvent and serve as sacrificial inhibitors of the catalytic centers. Without the additive, the surface oxidation of the solvent (like solvent oxidation in the bulk) yields H loss radicals and releases the proton that can combine with anions forming corrosive acids. This proton-release reaction is demonstrated experimentally for boronate additives.more » Specific radical reactions for the latter additives on the electrode surface are suggested. Furthermore, the same approach can be used to rationalize the protective action of other additives and account for various observations regarding their performance.« less

Electrocatalysis paradigm for protection of cathode materials in high-voltage lithium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shkrob, Ilya A.; Abraham, Daniel P.

A new mechanistic framework is suggested to account for the protective action of certain electrolyte additives on high-voltage positive electrode (cathode) materials. The mechanism involves inactivation of catalytically active centers on the electrode active materials through fragmentation reactions involving molecules at its surface. The cathode protection additives oxidize before the solvent and serve as sacrificial inhibitors of the catalytic centers. Without the additive, the surface oxidation of the solvent (like solvent oxidation in the bulk) yields H loss radicals and releases the proton that can combine with anions forming corrosive acids. This proton-release reaction is demonstrated experimentally for boronate additives.more » Specific radical reactions for the latter additives on the electrode surface are suggested. Furthermore, the same approach can be used to rationalize the protective action of other additives and account for various observations regarding their performance.« less

Hydridosiloxanes as precursors to ceramic products

DOEpatents

Blum, Yigal D.; Johnson, Sylvia M.; Gusman, Michael I.

1997-01-01

A method is provided for preparing ceramic precursors from hydridosiloxane starting materials and then pyrolyzing these precursors to give rise to silicious ceramic materials. Si--H bonds present in the hydridosiloxane starting materials are catalytically activated, and the activated hydrogen atoms may then be replaced with nonhydrogen substituents. These preceramic materials are pyrolyzed in a selected atmosphere to give the desired ceramic product. Ceramic products which may be prepared by this technique include silica, silicon oxynitride, silicon carbide, metal silicates, and mullite.

Hydridosiloxanes as precursors to ceramic products

DOEpatents

Blum, Y.D.; Johnson, S.M.; Gusman, M.I.

1997-06-03

A method is provided for preparing ceramic precursors from hydridosiloxane starting materials and then pyrolyzing these precursors to give rise to silicious ceramic materials. Si-H bonds present in the hydridosiloxane starting materials are catalytically activated, and the activated hydrogen atoms may then be replaced with nonhydrogen substituents. These preceramic materials are pyrolyzed in a selected atmosphere to give the desired ceramic product. Ceramic products which may be prepared by this technique include silica, silicon oxynitride, silicon carbide, metal silicates, and mullite.

Catalytic fast pyrolysis of biomass impregnated with potassium phosphate in a hydrogen atmosphere for the production of phenol and activated carbon

NASA Astrophysics Data System (ADS)

Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

2018-02-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550 oC in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1605 m2/g.

Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

PubMed Central

Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

2018-01-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994

Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon.

PubMed

Lu, Qiang; Zhang, Zhen-Xi; Wang, Xin; Guo, Hao-Qiang; Cui, Min-Shu; Yang, Yong-Ping

2018-01-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K 3 PO 4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K 3 PO 4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K 3 PO 4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO 2 activation method, the specific surface area was as high as 1,605 m 2 /g.

Synthesis of urease hybrid nanoflowers and their enhanced catalytic properties.

PubMed

Somturk, Burcu; Yilmaz, Ismail; Altinkaynak, Cevahir; Karatepe, Aslıhan; Özdemir, Nalan; Ocsoy, Ismail

2016-05-01

Increasing numbers of materials have been extensively used as platforms for enzyme immobilization to enhance catalytic activity and stability. Although stability of enzyme was accomplished with immobilization approaches, activity of the most of the enzymes was declined after immobilization. Herein, we synthesize the flower shaped-hybrid nanomaterials called hybrid nanoflower (HNF) consisting of urease enzyme and copper ions (Cu(2+)) and report a mechanistic elucidation of enhancement in both activity and stability of the HNF. We demonstrated how experimental factors influence morphology of the HNF. We proved that the HNF (synthesized from 0.02mgmL(-1) urease in 10mM PBS (pH 7.4) at +4°C) exhibited the highest catalytic activity of ∼2000% and ∼4000% when stored at +4°C and RT, respectively compared to free urease. The highest stability was also achieved by this HNF by maintaining 96.3% and 90.28% of its initial activity within storage of 30 days at +4°C and RT, respectively. This dramatically enhanced activity is attributed to high surface area, nanoscale-entrapped urease and favorable urease conformation of the HNF. The exceptional catalytic activity and stability properties of HNF can be taken advantage of to use it in fields of biomedicine and chemistry. Copyright © 2015 Elsevier Inc. All rights reserved.

Nitrogen and sulfur dual-doped chitin-derived carbon/graphene composites as effective metal-free electrocatalysts for dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Di, Yi; Xiao, Zhanhai; Yan, Xiaoshuang; Ru, Geying; Chen, Bing; Feng, Jiwen

2018-05-01

The photovoltaic performance of dye-sensitized solar cell (DSSC) is strongly influenced by the electrocatalytic ability of its counter electrode (CE) materials. To obtain the affordable and high-performance electrocatalysts, the N/S dual-doped chitin-derived carbon materials SCCh were manufactured via in-situ S-doped method in the annealing process, where richer active sites are created compared to the pristine chitin-derived carbon matrix CCh, thus enhancing the intrinsic catalytic activity of carbon materials. When SCCh is incorporated with graphene, the yielded composites hold a further boosted catalytic activity due to facilitating the electronic fast transfer. The DSSC assembled with the optimizing rGO-SCCh-3 composite CE shows a favourable power conversion efficiency of 6.36%, which is comparable with that of the Pt-sputtering electrode (6.30%), indicate of the outstanding I3- reduction ability of the composite material. The electrochemical characterizations demonstrate that the low charge transfer resistance and excellent electrocatalytic activity all contribute to the superior photovoltaic performance. More importantly, the composite CE exhibits good electrochemical stability in the practical operation. In consideration of the low cost and the simple preparation procedure, the present metal-free carbonaceous composites could be used as a promising counter electrode material in future large scale production of DSSCs.

Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation.

PubMed

Julcour Lebigue, Carine; Andriantsiferana, Caroline; N'Guessan Krou; Ayral, Catherine; Mohamed, Elham; Wilhelm, Anne-Marie; Delmas, Henri; Le Coq, Laurence; Gerente, Claire; Smith, Karl M; Pullket, Suangusa; Fowler, Geoffrey D; Graham, Nigel J D

2010-12-01

This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L(-1)). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption-oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles. Copyright © 2010 Elsevier Ltd. All rights reserved.

Development of SiO2@TiO2 core-shell nanospheres for catalytic applications

NASA Astrophysics Data System (ADS)

Kitsou, I.; Panagopoulos, P.; Maggos, Th.; Arkas, M.; Tsetsekou, A.

2018-05-01

Silica-titania core-shell nanospheres, CSNp, were prepared via a simple and environmentally friendly two step route. First, silica cores were prepared through the hydrolysis-condensation reaction of silicic acid in the presence of hyperbranched poly(ethylene)imine (HBPEI) followed by repeating washing, centrifugation and, finally, calcination steps. To create the core-shell structure, various amounts of titanium isopropoxide were added to the cores and after that a HBPEI-water solution was added to hydrolyze the titanium precursor. Washing with ethanol and heat treatment followed. The optimization of processing parameters led to well-developed core-shell structures bearing a homogeneous nanocrystalline anatase coating over each silica core. The photocatalytic activity for NO was examined in a continuous flux photocatalytic reactor under real environmental conditions. The results revealed a very potent photocatalyst as the degradation percentage reached 84.27% for the core-shell material compared to the 82% of pure titania with the photodecomposition rates measured at 0.62 and 0.55 μg·m-2·s-1, respectively. In addition, catalytic activities of the CSNp and pure titania were investigated by monitoring the reduction of 4-nitrophenol to 4-aminophenol by an excess of NaBH4. Both materials exhibited excellent catalytic activity (100%), making the core-shell material a promising alternative catalyst to pure titania for various applications.

The physical chemistry and materials science behind sinter-resistant catalysts.

PubMed

Dai, Yunqian; Lu, Ping; Cao, Zhenming; Campbell, Charles T; Xia, Younan

2018-06-18

Catalyst sintering, a main cause of the loss of catalytic activity and/or selectivity at high reaction temperatures, is a major concern and grand challenge in the general area of heterogeneous catalysis. Although all heterogeneous catalysts are inevitably subjected to sintering during their operation, the immediate and drastic consequences can be mitigated by carefully engineering the catalytic particles and their interactions with the supports. In this tutorial review, we highlight recent progress in understanding the physical chemistry and materials science involved in sintering, including the discussion of advanced techniques, such as in situ microscopy and spectroscopy, for investigating the sintering process and its rate. We also discuss strategies for the design and rational fabrication of sinter-resistant catalysts. Finally, we showcase recent success in improving the thermal stability and thus sinter resistance of supported catalytic systems.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

Catalytic micromotor generating self-propelled regular motion through random fluctuation.

PubMed

Yamamoto, Daigo; Mukai, Atsushi; Okita, Naoaki; Yoshikawa, Kenichi; Shioi, Akihisa

2013-07-21

Most of the current studies on nano∕microscale motors to generate regular motion have adapted the strategy to fabricate a composite with different materials. In this paper, we report that a simple object solely made of platinum generates regular motion driven by a catalytic chemical reaction with hydrogen peroxide. Depending on the morphological symmetry of the catalytic particles, a rich variety of random and regular motions are observed. The experimental trend is well reproduced by a simple theoretical model by taking into account of the anisotropic viscous effect on the self-propelled active Brownian fluctuation.

Catalytic micromotor generating self-propelled regular motion through random fluctuation

NASA Astrophysics Data System (ADS)

Yamamoto, Daigo; Mukai, Atsushi; Okita, Naoaki; Yoshikawa, Kenichi; Shioi, Akihisa

2013-07-01

Most of the current studies on nano/microscale motors to generate regular motion have adapted the strategy to fabricate a composite with different materials. In this paper, we report that a simple object solely made of platinum generates regular motion driven by a catalytic chemical reaction with hydrogen peroxide. Depending on the morphological symmetry of the catalytic particles, a rich variety of random and regular motions are observed. The experimental trend is well reproduced by a simple theoretical model by taking into account of the anisotropic viscous effect on the self-propelled active Brownian fluctuation.

Nanoporous Gold as a Platform for a Building Block Catalyst

DOE PAGES

Wittstock, Arne; Wichmann, Andre; Baeumer, Marcus

2012-09-25

The porous bulk materials are of great interest in catalysis because they can be employed in heterogeneous gas and liquid phase catalysis, electrocatalysis, and in electrocatalytic sensing. Nanoporous gold gained considerable attraction in this context because it is the prime example of a corrosion-derived nanoporous bulk metal. Moreover, the material was shown to be a very active and selective Au type catalyst for a variety of oxidation reactions. In leveraging the functionalization of the surface of the material with various additives, its catalytic applications can be extended and tuned. In this review, we will summarize recent developments in using nanoporousmore » gold as the platform for the development of high performance catalytic materials by adding metals, metal oxides, and molecular functionalities as building blocks.« less

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.

Synthesis and characterization of supported polysugar-stabilized palladium nanoparticle catalysts for enhanced hydrodechlorination of trichloroethylene

NASA Astrophysics Data System (ADS)

Bacik, Deborah B.; Zhang, Man; Zhao, Dongye; Roberts, Christopher B.; Seehra, Mohinar S.; Singh, Vivek; Shah, Naresh

2012-07-01

Palladium (Pd) nanoparticle catalysts were successfully synthesized within an aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping ligand which offers a green alternative to conventional nanoparticle synthesis techniques. The CMC-stabilized Pd nanoparticles were subsequently dispersed within support materials using the incipient wetness impregnation technique for utilization in heterogeneous catalyst systems. The unsupported and supported (both calcined and uncalcined) Pd nanoparticle catalysts were characterized using transmission electron microscopy, energy dispersive x-ray spectrometry, x-ray diffraction, and Brunauer-Emmett-Teller surface area measurement and their catalytic activity toward the hydrodechlorination of trichloroethylene (TCE) in aqueous media was examined using homogeneous and heterogeneous catalyst systems, respectively. The unsupported Pd nanoparticles showed considerable activity toward the degradation of TCE, as demonstrated by the reaction kinetics. Although the supported Pd nanoparticle catalysts had a lower catalytic activity than the unsupported particles that were homogeneously dispersed in the aqueous solutions, the supported catalysts retained sufficient activity toward the degradation of TCE. In addition, the use of the hydrophilic Al2O3 support material induced a mass transfer resistance to TCE that affected the initial hydrodechlorination rate. This paper demonstrates that supported Pd catalysts can be applied to the heterogeneous catalytic hydrodechlorination of TCE.

Versatile Three-Dimensional Porous Cu@Cu2 O Aerogel Networks as Electrocatalysts and Mimicking Peroxidases.

PubMed

Ling, Pinghua; Zhang, Qiang; Cao, Tingting; Gao, Feng

2018-06-04

A facile strategy is presented to form 3D porous Cu@Cu 2 O aerogel networks by self-assembling Cu@Cu 2 O nanoparticles with the diameters of ca. 40 nm for constructing catalytic interfaces. Unexpectedly, the prepared Cu@Cu 2 O aerogel networks display excellent electrocatalytic activity to glucose oxidation at a low onset potential of ca. 0.25 V. Moreover, the Cu@Cu 2 O aerogels also can act as mimicking-enzymes including horseradish peroxidase and NADH peroxidase, and show obvious enzymatic catalytic activities to the oxidation of dopamine (DA), o-phenyldiamine (OPD), 3,3,5,5-tetramethylbenzidine (TMB), and dihydronicotinamide adenine dinucleotide (NADH) in the presence of H 2 O 2 . These 3D Cu@Cu 2 O aerogel networks are a new class of porous catalytic materials as mimic peroxidases and electrocatalysts and offer a novel platform to construct catalytic interfaces for promising applications in electrochemical sensors and artificial enzymatic catalytic systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces

DOE PAGES

Chen, Chen; Kang, Yijin; Huo, Ziyang; ...

2014-02-27

Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi 3 polyhedra, transforms in solution by interior erosion into Pt 3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi 3 polyhedra are maintained in the final Pt 3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skinmore » structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt 3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.« less

Chemically-modified cellulose paper as a microstructured catalytic reactor.

PubMed

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.

Metal Nanoparticles Covered with a Metal-Organic Framework: From One-Pot Synthetic Methods to Synergistic Energy Storage and Conversion Functions.

PubMed

Kobayashi, Hirokazu; Mitsuka, Yuko; Kitagawa, Hiroshi

2016-08-01

Hybrid materials composed of metal nanoparticles and metal-organic frameworks (MOFs) have attracted much attention in many applications, such as enhanced gas storage and catalytic, magnetic, and optical properties, because of the synergetic effects between the metal nanoparticles and MOFs. In this Forum Article, we describe our recent progress on novel synthetic methods to produce metal nanoparticles covered with a MOF (metal@MOF). We first present Pd@copper(II) 1,3,5-benzenetricarboxylate (HKUST-1) as a novel hydrogen-storage material. The HKUST-1 coating on Pd nanocrystals results in a remarkably enhanced hydrogen-storage capacity and speed in the Pd nanocrystals, originating from charge transfer from Pd nanocrystals to HKUST-1. Another material, Pd-Au@Zn(MeIM)2 (ZIF-8, where HMeIM = 2-methylimidazole), exhibits much different catalytic activity for alcohol oxidation compared with Pd-Au nanoparticles, indicating a design guideline for the development of composite catalysts with high selectivity. A composite material composed of Cu nanoparticles and Cr3F(H2O)2O{C6H3(CO2)3}2 (MIL-100-Cr) demonstrates higher catalytic activity for CO2 reduction into methanol than Cu/γ-Al2O3. We also present novel one-pot synthetic methods to produce composite materials including Pd/ZIF-8 and Ni@Ni2(dhtp) (MOF-74, where H4dhtp = 2,5-dihydroxyterephthalic acid).

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions.

PubMed

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.

Iron encapsulated in 3D N-doped carbon nanotube/porous carbon hybrid from waste biomass for enhanced oxidative activity.

PubMed

Yao, Yunjin; Zhang, Jie; Wu, Guodong; Wang, Shaobin; Hu, Yi; Su, Cong; Xu, Tongwen

2017-03-01

Novel iron encapsulated in nitrogen-doped carbon nanotubes (CNTs) supported on porous carbon (Fe@N-C) 3D structured materials for degrading organic pollutants were fabricated from a renewable, low-cost biomass, melamine, and iron salt as the precursors. SEM and TEM micrographs show that iron encapsulated bamboo shaped CNTs are vertically standing on carbon sheets, and thus, a 3D hybrid was formed. The catalytic activities of the prepared samples were thoroughly evaluated by activation of peroxymonosulfate for catalytic oxidation of Orange II solutions. The influences of some reaction conditions (pH, temperature, and concentrations of reactants, peroxymonosulfate, and dye) were extensively evaluated. It was revealed that the adsorption could enrich the pollutant which was then rapidly degraded by the catalytically generated radicals, accelerating the continuous adsorption of residual pollutant. Remarkable carbon structure, introduction of CNTs, and N/Fe doping result in promoted adsorption capability and catalytic performances. Due to the simple synthetic process and cheap carbon precursor, Fe@N-C 3D hybrid can be easily scaled up and promote the development of Fenton-like catalysts.

In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

PubMed

Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

2012-03-20

The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

Synthesis and visible-light-induced catalytic activity of Ag2S-coupled TiO2 nanoparticles and nanowires

NASA Astrophysics Data System (ADS)

Xie, Yi; Heo, Sung Hwan; Kim, Yong Nam; Yoo, Seung Hwa; Cho, Sung Oh

2010-01-01

We present the synthesis and visible-light-induced catalytic activity of Ag2S-coupled TiO2 nanoparticles (NPs) and TiO2 nanowires (NWs). Through a simple wet chemical process from a mixture of peroxo titanic acid (PTA) solution, thiourea and AgAc, a composite of Ag2S NPs and TiO2 NPs with sizes of less than 7 nm was formed. When the NP composite was further treated with NaOH solution followed by annealing at ambient conditions, a new nanocomposite material comprising Ag2S NPs on TiO2 NWs was created. Due to the coupling with such a low bandgap material as Ag2S, the TiO2 nanocomposites could have a visible-light absorption capability much higher than that of pure TiO2. As a result, the synthesized Ag2S/TiO2 nanocomposites exhibited much higher catalytic efficiency for the decomposition of methyl orange than commercial TiO2 (Degussa P25, Germany) under visible light.

Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buru, Cassandra T.; Li, Peng; Mehdi, B. Layla

2017-05-22

A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Finally, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.

A new approach for crystallization of copper(ii) oxide hollow nanostructures with superior catalytic and magnetic response

NASA Astrophysics Data System (ADS)

Singh, Inderjeet; Landfester, Katharina; Chandra, Amreesh; Muñoz-Espí, Rafael

2015-11-01

We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism.We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism. Electronic supplementary information (ESI) available: Associated structural and morphological analysis, XPS characterization, BET surface area, catalytic measurements, recycle tests of the catalyst, and magnetic characterizations. See DOI: 10.1039/c5nr05579b

Heterogeneous fenton catalysts based on activated carbon and related materials.

PubMed

Navalon, Sergio; Dhakshinamoorthy, Amarajothi; Alvaro, Mercedes; Garcia, Hermenegildo

2011-12-16

The Fenton reaction is widely used for remediation of waste water and for the degradation of organic pollutants in water. Currently, there is considerable interest to convert the classical Fenton reaction, which consumes stoichiometric amounts of iron(II) salts, into a catalytic process that is promoted by a solid. This review describes the work that has used carbonaceous materials either directly as catalysts or, more frequently, as a large-area support for catalytically activated transition metals or metal-oxide nanoparticles. The interest in this type of catalyst derives from the wide use of carbon in conventional water treatments and the wide applicability of the Fenton reaction. After two general sections that illustrate the scope and background of Fenton chemistry, the review describes the activity of activated carbon in the absence or presence of metal-containing particles. The last sections of the review focus on different types of carbonaceous materials, such as carbon nanotubes and diamond nanoparticles. The review concludes with a section that anticipates future developments in this area, which are aimed at overcoming the current limitations of low activity and occurrence of metal leaching. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-throughput screening of nanoparticle catalysts made by flame spray pyrolysis as hydrocarbon/NO oxidation catalysts.

PubMed

Weidenhof, B; Reiser, M; Stöwe, K; Maier, W F; Kim, M; Azurdia, J; Gulari, E; Seker, E; Barks, A; Laine, R M

2009-07-08

We describe here the use of liquid-feed flame spray pyrolysis (LF-FSP) to produce high surface area, nonporous, mixed-metal oxide nanopowders that were subsequently subjected to high-throughput screening to assess a set of materials for deNO(x) catalysis and hydrocarbon combustion. We were able to easily screen some 40 LF-FSP produced materials. LF-FSP produces nanopowders that very often consist of kinetic rather than thermodynamic phases. Such materials are difficult to access or are completely inaccessible via traditional catalyst preparation methods. Indeed, our studies identified a set of Ce(1-x)Zr(x)O(2) and Al(2)O(3)-Ce(1-x)Zr(x)O(2) nanopowders that offer surprisingly good activities for both NO(x) reduction and propane/propene oxidation both in high-throughput screening and in continuous flow catalytic studies. All of these catalysts offer activities comparable to traditional Pt/Al(2)O(3) catalysts but without Pt. Thus, although Pt-free, they are quite active for several extremely important emission control reactions, especially considering that these are only first generation materials. Indeed, efforts to dope the active catalysts with Pt actually led to lower catalytic activities. Thus the potential exists to completely change the materials used in emission control devices, especially for high-temperature reactions as these materials have already been exposed to 1500 degrees C; however, much research must be done before this potential is verified.

Porous media for catalytic renewable energy conversion

NASA Astrophysics Data System (ADS)

Hotz, Nico

2012-05-01

A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

Preparation, characterization and catalytic properties of MCM-48 supported tungstophosphoric acid mesoporous materials for green synthesis of benzoic acid

NASA Astrophysics Data System (ADS)

Wu, Hai-Yan; Zhang, Xiao-Li; Chen, Xi; Chen, Ya; Zheng, Xiu-Cheng

2014-03-01

MCM-48 and tungstophosphoric acid (HPW) were prepared and applied for the synthesis of HPW/MCM-48 mesoporous materials. The characterization results showed that HPW/MCM-48 obtained retained the typical mesopore structure of MCM-48, and the textural parameters decreased with the increase loading of HPW. The catalytic oxidation results of benzyl alcohol and benzaldehyde with 30% H2O2 indicated that HPW/MCM-48 was an efficient catalyst for the green synthesis of benzoic acid. Furthermore, 35 wt% HPW/MCM-48 sample showed the highest activity under the reaction conditions.

A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer

NASA Astrophysics Data System (ADS)

Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

2016-01-01

Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated.Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06749a

Nanosized iron and chromium oxides supported on mesoporous CeO2 and SBA-15 silica: Physicochemical and catalytic study

NASA Astrophysics Data System (ADS)

Tsoncheva, Tanya; Roggenbuck, Jan; Paneva, Daniela; Dimitrov, Momtchil; Mitov, Ivan; Fröba, Michael

2010-11-01

Mesoporous ceria and SBA-15 silica were modified with iron and chromium oxide nanoparticles and characterized by XRD, N2-physisorption, FTIR, UV-vis, Moessbauer spectroscopy and TPR-TG in hydrogen. Their catalytic behaviour in methanol decomposition to CO and hydrogen was also studied. Stabilization of mono- and bi-chromate species, FeOx patches or isolated iron ions as well as Fe2O3 and Cr2O3 nanoparticles in different ratio depending on the nature of the porous matrix was observed. The simultaneous presence of iron and chromium oxides lead to change in their dispersion, providing easier reducibility, higher catalytic activity and stability of the obtained materials in comparison with the corresponding mono-component ones. The "intimate contact" at the interface of both loaded metal oxide nanoparticles and the support was discussed with respect to explain the differences in the state of the active ingredient and its specific catalytic behaviour.

Electro-catalytic oxidation device for removing carbon from a fuel reformate

DOEpatents

Liu, Di-Jia [Naperville, IL

2010-02-23

An electro-catalytic oxidation device (ECOD) for the removal of contaminates, preferably carbonaceous materials, from an influent comprising an ECOD anode, an ECOD cathode, and an ECOD electrolyte. The ECOD anode is at a temperature whereby the contaminate collects on the surface of the ECOD anode as a buildup. The ECOD anode is electrically connected to the ECOD cathode, which consumes the buildup producing electricity and carbon dioxide. The ECOD anode is porous and chemically active to the electro-catalytic oxidation of the contaminate. The ECOD cathode is exposed to oxygen, and made of a material which promotes the electro-chemical reduction of oxygen to oxidized ions. The ECOD electrolyte is non-permeable to gas, electrically insulating and a conductor to oxidized. The ECOD anode is connected to the fuel reformer and the fuel cell. The ECOD electrolyte is between and in ionic contact with the ECOD anode and the ECOD cathode.

Nanoscale zero-valent iron incorporated with nanomagnetic diatomite for catalytic degradation of methylene blue in heterogeneous Fenton system.

PubMed

Zha, Yiming; Zhou, Ziqing; He, Haibo; Wang, Tianlin; Luo, Liqiang

2016-01-01

Nanoscale zero-valent iron (nZVI) incorporated with nanomagnetic diatomite (DE) composite material was prepared for catalytic degradation of methylene blue (MB) in heterogeneous Fenton system. The material was constructed by two facile steps: Fe3O4 magnetic nanoparticles were supported on DE by chemical co-precipitation method, after which nZVI was incorporated into magnetic DE by liquid-phase chemical reduction strategy. The as-prepared catalyst was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, magnetic properties measurement and nitrogen adsorption-desorption isotherm measurement. The novel nZVI@Fe3O4-diatomite nanocomposites showed a distinct catalytic activity and a desirable effect for degradation of MB. MB could be completely decolorized within 8 min and the removal efficiency of total organic carbon could reach to 90% after reaction for 1 h.

Thermo-Responsive Amphiphilic Block Copolymers Stablilized Gold Nanoparticles: Synthesis and High Catalytic Properties.

PubMed

Lü, Jianhua; Yang, Yu; Gao, Junfang; Duan, Haichao; Lü, Changli

2018-06-19

A series of novel well-defined 8-hydroxyquinoline (HQ)-containing thermo-responsive amphiphilic diblock copolymers poly(styrene-co-5-(2-methacryloylethyloxy- methyl)-8-quinolinol)-b-poly(N-isopropylacrylamide) P(St-co-MQ)-b-PNIPAm (P1,2), P(NIPAm- co-MQ)-b-PSt (P3,4) and triblock copolymer poly(N-isopropylacrylamide)-b-poly(methyl- methacrylate-co-5-(2-methacryloylethyloxymethyl)-8-quinolinol)-b-polystyrene PNIPAm-b- P(MMA-co-MQ)-b-PSt (P5) were prepared by reversible addition fragmentation chain transfer (RAFT) polymerization, and their self-assembly behaviors were studied. The block copolymers P1-P5 stabilized gold nanoparticles (Au@P1-Au@P5) with small size and narrow distribution were obtained through in situ reduction of gold precursors in aqueous solution of polymer micelles with HQ as the coordination groups. The resulting Au@P nanohybrids possessed excellent catalytic activities for the reduction of nitrophenols using NaBH4. The size, morphology and surface chemistry of Au NPs could be controlled by adjusting the structure of block polymers with HQ in different block positions, which plays an important role in the catalytic properties. It was found that longer chain length of hydrophilic or hydrophobic segments of block copolymers were beneficial to elevate the catalytic activity of Au NPs for the reduction of nitrophenols, and the spherical nanoparticles (Au@P5) stabilized with triblock copolymer exhibit higher catalytic performance. Surprisingly, the gold nanowires (Au@P4) produced with P4 have a highest catalytic activity due to large abundance of grain boundaries. Excellent thermo-responsive behaviors for catalytic reaction make the as-prepared Au@P hybrids become an environmentally responsive nano-catalytic materials.

Zinc sulfide liquefaction catalyst

DOEpatents

Garg, Diwakar

1984-01-01

A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

Ultrahigh-sensitive sensing platform based on p-type dumbbell-like Co3O4 network

NASA Astrophysics Data System (ADS)

Zhou, Tingting; Zhang, Tong; Zhang, Rui; Lou, Zheng; Deng, Jianan; Wang, Lili

2017-12-01

Development of high performance room temperature sensors remains a grand challenge for high demand of practical application. Metal oxide semiconductors (MOSs) have many advantages over others due to their easy functionalization, high surface area, and low cost. However, they typically need a high work temperature during sensing process. Here, p-type sensing layer is reported, consisting of pore-rich dumbbell-like Co3O4 particles (DP-Co3O4) with intrinsic high catalytic activity. The gas sensor (GS) based DP-Co3O4 catalyst exhibits ultrahigh NH3 sensing activity along with excellent stability over other structure based NH3 GSs in room temperature work environment. In addition, the unique structure of DP-Co3O4 with pore-rich and high catalytic activity endows fast gas diffusion rate and high sensitivity at room temperature. Taken together, the findings in this work highlight the merit of integrating highly active materials in p-type materials, offering a framework to develop high-sensitivity room temperature sensing platforms.

Nano-array based monolithic catalysts: Concept, rational materials design and tunable catalytic performance

DOE PAGES

Ren, Zheng; Guo, Yanbing; Gao, Pu-Xian

2015-03-20

Monolithic catalysts, also known as structured catalysts, represent an important catalyst configuration widely used in automotive, chemical, and energy industries. However, several issues associated with washcoat based monolithic catalyst preparation are ever present, such as compromised materials utilization efficiency due to a less-than-ideal wash coating process, difficulty in precise and optimum microstructure control and lack of structure-property correlation. Here, in this mini-review, we introduce the concept of nano-array catalyst, a new type of monolithic catalyst featuring high catalyst utilization efficiency, good thermal/mechanical robustness, and catalytic performance tunability. A comprehensive overview is presented with detailed discussion of the strategies for nano-arraymore » catalyst preparation and rational catalytic activity adjustment enabled by the well-defined nano-array geometry. Specifically their scalable fabrication processes are reviewed in conjunction with discussion of their various catalytic oxidation reaction performances at low temperature. Finally, we hope this review will serve as a timely and useful research guide for rational design and utilization of the new type of monolithic catalysts.« less

Effect of Hydrothermal Treatment on Structural and Catalytic Properties of [CTA]-MCM-41 Silica.

PubMed

Zapelini, Iago W; Silva, Laura L; Cardoso, Dilson

2018-05-21

The [CTA]-MCM-41 hybrid silica is a useful and simply prepared heterogeneous basic catalyst for the transesterification reaction. Here, the effect of hydrothermal treatment during catalyst preparation was investigated, with the aim of improving the structural stability of this catalyst during the reaction. It was observed that the hydrothermal step led to the formation of a material with a higher degree of organization and a greater wall thickness, which improved its structural stability. However, the catalyst prepared using this treatment presented lower catalytic activity, due to the presence of fewer active sites.

Functionalized Graphene Metal-Free Carbocatalysis of Persulfate and Emerging Contaminant Oxidative Degradation

NASA Astrophysics Data System (ADS)

Carroll, K. C.; Chen, H.

2016-12-01

We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L-1) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 hours, and NH2-GP (50 mg L-1) activated PS (1 mM) can also remove 50% SMX within 10 hours. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 hours to 1 hour when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L-1) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

Silica-Protection-Assisted Encapsulation of Cu2 O Nanocubes into a Metal-Organic Framework (ZIF-8) To Provide a Composite Catalyst.

PubMed

Li, Bo; Ma, Jian-Gong; Cheng, Peng

2018-06-04

The integration of metal/metal oxide nanoparticles (NPs) into metal-organic frameworks (MOFs) to form composite materials has attracted great interest due to the broad range of applications. However, to date, it has not been possible to encapsulate metastable NPs with high catalytic activity into MOFs, due to their instability during the preparation process. For the first time, we have successfully developed a template protection-sacrifice (TPS) method to encapsulate metastable NPs such as Cu 2 O into MOFs. SiO 2 was used as both a protective shell for Cu 2 O nanocubes and a sacrificial template for forming a yolk-shell structure. The obtained Cu 2 O@ZIF-8 composite exhibits excellent cycle stability in the catalytic hydrogenation of 4-nitrophenol with high activity. This is the first report of a Cu 2 O@MOF-type composite material. The TPS method provides an efficient strategy for encapsulating unstable active metal/metal oxide NPs into MOFs or maybe other porous materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical Fluorescence Microscopy for Spatially Characterizing Electron Transfer across a Solid-Liquid Interface on Heterogeneous Electrodes.

PubMed

Choudhary, Eric; Velmurugan, Jeyavel; Marr, James M; Liddle, James A; Szalai, Veronika

2016-01-01

Heterogeneous catalytic materials and electrodes are used for (electro)chemical transformations, including those important for energy storage and utilization. 1, 2 Due to the heterogeneous nature of these materials, activity measurements with sufficient spatial resolution are needed to obtain structure/activity correlations across the different surface features (exposed facets, step edges, lattice defects, grain boundaries, etc.). These measurements will help lead to an understanding of the underlying reaction mechanisms and enable engineering of more active materials. Because (electro)catalytic surfaces restructure with changing environments, 1 it is important to perform measurements in operando . Sub-diffraction fluorescence microscopy is well suited for these requirements because it can operate in solution with resolution down to a few nm. We have applied sub-diffraction fluorescence microscopy to a thin cell containing an electrocatalyst and a solution containing the redox sensitive dye p-aminophenyl fluorescein to characterize reaction at the solid-liquid interface. Our chosen dye switches between a nonfluorescent reduced state and a one-electron oxidized bright state, a process that occurs at the electrode surface. This scheme is used to investigate the activity differences on the surface of polycrystalline Pt, in particular to differentiate reactivity at grain faces and grain boundaries. Ultimately, this method will be extended to study other dye systems and electrode materials.

Efficient decomposition of formaldehyde at room temperature over Pt/honeycomb ceramics with ultra-low Pt content.

PubMed

Nie, Longhui; Zheng, Yingqiu; Yu, Jiaguo

2014-09-14

Pt/honeycomb ceramic (Pt/HC) catalysts with ultra-low Pt content (0.005-0.055 wt%) were for the first time prepared by an impregnation of honeycomb ceramics with Pt precursor and NaBH4-reduction combined method. The microstructures, morphologies and textural properties of the resulting samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The obtained Pt/HC catalysts were used for catalytic oxidative decomposition of formaldehyde (HCHO) at room temperature. It was found that the as-prepared Pt/HC catalysts can efficiently decompose HCHO in air into CO2 and H2O at room temperature. The catalytic activity of the Pt/HC catalysts increases with increasing the Pt loading in the range of 0.005-0.013 wt%, and the further increase of the Pt loading does not obviously improve catalytic activity. From the viewpoint of cost and catalytic performance, 0.013 wt% Pt loading is the optimal Pt loading amount, and the Pt/HC catalyst with 0.013 wt% Pt loading also exhibited good catalytic stability. Considering practical applications, this work will provide new insights into the low-cost and large-scale fabrication of advanced catalytic materials for indoor air purification.

Pt nanocatalysts supported on reduced graphene oxide for selective conversion of cellulose or cellobiose to sorbitol.

PubMed

Wang, Ding; Niu, Wenqi; Tan, Minghui; Wu, Mingbo; Zheng, Xuejun; Li, Yanpeng; Tsubaki, Noritatsu

2014-05-01

Pt nanocatalysts loaded on reduced graphene oxide (Pt/RGO) were prepared by means of a convenient microwave-assisted reduction approach with ethylene glycol as reductant. The conversion of cellulose or cellobiose into sorbitol was used as an application reaction to investigate their catalytic performance. Various metal nanocatalysts loaded on RGO were compared and RGO-supported Pt exhibited the highest catalytic activity with 91.5 % of sorbitol yield from cellobiose. The catalytic performances of Pt nanocatalysts supported on different carbon materials or on silica support were also compared. The results showed that RGO was the best catalyst support, and the yield of sorbitol was as high as 91.5 % from cellobiose and 58.9 % from cellulose, respectively. The improvement of catalytic activity was attributed to the appropriate Pt particle size and hydrogen spillover effect of Pt/RGO catalyst. Interestingly, the size and dispersion of supported Pt particles could be easily regulated by convenient adjustment of the microwave heating temperature. The catalytic performance was found to initially increase and then decrease with increasing particle size. The optimum Pt particle size was 3.6 nm. These findings may offer useful guidelines for designing novel catalysts with beneficial catalytic performance for biomass conversion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic enantioselective addition of Grignard reagents to aromatic silyl ketimines

NASA Astrophysics Data System (ADS)

Rong, Jiawei; Collados, Juan F.; Ortiz, Pablo; Jumde, Ravindra P.; Otten, Edwin; Harutyunyan, Syuzanna R.

2016-12-01

α-Chiral amines are of significant importance in medicinal chemistry, asymmetric synthesis and material science, but methods for their efficient synthesis are scarce. In particular, the synthesis of α-chiral amines with the challenging tetrasubstituted carbon stereocentre is a long-standing problem and catalytic asymmetric additions of organometallic reagents to ketimines that would give direct access to these molecules are underdeveloped. Here we report a highly enantioselective catalytic synthesis of N-sulfonyl protected α-chiral silyl amines via the addition of inexpensive, easy to handle and readily available Grignard reagents to silyl ketimines. The key to this success was our ability to suppress any unselective background addition reactions and side reduction pathway, through the identification of an inexpensive, chiral Cu-complex as the catalytically active structure.

Nickel-silver composition shows promise as catalyst for hydrogen-oxygen fuel cells

NASA Technical Reports Server (NTRS)

Magerl, J. A.; Murray, J. N.

1970-01-01

Carburized 3-1 nickel-silver preparation exhibits considerable catalytic activity, although not as high as platinum black. Cost and availability factors warrant further evaluation of nickel-silver materials.

Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

DOE PAGES

Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; ...

2015-12-09

The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs).more » Our results including unique mechanistic studies demonstrate that the SrRuO 3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO 3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO 3 composite catalyst material.« less

Synthesis of Densely Packaged, Ultrasmall Pt02 Clusters within a Thioether-Functionalized MOF: Catalytic Activity in Industrial Reactions at Low Temperature.

PubMed

Mon, Marta; Rivero-Crespo, Miguel A; Ferrando-Soria, Jesús; Vidal-Moya, Alejandro; Boronat, Mercedes; Leyva-Pérez, Antonio; Corma, Avelino; Hernández-Garrido, Juan C; López-Haro, Miguel; Calvino, José J; Ragazzon, Giulio; Credi, Alberto; Armentano, Donatella; Pardo, Emilio

2018-05-22

The gram-scale synthesis, stabilization, and characterization of well-defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X-ray snapshots of Pt 0 2 clusters, homogenously distributed and densely packaged within the channels of a metal-organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140 °C), energetically costly industrial reactions in the gas phase such as HCN production, CO 2 methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal clusters in solids for technically easier, cheaper, and dramatically less-dangerous industrial reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bedford, Nicholas M.; Hughes, Zak E.; Tang, Zhenghua

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 datamore » 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.« less

Catalytic ozonation of p-chlorobenzoic acid by activated carbon and nickel supported activated carbon prepared from petroleum coke.

PubMed

Li, Xukai; Zhang, Qiuyun; Tang, Lili; Lu, Ping; Sun, Fengqiang; Li, Laisheng

2009-04-15

The aim of this research was to investigate catalytic activity of petroleum coke, activated carbon (AC) prepared from this material, Ni supported catalyst on activated carbon (Ni/AC) in the ozonation of aqueous phase p-chlorobenzoic acid (p-CBA). Activated carbon and Ni/AC catalyst were characterized by XRD and SEM. The presence of petroleum coke did not improve the degradation of p-CBA compared to ozonation alone, but it was advantageous for p-CBA mineralization (total organic carbon, TOC, reduction), indicating the generation of highly oxidant species (*OH) in the medium. The presence of either activated carbon or Ni/AC considerably improves TOC removal during p-CBA ozonation. Ni/AC catalyst shows the better catalytic activity and stability based on five repeated tests during p-CBA ozonation. During the ozonation (50 mg/h ozone flow rate) of a 10 mg/L p-CBA (pH 4.31), it can be more mineralized in the presence of Ni/AC catalyst (5.0 g/L), TOC removal rate is over 60% in 60 min, 43% using activated carbon as catalyst, only 30% with ozonation alone.

Templated Assembly of a Functional Ordered Protein Macromolecular Framework from P22 Virus-like Particles.

PubMed

McCoy, Kimberly; Uchida, Masaki; Lee, Byeongdu; Douglas, Trevor

2018-04-24

Bottom-up construction of mesoscale materials using biologically derived nanoscale building blocks enables engineering of desired physical properties using green production methods. Virus-like particles (VLPs) are exceptional building blocks due to their monodispersed sizes, geometric shapes, production ease, proteinaceous composition, and our ability to independently functionalize the interior and exterior interfaces. Here a VLP, derived from bacteriophage P22, is used as a building block for the fabrication of a protein macromolecular framework (PMF), a tightly linked 3D network of functional protein cages that exhibit long-range order and catalytic activity. Assembly of PMFs was electrostatically templated, using amine-terminated dendrimers, then locked into place with a ditopic cementing protein that binds to P22. Long-range order is preserved on removal of the dendrimer, leaving a framework material composed completely of protein. Encapsulation of β-glucosidase enzymes inside of P22 VLPs results in formation of stable, condensed-phase materials with high local concentration of enzymes generating catalytically active PMFs.

Catalytic properties of new anode materials for solid oxide fuel cells operated under methane at intermediary temperature

NASA Astrophysics Data System (ADS)

Sauvet, A.-L.; Fouletier, J.

The recent trend in solid oxide fuel cell concerns the use of natural gas as fuel. Steam reforming of methane is a well-established process for producing hydrogen directly at the anode side. In order to develop new anode materials, the catalytic activities of several oxides for the steam reforming of methane were characterized by gas chromatography. We studied the catalytic activity as a function of steam/carbon ratios r. The methane and the steam content were varied between 5 and 30% and between 1.5 and 3.5%, respectively, corresponding to r-values between 0.07 and 0.7. Catalyst (ruthenium and vanadium)-doped lanthanum chromites substituted with strontium, gadolinium-doped ceria (Ce 0.9Gd 0.1O 2) referred as to CeGdO 2, praseodymium oxide, molybdenum oxide and copper oxide were tested. The working temperature was fixed at 850°C, except for 5% ruthenium-doped La 1- xSr xCrO 3 where the temperature was varied between 700 and 850°C. Two types of behavior were observed as a function of the activity of the catalyst. The higher steam reforming efficiency was observed with 5% of ruthenium above 750°C.

Synthesis, characterization of double perovskite Ca{sub 2}MSbO{sub 6} (M = Dy, Fe, Cr, Al) materials via sol–gel auto-combustion and their catalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feraru, S.; Samoila, P.; Borhan, A.I.

2013-10-15

Double perovskite-type oxide Ca{sub 2}MSbO{sub 6} materials, where M = Dy, Fe, Cr, and Al, were prepared by using the sol–gel auto-combustion method. The role of different B-site cations on their synthesis, structures, morphologies and catalytic properties was investigated. The progress of double-perovskite type structure formation and the disappearance of the organic phases were monitored by infrared absorption spectroscopy (FTIR). Double perovskite oxide structures were evaluated using X-ray diffraction (XRD), while the microstructure of obtained compounds was studied using scanning electron microscopy (SEM). Also, BET surface areas were measured at the liquid nitrogen temperature by nitrogen adsorption. Catalytic properties ofmore » the obtained compounds were evaluated by test reaction of hydrogen peroxide decomposition. - Highlights: • Ca{sub 2}MSbO{sub 6} double perovskites were obtained by sol–gel auto-combustion method. • Ca{sub 2}MSbO{sub 6} (M = Dy, Fe, Cr and Al) as catalysts in H{sub 2}O{sub 2} decomposition • Strong relationship between particles' shape, BET area and catalytic performance • Ca{sub 2}FeSbO{sub 6} spherical grains show superior catalytic activity.« less

Adsorption of a catalytically accessible polyoxometalate in a mesoporous channel-type metal–organic framework

DOE PAGES

Buru, Cassandra T.; Li, Peng; Mehdi, B. Layla; ...

2017-05-24

A Keggin-type polyoxometalate (H 3PW 12O 40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW 12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Lastly, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW 12@NU-1000 was shown to have a higher catalytic activity than eithermore » of the individual constituents alone.« less

A Ta/W mixed addenda heteropolyacid with excellent acid catalytic activity and proton-conducting property

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Shujun; Peng, Qingpo; Chen, Xuenian, E-mail: xnchen@htu.edu.cn

A new HPAs H{sub 20}[P{sub 8}W{sub 60}Ta{sub 12}(H{sub 2}O){sub 4}(OH){sub 8}O{sub 236}]·125H{sub 2}O (H-1) which comprises a Ta/W mixed addenda heteropolyanion, 20 protons, and 125 crystalline water molecules has been prepared through ion-exchange method. The structure and properties of H-1 have been explored in detail. AC impedance measurements indicate that H-1 is a good solid state proton conducting material at room temperature with a conductivity value of 7.2×10{sup −3} S cm{sup −1} (25 °C, 30% RH). Cyclic voltammograms of H-1 indicate the electrocatalytic activity towards the reduction of nitrite. Hammett acidity constant H{sub 0} of H-1 in CH{sub 3}CN ismore » −2.91, which is the strongest among the present known HPAs. Relatively, H-1 exhibits excellent catalytic activities toward acetal reaction. - Highlights: • A Ta/W mixed addenda Heteropolyacid (H-1) was isolated. • Hammett acidity constant H{sub 0} of H-1 is the strongest among the present known HPAs. • H-1 exhibits excellent catalytic activities toward acetal reaction. • H-1 is a good solid state proton conducting material at room temperature.« less

Synthesis, Characterization, and Photoelectrochemical Catalytic Studies of a Water-Stable Zinc-Based Metal-Organic Framework.

PubMed

Altaf, Muhammad; Sohail, Manzar; Mansha, Muhammad; Iqbal, Naseer; Sher, Muhammad; Fazal, Atif; Ullah, Nisar; Isab, Anvarhusein A

2018-02-09

Metal-organic frameworks (MOFs) are class of porous materials that can be assembled in a modular manner by using different metal ions and organic linkers. Owing to their tunable structural properties, these materials are found to be useful for gas storage and separation technologies, as well as for catalytic applications. A cost-effective zinc-based MOF ([Zn(bpcda)(bdc)] n ) is prepared by using N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine [N,N'-bis(pyridin-4-ylmethylene)cyclohexane-1,4-diamine] and benzenedicarboxylic acid (bdc) linkers. This new material exhibits remarkable photoelectrochemical (PEC) catalytic activity in water splitting for the evolution of oxygen. Notably, this non-noble metal-based MOF, without requiring immobilization on other supports or containing metal particles, produced a highest photocurrent density of 31 μA cm -2 at 0.9 V, with appreciable stability and negligible photocorrosion. Advantageously for the oxygen evolution process, no external reagents or sacrificial agents are required in the aqueous electrolyte solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic Reforming of Oxygenates: State of the Art and Future Prospects.

PubMed

Li, Di; Li, Xinyu; Gong, Jinlong

2016-10-12

This Review describes recent advances in the design, synthesis, reactivity, selectivity, structural, and electronic properties of the catalysts for reforming of a variety of oxygenates (e.g., from simple monoalcohols to higher polyols, then to sugars, phenols, and finally complicated mixtures like bio-oil). A comprehensive exploration of the structure-activity relationship in catalytic reforming of oxygenates is carried out, assisted by state-of-the-art characterization techniques and computational tools. Critical emphasis has been given on the mechanisms of these heterogeneous-catalyzed reactions and especially on the nature of the active catalytic sites and reaction pathways. Similarities and differences (reaction mechanisms, design and synthesis of catalysts, as well as catalytic systems) in the reforming process of these oxygenates will also be discussed. A critical overview is then provided regarding the challenges and opportunities for research in this area with a focus on the roles that systems of heterogeneous catalysis, reaction engineering, and materials science can play in the near future. This Review aims to present insights into the intrinsic mechanism involved in catalytic reforming and provides guidance to the development of novel catalysts and processes for the efficient utilization of oxygenates for energy and environmental purposes.

Synergistic Enhancement of Electrocatalytic CO 2 Reduction with Gold Nanoparticles Embedded in Functional Graphene Nanoribbon Composite Electrodes

DOE PAGES

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

Stainless steel wire mesh-supported ZnO for the catalytic photodegradation of methylene blue under ultraviolet irradiation.

PubMed

Vu, Tan T; del Río, Laura; Valdés-Solís, Teresa; Marbán, Gregorio

2013-02-15

The aim of this study was to assess the activity of catalysts formed by nanostructured zinc oxide supported on stainless steel wire mesh for the photocatalytic degradation of methylene blue under UV irradiation. Catalysts prepared by means of different low temperature synthesis methods, as described in a previous work (Vu et al., Mater. Res. Bull. 47 (2012) 1577-1586) were tested. A new activity parameter was introduced in order to compare the catalytic activity of the different catalysts. The best catalyst showed a catalytic activity higher than that of the reference material TiO(2) P25 (Degussa-Evonik). This high activity is attributed to a higher quantum yield derived from the small particle length of the ZnO deposited on the wire mesh. The photocatalytic degradation kinetics of methylene blue fitted a potential model with n orders ranging from 0.5 to 6.9. Reaction orders over 1 were attributed to catalyst deactivation during the reaction resulting from the photocorrosion of ZnO. Copyright © 2012 Elsevier B.V. All rights reserved.

Delayed ignition and propulsion of catalytic microrockets based on fuel-induced chemical dealloying of the inner alloy layer.

PubMed

Jodra, Adrián; Soto, Fernando; Lopez-Ramirez, Miguel Angel; Escarpa, Alberto; Wang, Joseph

2016-09-27

The delayed ignition and propulsion of catalytic tubular microrockets based on fuel-induced chemical dealloying of an inner alloy layer is demonstrated. Such timed delay motor activation process relies on the preferential gradual corrosion of Cu from the inner Pt-Cu alloy layer by the peroxide fuel. The dealloying process exposes the catalytically active Pt surface to the chemical fuel, thus igniting the microrockets propulsion autonomously without external stimuli. The delayed motor activation relies solely on the intrinsic material properties of the micromotor and the surrounding solution. The motor activation time can thus be tailored by controlling the composition of the Cu-Pt alloy layer and the surrounding media, including the fuel and NaCl concentrations and local pH. Speed acceleration in a given fuel solution is also demonstrated and reflects the continuous exposure of the Pt surface. The versatile "blastoff" control of these chemical microrockets holds considerable promise for designing self-regulated chemically-powered nanomachines with a "built-in" activation mechanism for diverse tasks.

Experimental Observation of Redox-Induced Fe-N Switching Behavior as a Determinant Role for Oxygen Reduction Activity.

PubMed

Jia, Qingying; Ramaswamy, Nagappan; Hafiz, Hasnain; Tylus, Urszula; Strickland, Kara; Wu, Gang; Barbiellini, Bernardo; Bansil, Arun; Holby, Edward F; Zelenay, Piotr; Mukerjee, Sanjeev

2015-12-22

The commercialization of electrochemical energy conversion and storage devices relies largely upon the development of highly active catalysts based on abundant and inexpensive materials. Despite recent achievements in this respect, further progress is hindered by the poor understanding of the nature of active sites and reaction mechanisms. Herein, by characterizing representative iron-based catalysts under reactive conditions, we identify three Fe-N4-like catalytic centers with distinctly different Fe-N switching behaviors (Fe moving toward or away from the N4-plane) during the oxygen reduction reaction (ORR), and show that their ORR activities are essentially governed by the dynamic structure associated with the Fe(2+/3+) redox transition, rather than the static structure of the bare sites. Our findings reveal the structural origin of the enhanced catalytic activity of pyrolyzed Fe-based catalysts compared to nonpyrolyzed Fe-macrocycle compounds. More generally, the fundamental insights into the dynamic nature of transition-metal compounds during electron-transfer reactions will potentially guide rational design of these materials for broad applications.

Metal–organic and covalent organic frameworks as single-site catalysts

PubMed Central

Rogge, S. M. J.; Bavykina, A.; Hajek, J.; Garcia, H.; Olivos-Suarez, A. I.; Sepúlveda-Escribano, A.; Vimont, A.; Clet, G.; Bazin, P.; Kapteijn, F.

2017-01-01

Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions. PMID:28338128

Novel yolk-shell-structured Fe3O4@γ-AlOOH nanocomposite modified with Pd nanoparticles as a recyclable catalyst with excellent catalytic activity

NASA Astrophysics Data System (ADS)

Cui, Xueliang; Zheng, Yunfeng; Tian, Meng; Dong, Zhengping

2017-09-01

A novel yolk-shell-structured material (Fe3O4@γ-AlOOH-YSMs) with hierarchical γ-AlOOH flakes as the mesoporous shell and Fe3O4 nanoparticles (NPs) in the hollow core was prepared by using Fe3O4@SiO2 NPs as the seeds as well as NaAlO2 and urea as the precursor. The prepared Fe3O4@γ-AlOOH-YSMs were used as a catalyst support for fabricating a Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst with no obvious aggregation of the Pd NPs. The Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst was utilized for the catalytic reduction of the widely used and highly toxic 4-nitrophenol, rhodamine B, methylene blue, and methyl orange; and showed excellent catalytic activity as compared with other noble-metal-based catalysts. Furthermore, the Pd/Fe3O4@γ-AlOOH-YSMs nanocatalyst also can be easily separated from the reaction mixture and reused for at least ten times without any obvious decrease in the catalytic activity, indicating its reusability and stability.

Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

T. Brent Gunnoe

2011-02-17

Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials.more » A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt, which has provided a comprehensive understanding of the impact of steric and electronic parameters of 'L' on the catalytic hydroarylation of olefins. (3) We have completed and published a detailed mechanistic study of stoichiometric aromatic C-H activation by TpRu(L)(NCMe)Ph (L = CO or PMe{sub 3}). These efforts have probed the impact of functionality para to the site of C-H activation for benzene substrates and have allowed us to develop a detailed model of the transition state for the C-H activation process. These results have led us to conclude that the C-H bond cleavage occurs by a {sigma}-bond metathesis process in which the C-H transfer is best viewed as an intramolecular proton transfer. (4) We have completed studies of Ru complexes possessing the N-heterocyclic carbene IMes (IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene). One of these systems is a unique four-coordinate Ru(II) complex that catalyzes the oxidative hydrophenylation of ethylene (in low yields) to produce styrene and ethane (utilizing ethylene as the hydrogen acceptor) as well as the hydrogenation of olefins, aldehydes and ketones. These results provide a map for the preparation of catalysts that are selective for oxidative olefin hydroarylation. (5) The ability of TpRu(PMe{sub 3})(NCMe)R systems to activate sp{sup 3} C-H bonds has been demonstrated including extension to subsequent C-C bond forming steps. These results open the door to the development of catalysts for the functionalization of more inert C-H bonds. (6) We have discovered that Pt(II) complexes supported by simple nitrogen-based ligands serve as catalysts for the hydroarylation of olefins. Given the extensive studies of Pt-based catalytic C-H activation, we believe these results will provide an entry point into an array of possible catalysts for hydrocarbon functionalization.« less

Composite electrode/electrolyte structure

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2004-01-27

Provided is an electrode fabricated from highly electronically conductive materials such as metals, metal alloys, or electronically conductive ceramics. The electronic conductivity of the electrode substrate is maximized. Onto this electrode in the green state, a green ionic (e.g., electrolyte) film is deposited and the assembly is co-fired at a temperature suitable to fully densify the film while the substrate retains porosity. Subsequently, a catalytic material is added to the electrode structure by infiltration of a metal salt and subsequent low temperature firing. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in ionic (electrochemical) devices such as fuel cells and electrolytic gas separation systems.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons.

PubMed

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zheng; Li, Zhilin; Institute of Carbon Fibers and Composites, Beijing University of Chemical Technology, Beijing 100029

Graphical abstract: The MWCNT/Ni-B catalyst has been successfully prepared by an electroless deposition process. The Ni-B nanoparticles on the supporter are amorphous and are well-distributed. The catalytic conversion towards hydrogenation of styrene shows excellent catalytic activity of the obtained materials. Highlights: Black-Right-Pointing-Pointer A two-step treatment of MWCNTs enabled the homogeneous growth of Ni-B nanoparticles. Black-Right-Pointing-Pointer Ni-B nanoparticles were amorphous with an average size of 60 nm. Black-Right-Pointing-Pointer There were electron transfer between Ni and B. Black-Right-Pointing-Pointer The catalyst had excellent catalytic activity towards hydrogenation of styrene. -- Abstract: Nickel-boron (Ni-B) nanoparticles supported on multi-walled carbon nanotubes (MWCNTs) were successfully synthesizedmore » through an electroless deposition process using the plating bath with sodium borohydride as a reducing agent. The structural and morphological analyses using field-emission scanning electron microscopy, X-ray diffractometry and high-resolution transmission electron microscopy have shown that the Ni-B nanoparticles deposited on the sidewalls of MWCNTs are fine spheres comprised of amorphous structure with the morphologically unique fine-structure like flowers, and homogenously dispersed with a narrow particle size distribution centered at around 60 nm diameter. The catalytic activity of MWCNT/Ni-B nanoparticles was evaluated with respect to hydrogenation of styrene. The hydrogenation catalyzed by MWCNT-supported Ni-B nanoparticles has been found to make styrene selectively converted into ethylbenzene. The highest conversion reaches 99.8% under proper reaction conditions, which demonstrates the high catalytic activity of MWCNT/Ni-B nanoparticles.« less

High activity of g-C3N4/multiwall carbon nanotube in catalytic ozonation promotes electro-peroxone process.

PubMed

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.

PdNP Decoration of Halloysite Lumen via Selective Grafting of Ionic Liquid onto the Aluminol Surfaces and Catalytic Application.

PubMed

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.

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.

Palladium nanoparticles dispersed on the hollow aluminosilicate microsphere@hierarchical γ-AlOOH as an excellent catalyst for the hydrogenation of nitroarenes under ambient conditions

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.

Greener synthesis of Cu-MOF-74 and its catalytic use for the generation of vanillin.

PubMed

Flores, J Gabriel; Sánchez-González, Elí; Gutiérrez-Alejandre, Aída; Aguilar-Pliego, Julia; Martínez, Ana; Jurado-Vázquez, Tamara; Lima, Enrique; González-Zamora, Eduardo; Díaz-García, Manuel; Sánchez-Sánchez, Manuel; Ibarra, Ilich A

2018-03-26

A greener synthesis of Cu-MOF-74 was obtained, for the first time, in methanol as the unique solvent and at room temperature. Full characterisation of the MOF material showed its purity and also its nanocrystalline nature. Complete activation (150 °C for 1 h and 10-3 bar) of Cu-MOF-74 afforded unsaturated Cu metal sites and this was corroborated by in situ DRIFT spectroscopy. The access to these Cu open metal sites was tested for the catalytic transformation of trans-ferulic acid to vanillin (yield of 71% and 97% selectivity) and a plausible catalytic reaction mechanism was postulated based on quantum chemical calculations.

New Element Organic Frameworks Based on Sn, Sb, and Bi, with Permanent Porosity and High Catalytic Activity

PubMed Central

Fritsch, Julia; Rose, Marcus; Wollmann, Philipp; Böhlmann, Winfried; Kaskel, Stefan

2010-01-01

We present new element organic frameworks based on Sn, Sb and Bi atoms connected via organic linkers by element-carbon bonds. The open frameworks are characterized by specific surface areas (BET) of up to 445 m2 g-1 and a good stability under ambient conditions resulting from a highly hydrophobic inner surface. They show good performance as heterogeneous catalysts in the cyanosylilation of benzaldehyde as a test reaction. Due to their catalytic activity, this class of materials might be able to replace common homogeneous element-organic and often highly toxic catalysts especially in the food industry.

Catalytic upgrading of duckweed biocrude in subcritical water.

PubMed

Zhang, Caicai; Duan, Peigao; Xu, Yuping; Wang, Bing; Wang, Feng; Zhang, Lei

2014-08-01

Herein, a duckweed biocrude produced from the hydrothermal liquefaction of Lemna minor was treated in subcritical water with added H₂. Effects of several different commercially available materials such as Ru/C, Pd/C, Pt/C, Pt/γ-Al₂O₃, Pt/C-sulfide, Rh/γ-Al₂O₃, activated carbon, MoS₂, Mo₂C, Co-Mo/γ-Al₂O₃, and zeolite on the yields of product fractions and the deoxygenation, denitrogenation, and desulfurization of biocrude at 350°C were examined, respectively. All the materials showed catalytic activity for deoxygenation and desulfurization of the biocrude and only Ru/C showed activity for denitrogenation. Of those catalysts examined, Pt/C showed the best performance for deoxygenation. Among all the upgraded oils, the oil produced with Ru/C shows the lowest sulfur, the highest hydrocarbon content (25.6%), the highest energy recovery (85.5%), and the highest higher heating value (42.6 MJ/kg). The gaseous products were mainly unreacted H₂, CH₄, CO₂, and C₂H6. Copyright © 2014 Elsevier Ltd. All rights reserved.

Hierarchical nano-on-micro copper with enhanced catalytic activity towards electro-oxidation of hydrazine

NASA Astrophysics Data System (ADS)

Yan, Xiaodong; Liu, Yuan; Scheel, Kyle R.; Li, Yong; Yu, Yunhua; Yang, Xiaoping; Peng, Zhonghua

2018-03-01

The electrochemical properties of catalyst materials are highly dependent on the materials structure and architecture. Herein, nano-on-micro Cu electrodes are fabricated by growing Cu microcrystals on Ni foam substrate, followed by introducing Cu nanocrystals onto the surface of the Cu microcrystals. The introduction of Cu nanocrystals onto the surface of Cu microcrystals is shown to dramatically increase the electrochemically active surface area and thus significantly enhances the catalytic activity of the catalyst electrode towards electro-oxidation of hydrazine. The onset potential (-1.04 V vs. Ag/AgCl) of the nano-on-micro Cu electrode is lower than those of the reported Cu-based catalysts under similar testing conditions, and a current density of 16 mA·cm-2, which is 2 times that of the microsized Cu electrode, is achieved at a potential of -0.95 V vs. Ag/AgCl. Moreover, the nano-on-micro Cu electrode demonstrates good long-term stability.

Shape-Dependent Photocatalytic Activity of Hydrothermally Synthesized Cadmium Sulfide Nanostructures.

PubMed

Kundu, Joyjit; Khilari, Santimoy; Pradhan, Debabrata

2017-03-22

The effective surface area of the nanostructured materials is known to play a prime role in catalysis. Here we demonstrate that the shape of the nanostructured materials plays an equally important role in their catalytic activity. Hierarchical CdS microstructures with different morphologies such as microspheres assembled of nanoplates, nanorods, nanoparticles, and nanobelts are synthesized using a simple hydrothermal method by tuning the volume ratio of solvents, i.e., water or ethylenediamine (en). With an optimum solvent ratio of 3:1 water:en, the roles of other synthesis parameters such as precursor's ratio, temperature, and precursor combinations are also explored and reported here. Four selected CdS microstructures are used as photocatalysts for the degradation of methylene blue and photoelectrochemical water splitting for hydrogen generation. In spite of smaller effective surface area of CdS nanoneedles/nanorods than that of CdS nanowires network, the former exhibits higher catalytic activity under visible light irradiation which is ascribed to the reduced charge recombination as confirmed from the photoluminescence study.

Facile and Green Synthesis of Palladium Nanoparticles-Graphene-Carbon Nanotube Material with High Catalytic Activity

NASA Astrophysics Data System (ADS)

Sun, Tai; Zhang, Zheye; Xiao, Junwu; Chen, Chen; Xiao, Fei; Wang, Shuai; Liu, Yunqi

2013-08-01

We report a facile and green method to synthesize a new type of catalyst by coating Pd nanoparticles (NPs) on reduced graphene oxide (rGO)-carbon nanotube (CNT) nanocomposite. An rGO-CNT nanocomposite with three-dimensional microstructures was obtained by hydrothermal treatment of an aqueous dispersion of graphene oxide (GO) and CNTs. After the rGO-CNT composites have been dipped in K2PdCl4 solution, the spontaneous redox reaction between the GO-CNT and PdCl42- led to the formation of nanohybrid materials consisting rGO-CNT decorated with 4 nm Pd NPs, which exhibited excellent and stable catalytic activity: the reduction of 4-nitrophenol to 4-aminophenol using NaBH4 as a catalyst was completed in only 20 s at room temperature, even when the Pd content of the catalyst was 1.12 wt%. This method does not require rigorous conditions or toxic agents and thus is a rapid, efficient, and green approach to the fabrication of highly active catalysts.

Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures

PubMed Central

Zhang, Xing; Wu, Zishan; Zhang, Xiao; Li, Liewu; Li, Yanyan; Xu, Haomin; Li, Xiaoxiao; Yu, Xiaolu; Zhang, Zisheng; Liang, Yongye; Wang, Hailiang

2017-01-01

Electrochemical reduction of carbon dioxide with renewable energy is a sustainable way of producing carbon-neutral fuels. However, developing active, selective and stable electrocatalysts is challenging and entails material structure design and tailoring across a range of length scales. Here we report a cobalt-phthalocyanine-based high-performance carbon dioxide reduction electrocatalyst material developed with a combined nanoscale and molecular approach. On the nanoscale, cobalt phthalocyanine (CoPc) molecules are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for carbon monoxide, and enhanced durability. On the molecular level, the catalytic performance is further enhanced by introducing cyano groups to the CoPc molecule. The resulting hybrid catalyst exhibits >95% Faradaic efficiency for carbon monoxide production in a wide potential range and extraordinary catalytic activity with a current density of 15.0 mA cm−2 and a turnover frequency of 4.1 s−1 at the overpotential of 0.52 V in a near-neutral aqueous solution. PMID:28272403

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei

The catalyzed conversion of shale gas-derived light hydrocarbons, e.g. methane to methanol, for further application as automotive fuels and/or bulk chemicals is especially attractive in light of improved methods of hydrocarbon extraction. MOF based catalysts have previously been demonstrated to be active for a range of catalytic reactions. In this work we used Cu-NU1000 as a methane-to-methanol oxidation catalyst. In addition to product studies, in-situ X-ray Absorption Spectroscopic (XAS) experiments are performed under catalytic conditions in order to follow the modification of the Cu-species and directly probe the structure/activity properties of the Cu-NU1000 system. The insights reported herein serve asmore » a first look at metal-organic framework materials as catalysts for methane oxidation and be the basis for development of the subsequent generations of materials.« less

Carbothermal reduction of Ti-modified IRMOF-3: an adaptable synthetic method to support catalytic nanoparticles on carbon.

PubMed

Kim, Jongsik; McNamara, Nicholas D; Her, Theresa H; Hicks, Jason C

2013-11-13

This work describes a novel method for the preparation of titanium oxide nanoparticles supported on amorphous carbon with nanoporosity (Ti/NC) via the post-synthetic modification of a Zn-based MOF with an amine functionality, IRMOF-3, with titanium isopropoxide followed by its carbothermal pyrolysis. This material exhibited high purity, high surface area (>1000 m(2)/g), and a high dispersion of metal oxide nanoparticles while maintaining a small particle size (~4 nm). The material was shown to be a promising catalyst for oxidative desulfurization of diesel using dibenzothiophene as a model compound as it exhibited enhanced catalytic activity as compared with titanium oxide supported on activated carbon via the conventional incipient wetness impregnation method. The formation mechanism of Ti/NC was also proposed based on results obtained when the carbothermal reduction temperature was varied.

Lignases and aldo-keto reductases for conversion of lignin-containing materials to fermentable products

DOEpatents

Scharf, Michael; Sethi, Amit

2016-09-13

Termites have specialized digestive systems that overcome the lignin barrier in wood to release fermentable simple sugars. Using the termite Reticulitermes flavipes and its gut symbionts, high-throughput titanium pyrosequencing and proteomics approaches experimentally compared the effects of lignin-containing diets on host-symbiont digestome composition. Proteomic investigations and functional digestive studies with recombinant lignocellulases conducted in parallel provided strong evidence of congruence at the transcription and translational levels and provide enzymatic strategies for overcoming recalcitrant lignin barriers in biofuel feedstocks. Briefly described, therefore, the disclosure provides a system for generating a fermentable product from a lignified plant material, the system comprising a cooperating series of at least two catalytically active polypeptides, where said catalytically active polypeptides are selected from the group consisting of: cellulase Cell-1, .beta.-glu cellulase, an aldo-keto-reductase, a catalase, a laccase, and an endo-xylanase.

Electrochemically assisted localized etching of ZnO single crystals in water using a catalytically active Pt-coated atomic force microscopy probe

NASA Astrophysics Data System (ADS)

Shibata, Takayuki; Yamamoto, Kota; Sasano, Junji; Nagai, Moeto

2017-09-01

This paper presents a nanofabrication technique based on the electrochemically assisted chemical dissolution of zinc oxide (ZnO) single crystals in water at room temperature using a catalytically active Pt-coated atomic force microscopy (AFM) probe. Fabricated grooves featured depths and widths of several tens and several hundreds of nanometers, respectively. The material removal rate of ZnO was dramatically improved by controlling the formation of hydrogen ions (H+) on the surface of the catalytic Pt-coated probe via oxidation of H2O molecules; this reaction can be enhanced by applying a cathodic potential to an additional Pt-wire working electrode in a three-electrode configuration. Consequently, ZnO can be dissolved chemically in water as a soluble Zn2+ species via a reaction with H+ species present in high concentrations in the immediate vicinity of the AFM tip apex.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camacho-Bunquin, Jeffrey; Shou, Heng; Aich, Payoli

An integrated atomic layer deposition-catalysis (I-ALD-CAT) tool was developed, combining an ALD manifold with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT system can deliver gaseous reagents comprised of 12 different metal ALD precursors, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10-3–1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph and a mass spectrometer unitmore » for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the ALD of platinum active sites and Al2O3 overcoats, and evaluation of catalyst propylene hydrogenation activity.« less

Catalytic properties of mesoporous Al–La–Mn oxides prepared via spray pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Goun; Jung, Kyeong Youl; Lee, Choul-Ho

Highlights: • Al–La–Mn oxides were prepared using spray pyrolysis. • Al–La–Mn oxides exhibit large and uniform pore sizes. • Mesoporous Al–La–Mn oxides were compared with those prepared by conventional precipitation. • Mesoporous Al–La–Mn oxides show superior activity in decomposition of hydrogen peroxide. - Abstract: Mesoporous Al–La–Mn oxides are prepared via spray pyrolysis and are applied to the catalytic decomposition of hydrogen peroxide. The characteristics of the mesoporous Al–La–Mn oxides are examined using N{sub 2} adsorption, X-ray diffraction, and X-ray fluorescence measurements. The surface area and pore size of the Al–La–Mn oxides prepared via spray pyrolysis are larger than those ofmore » the Al–La–Mn oxides prepared using a precipitation method. The catalytic performance of the materials during the decomposition of hydrogen peroxide is examined in a pulse-injection reactor. It is confirmed that the mesoporous Al–La–Mn oxides prepared via spray pyrolysis exhibit higher catalytic activity and stability in the decomposition of hydrogen peroxide than Al–La–Mn oxides prepared using a conventional precipitation method.« less

Density Functional Theory Study of Oxygen Reduction Activity on Ultrathin Platinum Nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2012-07-13

The structure, stability, and catalytic activity of a number of single- and double-wall platinum (n,m) nanotubes ranging in diameter from 0.3 to 2.0 nm were studied using plane-wave based density functional theory in the gas phase and water environment. The change in the catalytic activity toward the oxygen reduction reaction (ORR) with the size and chirality of the nanotube was studied by calculating equilibrium adsorption potentials for ORR intermediates and by constructing free energy diagrams in the ORR dissociative mechanism network. In addition, the stability of the platinum nanotubes is investigated in terms of electrochemical dissolution potentials and by determiningmore » the most stable state of the material as a function of pH and potential, as represented in Pourbaix diagrams. Our results show that the catalytic activity and the stability toward electrochemical dissolution depend greatly on the diameter and chirality of the nanotube. On the basis of the estimated overpotentials for ORR, we conclude that smaller, approximately 0.5 nm in diameter single-wall platinum nanotubes consistently show a huge, up to 400 mV larger overpotential than platinum, indicating very poor catalytic activity toward ORR. This is the result of substantial structural changes induced by the adsorption of any chemical species on these tubes. Single-wall n = m platinum nanotubes with a diameter larger than 1 nm have smaller ORR overpotentials than bulk platinum for up to 180 mV and thus show improved catalytic activity relative to bulk. We also predict that these nanotubes can endure the highest cell potentials but dissolution potentials are still for 110 mV lower than for the bulk, indicating a possible corrosion problem.« less

Improving gold catalysis of nitroarene reduction with surface Pd

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pretzer, Lori A.; Heck, Kimberly N.; Kim, Sean S.

2016-04-01

Nitroarene reduction reactions are commercialized catalytic processes that play a key role in the synthesisof many products including medicines, rubbers, dyes, and herbicides. Whereas bimetallic compositionshave been studied, a better understanding of the bimetallic structure effects may lead to improved indus-trial catalysts. In this work, the influence of surface palladium atoms supported on 3-nm Au nanoparticles(Pd-on-Au NPs) on catalytic activity for 4-nitrophenol reduction is explored. Batch reactor studies indi-cate Pd-on-Au NPs exhibit maximum catalytic activity at a Pd surface coverage of 150 sc%, with aninitial turnover frequency of ~3.7 mol-nitrophenol/mol-metalsurface/s, which was ~5.5× and ~13× moreactive than pure Au NPsmore » and Pd NPs, respectively. Pd NPs, Au NPs, and Pd-on-Au NPs below 175 sc%show compensation behavior. Three-dimensional Pd surface ensembles (with ~4–5 atoms) previouslyidentified through X-ray adsorption spectroscopy provide the active sites responsible for the catalyticmaximum. These results demonstrate the ability to adjust systematically a structural feature (i.e., Pdsurface coverage) to yield a more active material.« less

Cavitational synthesis of nanostructured inorganic materials for enhanced heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Krausz, Ivo Michael

The synthesis of nanostructured inorganic materials by hydrodynamic cavitation processing was investigated. The goal of this work was to develop a general synthesis technique for nanostructured materials with a control over crystallite size in the 1--20 nm range. Materials with crystallite sizes in this range have shown enhanced catalytic activity compared to materials with larger crystallite sizes. Several supported and unsupported inorganic materials were studied to understand the effects of cavitation on crystallite size. Cavitation processing of calcium fluoride resulted in more spherical particles, attached to one another by melted necks. This work produced the first evidence of shock wave heating of nanostructured materials by hydrodynamic cavitation processing. Hydrodynamic cavitation synthesis of various catalytic support materials indicated that their phase composition and purity could be controlled by adjustment of the processing parameters. Zirconia/alumina supports synthesized using hydro-dynamic cavitation and calcined to 1368 K retained a high purity cubic zirconia phase, whereas classically prepared samples showed a phase transformation to monoclinic zirconia. Similarly, the synthesis of alumina resulted in materials with varying Bohmite and Bayerite contents as a function of the process parameters. High temperature calcination resulted in stable alumina supports with varying amounts of delta-, and theta-alumina. Synthesis studies of palladium and silver showed modest variations in crystallite size as a function of cavitation process parameters. Calcination resulted in larger grain materials, indicating a disappearance of intergrain boundaries. Based on these results, a new synthesis method was studied involving controlled agglomeration of small silver crystallites by hydrodynamic cavitation processing, followed by deposition on alumina. The optimal pH, concentration, and processing time for controlling the silver crystallite size in the cavitation equipment were determined using a statistical design of experiments approach. Three series of alumina supported silver catalysts were prepared, with silver weight loadings of 1%, 2%, and 5%. Variation of cavitation processing time between 1--64 min allowed the systematic control of silver crystallite size in the range of 3--19 nm. The preferred oxidation of CO in hydrogen (PROX) was chosen as a catalytic test reaction, because of its increasing importance for fuel cell applications. It was found that the catalytic activity was significantly increased for silver crystallite sizes below 5 nm. This work is the first experimental evidence of independent crystallite size control by hydrodynamic cavitation for alumina supported silver catalysts. The synthesis method involving controlled agglomeration and calcination is a general synthesis procedure that can be used to synthesize a wide range of novel catalysts and advanced materials.

Chapter 19: Catalysis by Metal Carbides and Nitrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaidle, Joshua A; Nash, Connor P; Yung, Matthew M

Early transition metal carbides and nitrides (ETMCNs), materials in which carbon or nitrogen occupies interstitial sites within a parent metal lattice, possess unique physical and chemical properties that motivate their use as catalysts. Specifically, these materials possess multiple types of catalytic sites, including metallic, acidic, and basic sites, and as such, exhibit reactivities that differ from their parent metals. Moreover, their surfaces are dynamic under reaction conditions. This chapter reviews recent (since 2010) experimental and computational investigations into the catalytic properties of ETMCN materials for applications including biomass conversion, syngas and CO2 upgrading, petroleum and natural gas refining, and electrocatalyticmore » energy conversion, energy storage, and chemicals production, and attempts to link catalyst performance to active site identity/surface structure in order to elucidate the present level of understanding of structure-function relationships for these materials. The chapter concludes with a perspective on leveraging the unique properties of these materials to design and develop improved catalysts through a dedicated, multidisciplinary effort.« less

Metal-free catalysis of persulfate activation and organic-pollutant degradation by nitrogen-doped graphene and aminated graphene.

PubMed

Chen, Hao; Carroll, Kenneth C

2016-08-01

We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L(-1)) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L(-1)) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L(-1)) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Generation and Characterization of Six Recombinant Botulinum Neurotoxins as Reference Material to Serve in an International Proficiency Test.

PubMed

Weisemann, Jasmin; Krez, Nadja; Fiebig, Uwe; Worbs, Sylvia; Skiba, Martin; Endermann, Tanja; Dorner, Martin B; Bergström, Tomas; Muñoz, Amalia; Zegers, Ingrid; Müller, Christian; Jenkinson, Stephen P; Avondet, Marc-Andre; Delbrassinne, Laurence; Denayer, Sarah; Zeleny, Reinhard; Schimmel, Heinz; Åstot, Crister; Dorner, Brigitte G; Rummel, Andreas

2015-11-26

The detection and identification of botulinum neurotoxins (BoNT) is complex due to the existence of seven serotypes, derived mosaic toxins and more than 40 subtypes. Expert laboratories currently use different technical approaches to detect, identify and quantify BoNT, but due to the lack of (certified) reference materials, analytical results can hardly be compared. In this study, the six BoNT/A1-F1 prototypes were successfully produced by recombinant techniques, facilitating handling, as well as improving purity, yield, reproducibility and biosafety. All six BoNTs were quantitatively nicked into active di-chain toxins linked by a disulfide bridge. The materials were thoroughly characterized with respect to purity, identity, protein concentration, catalytic and biological activities. For BoNT/A₁, B₁ and E₁, serotypes pathogenic to humans, the catalytic activity and the precise protein concentration were determined by Endopep-mass spectrometry and validated amino acid analysis, respectively. In addition, BoNT/A₁, B₁, E₁ and F₁ were successfully detected by immunological assays, unambiguously identified by mass spectrometric-based methods, and their specific activities were assigned by the mouse LD50 bioassay. The potencies of all six BoNT/A1-F1 were quantified by the ex vivo mouse phrenic nerve hemidiaphragm assay, allowing a direct comparison. In conclusion, highly pure recombinant BoNT reference materials were produced, thoroughly characterized and employed as spiking material in a worldwide BoNT proficiency test organized by the EQuATox consortium.

Biochar-based nano-composites for the decontamination of wastewater: A review.

PubMed

Tan, Xiao-Fei; Liu, Yun-Guo; Gu, Yan-Ling; Xu, Yan; Zeng, Guang-Ming; Hu, Xin-Jiang; Liu, Shao-Bo; Wang, Xin; Liu, Si-Mian; Li, Jiang

2016-07-01

Synthesizing biochar-based nano-composites can obtain new composites and combine the advantages of biochar with nano-materials. The resulting composites usually exhibit great improvement in functional groups, pore properties, surface active sites, catalytic degradation ability and easy to separation. These composites have excellent abilities to adsorb a range of contaminants from aqueous solutions. Particularly, catalytic material-coated biochar can exert simultaneous adsorption and catalytic degradation function for organic contaminants removal. Synthesizing biochar-based nano-composites has become an important practice for expanding the environmental applications of biochar and nanotechnology. This paper aims to review and summarize the various synthesis techniques for biochar-based nano-composites and their effects on the decontamination of wastewater. The characteristic and advantages of existing synthesis methods are summarized and discussed. Application of biochar-based nano-composites for different contaminants removal and the underlying mechanisms are reviewed. Furthermore, knowledge gaps that exist in the fabrication and application of biochar-based nano-composites are also identified. Copyright © 2016 Elsevier Ltd. All rights reserved.

A sinter-resistant catalyst using an alumina support recycled from AlP fumigation residue: trash to treasure.

PubMed

Dong, Jinshi; Wang, Jun; Wang, Jianqiang; Cheng, Guanghao; Huang, Tianming; Shen, Meiqing

2018-05-07

Sintering is a long-standing issue especially in high temperature catalytic applications. In this paper, we report an effective method to slow down metal particle migration and coalescence (PMC) by using a thermally stable alumina support. Noteworthily, the alumina sample was developed from AlP fumigation residue, which is a very dangerous substance for living creatures and environment protection. By optimizing the heated hydrolysis and ball-milling conditions, we recycled a phosphate-stabilized alumina material that retained a 117 m 2 g -1 surface area after 1050 °C hydrothermal aging. The catalyst using this newly developed alumina support had Pd dispersion 1.7 times higher than that using a commercial alumina support after aging. The kinetics and XPS experiments showed that phosphate neither participated in the catalytic reaction process nor changed the active sites. This catalyst also exhibited extraordinary water tolerance and durability, making it a promising material in automotive exhaust purification and other catalytic applications.

Fe3C nanoparticle decorated Fe/N doped graphene for efficient oxygen reduction reaction electrocatalysis

NASA Astrophysics Data System (ADS)

Niu, Yanli; Huang, Xiaoqin; Hu, Weihua

2016-11-01

Oxygen reduction reaction (ORR) electrocatalysts with high activity, low cost and good durability are crucial to promote the large-scale practical application of fuel cells. Particularly, iron carbide (Fe3C) supported on nitrogen-doped carbon has recently demonstrated compelling promise for ORR electrocatalysis. In this paper, we report the facile synthesis of mesoporous Fe/N-doped graphene with encapsulated Fe3C nanoparticles (Fe3C@Fe/N-graphene) and its superior ORR catalytic activity. This hybrid material was synthesized by the spontaneous oxidative polymerization of dopamine on graphene oxide (GO) sheets in the presence of iron ion, followed by thermal annealing in Argon (Ar) atmosphere. As-prepared material shows high ORR catalytic activity with overwhelming four-electron reduction pathway, long-term durability and high methanol tolerance in alkaline media. This work reports a facile method to synthesize promising ORR electrocatalysis with multiple components and hierarchical architecture, and may offer valuable insight into the underlying mechanism of Fe3C-boosted ORR activity of Fe/N doped carbon.

Oxygen storage properties and catalytic activity of layer-ordered perovskites BaY 1-xGd xMn 2O 5+δ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klimkowicz, A.; Świerczek, K.; Rząsa, T.

2016-05-01

Crystal structure, oxygen storage-related and preliminary anaerobic methane combustion studies were conducted for BaY 1-xGd xMn 2O 5+δ (0, 0.25, 0.5, 0.75 and 1) series of oxides prepared by a sol–gel method. All samples were found to possess layered-type A-site cation ordering, with the unit cell volume linearly dependent on the average radius of Y 1-xGd x for both the reduced and the oxidized materials. The oxygen content in the temperature range of 400 °C–600 °C indicates change on the order of 1 atomic mole, occurring when the sample's surrounding atmosphere was changed from air to 5 vol.% H 2more » in Ar. The time dependence of the reduction shows activated character on temperature, with an activation energy, which seems to be related to the oxygen diffusion in the bulk of the materials. Initial data concerning methane combustion in oxygen-free conditions show promising catalytic activity of BaYMn 2O 6 at elevated temperatures.« less

Metal-Organic Framework-Templated Porous Carbon for Highly Efficient Catalysis: The Critical Role of Pyrrolic Nitrogen Species.

PubMed

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.

Method for making oxygen-reducing catalyst layers

DOEpatents

O'Brien, Dennis P.; Schmoeckel, Alison K.; Vernstrom, George D.; Atanasoski, Radoslav; Wood, Thomas E.; O'Neill, David G.

2010-06-22

Methods are provided for making oxygen-reducing catalyst layers, which include simultaneous or sequential stops of physical vapor depositing an oxygen-reducing catalytic material onto a substrate, the catalytic material comprising a transition metal that is substantially free of platinum; and thermally treating the catalytic material. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

Three-dimensional Nitrogen-Doped Graphene Supported Molybdenum Disulfide Nanoparticles as an Advanced Catalyst for Hydrogen Evolution Reaction

PubMed Central

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

Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bedford, Nicholas M.; Ramezani-Dakhel, Hadi; Slocik, Joseph M.

Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, whichmore » was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then eluddated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences« less

Elucidation of peptide-directed palladium surface structure for biologically tunable nanocatalysts.

PubMed

Bedford, Nicholas M; Ramezani-Dakhel, Hadi; Slocik, Joseph M; Briggs, Beverly D; Ren, Yang; Frenkel, Anatoly I; Petkov, Valeri; Heinz, Hendrik; Naik, Rajesh R; Knecht, Marc R

2015-05-26

Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, which was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then elucidated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences.

Improvement Photocatalytic Activity of P25 by Modification with a Rare Earth-Free Upconversion Nanocrystal.

PubMed

Yin, Dongguang; Liu, Yumin; Zhao, Feifei; Zhang, Xinyu; Zhang, Tingting; Wu, Chenglong; Chang, Na; Chen, Zhiwen

2018-05-01

It has been reported that coupling TiO2 with rare earth upconversion nanocrystals (UCNCs) is an efficient strategy to significantly improve photocatalytic activity of TiO2. However, the rare earth materials are scarcity and cost, and the synthesis process of UCNCs using the rare earth materials is complicated. In the present study, we have designed a new approach using a rare earth-free upconversion nanocrystal (REF-UCNCs) as upconversion luminescent material to replace the rare earth UCNCs. A novel nanocomposite photocatalyst of REF-UCNCs@P25: Mo/GN was developed for the first time. Based on the designed structure, the REF-UCNCs, Mo-doping, and GN (graphene) have a synergistic effect that can improve catalytic activity of P25 significantly. The results of photocatalytic experiments using RhB as a model pollutant under simulated solar light irradiation show that the photocatalytic efficiency of the as-prepared catalyst is 3-folds higher than that of benchmark substance P25. This work provides a new strategy for efficiently improving catalytic activity of semiconductor photocatalysts by coupling with REF-UCNCs. This approach is facile and low-cost which can be widely applied for modification of semiconductor photocatalysts and facilitates their applications in environmental protection issues using solar light.

Structured mesoporous Mn, Fe, and Co oxides: Synthesis, physicochemical, and catalytic properties

NASA Astrophysics Data System (ADS)

Maerle, A. A.; Karakulina, A. A.; Rodionova, L. I.; Moskovskaya, I. F.; Dobryakova, I. V.; Egorov, A. V.; Romanovskii, B. V.

2014-02-01

Structured mesoporous Mn, Fe, and Co oxides are synthesized using "soft" and "hard" templates; the resulting materials are characterized by XRD, SEM, TEM, BET, and TG. It is shown that in the first case, the oxides have high surface areas of up to 450 m2/g that are preserved after calcination of the material up to 300°C. Even though, the surface area of the oxides prepared by the "hard-template" method does not exceed 100 m2/g; it is, however, thermally stable up to 500°C. Catalytic activity of mesoporous oxides in methanol conversion was found to depend on both the nature of the transition metal and the type of template used in synthesis.

Facile synthesis of three-dimensional diatomite/manganese silicate nanosheet composites for enhanced Fenton-like catalytic degradation of malachite green dye

NASA Astrophysics Data System (ADS)

Jiang, De Bin; Yuan, Yunsong; Zhao, Deqiang; Tao, Kaiming; Xu, Xuan; Zhang, Yu Xin

2018-05-01

In this work, we demonstrate a novel and simple approach for fabrication of the complex three-dimensional (3D) diatomite/manganese silicate nanosheet composite (DMSNs). The manganese silicate nanosheets are uniformly grown on the inner and outer surface of diatomite with controllable morphology using a hydrothermal method. Such structural features enlarged the specific surface area, resulting in more catalytic active sites. In the heterogeneous Fenton-like reaction, the DMSNs exhibited excellent catalytic capability for the degradation of malachite green (MG). Under optimum condition, 500 mg/L MG solution was nearly 93% decolorized at 70 min in the reaction. The presented results show an enhanced catalytic behavior of the DMSNs prepared by the low-cost natural diatomite material and simple controllable process, which indicates their potential for environmental remediation applications. [Figure not available: see fulltext.

Direct decarbonylation of furfural to furan: A density functional theory study on Pt-graphene

NASA Astrophysics Data System (ADS)

Fellah, Mehmet Ferdi

2017-05-01

The catalytic mechanism of direct decarbonylation of furfural to furan on Pt graphene surface has been investigated by means of density functional theory (DFT) calculations. The main catalytic mechanism proposed in this study has six steps such as furfural adsorption, dissociation of H from adsorbed furfural, dissociation of carbon monoxide (molecularly) from adsorbed complex, furan formation and desorption of products. It has been concluded that the rate determining step for direct decarbonylation of furfural to furan is furan formation step and global activation barrier for this catalytic system is 82 kJ/mol consisting of zero point energy and thermal energy corrections. Pt-graphene structure has an important role on the catalytic decarbonylation of furfural to furan without any other reactants. This accordingly points out that Pt doped graphene structure might be an encouraging catalyst for direct decarbonylation of furfural to furan molecule as a valuable chemical material.

Enhanced Intrinsic Catalytic Activity of λ-MnO2 by Electrochemical Tuning and Oxygen Vacancy Generation.

PubMed

Lee, Sanghan; Nam, Gyutae; Sun, Jie; Lee, Jang-Soo; Lee, Hyun-Wook; Chen, Wei; Cho, Jaephil; Cui, Yi

2016-07-18

Chemically prepared λ-MnO2 has not been intensively studied as a material for metal-air batteries, fuel cells, or supercapacitors because of their relatively poor electrochemical properties compared to α- and δ-MnO2 . Herein, through the electrochemical removal of lithium from LiMn2 O4 , highly crystalline λ-MnO2 was prepared as an efficient electrocatalyst for the oxygen reduction reaction (ORR). The ORR activity of the material was further improved by introducing oxygen vacancies (OVs) that could be achieved by increasing the calcination temperature during LiMn2 O4 synthesis; a concentration of oxygen vacancies in LiMn2 O4 could be characterized by its voltage profile as the cathode in a lithiun-metal half-cell. λ-MnO2-z prepared with the highest OV exhibited the highest diffusion-limited ORR current (5.5 mA cm(-2) ) among a series of λ-MnO2-z electrocatalysts. Furthermore, the number of transferred electrons (n) involved in the ORR was >3.8, indicating a dominant quasi-4-electron pathway. Interestingly, the catalytic performances of the samples were not a function of their surface areas, and instead depended on the concentration of OVs, indicating enhancement in the intrinsic catalytic activity of λ-MnO2 by the generation of OVs. This study demonstrates that differences in the electrochemical behavior of λ-MnO2 depend on the preparation method and provides a mechanism for a unique catalytic behavior of cubic λ-MnO2 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous Ag-TiO2-SiO2 composite materials as novel catalytic systems for selective epoxidation of cyclohexene by H2O2

PubMed Central

Wang, Xin; Xue, Jianyue; Wang, Xinyun; Liu, Xiaoheng

2017-01-01

TiO2-SiO2 composites were synthesized using cetyl trimethyl ammonium bromide (CTAB) as the structure directing template. Self-assembly hexadecyltrimethyl- ammonium bromide TiO2-SiO2/(CTAB) were soaked into silver nitrate (AgNO3) aqueous solution. The Ag-TiO2-SiO2(Ag-TS) composite were prepared via a precipitation of AgBr in soaking process and its decomposition at calcination stage. Structural characterization of the materials was carried out by various techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption and ultraviolet visible spectroscopy (UV-Vis). Characterization results revealed that Ag particles were incorporated into hierarchical TiO2-SiO2 without significantly affecting the structures of the supports. Further heating-treatment at 723 K was more favorable for enhancing the stability of the Ag-TS composite. The cyclohexene oxide was the major product in the epoxidation using H2O2 as the oxidant over the Ag-TS catalysts. Besides, the optimum catalytic activity and stability of Ag-TS catalysts were obtained under operational conditions of calcined at 723 K for 2 h, reaction time of 120 min, reaction temperature of 353 K, catalyst amount of 80 mg, aqueous H2O2 (30 wt.%) as oxidant and chloroform as solvent. High catalytic activity with conversion rate up to 99.2% of cyclohexene oxide could be obtainable in water-bathing. The catalyst was found to be stable and could be reused three times without significant loss of catalytic activity under the optimized reaction conditions. PMID:28493879

Bi2S3microspheres grown on graphene sheets as low-cost counter-electrode materials for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Li, Guang; Chen, Xiaoshuang; Gao, Guandao

2014-02-01

In this work, we synthesized 3D Bi2S3 microspheres comprised of nanorods grown along the (211) facet on graphene sheets by a solvothermal route, and investigated its catalytic activities through I-V curves and conversion efficiency tests as the CE in DSSCs. Although the (211) facet has a large band gap for a Bi2S3 semiconductor, owing to the introduction of graphene into the system, its short-circuit current density, open-circuit voltage, fill factor, and efficiency were Jsc = 12.2 mA cm-2, Voc = 0.75 V, FF = 0.60, and η = 5.5%, respectively. By integrating it with graphene sheets, our material achieved the conversion efficiency of 5.5%, which is almost triple the best conversion efficiency value of the DSSCs with (211)-faceted 3D Bi2S3 without graphene (1.9%) reported in the latest literature. Since this conversion-efficient 3D material grown on the graphene sheets significantly improves its catalytic properties, it paves the way for designing and applying low-cost Pt-free CE materials in DSSC from inorganic nanostructures.In this work, we synthesized 3D Bi2S3 microspheres comprised of nanorods grown along the (211) facet on graphene sheets by a solvothermal route, and investigated its catalytic activities through I-V curves and conversion efficiency tests as the CE in DSSCs. Although the (211) facet has a large band gap for a Bi2S3 semiconductor, owing to the introduction of graphene into the system, its short-circuit current density, open-circuit voltage, fill factor, and efficiency were Jsc = 12.2 mA cm-2, Voc = 0.75 V, FF = 0.60, and η = 5.5%, respectively. By integrating it with graphene sheets, our material achieved the conversion efficiency of 5.5%, which is almost triple the best conversion efficiency value of the DSSCs with (211)-faceted 3D Bi2S3 without graphene (1.9%) reported in the latest literature. Since this conversion-efficient 3D material grown on the graphene sheets significantly improves its catalytic properties, it paves the way for designing and applying low-cost Pt-free CE materials in DSSC from inorganic nanostructures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06093d

Electron microscopy study of gold nanoparticles deposited on transition metal oxides.

PubMed

Akita, Tomoki; Kohyama, Masanori; Haruta, Masatake

2013-08-20

Many researchers have investigated the catalytic performance of gold nanoparticles (GNPs) supported on metal oxides for various catalytic reactions of industrial importance. These studies have consistently shown that the catalytic activity and selectivity depend on the size of GNPs, the kind of metal oxide supports, and the gold/metal oxide interface structure. Although researchers have proposed several structural models for the catalytically active sites and have identified the specific electronic structures of GNPs induced by the quantum effect, recent experimental and theoretical studies indicate that the perimeter around GNPs in contact with the metal oxide supports acts as an active site in many reactions. Thus, it is of immense importance to investigate the detailed structures of the perimeters and the contact interfaces of gold/metal oxide systems by using electron microscopy at an atomic scale. This Account describes our investigation, at the atomic scale using electron microscopy, of GNPs deposited on metal oxides. In particular, high-resolution transmission electron microscopy (HRTEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) are valuable tools to observe local atomic structures, as has been successfully demonstrated for various nanoparticles, surfaces, and material interfaces. TEM can be applied to real powder catalysts as received without making special specimens, in contrast to what is typically necessary to observe bulk materials. For precise structure analyses at an atomic scale, model catalysts prepared by using well-defined single-crystalline substrates are also adopted for TEM observations. Moreover, aberration-corrected TEM, which has high spatial resolution under 0.1 nm, is a promising tool to observe the interface structure between GNPs and metal oxide supports including oxygen atoms at the interfaces. The oxygen atoms in particular play an important role in the behavior of gold/metal oxide interfaces, because they may participate in catalytic reaction steps. Detailed information about the interfacial structures between GNPs and metal oxides provides valuable structure models for theoretical calculations which can elucidate the local electronic structure effective for activating a reactant molecule. Based on our observations with HRTEM and HAADF-STEM, we report the detailed structure of gold/metal oxide interfaces.

Dual Role of Water in Heterogeneous Catalytic Hydrolysis of Sarin by Zirconium-Based Metal-Organic Frameworks.

PubMed

Momeni, Mohammad R; Cramer, Christopher J

2018-05-22

Recent experimental studies on Zr IV -based metal-organic frameworks (MOFs) have shown the extraordinary effectiveness of these porous materials for the detoxification of phosphorus-based chemical warfare agents (CWAs). However, pressing challenges remain with respect to characterizing these catalytic processes both at the molecular and crystalline levels. We here use theory to compare the reactivity of different zirconium-based MOFs for the catalytic hydrolysis of the CWA sarin, using both periodic and cluster modeling. We consider both hydrated and dehydrated secondary building units, as well as linker functionalized MOFs, to more fully understand and rationalize available experimental findings as well as to enable concrete predictions for achieving higher activities for the decomposition of CWAs.

Quantum dynamics of nuclear spins and spin relaxation in organic semiconductors

DOE PAGES

Mkhitaryan, V. V.; Dobrovitski, V. V.

2017-06-12

3D printing of materials with active functional groups can provide custom-designed structures that promote chemical conversions. Herein, catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. As proof of principle, chemically activemore » cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azide-alkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints.« less

The Design, Synthesis, and Characterization of Open Sites on Metal Clusters

NASA Astrophysics Data System (ADS)

Nigra, Michael Mark

Coordinatively unsaturated corner and edge atoms have been hypothesized to have the highest activity of sites responsible for many catalytic reactions on a metal surface. Recent studies have validated this hypothesis in varied reaction systems. However, quantification of different types of coordinatively unsaturated sites, and elucidation of their individual catalytic rates has remained a largely unresolved challenge when understanding catalysis on metal surfaces. Yet such structure-function knowledge would be invaluable to the design of more active and selective metal-surface catalysts in the future. I investigated the catalytic contributions of undercoordinated sites such as corner and edge atoms are investigated in a model reaction system using organic ligands bound to the gold nanoparticle surface. The catalyst consisted of 4 nm gold nanoparticles on a metal oxide support, using resazurin to resorufin as a model reaction system. My results demonstrate that in this system, corner atom sites are the most undercoordinated sites, and are over an order of magnitude more active when compared to undercoordinated edge atom sites, while terrace sites remain catalytically inactive for the reduction reaction of resazurin to resorufin. Catalytic activity has been also demonstrated for calixarene-bound gold nanoparticles using the reduction of 4-nitrophenol. With the 4-nitrophenol reduction reaction, a comparative study was undertaken to compare calixarene phosphine and calixarene thiol bound 4 nm gold particles. The results of the study suggested that a leached site was responsible for catalysis and not sites on the original gold nanoparticles. Future experiments with calixarene bound gold clusters could investigate ligand effects in reactions where the active site is not a leached or aggregated gold species, possibly in oxidation reactions, where electron-rich gold is hypothesized to be a good catalyst. The results that emphasize the enhanced catalytic activity of undercoordinated sites led me to synthesize small gold clusters consisting of a high fraction of coordinatively unsaturated open sites. This was enabled through an approach that utilized bulky calix[4]arene ligands that are bound to a gold core. Since the size of the calix[4]arene ligand is commensurate with the size of the gold cluster core, the calix[4]arene ligand does not pack closely together on the gold cluster surface. This in turn results in areas of accessible gold atom sites between ligands. Additionally, these calix[4]arene ligands prevent cluster aggregation and electronically tune the gold core in a manner conceptually similar to enzymes affecting reactivity through organic side-chains acting as ligands. I quantified the number of open sites that result from this packing problem on the gold cluster surface, using fluorescence probe chemisorption experiments. The results of these chemisorption measurements support the mechanical model of accessibility whereby accessibility is not dependent on the identity of the functional group, whether it be calixarene phosphines or N-heterocyclic carbenes, bound to the gold surface, but rather to the relative radii of curvature of bound ligands and the gold cluster core. Additional materials characterization was completed with transmission electron microscopy in both bright-field imaging of zeolites, in MCM-22 and delaminated ITQ-2 and UCB-1 materials, and in dark field imaging of glucan coatings on oxide particles. These materials could prove to be interesting materials as to use as supports for the calixarene-bound metal clusters described above or for other metal clusters.

Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets

DOE PAGES

Yin, Ying; Han, Jiecai; Zhang, Yumin; ...

2016-06-07

Molybdenum disulfide (MoS 2) is a promising nonprecious catalyst for the hydrogen evolution reaction (HER) that has been extensively studied due to its excellent performance, but the lack of understanding of the factors that impact its catalytic activity hinders further design and enhancement of MoS 2-based electrocatalysts. Here, by using novel porous (holey) metallic 1T phase MoS 2 nanosheets synthesized by a liquid-ammonia-assisted lithiation route, we systematically investigated the contributions of crystal structure (phase), edges, and sulfur vacancies (S-vacancies) to the catalytic activity toward HER from five representative MoS 2 nanosheet samples, including 2H and 1T phase, porous 2H andmore » 1T phase, and sulfur-compensated porous 2H phase. Superior HER catalytic activity was achieved in the porous 1T phase MoS 2 nanosheets that have even more edges and S-vacancies than conventional 1T phase MoS 2. A comparative study revealed that the phase serves as the key role in determining the HER performance, as 1T phase MoS 2 always outperforms the corresponding 2H phase MoS 2 samples, and that both edges and S-vacancies also contribute significantly to the catalytic activity in porous MoS 2 samples. Then, using combined defect characterization techniques of electron spin resonance spectroscopy and positron annihilation lifetime spectroscopy to quantify the S-vacancies, the contributions of each factor were individually elucidated. Furthermore, this study presents new insights and opens up new avenues for designing electrocatalysts based on MoS 2 or other layered materials with enhanced HER performance.« less

Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Ying; Han, Jiecai; Zhang, Yumin

Molybdenum disulfide (MoS 2) is a promising nonprecious catalyst for the hydrogen evolution reaction (HER) that has been extensively studied due to its excellent performance, but the lack of understanding of the factors that impact its catalytic activity hinders further design and enhancement of MoS 2-based electrocatalysts. Here, by using novel porous (holey) metallic 1T phase MoS 2 nanosheets synthesized by a liquid-ammonia-assisted lithiation route, we systematically investigated the contributions of crystal structure (phase), edges, and sulfur vacancies (S-vacancies) to the catalytic activity toward HER from five representative MoS 2 nanosheet samples, including 2H and 1T phase, porous 2H andmore » 1T phase, and sulfur-compensated porous 2H phase. Superior HER catalytic activity was achieved in the porous 1T phase MoS 2 nanosheets that have even more edges and S-vacancies than conventional 1T phase MoS 2. A comparative study revealed that the phase serves as the key role in determining the HER performance, as 1T phase MoS 2 always outperforms the corresponding 2H phase MoS 2 samples, and that both edges and S-vacancies also contribute significantly to the catalytic activity in porous MoS 2 samples. Then, using combined defect characterization techniques of electron spin resonance spectroscopy and positron annihilation lifetime spectroscopy to quantify the S-vacancies, the contributions of each factor were individually elucidated. Furthermore, this study presents new insights and opens up new avenues for designing electrocatalysts based on MoS 2 or other layered materials with enhanced HER performance.« less

A polymer supported Cu(I) catalyst for the 'click reaction' in aqueous media.

PubMed

Ul Islam, Rafique; Taher, Abu; Choudhary, Meenakshi; Witcomb, Michael J; Mallick, Kaushik

2015-01-21

Polymer stabilized monovalent copper has been synthesized using an in situ chemical transformation route and was characterized by means of different microscopic, optical and surface characterization techniques, which offered information about the chemical structure of the polymer and the morphology of the complex. The supramolecular material, Cu(i)-poly(2-aminobenzoic acid), denoted Cu(i)-pABA, showed catalytic activity for the cycloaddition reaction between terminal alkynes and azides to synthesize 1,2,3-triazoles with excellent yields. The catalyst was recovered from the reaction mixture and recycled several times without an appreciable loss of catalytic activity. The whole strategy was done under ambient conditions and in the presence of water as a solvent.

Are Diatoms "Green" Aluminosilicate Synthesis Microreactors for Future Catalyst Production?

PubMed

Köhler, Lydia; Machill, Susanne; Werner, Anja; Selzer, Carolin; Kaskel, Stefan; Brunner, Eike

2017-12-16

Diatom biosilica may offer an interesting perspective in the search for sustainable solutions meeting the high demand for heterogeneous catalysts. Diatomaceous earth (diatomite), i.e., fossilized diatoms, is already used as adsorbent and carrier material. While diatomite is abundant and inexpensive, freshly harvested and cleaned diatom cell walls have other advantages, with respect to purity and uniformity. The present paper demonstrates an approach to modify diatoms both in vivo and in vitro to produce a porous aluminosilicate that is serving as a potential source for sustainable catalyst production. The obtained material was characterized at various processing stages with respect to morphology, elemental composition, surface area, and acidity. The cell walls appeared normal without morphological changes, while their aluminum content was raised from the molar ratio n (Al): n (Si) 1:600 up to 1:50. A specific surface area of 55 m²/g was measured. The acidity of the material increased from 149 to 320 µmol NH₃/g by ion exchange, as determined by NH₃ TPD. Finally, the biosilica was examined by an acid catalyzed test reaction, the alkylation of benzene. While the cleaned cell walls did not catalyze the reaction at all, and the ion exchanged material was catalytically active. This demonstrates that modified biosilica does indeed has potential as a basis for future catalytically active materials.

Preparation and characterization of TiO2/HZSM-11 zeolite for photodegradation of dichlorvos in aqueous solution.

PubMed

Gomez, Silvina; Marchena, Candelaria Leal; Pizzio, Luis; Pierella, Liliana

2013-08-15

The TiO2/HZSM-11 materials were synthesized using titanium isopropoxide as a TiO2 precursor and HZSM-11 a medium pore size zeolite with high thermal and chemical resistance as support. The amount of titanium isopropoxide was varied in order to obtain TiO2 concentrations of 3, 10, 20, 30 and 50 wt% in the final material. They were characterized by a series of complementary techniques: X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance spectroscopy (DRS), transmittance Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The surface area of the TiO2/HZSM-11 samples decreased with the increment of TiO2 loading. As result of the increment of the calcination temperature from 450 to 800°C an increase in the size of the anatase crystals was observed. However, the X-ray diffraction patterns of the solids only presented the characteristic peaks of the anatase phase. The catalytic activity of the materials in the photodegradation of Dichlorvos (DDVP) depended on the TiO2 amount the thermal treatment temperature. The sample containing 30% TiO2 calcined at 450°C showed the best catalytic performance and it can be reused without noticeable activity loss during at least four cycles. The catalytic performance was similar to that of the P25 Degussa used as a reference but its separation, recovery and reuse was easier. Copyright © 2013 Elsevier B.V. All rights reserved.

Motion-Based pH Sensing Based on the Cartridge-Case-like Micromotor.

PubMed

Su, Yajun; Ge, Ya; Liu, Limei; Zhang, Lina; Liu, Mei; Sun, Yunyu; Zhang, Hui; Dong, Bin

2016-02-17

In this paper, we report a novel cartridge-case-like micromotor. The micromotor, which is fabricated by the template synthesis method, consists of a gelatin shell with platinum nanoparticles decorating its inner surface. Intriguingly, the resulting cartridge-case-like structure exhibits a pH-dependent "open and close" feature, which originates from the pH responsiveness of the gelatin material. On the basis of the catalytic activity of the platinum nanoparticle inside the gelatin shell, the resulting cartridge-case-like structure is capable of moving autonomously in the aqueous solution containing the hydrogen peroxide fuel. More interestingly, we find out that the micromotor can be utilized as a motion-based pH sensor over the whole pH range. The moving velocity of the micromotor increases monotonically with the increase of pH of the analyte solution. Three different factors are considered to be responsible for the proportional relation between the motion speed and pH of the analyte solution: the peroxidase-like and oxidase-like catalytic behavior of the platinum nanoparticle at low and high pH, the volumetric decomposition of the hydrogen peroxide under the basic condition and the pH-dependent catalytic activity of the platinum nanoparticle caused by the swelling/deswelling behavior of the gelatin material. The current work highlights the impact of the material properties on the motion behavior of a micromotor, thus paving the way toward its application in the motion-based sensing field.

Engineering Ni-Mo-S Nanoparticles for Hydrodesulfurization.

PubMed

Bodin, Anders; Christoffersen, Ann-Louise N; Elkjær, Christian F; Brorson, Michael; Kibsgaard, Jakob; Helveg, Stig; Chorkendorff, Ib

2018-06-13

Nanoparticle engineering for catalytic applications requires both a synthesis technique for the production of well-defined nanoparticles and measurements of their catalytic performance. In this paper, we present a new approach to rationally engineering highly active Ni-Mo-S nanoparticle catalysts for hydrodesulfurization (HDS), i.e., the removal of sulfur from fossil fuels. Nanoparticle catalysts are synthesized by the sputtering of a Mo 75 Ni 25 metal target in a reactive atmosphere of Ar and H 2 S followed by the gas aggregation of the sputtered material into nanoparticles. The nanoparticles are filtered by a quadrupole mass filter and subsequently deposited on a planar substrate, such as a grid for electron microscopy or a microreactor. By varying the mass of the deposited nanoparticles, it is demonstrated that the Ni-Mo-S nanoparticles can be tuned into fullerene-like particles, flat-lying platelets, and upright-oriented platelets. The nanoparticle morphologies provide different abundances of Ni-Mo-S edge sites, which are commonly considered the catalytically important sites. Using a microreactor system, we assess the catalytic activity of the Ni-Mo-S nanoparticles for the HDS of dibenzothiophene. The measurements show that platelets are twice as active as the fullerene-like particles, demonstrating that the Ni-Mo-S edges are more active than basal planes for the HDS. Furthermore, the upright-standing orientation of platelets show an activity that is six times higher than the fullerene-like particles, demonstrating the importance of the edge site number and accessibility to reducing, e.g., sterical hindrance for the reacting molecules.

An Operando Investigation of (Ni–Fe–Co–Ce)O x System as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction

DOE PAGES

Favaro, Marco; Drisdell, Walter S.; Marcus, Matthew A.; ...

2016-12-27

The oxygen evolution reaction (OER) is a critical component of industrial processes such as electrowinning of metals and the chlor-alkali process. It also plays a central role in the development of a renewable energy field for generation a solar fuels by providing both the protons and electrons needed to generate fuels such as H 2 or reduced hydrocarbons from CO 2. To improve these processes, it is necessary to expand the fundamental understanding of catalytically active species at low overpotential, which will further the development of electrocatalysts with high activity and durability. In this context, performing experimental investigations of themore » electrocatalysts under realistic working regimes (i.e., under operando conditions) is of crucial importance. In this paper, we study a highly active quinary transition-metal-oxide-based OER electrocatalyst by means of operando ambient-pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy performed at the solid/liquid interface. We observe that the catalyst undergoes a clear chemical-structural evolution as a function of the applied potential with Ni, Fe, and Co oxyhydroxides comprising the active catalytic species. Finally, while CeO 2 is redox inactive under catalytic conditions, its influence on the redox processes of the transition metals boosts the catalytic activity at low overpotentials, introducing an important design principle for the optimization of electrocatalysts and tailoring of high-performance materials.« less

Ultra-long Pt nanolawns supported on TiO2-coated carbon fibers as 3D hybrid catalyst for methanol oxidation

PubMed Central

2012-01-01

In this study, TiO2 thin film photocatalyst on carbon fibers was used to synthesize ultra-long single crystalline Pt nanowires via a simple photoreduction route (thermally activated photoreduction). It also acted as a co-catalytic material with Pt. Taking advantage of the high-aspect ratio of the Pt nanostructure as well as the excellent catalytic activity of TiO2, this hybrid structure has the great potential as the active anode in direct methanol fuel cells. The electrochemical results indicate that TiO2 is capable of transforming CO-like poisoning species on the Pt surface during methanol oxidation and contributes to a high CO tolerance of this Pt nanowire/TiO2 hybrid structure. PMID:22546416

Ultra-long Pt nanolawns supported on TiO2-coated carbon fibers as 3D hybrid catalyst for methanol oxidation

NASA Astrophysics Data System (ADS)

Shen, Yu-Lin; Chen, Shih-Yun; Song, Jenn-Ming; Chen, In-Gann

2012-06-01

In this study, TiO2 thin film photocatalyst on carbon fibers was used to synthesize ultra-long single crystalline Pt nanowires via a simple photoreduction route (thermally activated photoreduction). It also acted as a co-catalytic material with Pt. Taking advantage of the high-aspect ratio of the Pt nanostructure as well as the excellent catalytic activity of TiO2, this hybrid structure has the great potential as the active anode in direct methanol fuel cells. The electrochemical results indicate that TiO2 is capable of transforming CO-like poisoning species on the Pt surface during methanol oxidation and contributes to a high CO tolerance of this Pt nanowire/TiO2 hybrid structure.

Cu@C nanoporous composites containing little copper oxides derived from dimethyl imidazole modified MOF199 as electrocatalysts for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Wei, Xuedong; Li, Na; Zhang, Xianming

2017-12-01

It remains a huge challenge to develop non precious electrocatalysts with high activity to substitute commercial Pt catalysts for hydrogen evolution reactions (HER). Here, the C-Cu-DI and C-Cu materials with the copper based nanoporous carbon structures were synthesized by carbonizing MOF199 and DI-MOF199. The composite structure and HER electrocatalytic properties of the C-Cu-DI and C-Cu materials are studied. The results show that C-Cu-DI and C-Cu samples exhibit good catalytic activity. And C-Cu-DI sample through the addition of Dimethyl imidazole(DI) in the DI-MOF199 precursor has higher electrocatalytic activity than the C-Cu sample. The superior catalytic activity is attributed to the special composite structure of nanoscale deposition particles on the framework with plenty of nano pores and nano copper and few copper oxidation particles distributed or wrapped into the amorphous porous carbon phase. The nano copper and few copper oxidation particles in the C-Cu and C-Cu-DI catalysts maybe provide the more effective catalytic activity sites. The C-Cu-DI composite with large size spherical hollow deposition particles has higher conductivity, better BET surface area and reasonable micro-meso-macro porous distribution, so the overpotentials at the current density of 1 mA cm-2 and 10 mA cm-2 are respectively 270 mV and 390 mV vs. RHE. Although the HER activity has a big gap with commercial platinum catalyst, this study can provide an important experimental exploration for the design of copper based non noble metal/nano porous carbon composite HER electrocatalyst.

LiFePO4 microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G.

PubMed

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.

A tailored biocatalyst achieved by the rational anchoring of imidazole groups on a natural polymer: furnishing a potential artificial nuclease by sustainable materials engineering.

PubMed

Ferreira, José G L; Grein-Iankovski, Aline; Oliveira, Marco A S; Simas-Tosin, Fernanda F; Riegel-Vidotti, Izabel C; Orth, Elisa S

2015-04-11

Foreseeing the development of artificial enzymes by sustainable materials engineering, we rationally anchored reactive imidazole groups on gum arabic, a natural biocompatible polymer. The tailored biocatalyst GAIMZ demonstrated catalytic activity (>10(5)-fold) in dephosphorylation reactions with recyclable features and was effective in cleaving plasmid DNA, comprising a potential artificial nuclease.

K1.33Mn8O16 as an electrocatalyst and a cathode

NASA Astrophysics Data System (ADS)

Jalili, Seifollah; Moharramzadeh Goliaei, Elham; Schofield, Jeremy

2017-02-01

Density functional theory (DFT) calculations are carried out to investigate the electronic, magnetic and thermoelectric properties of bulk and nanosheet K1.33Mn8O16 materials. The catalytic activity and cathodic performance of bulk and nanosheet structures are examined using the Tran-Blaha modified Becke-Johnson (TB-mBJ) exchange potential. Electronic structure calculations reveal an anti-ferromagnetic ground state, with a TB-mMBJ band gap in bulk K1.33Mn8O16 that is in agreement with experimental results. Density of state plots indicate a partial reduction of Mn4+ ions to Mn3+, without any obvious sign of Jahn-Teller distortion. Moreover, use of the O p-band center as a descriptor of catalytic activity suggests that the nanosheet has enhanced catalytic activity compared to the bulk structure. Thermoelectric parameters such as the Seebeck coefficient, electrical conductivity, and thermal conductivity are also calculated, and it is found that the Seebeck coefficients decrease with increasing temperature. High Seebeck coefficients for both spin-up and spin-down states are found in the nanosheet relative to their value in the bulk K1.33Mn8O16 structure, whereas the electrical and thermal conductivity are reduced relative to the bulk. In addition, figures of merit values are calculated as a function of the chemical potential and it is found that the nanosheet has a figure of merit of 1 at room temperature, compared to 0.5 for the bulk material. All results suggest that K1.33Mn8O16 nanosheets can be used both as a material in waste heat recovery and as an electrocatalyst in fuel cells and batteries.

Generation and Characterization of Six Recombinant Botulinum Neurotoxins as Reference Material to Serve in an International Proficiency Test

PubMed Central

Weisemann, Jasmin; Krez, Nadja; Fiebig, Uwe; Worbs, Sylvia; Skiba, Martin; Endermann, Tanja; Dorner, Martin B.; Bergström, Tomas; Muñoz, Amalia; Zegers, Ingrid; Müller, Christian; Jenkinson, Stephen P.; Avondet, Marc-Andre; Delbrassinne, Laurence; Denayer, Sarah; Zeleny, Reinhard; Schimmel, Heinz; Åstot, Crister; Dorner, Brigitte G.; Rummel, Andreas

2015-01-01

The detection and identification of botulinum neurotoxins (BoNT) is complex due to the existence of seven serotypes, derived mosaic toxins and more than 40 subtypes. Expert laboratories currently use different technical approaches to detect, identify and quantify BoNT, but due to the lack of (certified) reference materials, analytical results can hardly be compared. In this study, the six BoNT/A1–F1 prototypes were successfully produced by recombinant techniques, facilitating handling, as well as improving purity, yield, reproducibility and biosafety. All six BoNTs were quantitatively nicked into active di-chain toxins linked by a disulfide bridge. The materials were thoroughly characterized with respect to purity, identity, protein concentration, catalytic and biological activities. For BoNT/A1, B1 and E1, serotypes pathogenic to humans, the catalytic activity and the precise protein concentration were determined by Endopep-mass spectrometry and validated amino acid analysis, respectively. In addition, BoNT/A1, B1, E1 and F1 were successfully detected by immunological assays, unambiguously identified by mass spectrometric-based methods, and their specific activities were assigned by the mouse LD50 bioassay. The potencies of all six BoNT/A1–F1 were quantified by the ex vivo mouse phrenic nerve hemidiaphragm assay, allowing a direct comparison. In conclusion, highly pure recombinant BoNT reference materials were produced, thoroughly characterized and employed as spiking material in a worldwide BoNT proficiency test organized by the EQuATox consortium. PMID:26703728

Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

PubMed

Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

2014-01-22

Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

Chitin-Lignin Material as a Novel Matrix for Enzyme Immobilization

PubMed Central

Zdarta, Jakub; Klapiszewski, Łukasz; Wysokowski, Marcin; Norman, Małgorzata; Kołodziejczak-Radzimska, Agnieszka; Moszyński, Dariusz; Ehrlich, Hermann; Maciejewski, Hieronim; Stelling, Allison L.; Jesionowski, Teofil

2015-01-01

Innovative materials were made via the combination of chitin and lignin, and the immobilization of lipase from Aspergillus niger. Analysis by techniques including FTIR, XPS and 13C CP MAS NMR confirmed the effective immobilization of the enzyme on the surface of the composite support. The electrokinetic properties of the resulting systems were also determined. Results obtained from elemental analysis and by the Bradford method enabled the determination of optimum parameters for the immobilization process. Based on the hydrolysis reaction of para-nitrophenyl palmitate, a determination was made of the catalytic activity, thermal and pH stability, and reusability. The systems with immobilized enzymes were found to have a hydrolytic activity of 5.72 mU, and increased thermal and pH stability compared with the native lipase. The products were also shown to retain approximately 80% of their initial catalytic activity, even after 20 reaction cycles. The immobilization process, using a cheap, non-toxic matrix of natural origin, leads to systems with potential applications in wastewater remediation processes and in biosensors. PMID:25903282

Templated assembly of BiFeO3 nanocrystals into 3D mesoporous networks for catalytic applications

NASA Astrophysics Data System (ADS)

Papadas, I. T.; Subrahmanyam, K. S.; Kanatzidis, M. G.; Armatas, G. S.

2015-03-01

The self-assembly of uniform nanocrystals into large porous architectures is currently of immense interest for nanochemistry and nanotechnology. These materials combine the respective advantages of discrete nanoparticles and mesoporous structures. In this article, we demonstrate a facile nanoparticle templating process to synthesize a three-dimensional mesoporous BiFeO3 material. This approach involves the polymer-assisted aggregating assembly of 3-aminopropanoic acid-stabilized bismuth ferrite (BiFeO3) nanocrystals followed by thermal decomposition of the surfactant. The resulting material consists of a network of tightly connected BiFeO3 nanoparticles (~6-7 nm in diameter) and has a moderately high surface area (62 m2 g-1) and uniform pores (ca. 6.3 nm). As a result of the unique mesostructure, the porous assemblies of BiFeO3 nanoparticles show an excellent catalytic activity and chemical stability for the reduction of p-nitrophenol to p-aminophenol with NaBH4.The self-assembly of uniform nanocrystals into large porous architectures is currently of immense interest for nanochemistry and nanotechnology. These materials combine the respective advantages of discrete nanoparticles and mesoporous structures. In this article, we demonstrate a facile nanoparticle templating process to synthesize a three-dimensional mesoporous BiFeO3 material. This approach involves the polymer-assisted aggregating assembly of 3-aminopropanoic acid-stabilized bismuth ferrite (BiFeO3) nanocrystals followed by thermal decomposition of the surfactant. The resulting material consists of a network of tightly connected BiFeO3 nanoparticles (~6-7 nm in diameter) and has a moderately high surface area (62 m2 g-1) and uniform pores (ca. 6.3 nm). As a result of the unique mesostructure, the porous assemblies of BiFeO3 nanoparticles show an excellent catalytic activity and chemical stability for the reduction of p-nitrophenol to p-aminophenol with NaBH4. Electronic supplementary information (ESI) available: IR spectra and TG profiles of as-made BiFeO3 NPs and MBFA samples, TEM images of 3-APA-capped BiFeO3 NPs, EDS spectrum of MBFAs, N2 adsorption-desorption isotherms of randomly aggregated BiFeO3 NPs and catalytic data for 4-NP reduction by MBFAs and other nanostructured catalysts. See DOI: 10.1039/c5nr00185d

Stable carbonous catalyst particles and method for making and utilizing same

DOEpatents

Ganguli, Partha S.; Comolli, Alfred G.

2005-06-14

Stable carbonous catalyst particles composed of an inorganic catalytic metal/metal oxide powder and a carbonaceous binder material are formed having a basic inner substantially uniform-porous carbon coating of the catalytic powder, and may include an outer porous carbon coating layer. Suitable inorganic catalytic powders include zinc-chromite (ZnO/Cr.sub.2 03) and suitable carbonaceous liquid binders having molecular weight of 200-700 include partially polymerized furfuryl alcohol, which are mixed together, shaped and carbonized and partially oxidized at elevated temperature. Such stable carbonous catalyst particles such as 0.020-0.100 inch (0.51-2.54 mm) diameter extrudates, have total carbon content of 2-25 wt. % and improved crush strength of 1.0-5 1b/mn, 50-300 m.sup.2 /g surface area, and can be advantageously utilized in fixed bed or ebullated/fluidized bed reactor operations. This invention also includes method steps for making the stable carbonous catalyst particles having improved particle strength and catalytic activity, and processes for utilizing the active stable carbonous carbon-coated catalysts such as for syn-gas reactions in ebullated/fluidized bed reactors for producing alcohol products and Fischer-Tropsch synthesis liquid products.

Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

PubMed

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.

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.

Liquid-phase chemical hydrogen storage: catalytic hydrogen generation under ambient conditions.

PubMed

Jiang, Hai-Long; Singh, Sanjay Kumar; Yan, Jun-Min; Zhang, Xin-Bo; Xu, Qiang

2010-05-25

There is a demand for a sufficient and sustainable energy supply. Hence, the search for applicable hydrogen storage materials is extremely important owing to the diversified merits of hydrogen energy. Lithium and sodium borohydride, ammonia borane, hydrazine, and formic acid have been extensively investigated as promising hydrogen storage materials based on their relatively high hydrogen content. Significant advances, such as hydrogen generation temperatures and reaction kinetics, have been made in the catalytic hydrolysis of aqueous lithium and sodium borohydride and ammonia borane as well as in the catalytic decomposition of hydrous hydrazine and formic acid. In this Minireview we briefly survey the research progresses in catalytic hydrogen generation from these liquid-phase chemical hydrogen storage materials.

Green and facile synthesis of fibrous Ag/cotton composites and their catalytic properties for 4-nitrophenol reduction

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.

Coated mesh photocatalytic reactor for air treatment applications: comparative study of support materials.

PubMed

Passalía, Claudio; Nocetti, Emanuel; Alfano, Orlando; Brandi, Rodolfo

2017-03-01

An experimental comparative study of different meshes as support materials for photocatalytic applications in gas phase is presented. The photocatalytic oxidation of dichloromethane in air was addressed employing different coated meshes in a laboratory-scale, continuous reactor. Two fiberglass meshes and a stainless steel mesh were studied regarding the catalyst load, adherence, and catalytic activity. Titanium dioxide photocatalyst was immobilized on the meshes by dip-coating cycles. Results indicate the feasibility of the dichloromethane elimination in the three cases. When the number of coating cycles was doubled, the achieved conversion levels were increased twofold for stainless steel and threefold for the fiberglass meshes. One of the fiberglass meshes (FG2) showed the highest reactivity per mass of catalyst and per catalytic surface area.

Synthesis of Nitrogen-Doped Mesoporous Carbon for the Catalytic Oxidation of Ethylbenzene

NASA Astrophysics Data System (ADS)

Wang, Ruicong; Yu, Yifeng; Zhang, Yue; Lv, Haijun; Chen, Aibing

2017-06-01

Nitrogen-doped ordered mesoporous carbon (NOMC) was fabricated via a simple hard-template method by functionalized ionic liquids as carbon and nitrogen source, SBA-15 as a hard-template. The obtained NOMC materials have a high nitrogen content of 5.55 %, a high surface area of 446.2 m2 g-1, and an excellent performance in catalysing oxidation of ethylbenzene. The conversion rate of ethylbenzene can be up to 84.5% and the yield of acetophenone can be up to 69.9%, the results indicated that the NOMC materials have a faster catalytic rate and a higher production of acetophenone than catalyst-free and CMK-3, due to their uniform pore size, high surface area and rich active sites in the carbon pore walls.

CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

DOE PAGES

Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

2016-08-26

Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

Low Temperature Propane Oxidation over Co 3O 4 based Nano-array Catalysts. Ni Dopant Effect, Reaction Mechanism and Structural Stability

DOE PAGES

Ren, Zheng; Wu, Zili; Gao, Puxian; ...

2015-06-09

Low temperature propane oxidation has been achieved by Co 3O 4-based nano-array catalysts featuring low catalytic materials loading. The Ni doping into the Co 3O 4 lattice has led to enhanced reaction kinetics at low temperature by promoting the surface lattice oxygen activity. In situ DRIFTS investigation in tandem with isotopic oxygen exchange reveals that the propane oxidation proceeds via Mars-van Krevelen mechanism where surface lattice oxygen acts as the active site whereas O 2 in the reaction feed does not directly participate in CO 2 formation. The Ni doping promotes the formation of less stable carbonates on the surfacemore » to facilitate the CO 2 desorption. The thermal stability of Ni doped Co 3O 4 decreases with increased Ni concentration while catalytic activity increases. A balance between enhanced activity and compromised thermal stability shall be considered in the Ni doped Co 3O 4 nano-array catalysts for low temperature hydrocarbon oxidation. This study provides useful and timely guidance for rational catalyst design toward low temperature catalytic oxidation.« less

Synthesis of mesoporous TiO(2-x)N(x) spheres by template free homogeneous co-precipitation method and their photo-catalytic activity under visible light illumination.

PubMed

Parida, K M; Naik, Brundabana

2009-05-01

The article presents preparation, characterization and catalytic activity evaluation of an efficient nitrogen doped mesoporous titania sphere photo-catalyst for degradation of methylene blue (MB) and methyl orange (MO) under visible light illumination. Nitrogen doped titania was prepared by soft chemical route i.e. template free, slow and controlled homogeneous co-precipitation from titanium oxysulfate sulfuric acid complex hydrate, urea, ethanol and water. The molar composition of TiOSO(4) to urea was varied to prepare different atomic % nitrogen doped titania. Mesoporous anatase TiO(2-x)N(x) spheres with average crystallite size of 10 nm and formation of titanium oxynitride center were confirmed from HRTEM, XRD and XPS study. UV-vis DRS showed a strong absorption in the range of 400-500 nm which supports its use in visible spectrum of light. Nitrogen adsorption-desorption study supports the porous nature of the doped material. All the TiO(2-x)N(x) samples showed higher photo-catalytic activity than Degussa P(25) and undoped mesoporous titania. Sample containing around one atomic % nitrogen showed highest activity among the TiO(2-x)N(x) samples.

Spark plasma sintering synthesis of Ni1-xZnxFe2O4 ferrites: Mössbauer and catalytic study

NASA Astrophysics Data System (ADS)

Velinov, Nikolay; Manova, Elina; Tsoncheva, Tanya; Estournès, Claude; Paneva, Daniela; Tenchev, Krassimir; Petkova, Vilma; Koleva, Kremena; Kunev, Boris; Mitov, Ivan

2012-08-01

Nickel-zinc ferrite nanoparticles, Ni1-xZnxFe2O4 (x = 0, 0.2, 0.5, 0.8, 1.0) were prepared by combination of chemical precipitation and spark plasma sintering (SPS) techniques and conventional thermal treatment of the obtained precursors. The phase composition and structural properties of the obtained materials were investigated by X-ray diffraction and Mössbauer spectroscopy and their catalytic activity in methanol decomposition was tested. A strong effect of reaction medium leading to the transformation of ferrites to a complex mixture of different iron containing phases was detected. A tendency of formation of Fe-carbide was found for the samples synthesized by SPS, while predominantly iron-nickel alloys ware registered in TS obtained samples. The catalytic activity and selectivity in methanol decomposition to CO and methane depended on the current phase composition of the obtained ferrites, which was formed by the influence of the reaction medium.

Gold nanoparticles stabilized by poly(4-vinylpyridine) grafted cellulose nanocrystals as efficient and recyclable catalysts.

PubMed

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camacho-Bunquin, Jeffrey; Shou, Heng; Marshall, Christopher L.

An integrated atomic layer deposition synthesis-catalysis (I-ALD-CAT) tool was developed. It combines an ALD manifold in-line with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT delivery system consists of 12 different metal ALD precursor channels, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10{sup −3} to 1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph andmore » a mass spectrometer unit for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the synthesis of platinum active sites and Al{sub 2}O{sub 3} overcoats, and evaluation of catalyst propylene hydrogenation activity.« less

Novel Acid Catalysts from Waste-Tire-Derived Carbon: Application in Waste-to-Biofuel Conversion

DOE PAGES

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

Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry.

PubMed

Tokudome, Yasuaki; Morimoto, Tsuyoshi; Tarutani, Naoki; Vaz, Pedro D; Nunes, Carla D; Prevot, Vanessa; Stenning, Gavin B G; Takahashi, Masahide

2016-05-24

Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.

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

Atomic-scale identification of Pd leaching in nanoparticle catalyzed C–C coupling: Effects of particle surface disorder

DOE PAGES

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

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.

Development of second generation gold-supported palladium material with low-leaching and recyclable characteristics in aromatic amination.

PubMed

Al-Amin, Mohammad; Arai, Satoshi; Hoshiya, Naoyoki; Honma, Tetsuo; Tamenori, Yusuke; Sato, Takatoshi; Yokoyama, Mami; Ishii, Akira; Takeuchi, Masashi; Maruko, Tomohiro; Shuto, Satoshi; Arisawa, Mitsuhiro

2013-08-02

An improved process for the preparation of sulfur-modified gold-supported palladium material [SAPd, second generation] is presented. The developed preparation method is safer and generates less heat (aqueous Na2S2O8 and H2SO4) for sulfur fixation on a gold surface, and it is superior to the previous method of preparing SAPd (first generation), which requires the use of the more heat-generating and dangerous piranha solution (concentrated H2SO4 and 35% H2O2) in the sulfur fixation step. This safer and improved preparation method is particularly important for the mass production of SAPd (second generation) for which the catalytic activity was examined in ligand-free Buchwald-Hartwig cross-coupling reactions. The catalytic activities were the same between the first and second generation SAPds in aromatic aminations, but the lower palladium leaching properties and safer preparative method of second generation SAPd are a significant improvement over the first generation SAPd.

Microwave-assisted synthesis of palladium nanoparticles intercalated nitrogen doped reduced graphene oxide and their electrocatalytic activity for direct-ethanol fuel cells.

PubMed

Kumar, Rajesh; da Silva, Everson T S G; Singh, Rajesh K; Savu, Raluca; Alaferdov, Andrei V; Fonseca, Leandro C; Carossi, Lory C; Singh, Arvind; Khandka, Sarita; Kar, Kamal K; Alves, Oswaldo L; Kubota, Lauro T; Moshkalev, Stanislav A

2018-04-01

Palladium nanoparticles decorated reduced graphene oxide (Pd-rGO) and palladium nanoparticles intercalated inside nitrogen doped reduced graphene oxide (Pd-NrGO) hybrids have been synthesized by applying a very simple, fast and economic route using microwave-assisted in-situ reduction and exfoliation method. The Pd-NrGO hybrids materials show good activity as catalyst for ethanol electro oxidation for direct ethanol fuel cells (DEFCs) as compared to Pd-rGO hybrids. The enhanced direct ethanol fuel cell can serve as alternative to fossil fuels because it is renewable and environmentally-friendly with a high energy conversion efficiency and low pollutant emission. As proof of concept, the electrocatalytic activity of Pd-NrGO hybrid material was accessed by cyclic voltammetry in presence of ethanol to evaluate its applicability in direct-ethanol fuel cells (DEFCs). The Pd-NrGO catalyst presented higher electro active surface area (∼6.3 m 2  g -1 ) for ethanol electro-oxidation when compared to Pd-rGO hybrids (∼3.7 m 2  g -1 ). Despite the smaller catalytic activity of Pd-NrGO, which was attributed to the lower exfoliation rate of this material in relation to the Pd-rGO, Pd-NrGO showed to be very promising and its catalytic activity can be further improved by tuning the synthesis parameters to increase the exfoliation rate. Copyright © 2018 Elsevier Inc. All rights reserved.

Catalytic transformation of persistent contaminants using a new composite material based on nanosized zero-valent iron.

PubMed

Dror, Ishai; Jacov, Osnat Merom; Cortis, Andrea; Berkowitz, Brian

2012-07-25

A new composite material based on deposition of nanosized zerovalent iron (nZVI) particles and cyanocobalamine (vitamin B12) on a diatomite matrix is presented, for catalytic transformation of organic contaminants in water. Cyanocobalamine is known to be an effective electron mediator, having strong synergistic effects with nZVI for reductive dehalogenation reactions. This composite material also improves the reducing capacity of nZVI by preventing agglomeration of iron nanoparticles, thus increasing their active surface area. The porous structure of the diatomite matrix allows high hydraulic conductivity, which favors channeling of contaminated water to the reactive surface of the composite material resulting in faster rates of remediation. The composite material rapidly degrades or transforms completely a large spectrum of water contaminants, including halogenated solvents like TCE, PCE, and cis-DCE, pesticides like alachlor, atrazine and bromacyl, and common ions like nitrate, within minutes to hours. A field experiment where contaminated groundwater containing a mixture of industrial and agricultural persistent pollutants was conducted together with a set of laboratory experiments using individual contaminant solutions to analyze chemical transformations under controlled conditions.

Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting

NASA Astrophysics Data System (ADS)

Roeffaers, Maarten B. J.; Sels, Bert F.; Uji-I, Hiroshi; de Schryver, Frans C.; Jacobs, Pierre A.; de Vos, Dirk E.; Hofkens, Johan

2006-02-01

Catalytic processes on surfaces have long been studied by probing model reactions on single-crystal metal surfaces under high vacuum conditions. Yet the vast majority of industrial heterogeneous catalysis occurs at ambient or elevated pressures using complex materials with crystal faces, edges and defects differing in their catalytic activity. Clearly, if new or improved catalysts are to be rationally designed, we require quantitative correlations between surface features and catalytic activity-ideally obtained under realistic reaction conditions. Transmission electron microscopy and scanning tunnelling microscopy have allowed in situ characterization of catalyst surfaces with atomic resolution, but are limited by the need for low-pressure conditions and conductive surfaces, respectively. Sum frequency generation spectroscopy can identify vibrations of adsorbed reactants and products in both gaseous and condensed phases, but so far lacks sensitivity down to the single molecule level. Here we adapt real-time monitoring of the chemical transformation of individual organic molecules by fluorescence microscopy to monitor reactions catalysed by crystals of a layered double hydroxide immersed in reagent solution. By using a wide field microscope, we are able to map the spatial distribution of catalytic activity over the entire crystal by counting single turnover events. We find that ester hydrolysis proceeds on the lateral {1010} crystal faces, while transesterification occurs on the entire outer crystal surface. Because the method operates at ambient temperature and pressure and in a condensed phase, it can be applied to the growing number of liquid-phase industrial organic transformations to localize catalytic activity on and in inorganic solids. An exciting opportunity is the use of probe molecules with different size and functionality, which should provide insight into shape-selective or structure-sensitive catalysis and thus help with the rational design of new or more productive heterogeneous catalysts.

The Remarkable Amphoteric Nature of Defective UiO‐66 in Catalytic Reactions

PubMed Central

Hajek, Julianna; Bueken, Bart; Waroquier, Michel; De Vos, Dirk

2017-01-01

Abstract One of the major requirements in solid acid and base catalyzed reactions is that the reactants, intermediates or activated complexes cooperate with several functions of catalyst support. In this work the remarkable bifunctional behavior of the defective UiO‐66(Zr) metal organic framework is shown for acid‐base pair catalysis. The active site relies on the presence of coordinatively unsaturated zirconium sites, which may be tuned by removing framework linkers and by removal of water from the inorganic bricks using a dehydration treatment. To elucidate the amphoteric nature of defective UiO‐66, the Oppenauer oxidation of primary alcohols has been theoretically investigated using density functional theory (DFT) and the periodic approach. The presence of acid and basic centers within molecular distances is shown to be crucial for determining the catalytic activity of the material. Hydrated and dehydrated bricks have a distinct influence on the acidity and basicity of the active sites. In any case both functions need to cooperate in a concerted way to enable the chemical transformation. Experimental results on UiO‐66 materials of different defectivity support the theoretical observations made in this work. PMID:28736581

Design and functionalization of photocatalytic systems within mesoporous silica.

PubMed

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.

Temperature regulated Brønsted acidic ionic liquid-catalyze esterification of oleic acid for biodiesel application

NASA Astrophysics Data System (ADS)

Rafiee, Ezzat; Mirnezami, Fakhrosadat

2017-02-01

By combining phosphotungstic acid (PW) and SO3H- functioned zwitterion, heteropoly anion-based Brønsted acidic ionic liquids (HPA-ILs) were successfully obtained. Scanning electron microscopy and energy dispersive X-ray spectroscopy were provided the morphology and composition of the prepared material. Catalytic performance and reusability of the catalysts were evaluated through an esterification reaction between oleic acid and methanol for production of biodiesel. Relationship between catalytic activities and acidity of the catalysts have been discussed by potentiometric titration. The results showed that HPA-ILs had good activity and reusability. HPA-ILs dissolved in the reaction mixture during the reaction process and could be precipitated and separated from products at lower temperature.

Novel Montmorillonite/TiO₂/MnAl-Mixed Oxide Composites Prepared from Inverse Microemulsions as Combustion Catalysts.

PubMed

Napruszewska, Bogna D; Michalik-Zym, Alicja; Rogowska, Melania; Bielańska, Elżbieta; Rojek, Wojciech; Gaweł, Adam; Wójcik-Bania, Monika; Bahranowski, Krzysztof; Serwicka, Ewa M

2017-11-19

A novel design of combustion catalysts is proposed, in which clay/TiO₂/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts' thermal stability, two calcination temperatures were employed: 450 and 600 °C. The composites were characterized with XRF (X-ray fluorescence), XRD (X-ray diffraction), HR SEM (high resolution scanning electron microscopy, N₂ adsorption/desorption at -196 °C, and H₂ TPR (temperature programmed reduction). Profound differences in structural, textural and redox properties of the materials were observed, depending on the presence of the TiO₂ component, the type of neutralization agent used in the titania nanoparticles preparation (NaOH or NH₃ (aq)), and the temperature of calcination. Catalytic tests of toluene combustion revealed that the clay/TiO₂/MnAl-mixed oxide composites prepared with the use of ammonia showed excellent activity, the composites obtained from MnAl hydrotalcite nanoparticles trapped between the organoclay layers were less active, but displayed spectacular thermal stability, while the clay/TiO₂/MnAl-mixed oxide materials obtained with the aid of NaOH were least active. The observed patterns of catalytic activity bear a direct relation to the materials' composition and their structural, textural, and redox properties.

Identification of N-Terminal Lobe Motifs that Determine the Kinase Activity of the Catalytic Domains and Regulatory Strategies of Src and Csk Protein Tyrosine Kinases†

PubMed Central

Huang, Kezhen; Wang, Yue-Hao; Brown, Alex; Sun, Gongqin

2009-01-01

Csk and Src protein tyrosine kinases are structurally homologous, but use opposite regulatory strategies. The isolated catalytic domain of Csk is intrinsically inactive and is activated by interactions with the regulatory SH3 and SH2 domains, while the isolated catalytic domain of Src is intrinsically active and is suppressed by interactions with the regulatory SH3 and SH2 domains. The structural basis for why one isolated catalytic domain is intrinsically active while the other is inactive is not clear. In this current study, we identify the structural elements in the N-terminal lobe of the catalytic domain that render the Src catalytic domain active. These structural elements include the α-helix C region, a β-turn between the β-4 and β-5 strands, and an Arg residue at the beginning of the catalytic domain. These three motifs interact with each other to activate the Src catalytic domain, but the equivalent motifs in Csk directly interact with the regulatory domains that are important for Csk activation. The Src motifs can be grafted to the Csk catalytic domain to obtain an active Csk catalytic domain. These results, together with available Src and Csk tertiary structures, reveal an important structural switch that determines the kinase activity of a catalytic domain and dictates the regulatory strategy of a kinase. PMID:19244618

Diastereoselective Radical‐Type Cyclopropanation of Electron‐Deficient Alkenes Mediated by the Highly Active Cobalt(II) Tetramethyltetraaza[14]annulene Catalyst

PubMed Central

Chirila, Andrei; Gopal Das, Braja; Paul, Nanda D.

2017-01-01

Abstract A new protocol for the catalytic synthesis of cyclopropanes using electron‐deficient alkenes is presented, which is catalysed by a series of affordable, easy to synthesise and highly active substituted cobalt(II) tetraaza[14]annulenes. These catalysts are compatible with the use of sodium tosylhydrazone salts as precursors to diazo compounds in one‐pot catalytic transformations to afford the desired cyclopropanes in almost quantitative yields. The reaction takes advantage of the metalloradical character of the Co complexes to activate the diazo compounds. The reaction is practical and fast, and proceeds from readily available starting materials. It does not require the slow addition of diazo reagents or tosylhydrazone salts or heating and tolerates many solvents, which include protic ones such as MeOH. The CoII complexes derived from the tetramethyltetraaza[14]annulene ligand are easier to prepare than cobalt(II) porphyrins and present a similar catalytic carbene radical reactivity but are more active. The reaction proceeds at 20 °C in a matter of minutes and even at −78 °C in a few hours. The catalytic system is robust and can operate with either the alkene or the diazo reagent as the limiting reagent, which inhibits the dimerisation of diazo compounds totally. The protocol has been applied to synthesise a variety of substituted cyclopropanes. High yields and selectivities were achieved for various substrates with an intrinsic preference for trans cyclopropanes. PMID:28529668

Raney nickel catalytic device

DOEpatents

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.

Metal-Free Carbon Materials for CO2 Electrochemical Reduction.

PubMed

Duan, Xiaochuan; Xu, Jiantie; Wei, Zengxi; Ma, Jianmin; Guo, Shaojun; Wang, Shuangyin; Liu, Huakun; Dou, Shixue

2017-11-01

The rapid increase of the CO 2 concentration in the Earth's atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO 2 conversion, electrochemical reduction of CO 2 (CO 2 RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal-free electrocatalysts for the CO 2 RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high-temperature stability, and environmental friendliness. They exhibit remarkable CO 2 RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal-free catalysts for the CO 2 RR are highlighted. Recent advances regarding the identification of active sites for the CO 2 RR and the pathway of reduction of CO 2 to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom-doped carbon materials as metal-free electrocatalysts for the CO 2 RR are included. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of an ion-exchange membrane-catalytic electrode bonded material for electrolytic cells

NASA Technical Reports Server (NTRS)

Takenaka, H.; Torikai, E.

1986-01-01

A good bond is achieved by placing a metal salt in solution on one side of a membrane and a reducing agent on the other side so that the reducing agent penetrates the membrane and reduces the metal. Thus, a solution containing Pt, Rh, etc., is placed on one side of the membrane and a reducing agent such as NaBH, is placed on the other side. The bonded metal layer obtained is superior in catalytic activity and is suitable as an electrode in a cell such as for solid polymer electrolyte water electrolysis.

Preparation, Characterization and Photocatalytic Activity of Ag/TiO2 Nanoparticle Semiconductor Catalysts

NASA Astrophysics Data System (ADS)

Zhang, Yaoyao; Li, Mengyao; Guo, Yinli

2018-01-01

A series of Ag-doped TiO2 powder photocatalysts were prepared by the sol-gel method. The phase structure and morphology of the samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The persistent organic pollutant sodium pentachlorophenol ate (PCP-Na) was selected as the target pollutant, and the photocatalytic property of the material Ag/TiO2 was evaluated by PCP-Na degradation rate. It was found that the calcination at 450 °C was conducive to form the anatase structure with high catalytic activity, and the catalytic activity was higher when the silver mole fraction of Ag/TiO2 was 0.50%. The influence of Ag/TiO2 dosage, hydrogen peroxide volume, silver mole fraction and PCP-Na initial concentration was investigated by the single factor experiment.

Crystal-defect-induced facet-dependent electrocatalytic activity of 3D gold nanoflowers for the selective nanomolar detection of ascorbic acid.

PubMed

De, Sandip Kumar; Mondal, Subrata; Sen, Pintu; Pal, Uttam; Pathak, Biswarup; Rawat, Kuber Singh; Bardhan, Munmun; Bhattacharya, Maireyee; Satpati, Biswarup; De, Amitabha; Senapati, Dulal

2018-06-14

Understanding and exploring the decisive factors responsible for superlative catalytic efficiency is necessary to formulate active electrode materials for improved electrocatalysis and high-throughput sensing. This research demonstrates the ability of bud-shaped gold nanoflowers (AuNFs), intermediates in the bud-to-blossom gold nanoflower synthesis, to offer remarkable electrocatalytic efficiency in the oxidation of ascorbic acid (AA) at nanomolar concentrations. Multicomponent sensing in a single potential sweep is measured using differential pulse voltammetry while the kinetic parameters are estimated using electrochemical impedance spectroscopy. The outstanding catalytic activity of bud-structured AuNF [iAuNFp(Bud)/iGCp ≅ 100] compared with other bud-to-blossom intermediate nanostructures is explained by studying their structural transitions, charge distributions, crystalline patterns, and intrinsic irregularities/defects. Detailed microscopic analysis shows that density of crystal defects, such as edges, terraces, steps, ledges, kinks, and dislocation, plays a major role in producing the high catalytic efficiency. An associated ab initio simulation provides necessary support for the projected role of different crystal facets as selective catalytic sites. Density functional theory corroborates the appearance of inter- and intra-molecular hydrogen bonding within AA molecules to control the resultant fingerprint peak potentials at variable concentrations. Bud-structured AuNF facilitates AA detection at nanomolar levels in a multicomponent pathological sample.

Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

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

Synthesis, Characterization, and Catalytic Applications of Transition Metal Oxide/Carbonate Nanomaterials

NASA Astrophysics Data System (ADS)

Jin, Lei

2011-12-01

This thesis contains two parts: 1) Studies of novel synthesis methods and characterization of advanced functional manganese oxide octahedral molecular sieves (OMS) and their applications in Li/Air batteries, solvent free toluene oxidations, and ethane oxydehydrogenation (ODH) in the presence of CO2, recycling the green house gas. 2) Development of unique Ln2O2CO3 (Ln = rare earth) layered materials and ZnO/La2O2CO3 composites as clean energy biofuel catalysts. These parts are separated into five different focused topics included in this thesis. The first topic presents studies of catalytic activities of a single step synthesized gamma-MnO2 octahedral molecular sieve nano fiber in solvent free atmospheric oxidation of toluene with molecular oxygen. Solvent free atmospheric oxidation of toluene is a notoriously difficult liquid phase oxidation process due to the challenge of oxidizing sp³ hybridized carbon in inactive hydrocarbons. The synthesized gamma-MnO2 showed excellent catalytic activity and good selectivity under the mild atmospheric reflux system. Under optimized conditions, a 47.8% conversion of toluene, along with 57% selectivity of benzoic acid and 15% of benzaldehyde were obtained. The effects of reaction time, amount of catalyst and initiator, and the reusability of the catalyst were investigated. The second topic involves developing titanium containing gamma-MnO 2 (TM) hollow spheres as electrocatalysts in Li/Air Batteries. Li/air batteries have recently attracted interest because they have the largest theoretical specific energy (11,972 Wh.kg-1) among all practical electrochemical couples. In this study, unique hollow aspheric materials were prepared for the first time using a one-step synthesis method and fully characterized by various techniques. These prepared materials were found to have excellent electrocatalytic activation as cathode materials in lithium-air batteries with a very high specific capacity (up to 2.3 A.h/g of carbon). The third topic in this thesis presents studies of ethane oxydehydrogenation (ODH) in the presence of CO2 over the octahedral molecular sieve (OMS-2) catalyst. Conversion of CO2 into organic compounds has been studied intensively. Ethane catalytic oxydehydrogenation in the presence of CO2 offers an attractive route for converting CO2. In this study, using OMS-2 as the catalyst in C2H6 dehydrogenation in the presence of CO2 is an example where extreme conditions are used to drive high conversions of ethane (> 70%) and CO2 (up to 56%) with high selectivity towards ethylene (87%) with a short contact time (0.6 s). This inexpensive material also showed high stability during the process, and the presence of CO2 removed coke depositions throughout the catalyst. The results obtained from this study open up new possibilities for olefin dehydrogenations in the presence of CO2, a perfect feedstock for any process involving ethylene carbonylation with the recycling of the greenhouse gas. The fourth part of this thesis presents a ZnO/La2O2CO 3 composite prepared by a new and easy method and discusses the use of these materials as heterogeneous catalysts for ultra-fast microwave biodiesel production at low temperatures. The search for solid state materials with high catalytic activities is one of the key steps toward reducing the cost of producing biodiesel. We present a high biodiesel yield (> 95%) in less than 5 minutes under mild reaction conditions (< 100°C) on a ZnO/La 2O2CO3 heterogeneous catalyst, showing no Zn and La leaching into the reaction medium. The catalyst has a higher reaction rate than the homogeneous KOH catalyst with the assistance of microwave irradiation. All of these results promote the industrial application of the synthesized ZnO/La2O2CO3 as a potential heterogeneous catalyst for fast biodiesel production, avoiding many of the issues found in both commercial and independently published catalysts. Following the fourth part of this thesis, the fifth part presents the synthesis and characterization of a series of rare earth Ln2O 2CO3 (Ln = La, Eu, Nd, and Sm) layered materials as novel basic materials for the biodiesel production. Reports on rare earth oxycarbonate Ln2O2CO3 (Ln = rare earths) layered materials as heterogeneous basic catalysts having novel low temperature catalytic activities are rare. In this thesis I successfully synthesized active rare earth (Ln = La, Nd, Eu, and Sm) metal oxycarbonate based layered materials to catalyze the transesterification process under mild conditions (< 85°C), obtaining a high fatty acid methyl ester (FAME) yield (> 95%) in a short reaction time (< 20 minutes). The results of low temperature activities and short reaction times with minimum energy consumption show them to have solid potential as alkali metal hydroxide/alkoxide alternatives for industrial applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash, David J.; Restrepo, David T.; Parra, Natalia S.

Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. We report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. We achieved catalytic hydrogenation of olefins over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%)more » and turnover frequencies (6 × 10 –5–4 × 10 –3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (B N), vacancies (V B and V N), and Stone–Wales defects. SSNMR and binding-energy calculations show that V N are most likely the catalytically active sites. Our work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.« less

Graphene-supported Ag-based core-shell nanoparticles for hydrogen generation in hydrolysis of ammonia borane and methylamine borane.

PubMed

Yang, Lan; Luo, Wei; Cheng, Gongzhen

2013-08-28

Well-dispersed magnetically recyclable core-shell Ag@M (M = Co, Ni, Fe) nanoparticles (NPs) supported on graphene have been synthesized via a facile in situ one-step procedure, using methylamine borane (MeAB) as a reducing agent under ambient condition. Their catalytic activity toward hydrolysis of ammonia borane (AB) were studied. Although the Ag@Fe/graphene NPs are almost inactive, the as-prepared Ag@Co/graphene NPs are the most reactive catalysts, followed by Ag@Ni/graphene NPs. Compared with AB and NaBH4, the as-synthesized Ag@Co/graphene catalysts which reduced by MeAB exert the highest catalytic activity. Additionally, the Ag@Co NPs supported on graphene exhibit higher catalytic activity than the catalysts with other conventional supports, such as the SiO2, carbon black, and γ-Al2O3. The as-synthesized Ag@Co/graphene NPs exert satisfied catalytic activity, with the turnover frequency (TOF) value of 102.4 (mol H2 min(-1) (mol Ag)(-1)), and the activation energy Ea value of 20.03 kJ/mol. Furthermore, the as-synthesized Ag@Co/graphene NPs show good recyclability and magnetically reusability for the hydrolytic dehydrogenation of AB and MeAB, which make the practical reusing application of the catalysts more convenient. Moreover, this simple synthetic method indicates that MeAB could be used as not only a potential hydrogen storage material but also an efficient reducing agent. It can be easily extended to facile preparation of other graphene supported metal NPs.

Effective rate constants for nanostructured heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Hendy, Shaun; Gaston, Nicola; Zhang, Philip; Lund, Nat

2012-02-01

There is currently a high level of interest in the use of nanostructured materials for catalysis. For instance, gold, which is largely inert in the bulk, can exhibit strong catalytic activity when in nanoparticle form. With precious metal catalysts such as Pt and Pd in high demand, the use of these materials in nanoparticle form can also substantially reduce costs by exposure of more surface area for the same volume of material. When reactants are plentiful, the effective activity of a nanoparticulate catalyst will increase roughly with its surface area. However, under diffusion-limited conditions, the reactant must diffuse to active sites on the catalyst, so a high surface area and a high density of active sites may bring diminishing returns if reactant is consumed faster than it arrives. Here we apply a mathematical homogenisation approach to derive simple expressions for the effective reactivity of a nanostructured catalyst under diffusion limited conditions that relate the intrinsic rate constants of the surfaces presented by the catalyst to an effective rate constant. When highly active catalytic sites, such as step edges or other defects are present, we show that distinct limiting cases emerge depending on the degree of overlap of the reactant depletion zone about each site. In gases, the size of this depletion zone is approximately the mean free path, so the effective reactivity will depend on the structure of the catalyst on that scale. We discuss implications for the optimal design of nanoparticle catalysts.

Modeling of carbon monoxide oxidation kinetics over NASA carbon dioxide laser catalysts

NASA Technical Reports Server (NTRS)

Herz, Richard K.

1989-01-01

The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

Mixed ionic-electronic conductors for electrodes of barium cerate-based SOFCS

NASA Astrophysics Data System (ADS)

Wu, Zhonglin

Gadolinium doped barium cerates (BCGs) have been identified as promising electrolyte materials for intermediate-temperature solid oxide fuel cells (SOFCs). It is crucial to develop compatible electrode materials for such electrolytes. Mixed ionic-electronic conductor (MIEC) electrode materials developed for SOFCs based on yttrium-stabilized zirconia (YSZ) may be used as electrode materials for BCG-based SOFCs; but a careful re-evaluation is required due to the intrinsic differences between BCG and YSZ. The performance of these electrode materials depends critically the transport of ionic and electronic species as well as gas. Accordingly, a profound understanding of transport in MIEC electrodes is imperative to effective design of high performance SOFCs. In this thesis, ambipolar transport in composite MIEC electrodes has been modeled using percolation theory to predict the effect of volume fractions of constituent phases and porosity on ambipolar conductivity. Transport and electrode kinetics of homogeneous MIEC electrodes have also been formulated under a steady-state condition to predict the distributions of ionic defects and current carried by each defect in such electrodes. Effects of catalytic properties, transport properties, and microstructure of porous electrodes and interfaces on the electrode performance are investigated. Under the guidelines of the theoretical modeling, several MIEC electrode materials are developed. Lasb{1-x}Srsb{x}Cosb{1-x}Fesb{y}Osb{3-delta} homogeneous materials are studied as cathode materials. However, the interfacial resistance seems too high due to the lack of catalytic activity at intermediate temperatures. Results indicate that Ag-Bisb{1.5}Ysb{0.5}Osb3 composite MIECs are good cathode materials when the volume fractions of constituent phases and porosity are carefully controlled. Such electrodes have low interfacial resistance, better binding strength, and smaller thermal mismatch with the BCG electrolyte, compared to other metal electrodes (such as Pt and Ag). Ni-BCG composite MIECs are studied as anode materials. It is found that electrodes prepared from NiO and reduced to Ni in situ is not catalytically active because of diffusion of NiO into BCG, which forms a resistive layer. Electrodes prepared from Ni metal and fired in an inert or reducing atmosphere exhibit low interfacial resistance and good compatibility with BCG electrolyte. Stability of these developed electrode materials is investigated under conditions pertinent to SOFCs.

European Science Notes. Volume 39, Number 3.

DTIC Science & Technology

1985-03-01

on the body by measuring the inhi- from a nearby outstation of the UK’s bition of the hydrolytic activity of the Meteorological Office using both stan...process work on materials for time without undergoing the deteriora- defense which are unavailable from com- tion in catalytic activity common with mercial...contaminated protec- When a nerve agent is used in the tive clothing. Ultra- high

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala

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

Reactor for nano-focused x-ray diffraction and imaging under catalytic in situ conditions

NASA Astrophysics Data System (ADS)

Richard, M.-I.; Fernández, S.; Hofmann, J. P.; Gao, L.; Chahine, G. A.; Leake, S. J.; Djazouli, H.; De Bortoli, Y.; Petit, L.; Boesecke, P.; Labat, S.; Hensen, E. J. M.; Thomas, O.; Schülli, T.

2017-09-01

A reactor cell for in situ studies of individual catalyst nanoparticles or surfaces by nano-focused (coherent) x-ray diffraction has been developed. Catalytic reactions can be studied in flow mode in a pressure range of 10-2-103 mbar and temperatures up to 900 °C. This instrument bridges the pressure and materials gap at the same time within one experimental setup. It allows us to probe in situ the structure (e.g., shape, size, strain, faceting, composition, and defects) of individual nanoparticles using a nano-focused x-ray beam. Here, the setup was used to observe strain and facet evolution of individual model Pt catalysts during in situ experiments. It can be used for heating other (non-catalytically active) nanoparticles (e.g., nanowires) in inert or reactive gas atmospheres or vacuum as well.

Reactor for nano-focused x-ray diffraction and imaging under catalytic in situ conditions.

PubMed

Richard, M-I; Fernández, S; Hofmann, J P; Gao, L; Chahine, G A; Leake, S J; Djazouli, H; De Bortoli, Y; Petit, L; Boesecke, P; Labat, S; Hensen, E J M; Thomas, O; Schülli, T

2017-09-01

A reactor cell for in situ studies of individual catalyst nanoparticles or surfaces by nano-focused (coherent) x-ray diffraction has been developed. Catalytic reactions can be studied in flow mode in a pressure range of 10 -2 -10 3 mbar and temperatures up to 900 °C. This instrument bridges the pressure and materials gap at the same time within one experimental setup. It allows us to probe in situ the structure (e.g., shape, size, strain, faceting, composition, and defects) of individual nanoparticles using a nano-focused x-ray beam. Here, the setup was used to observe strain and facet evolution of individual model Pt catalysts during in situ experiments. It can be used for heating other (non-catalytically active) nanoparticles (e.g., nanowires) in inert or reactive gas atmospheres or vacuum as well.

Patched bimetallic surfaces are active catalysts for ammonia decomposition.

PubMed

Guo, Wei; Vlachos, Dionisios G

2015-10-07

Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core-shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core-shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

Patched bimetallic surfaces are active catalysts for ammonia decomposition

NASA Astrophysics Data System (ADS)

Guo, Wei; Vlachos, Dionisios G.

2015-10-01

Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core-shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core-shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

Salt melt synthesis of curved nitrogen-doped carbon nanostructures: ORR kinetics boost

NASA Astrophysics Data System (ADS)

Rybarczyk, Maria K.; Gontarek, Emilia; Lieder, Marek; Titirici, Maria-Magdalena

2018-03-01

Implementing metal-free electrocatalysts for the oxygen reduction reaction (ORR) and revealing crucial chemical or topographical parameters driving their activity are vital for the development of power cells. The carbon-based catalysts are very often synthesized through carbonization of biopolymers, in particular, those one containing nitrogen groups such as chitosan. Unfortunately, the resulting carbonaceous materials usually lack specific porosity and exhibit low catalytic activity. Here, we demonstrate that pyrolysis of chitosan in a ZnCl2 melt assisted by the presence of LiCl results not only in a highly porous activated carbon material with a specific surface area of 1317.97 m2/g and the total nitrogen content of 6.5%, but also induces unexpected curvature in the grown graphitic layers. This is the first work that shows curved graphene layers obtained from a biopolymer precursor by its pyrolytic decomposition in the melted salt media. On the other hand, a carbonaceous material obtained from chitosan but without the salts has very low specific surface area of 7.8 m2/g, possesses no specific structural features, and contains 4.7% of nitrogen. The electrochemical studies show, that the former material is highly active towards four-electron pathway of the ORR in terms of an onset potential (0.89 V vs RHE) and the turnover frequency (TOFmax = 0.095 e site-1 s-1). We attribute this high catalytic performance to the presence of the pyridinic and pyrrolic sites in the structure. The ORR kinetics is probably further promoted by curvature in the graphitic layers.

Sintering-Resistant Nanoparticles in Wide-Mouthed Compartments for Sustained Catalytic Performance

NASA Astrophysics Data System (ADS)

Liu, Jia; Ji, Qingmin; Imai, Tsubasa; Ariga, Katsuhiko; Abe, Hideki

2017-02-01

Particle sintering is one of the most significant impediments to functional nanoparticles in many valuable applications especially catalysis. Herein, we report that sintering-resistant nanoparticle systems can be realized through a simple materials-design which maximizes the particle-to-particle traveling distance of neighbouring nanoparticles. As a demonstration, Pt nanoparticles were placed apart from each other in wide-mouthed compartments tailored on the surface of self-assembled silica nanosheets. These Pt nanoparticles retained their particle size after calcination at elevated temperatures because the compartment wall elongates the particle-to-particle traveling distance to preclude the possibility of sintering. Moreover, these Pt nanoparticles in wide-mouthed compartments were fully accessible to the environment and exhibited much higher catalytic activity for CO oxidation than the nanoparticles confined in the nanochannels of mesoporous silica. The proposed materials-design strategy is applicable not only to industrial catalysts operating in harsh conditions, but also opens up possibilities in developing advanced nanoparticle-based materials with sustained performance.

Heteroatom-Doped Carbon Materials for Electrocatalysis.

PubMed

Asefa, Tewodros; Huang, Xiaoxi

2017-08-10

Fuel cells, water electrolyzers, and metal-air batteries are important energy systems that have started to play some roles in our renewable energy landscapes. However, despite much research works carried out on them, they have not yet found large-scale applications, mainly due to the unavailability of sustainable catalysts that can catalyze the reactions employed in them. Currently, noble metal-based materials are the ones that are commonly used as catalysts in most commercial fuel cells, electrolyzers, and metal-air batteries. Hence, there has been considerable research efforts worldwide to find alternative noble metal-free and metal-free catalysts composed of inexpensive, earth-abundant elements for use in the catalytic reactions employed in these energy systems. In this concept paper, a brief introduction on catalysis in renewable energy systems, followed by the recent efforts to develop sustainable, heteroatom-doped carbon and non-noble metal-based electrocatalysts, the challenges to unravel their structure-catalytic activity relationships, and the authors' perspectives on these topics and materials, are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Laboratory Test Setup for in Situ Measurements of the Dielectric Properties of Catalyst Powder Samples under Reaction Conditions by Microwave Cavity Perturbation: Set up and Initial Tests

PubMed Central

Dietrich, Markus; Rauch, Dieter; Porch, Adrian; Moos, Ralf

2014-01-01

The catalytic behavior of zeolite catalysts for the ammonia-based selective catalytic reduction (SCR) of nitrogen oxides (NOX) depends strongly on the type of zeolite material. An essential precondition for SCR is a previous ammonia gas adsorption that occurs on acidic sites of the zeolite. In order to understand and develop SCR active materials, it is crucial to know the amount of sorbed ammonia under reaction conditions. To support classical temperature-programmed desorption (TPD) experiments, a correlation of the dielectric properties with the catalytic properties and the ammonia sorption under reaction conditions appears promising. In this work, a laboratory test setup, which enables direct measurements of the dielectric properties of catalytic powder samples under a defined gas atmosphere and temperature by microwave cavity perturbation, has been developed. Based on previous investigations and computational simulations, a resonator cavity and a heating system were designed, installed and characterized. The resonator cavity is designed to operate in its TM010 mode at 1.2 GHz. The first measurement of the ammonia loading of an H-ZSM-5 zeolite confirmed the operating performance of the test setup at constant temperatures of up to 300 °C. It showed how both real and imaginary parts of the relative complex permittivity are strongly correlated with the mass of stored ammonia. PMID:25211199

Selective hydrogenation of phenol to cyclohexanone in water over Pd@N-doped carbons derived from ZIF-67: Role of dicyandiamide

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.

Kinetic and catalytic analysis of mesoporous Co3O4 on the oxidation of morin

NASA Astrophysics Data System (ADS)

Xaba, Morena. S.; Meijboom, Reinout

2017-11-01

Herein we report on the synthesis, characterization and catalytic evaluation of mesoporous cobalt oxides on the oxidation of morin. These mesoporous cobalt oxides were synthesized using an inverse surfactant micelle method, they are connected, well-defined with intra-particle voids. These materials were calcined to different final heating temperatures of 150, 250, 350, 450 and 550 °C, and each mesoporous cobalt oxide catalyst showed unique physical properties and catalytic behavior. Morin oxidation was used as a model reaction in the presence of hydrogen peroxide to evaluate the kinetic and catalytic activity of calcined mesoporous cobalt oxides. The adsorption-desorption equilibrium rate constants of morin and hydrogen peroxide were found to be inversely proportional to the crystallite size of the mesoporous cobalt oxide, and the characteristic path length in which the mass transfer takes place was found to be directly proportional to the crystallite size. The materials were characterized using powder X-Ray Diffraction (p-XRD), N2-sorption isotherms (BET), hydrogen temperature programmed reduction (H2-TPR) and High Resolution-Transmission Electron Microscopy (HR-TEM). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of morin at λmax = 410 nm. The surface reaction in this system is described in terms of the well-established Langmuir-Hinshelwood model. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability is demonstrated.

A laboratory test setup for in situ measurements of the dielectric properties of catalyst powder samples under reaction conditions by microwave cavity perturbation: set up and initial tests.

PubMed

Dietrich, Markus; Rauch, Dieter; Porch, Adrian; Moos, Ralf

2014-09-10

The catalytic behavior of zeolite catalysts for the ammonia-based selective catalytic reduction (SCR) of nitrogen oxides (NOX) depends strongly on the type of zeolite material. An essential precondition for SCR is a previous ammonia gas adsorption that occurs on acidic sites of the zeolite. In order to understand and develop SCR active materials, it is crucial to know the amount of sorbed ammonia under reaction conditions. To support classical temperature-programmed desorption (TPD) experiments, a correlation of the dielectric properties with the catalytic properties and the ammonia sorption under reaction conditions appears promising. In this work, a laboratory test setup, which enables direct measurements of the dielectric properties of catalytic powder samples under a defined gas atmosphere and temperature by microwave cavity perturbation, has been developed. Based on previous investigations and computational simulations, a resonator cavity and a heating system were designed, installed and characterized. The resonator cavity is designed to operate in its TM010 mode at 1.2 GHz. The first measurement of the ammonia loading of an H-ZSM-5 zeolite confirmed the operating performance of the test setup at constant temperatures of up to 300 °C. It showed how both real and imaginary parts of the relative complex permittivity are strongly correlated with the mass of stored ammonia.

Adsorbent catalytic nanoparticles and methods of using the same

DOEpatents

Slowing, Igor Ivan; Kandel, Kapil

2017-01-31

The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

Catalytic bioreactors and methods of using same

DOEpatents

Worden, Robert Mark; Liu, Yangmu Chloe

2017-07-25

Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

Gas-Phase Dimerization of Ethylene under Mild Conditions Catalyzed by MOF Materials Containing (bpy)Ni II Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Madrahimov, Sherzod T.; Gallagher, James R.; Zhang, Guanghui

2015-10-09

NU-1000-(bpy)Ni-II, a highly porous MOF material possessing well-defined (bpy)Ni-II moieties, was prepared through solvent-assisted ligand incorporation (SALI). Treatment with Et2AlCl affords a single-site catalyst with excellent catalytic activity for ethylene dimerization (intrinsic activity for butenes that is up to an order of magnitude higher than the corresponding (bpy)NiCl2 homogeneous analogue) and stability (can be reused at least three times). The high porosity of this catalyst results in outstanding levels of activity at ambient temperature in gas-phase ethylene dimerization reactions, both under batch and continuous flow conditions.

Hydrodeoxygenation of bio-oil using different mesoporous supports of NiMo catalysts

NASA Astrophysics Data System (ADS)

Rinaldi, Nino; Simanungkalit, Sabar P.; Kristiani, Anis

2017-11-01

Biomass as a renewable and sustainable resources need to utilize in many applications, especially for energy application. One of its energy application is about converting biomass into bio-oil. High oxygen content in bio-oil needs to be upgraded through hydrodeoxygenation process before being used as transportation fuel. The development of heterogenenous catalysts become an important aspect in hydrodeoxygenation process, in particular the upgrading process of bio-oil. Several supporting mesoporous materials, such as TiO2, Al2O3 and MCM-41 have unique properties, both physical and chemical properties that can be utilized in various application, including catalyst. These heterogeneous catalysts were modified their catalytic properties by impregnation with some transition metal. The effect of various supporting material and transition metal impregnated were also studied. Their chemical and physical properties were characterized by X-Ray Diffraction, X-Ray Fluororesence, Fourier Transform Infra-Red, and Surface Area Analyzer. The result of characterizations showed that Ni-Mo/TiO2 is more crystalline than Ni-Mo/MCM-41 and Ni-Mo/Al2O3. In other hand, the specific surface area of Ni-Mo/TiO2 is lower than others. These heterogeneous catalysts were tested their catalytic activity in upgrading bio-oil. The liquid products produced were analyzed by using Elemental Analyzer. The result of catalytic activity tests showed catalysts resulted Ni-Mo/TiO2 exhibits best catalytic activity in hydrodeoxygenation process. The oxygen content decreased significantly from 41.61% to 26.22% by using Ni-Mo/TiO2. Compared with Ni-Mo/TiO2, Ni-Mo/MCM-41 and Ni-Mo/Al2O3 decrease lower to 33.22% % and 28.34%, respectively. Ni-Mo/TiO2 also resulted the highest Deoxygenation Degree (DOD) as of 55% compared with Ni-Mo/MCM-41 and Ni-Mo/Al2O3 as of 31.99 % and 47.99%, respectively.

Catalytic conversion of light alkanes. Final report, January 1, 1990--October 31, 1994

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

During the course of the first three years of the Cooperative Agreement (Phase I-III), we uncovered a family of metal perhaloporphyrin complexes which had unprecedented activity for the selective air-oxidation of fight alkanes to alcohols. The reactivity of fight hydrocarbon substrates with air or oxygen was in the order: isobutane>propane>ethane>methane, in accord with their homolytic bond dissociation energies. Isobutane was so reactive that the proof-of concept stage of a process for producing tert-butyl alcohol from isobutane was begun (Phase V). It was proposed that as more active catalytic systems were developed (Phases IV, VI), propane, then ethane and finally methanemore » oxidations will move into this stage (Phases VII through IX). As of this writing, however, the program has been terminated during the later stages of Phases V and VI so that further work is not anticipated. We made excellent progress during 1994 in generating a class of less costly new materials which have the potential for high catalytic activity. New routes were developed for replacing costly perfluorophenyl groups in the meso-position of metalloporphyrin catalysts with far less expensive and lower molecular weight perfluoromethyl groups.« less

Efficient biocatalyst by encapsulating lipase into nanoporous gold

PubMed Central

2013-01-01

Lipases are one of the most important biocatalysts for biotechnological applications. Immobilization is an efficient method to increase the stability and reusability of lipases. In this study, nanoporous gold (NPG), a new kind of nanoporous material with tunable porosity and excellent biocompatibility, was employed as an effective support for lipase immobilization. The pore size of NPG and adsorption time played key roles in the construction of lipase-NPG biocomposites. The morphology and composition of NPG before and after lipase loading are verified using a scanning electron microscope, equipped with an energy-dispersive X-ray spectrometer. The resulting lipase-NPG biocomposites exhibited excellent catalytic activity and remarkable reusability. The catalytic activity of the lipase-NPG biocomposite with a pore size of 35 nm had no decrease after ten recycles. Besides, the lipase-NPG biocomposite exhibited high catalytic activity in a broader pH range and higher temperature than that of free lipase. In addition, the leaching of lipase from NPG could be prevented by matching the protein’s diameter and pore size. Thus, the encapsulation of enzymes within NPG is quite useful for establishing new functions and will have wide applications for different chemical processes. PMID:23601503

Development of new materials from waste electrical and electronic equipment: Characterization and catalytic application.

PubMed

Souza, J P; Freitas, P E; Almeida, L D; Rosmaninho, M G

2017-07-01

Wastes of electrical and electronic equipment (WEEE) represent an important environmental problem, since its composition includes heavy metals and organic compounds used as flame-retardants. Thermal treatments have been considered efficient processes on removal of these compounds, producing carbonaceous structures, which, together with the ceramic components of the WEEE (i.e. silica and alumina), works as support material for the metals. This mixture, associated with the metals present in WEEE, represents promising systems with potential for catalytic application. In this work, WEEE was thermally modified to generate materials that were extensively characterized. Raman spectrum for WEEE after thermal treatment showed two carbon associated bands. SEM images showed a metal nanoparticles distribution over a polymeric and ceramic support. After characterization, WEEE materials were applied in ethanol steam reforming reaction. The system obtained at higher temperature (800°C) exhibited the best activity, since it leads to high conversions (85%), hydrogen yield (30%) and H 2 /CO ratio (3,6) at 750°C. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

PubMed

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.

On the Synergistic Catalytic Properties of Bimetallic Mesoporous Materials Containing Aluminum and Zirconium: The Prins Cyclisation of Citronellal

PubMed Central

Telalović, Selvedin; Ramanathan, Anand; Ng, Jeck Fei; Maheswari, Rajamanickam; Kwakernaak, Cees; Soulimani, Fouad; Brouwer, Hans C; Chuah, Gaik Khuan; Weckhuysen, Bert M; Hanefeld, Ulf

2011-01-01

Bimetallic three-dimensional amorphous mesoporous materials, Al-Zr-TUD-1 materials, were synthesised by using a surfactant-free, one-pot procedure employing triethanolamine (TEA) as a complexing reagent. The amount of aluminium and zirconium was varied in order to study the effect of these metals on the Brønsted and Lewis acidity, as well as on the resulting catalytic activity of the material. The materials were characterised by various techniques, including elemental analysis, X-ray diffraction, high-resolution TEM, N2 physisorption, temperature-programmed desorption (TPD) of NH3, and 27Al MAS NMR, XPS and FT-IR spectroscopy using pyridine and CO as probe molecules. Al-Zr-TUD-1 materials are mesoporous with surface areas ranging from 700–900 m2 g−1, an average pore size of around 4 nm and a pore volume of around 0.70 cm3 g−1. The synthesised Al-Zr-TUD-1 materials were tested as catalyst materials in the Lewis acid catalysed Meerwein–Ponndorf–Verley reduction of 4-tert-butylcyclohexanone, the intermolecular Prins synthesis of nopol and in the intramolecular Prins cyclisation of citronellal. Although Al-Zr-TUD-1 catalysts possess a lower amount of acid sites than their monometallic counterparts, according to TPD of NH3, these materials outperformed those of the monometallic Al-TUD-1 as well as Zr-TUD-1 in the Prins cyclisation of citronellal. This proves the existence of synergistic properties of Al-Zr-TUD-1. Due to the intramolecular nature of the Prins cyclisation of citronellal, the hydrophilic surface of the catalyst as well as the presence of both Brønsted and Lewis acid sites synergy could be obtained with bimetallic Al-Zr-TUD-1. Besides spectroscopic investigation of the active sites of the catalyst material a thorough testing of the catalyst in different types of reactions is crucial in identifying its specific active sites. PMID:21259348

Direct synthesis of Ti-containing SBA-16-type mesoporous material by the evaporation-induced self-assembly method and its catalytic performance for oxidative desulfurization.

PubMed

Shah, Asma Tufail; Li, Baoshan; Abdalla, Zaki Eldin Ali

2009-08-15

A novel Ti-containing SBA-16-type mesoporous material (with various Ti loadings of 5, 10, and 15 wt%) was synthesized by an evaporation-induced self-assembly method using F127 copolymer as template. The materials were characterized by XRD, FTIR, TG-DTA, N(2) adsorption, SEM, HRTEM, and XPS. The characterization results show that the material possesses high thermal stability, thick pore walls (10.43-10.68 nm), and high surface area (642.26-691.5 m(2)/g) with a mesoporous worm-like structure, and titanium was successfully incorporated into the silica matrix with a tetrahedral environment. The material showed high activity in the oxidative desulfurization of DBT and its activity was not reduced even after three times recycling; further reuse resulted in a gradual decrease in its activity.

Evaluating the effectiveness of various biochars as porous media for biodiesel synthesis via pseudo-catalytic transesterification.

PubMed

Lee, Jechan; Jung, Jong-Min; Oh, Jeong-Ik; Ok, Yong Sik; Lee, Sang-Ryong; Kwon, Eilhann E

2017-05-01

This study focuses on investigating the optimized chemical composition of biochar used as porous material for biodiesel synthesis via pseudo-catalytic transesterification. To this end, six biochars from different sources were prepared and biodiesel yield obtained from pseudo-catalytic transesterification of waste cooking oil using six biochars were measured. Biodiesel yield and optimal reaction temperature for pseudo-catalytic transesterification were strongly dependent on the raw material of biochar. For example, biochar generated from maize residue exhibited the best performance, which yield was reached ∼90% at 300°C; however, the maximum biodiesel yield with pine cone biochar was 43% at 380°C. The maximum achievable yield of biodiesel was sensitive to the lignin content of biomass source of biochar but not sensitive to the cellulose and hemicellulose content. This study provides an insight for screening the most effective biochar as pseudo-catalytic porous material, thereby helping develop more sustainable and economically viable biodiesel synthesis process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ionizable side chains at catalytic active sites of enzymes.

PubMed

Jimenez-Morales, David; Liang, Jie; Eisenberg, Bob

2012-05-01

Catalytic active sites of enzymes of known structure can be well defined by a modern program of computational geometry. The CASTp program was used to define and measure the volume of the catalytic active sites of 573 enzymes in the Catalytic Site Atlas database. The active sites are identified as catalytic because the amino acids they contain are known to participate in the chemical reaction catalyzed by the enzyme. Acid and base side chains are reliable markers of catalytic active sites. The catalytic active sites have 4 acid and 5 base side chains, in an average volume of 1,072 Å(3). The number density of acid side chains is 8.3 M (in chemical units); the number density of basic side chains is 10.6 M. The catalytic active site of these enzymes is an unusual electrostatic and steric environment in which side chains and reactants are crowded together in a mixture more like an ionic liquid than an ideal infinitely dilute solution. The electrostatics and crowding of reactants and side chains seems likely to be important for catalytic function. In three types of analogous ion channels, simulation of crowded charges accounts for the main properties of selectivity measured in a wide range of solutions and concentrations. It seems wise to use mathematics designed to study interacting complex fluids when making models of the catalytic active sites of enzymes.

Ionizable Side Chains at Catalytic Active Sites of Enzymes

PubMed Central

Jimenez-Morales, David; Liang, Jie

2012-01-01

Catalytic active sites of enzymes of known structure can be well defined by a modern program of computational geometry. The CASTp program was used to define and measure the volume of the catalytic active sites of 573 enzymes in the Catalytic Site Atlas database. The active sites are identified as catalytic because the amino acids they contain are known to participate in the chemical reaction catalyzed by the enzyme. Acid and base side chains are reliable markers of catalytic active sites. The catalytic active sites have 4 acid and 5 base side chains, in an average volume of 1072 Å3. The number density of acid side chains is 8.3 M (in chemical units); the number density of basic side chains is 10.6 M. The catalytic active site of these enzymes is an unusual electrostatic and steric environment in which side chains and reactants are crowded together in a mixture more like an ionic liquid than an ideal infinitely dilute solution. The electrostatics and crowding of reactants and side chains seems likely to be important for catalytic function. In three types of analogous ion channels, simulation of crowded charges accounts for the main properties of selectivity measured in a wide range of solutions and concentrations. It seems wise to use mathematics designed to study interacting complex fluids when making models of the catalytic active sites of enzymes. PMID:22484856

ZnO/perovskite core–shell nanorod array based monolithic catalysts with enhanced propane oxidation and material utilization efficiency at low temperature

DOE PAGES

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

Pulsed laser synthesis in liquid of efficient visible-light-active ZnO/rGO nanocomposites for improved photo-catalytic activity

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.

Green synthesis, characterization and catalytic activity of the Pd/TiO2 nanoparticles for the ligand-free Suzuki-Miyaura coupling reaction.

PubMed

Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad

2016-03-01

A green synthesis process was developed for production of the Pd/TiO2 nanoparticles (NPs) without using toxic, hazardous and dangerous materials. Myrtus communis L. leaf extract serves as a mild, renewable and non-toxic reducing agent. The advantages of this biosynthesis method include use of cheap, clean, nontoxic and environmentally benign precursors and simple procedures without time-consuming polymerization and problems with treatment of a highly viscous polymeric resin. More importantly, the synthesized Pd/TiO2 NPs presented excellent catalytic activity for ligand-free Suzuki-Miyaura coupling which could be easily separated from the reaction mixture and reused many times with no loss of activity. Therefore, these properties indicate demonstrative benefits of the catalyst. The Pd/TiO2 NPs was characterized by FESEM, TEM, FT-IR, UV-vis spectroscopy and EDS. Copyright © 2015 Elsevier Inc. All rights reserved.

Conversion of biomass-derived sorbitol to glycols over carbon-materials supported Ru-based catalysts

PubMed Central

Guo, Xingcui; Guan, Jing; Li, Bin; Wang, Xicheng; Mu, Xindong; Liu, Huizhou

2015-01-01

Ruthenium (Ru) supported on activated carbon (AC) and carbon nanotubes (CNTs) was carried out in the hydrogenolysis of sorbitol to ethylene glycol (EG) and 1,2-propanediol (1,2-PD) under the promotion of tungsten (WOx) species and different bases. Their catalytic activities and glycols selectivities strongly depended on the support properties and location of Ru on CNTs, owning to the altered metal-support interactions and electronic state of ruthenium. Ru located outside of the tubes showed excellent catalytic performance than those encapsulated inside the nanotubes. Additionally, the introduction of WOx into Ru/CNTs significantly improved the hydrogenolysis activities, and a complete conversion of sorbitol with up to 60.2% 1,2-PD and EG yields was obtained on RuWOx/CNTs catalyst upon addition of Ca(OH)2. Stability study showed that this catalyst was highly stable against leaching and poisoning and could be recycled several times. PMID:26578426

Conversion of biomass-derived sorbitol to glycols over carbon-materials supported Ru-based catalysts

NASA Astrophysics Data System (ADS)

Guo, Xingcui; Guan, Jing; Li, Bin; Wang, Xicheng; Mu, Xindong; Liu, Huizhou

2015-11-01

Ruthenium (Ru) supported on activated carbon (AC) and carbon nanotubes (CNTs) was carried out in the hydrogenolysis of sorbitol to ethylene glycol (EG) and 1,2-propanediol (1,2-PD) under the promotion of tungsten (WOx) species and different bases. Their catalytic activities and glycols selectivities strongly depended on the support properties and location of Ru on CNTs, owning to the altered metal-support interactions and electronic state of ruthenium. Ru located outside of the tubes showed excellent catalytic performance than those encapsulated inside the nanotubes. Additionally, the introduction of WOx into Ru/CNTs significantly improved the hydrogenolysis activities, and a complete conversion of sorbitol with up to 60.2% 1,2-PD and EG yields was obtained on RuWOx/CNTs catalyst upon addition of Ca(OH)2. Stability study showed that this catalyst was highly stable against leaching and poisoning and could be recycled several times.

Porous metallosilicates for heterogeneous, liquid-phase catalysis: perspectives and pertaining challenges

PubMed Central

Padovan, Daniele; Tarantino, Giulia

2018-01-01

Porous silicates containing dilute amounts of tri-, tetra- and penta-valent metal sites, such as TS-1, Sn-β and Fe-ZSM-5, have recently emerged as state of the art catalysts for a variety of sustainable chemical transformations. In contrast with their aluminosilicate cousins, which are widely employed throughout the refinery industry for gas-phase catalytic transformations, such metallosilicates have exhibited unprecedented levels of performance for a variety of liquid-phase catalytic processes, including the conversion of biomass to chemicals, and sustainable oxidation technologies with H2O2. However, despite their unique levels of performance for these new types of chemical transformations, increased utilization of these promising materials is complicated by several factors. For example, their utilization in a liquid, and often polar, medium hinders process intensification (scale-up, catalyst deactivation). Moreover, such materials do not generally exhibit the active-site homogeneity of conventional aluminosilicates, and they typically possess a wide variety of active-site ensembles, only some of which may be directly involved in the catalytic chemistry of interest. Consequently, mechanistic understanding of these catalysts remains relatively low, and competitive reactions are commonly observed. Accordingly, unified approaches towards developing more active, selective and stable porous metallosilicates have not yet been achieved. Drawing on some of the most recent literature in the field, the purpose of this mini review is both to highlight the breakthroughs made with regard to the use of porous metallosilicates as heterogeneous catalysts for liquid-phase processing, and to highlight the pertaining challenges that we, and others, aim to overcome during the forthcoming years. PMID:29515849

Porous metallosilicates for heterogeneous, liquid-phase catalysis: perspectives and pertaining challenges

NASA Astrophysics Data System (ADS)

Hammond, Ceri; Padovan, Daniele; Tarantino, Giulia

2018-02-01

Porous silicates containing dilute amounts of tri-, tetra- and penta-valent metal sites, such as TS-1, Sn-β and Fe-ZSM-5, have recently emerged as state of the art catalysts for a variety of sustainable chemical transformations. In contrast with their aluminosilicate cousins, which are widely employed throughout the refinery industry for gas-phase catalytic transformations, such metallosilicates have exhibited unprecedented levels of performance for a variety of liquid-phase catalytic processes, including the conversion of biomass to chemicals, and sustainable oxidation technologies with H2O2. However, despite their unique levels of performance for these new types of chemical transformations, increased utilization of these promising materials is complicated by several factors. For example, their utilization in a liquid, and often polar, medium hinders process intensification (scale-up, catalyst deactivation). Moreover, such materials do not generally exhibit the active-site homogeneity of conventional aluminosilicates, and they typically possess a wide variety of active-site ensembles, only some of which may be directly involved in the catalytic chemistry of interest. Consequently, mechanistic understanding of these catalysts remains relatively low, and competitive reactions are commonly observed. Accordingly, unified approaches towards developing more active, selective and stable porous metallosilicates have not yet been achieved. Drawing on some of the most recent literature in the field, the purpose of this mini review is both to highlight the breakthroughs made with regard to the use of porous metallosilicates as heterogeneous catalysts for liquid-phase processing, and to highlight the pertaining challenges that we, and others, aim to overcome during the forthcoming years.

Active Iron Sites of Disordered Mesoporous Silica Catalyst FeKIL-2 in the Oxidation of Volatile Organic Compounds (VOC)

PubMed Central

Rangus, Mojca; Mazaj, Matjaž; Dražić, Goran; Popova, Margarita; Tušar, Nataša Novak

2014-01-01

Iron-functionalized disordered mesoporous silica (FeKIL-2) is a promising, environmentally friendly, cost-effective and highly efficient catalyst for the elimination of volatile organic compounds (VOCs) from polluted air via catalytic oxidation. In this study, we investigated the type of catalytically active iron sites for different iron concentrations in FeKIL-2 catalysts using advanced characterization of the local environment of iron atoms by a combination of X-ray Absorption Spectroscopy Techniques (XANES, EXAFS) and Atomic-Resolution Scanning Transmission Electron Microscopy (AR STEM). We found that the molar ratio Fe/Si ≤ 0.01 leads to the formation of stable, mostly isolated Fe3+ sites in the silica matrix, while higher iron content Fe/Si > 0.01 leads to the formation of oligonuclear iron clusters. STEM imaging and EELS techniques confirmed the existence of these clusters. Their size ranges from one to a few nanometers, and they are unevenly distributed throughout the material. The size of the clusters was also found to be similar, regardless of the nominal concentration of iron (Fe/Si = 0.02 and Fe/Si = 0.05). From the results obtained from sample characterization and model catalytic tests, we established that the enhanced activity of FeKIL-2 with the optimal Fe/Si = 0.01 ratio can be attributed to: (1) the optimal concentration of stable isolated Fe3+ in the silica support; and (2) accelerated diffusion of the reactants in disordered mesoporous silica (FeKIL-2) when compared to ordered mesoporous silica materials (FeSBA-15, FeMCM-41). PMID:28788674

Photo-Catalytic Properties of TiO2 Supported on MWCNTs, SBA-15 and Silica-Coated MWCNTs Nanocomposites.

PubMed

Ramoraswi, Nteseng O; Ndungu, Patrick G

2015-12-01

Mesoporous silica, specifically SBA-15, acid-treated multi-walled carbon nanotubes and a hybrid nanocomposite of SBA-15 coated onto the sidewalls acid-treated multi-walled carbon nanotubes (CNTs) were prepared and used as supports for anatase TiO2. Sol-gel methods were adapted for the synthesis of selected supports and for coating the materials with selected wt% loading of titania. Physical and chemical properties of the supports and catalyst composite materials were investigated by powder X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis, scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), UV-vis diffuse reflectance spectroscopy and fluorescence spectroscopy. The photo-activity of the catalyst composites were evaluated on the decolorisation of methylene blue as a model pollutant. Coating CNTs with SBA-15 improved the thermal stability and textural properties of the nanotubes. All supported titania composites had high surface areas (207-301 m(2)/g), altered band gap energies and reduced TiO2 crystallite sizes. The TiO2/SBA-CNT composite showed enhanced photo-catalytic properties and activity than the TiO2/SBA-15 and TiO2/CNT composites. In addition, an interesting observation was noted with the TiO2/SBA-15 nanocomposites, which had a significantly greater photo-catalytic activity than the TiO2/CNT nanocomposites in spite of the high electron-hole recombination phenomena observed with the photoluminescence results. Discussions in terms of morphological, textural and physical-chemical aspects to account for the result are presented.

Photo-Catalytic Properties of TiO2 Supported on MWCNTs, SBA-15 and Silica-Coated MWCNTs Nanocomposites

NASA Astrophysics Data System (ADS)

Ramoraswi, Nteseng O.; Ndungu, Patrick G.

2015-10-01

Mesoporous silica, specifically SBA-15, acid-treated multi-walled carbon nanotubes and a hybrid nanocomposite of SBA-15 coated onto the sidewalls acid-treated multi-walled carbon nanotubes (CNTs) were prepared and used as supports for anatase TiO2. Sol-gel methods were adapted for the synthesis of selected supports and for coating the materials with selected wt% loading of titania. Physical and chemical properties of the supports and catalyst composite materials were investigated by powder X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis, scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), UV-vis diffuse reflectance spectroscopy and fluorescence spectroscopy. The photo-activity of the catalyst composites were evaluated on the decolorisation of methylene blue as a model pollutant. Coating CNTs with SBA-15 improved the thermal stability and textural properties of the nanotubes. All supported titania composites had high surface areas (207-301 m2/g), altered band gap energies and reduced TiO2 crystallite sizes. The TiO2/SBA-CNT composite showed enhanced photo-catalytic properties and activity than the TiO2/SBA-15 and TiO2/CNT composites. In addition, an interesting observation was noted with the TiO2/SBA-15 nanocomposites, which had a significantly greater photo-catalytic activity than the TiO2/CNT nanocomposites in spite of the high electron-hole recombination phenomena observed with the photoluminescence results. Discussions in terms of morphological, textural and physical-chemical aspects to account for the result are presented.

Water oxidation by size selected Co 27 clusters supported on Fe 2O 3

DOE PAGES

Pellin, Michael J.; Riha, Shannon C.; Tyo, Eric C.; ...

2016-09-22

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co 27) deposited on hematite (Fe 2O 3) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) characterization of the anodes before and after electrochemical cycling demonstrates that these Co 27 clusters are stable to dissolution even in the harsh water oxidation electrochemical environment. They are also stable under illumination atmore » the equivalent of 0.4suns irradiation. The clusters show turnover rates for water oxidation that are comparable or higher than those reported for Pd- and Co-based materials or for hematite. The support for the Co 27 clusters is Fe 2O 3 grown by atomic layer deposition on a Si chip. We have chosen to deposit a Fe2O3 layer that is only a few unit cells thick (2nm), to remove complications related to exciton diffusion. We find that the electrocatalytic and the photoelectrocatalytic activity of the Co 27/Fe 2O 3 material is significantly improved when the samples are annealed (with the clusters already deposited). Lastly, given that the support is thin and that the cluster deposition density is equivalent to approximately 5% of an atomic monolayer, we suggest that annealing may significantly improve the exciton diffusion from the support to the catalytic moiety.« less

Switchable Hydrolase Based on Reversible Formation of Supramolecular Catalytic Site Using a Self-Assembling Peptide.

PubMed

Zhang, Chunqiu; Shafi, Ramim; Lampel, Ayala; MacPherson, Douglas; Pappas, Charalampos G; Narang, Vishal; Wang, Tong; Maldarelli, Charles; Ulijn, Rein V

2017-11-13

The reversible regulation of catalytic activity is a feature found in natural enzymes which is not commonly observed in artificial catalytic systems. Here, we fabricate an artificial hydrolase with pH-switchable activity, achieved by introducing a catalytic histidine residue at the terminus of a pH-responsive peptide. The peptide exhibits a conformational transition from random coil to β-sheet by changing the pH from acidic to alkaline. The β-sheet self-assembles to form long fibrils with the hydrophobic edge and histidine residues extending in an ordered array as the catalytic microenvironment, which shows significant esterase activity. Catalytic activity can be reversible switched by pH-induced assembly/disassembly of the fibrils into random coils. At higher concentrations, the peptide forms a hydrogel which is also catalytically active and maintains its reversible (de-)activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hollow mesoporous silica nanotubes modified with palladium nanoparticles for environmental catalytic applications.

PubMed

Tian, Meng; Long, Yu; Xu, Dan; Wei, Shuoyun; Dong, Zhengping

2018-07-01

Nowadays, chemical catalytic methods for the treatment of organic wastes are attracting more and more research attention. In the current research, novel catalysts with palladium nanoparticles (Pd NPs) supported on the hollow mesoporous silica nanotubes (h-mSiO 2 ) were synthesized for the catalytic reduction of 4-nitrophenol (4-NP) and hydrodechlorination (HDC) of 4-chlorophenol (4-CP). The key point for the fabrication of the catalysts is that a certain thickness of the silica shell was wrapped on the multiwalled carbon nanotubes (MWNTs) or Pd/MWNTs through biphase stratification approach, and then the samples were calcined to remove the MWNTs. Thereby, h-mSiO 2 and Pd@h-mSiO 2 samples were obtained. The prepared materials have excellent pore structure and exhibit high specific surface areas. The reduction of 4-NP by the Pd/h-mSiO 2 and Pd@h-mSiO 2 catalysts showed higher TOF values than many other catalysts, and the yield of HDC of 4-CP to phenol reached 100% with a low loading of Pd in water solvent. The excellent catalytic activities of the Pd/h-mSiO 2 and Pd@h-mSiO 2 catalysts should attribute to the excellent connectivity of the h-mSiO 2 which not only can increase the accessibility of the Pd active sites but also enhance the mass transfer of the reactants. It is worth mention that, there is almost no Pd NPs aggregation or losing during the reaction process, and the prepared catalysts still showed good catalytic activity and physical stability after recycling. Moreover, the catalyst shows potential for catalytic reduction of nitroarenes in a fixed bed reactor, thus could be used for continuously treat nitroarenes polluted water. Copyright © 2018 Elsevier Inc. All rights reserved.

Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

NASA Astrophysics Data System (ADS)

Cuba Torres, Christian Martin

On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

Direct Synthetic Control over the Size, Composition, and Photocatalytic Activity of Octahedral Copper Oxide Materials: Correlation Between Surface Structure and Catalytic Functionality.

PubMed

Nguyen, Michelle A; Bedford, Nicholas M; Ren, Yang; Zahran, Elsayed M; Goodin, Robert C; Chagani, Fatima F; Bachas, Leonidas G; Knecht, Marc R

2015-06-24

We report a synthetic approach to form octahedral Cu2O microcrystals with a tunable edge length and demonstrate their use as catalysts for the photodegradation of aromatic organic compounds. In this particular study, the effects of the Cu(2+) and reductant concentrations and stoichiometric ratios were carefully examined to identify their roles in controlling the final material composition and size under sustainable reaction conditions. Varying the ratio and concentrations of Cu(2+) and reductant added during the synthesis determined the final morphology and composition of the structures. Octahedral particles were prepared at selected Cu(2+):glucose ratios that demonstrated a range of photocatalytic reactivity. The results indicate that material composition, surface area, and substrate charge effects play important roles in controlling the overall reaction rate. In addition, analysis of the post-reacted materials revealed photocorrosion was inhibited and that surface etching had preferentially occurred at the particle edges during the reaction, suggesting that the reaction predominately occurred at these interfaces. Such results advance the understanding of how size and composition affect the surface interface and catalytic functionality of materials.

Catalytic devices

DOEpatents

Liu, Ming; Zhang, Xiang

2018-01-23

This disclosure provides systems, methods, and apparatus related to catalytic devices. In one aspect, a device includes a substrate, an electrically insulating layer disposed on the substrate, a layer of material disposed on the electrically insulating layer, and a catalyst disposed on the layer of material. The substrate comprises an electrically conductive material. The substrate and the layer of material are electrically coupled to one another and configured to have a voltage applied across them.

Synthesis of a Ni2P/Ni12P5 bi-phase nanocomposite for the efficient catalytic reduction of 4-nitrophenol based on the unique n-n heterojunction effects.

PubMed

Tian, Feng-Yu; Hou, Dongfang; Zhang, Wei-Min; Qiao, Xiu-Qing; Li, Dong-Sheng

2017-10-24

A novel heterostructure catalyst of Ni 2 P/Ni 12 P 5 has been fabricated through a simple solvothermal method by modifying the molar ratio of the initial raw materials. The products are characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It is found that the two phases, Ni 2 P and Ni 12 P 5 , are interlaced with one another in the as-formed nanocomposite, resulting in more interfaces. The bi-phase catalyst exhibits a markedly enhanced catalytic activity in the reduction of 4-nitrophenol, as compared to that of single Ni 2 P or Ni 12 P 5 . The enhanced catalytic activity can be attributed to the unique n-n series effects, which result in the increased ease of electron transfer over the Ni 2 P/Ni 12 P 5 bi-phase catalyst.

Fabrication of Nitrogen-Doped Mesoporous-Carbon-Coated Palladium Nanoparticles: An Intriguing Electrocatalyst for Methanol and Formic Acid Oxidation.

PubMed

Ray, Chaiti; Dutta, Soumen; Sahoo, Ramkrishna; Roy, Anindita; Negishi, Yuichi; Pal, Tarasankar

2016-05-20

Inspired by the attractive catalytic properties of palladium and the inert nature of carbon supports in catalysis, a concise and simple methodology for in situ nitrogen-doped mesoporous-carbon-supported palladium nanoparticles (Pd/N-C) has been developed by carbonizing a palladium dimethylglyoximate complex. The as-synthesized Pd/N-C has been exfoliated as a fuel cell catalyst by studying the electro-oxidation of methanol and formic acid. The material synthesized at 400 °C,namely, Pd/N-C-400,exhibitssuperior mass activity and stability among catalysts synthesized under different carbonization temperaturesbetween300 and 500 °C. The unique 1D porous structure in Pd/N-C-400 helps better electron transport at the electrode surface, which eventually leads to about five times better catalytic activity and about two times higher stability than that of commercial Pd/C. Thus, our designed sacrificial metal-organic templatedirected pathway becomes a promising technique for Pd/N-C synthesis with superior catalytic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

NASA Astrophysics Data System (ADS)

Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

2017-07-01

We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

Catalytic Activity of a Binary Informational Macromolecule

NASA Technical Reports Server (NTRS)

Reader, John S.; Joyce, Gerald F.

2003-01-01

RNA molecules are thought to have played a prominent role in the early history of life on Earth based on their ability both to encode genetic information and to exhibit catalytic function. The modern genetic alphabet relies on two sets of complementary base pairs to store genetic information. However, due to the chemical instability of cytosine, which readily deaminates to uracil, a primitive genetic system composed of the bases A, U, G and C may have been difficult to establish. It has been suggested that the first genetic material instead contained only a single base-pairing unie'. Here we show that binary informational macromolecules, containing only two different nucleotide subunits, can act as catalysts. In vitro evolution was used to obtain ligase ribozymes composed of only 2,6-diaminopurine and uracil nucleotides, which catalyze the template-directed joining of two RNA molecules, one bearing a 5'-triphosphate and the other a 3'-hydroxyl. The active conformation of the fastest isolated ribozyme had a catalytic rate that was about 36,000-fold faster than the uncatalyzed rate of reaction. This ribozyme is specific for the formation of biologically relevant 3',5'-phosphodiester linkages.

Method For Selective Catalytic Reduction Of Nitrogen Oxides

DOEpatents

Mowery-Evans, Deborah L.; Gardner, Timothy J.; McLaughlin, Linda I.

2005-02-15

A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

Method for selective catalytic reduction of nitrogen oxides

DOEpatents

Mowery-Evans, Deborah L [Broomfield, CO; Gardner, Timothy J [Albuquerque, NM; McLaughlin, Linda I [Albuquerque, NM

2005-02-15

A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

Fe/Al synergy in Fe(2)O(3) nanoparticles supported on porous aluminosilicate materials: excelling activities in oxidation reactions.

PubMed

Mariana Balu, Alina; Pineda, Antonio; Yoshida, Kenta; Manuel Campelo, Juan; Gai, Pratibha L; Luque, Rafael; Angel Romero, Antonio

2010-11-07

A synergetic Fe-Al effect in Fe(2)O(3) nanoparticles supported on mesoporous aluminosilicates compared to pure siliceous silicates has been demonstrated, for the first time, by a remarkably superior catalytic activity of the former in the microwave-assisted selective oxidation of benzyl alcohol to benzaldehyde. This significant finding, that also deeply influences the acidity of the materials (increasing total and particularly Lewis acidity), can have important consequences in the improved efficiency of these systems in related oxidations as well as in acid catalysed processes.

Catalytic systems used for polymerization, biomass conversion, and enhancing diffusion

NASA Astrophysics Data System (ADS)

Pong, Frances

A significant amount of research has been dedicated towards the study and improvement of catalysts. A better understanding of how catalysts work can lead to developing more cost-efficient catalytic systems for a variety of applications. My research is focuses on catalytic systems used in three different fields, which are (i) organometallic polymerization catalysts, (ii) molecular motors and (iii) biomass conversion. Researchers have long studied and modified organometallic catalysts for use in the direct co- and homopolymerization of monomers with polar functional groups. The ability to add polar moieties to polymers, which can potentially yield materials with a wider range of physical properties, is highly desirable. In this study (i), a series of naphthoxyimine palladium(II) catalysts -- in which the naphthyl backbone had been functionalized with different moieties -- were synthesized and systematically studied to determine the ligand structure's impact on catalytic activity. The study showed that slight modifications of the naphthyl backbone led to significant changes in the polymer's molecular weight and polydispersity index. The catalysts were also displayed some ability to co-polymerize ethylene and functionalized norbornene. These positive results suggest that further exploration of naphthoxyimine palladium (II) catalysts may be fundamentally interesting. The effect of active, motile particles at the nanoscale has been vigorously researched during the past decade. By understanding how such active suspensions behave, researchers can gain new insights which can potentially provide new applications in many fields. Here (ii) the momentum transfer of active catalysts (Grubbs' 2nd generation catalyst with a hydrodynamic radius of 6A) to their immediate surroundings is observed in an organic suspension. This phenomenon, which has been coined "enhanced diffusion," has not been well studied at the angstrom scale until now. Diffusion-NMR spectroscopy surprisingly revealed that these angstrom sized catalysts nearly double the speed of diffusion of passive molecular tracers in their immediate surroundings. This result is particularly intriguing because in this size regime, the viscosity of the surroundings is expected to completely overcome the inertial forces of these catalysts. This study has prompted further diffusion-NMR studies of molecular catalysts and enzymes as molecular motors. Catalytic systems play a crucial role in the conversion of renewable biomasses into energy and useful materials. This field of research has become increasingly important and lucrative as fossil fuel sources continue to decline/destabilize in the face of increased worldwide demand for more resources. In this work (iii), the efficacy of a hydrogen-pressurized, biphasic catalytic system to convert linear sugar polyols to iodoalkanes was examined. These iodoalkanes can easily be converted to 1-alkenes which can then be used for the synthesis of low density polyethylene. The results indicated that the system products were relatively pure and that the catalytic layer had a degree of recyclability, hinting that such a system may be viable for industrial use.

Heterogeneous Metal-Free Hydrogenation over Defect-Laden Hexagonal Boron Nitride

DOE PAGES

Nash, David J.; Restrepo, David T.; Parra, Natalia S.; ...

2016-12-21

Catalytic hydrogenation is an important process used for the production of everything from foods to fuels. Current heterogeneous implementations of this process utilize metals as the active species. Until recently, catalytic heterogeneous hydrogenation over a metal-free solid was unknown; implementation of such a system would eliminate the health, environmental, and economic concerns associated with metal-based catalysts. We report good hydrogenation rates and yields for a metal-free heterogeneous hydrogenation catalyst as well as its unique hydrogenation mechanism. We achieved catalytic hydrogenation of olefins over defect-laden h-BN (dh-BN) in a reactor designed to maximize the defects in h-BN sheets. Good yields (>90%)more » and turnover frequencies (6 × 10 –5–4 × 10 –3) were obtained for the hydrogenation of propene, cyclohexene, 1,1-diphenylethene, (E)- and (Z)-1,2-diphenylethene, octadecene, and benzylideneacetophenone. Temperature-programmed desorption of ethene over processed h-BN indicates the formation of a highly defective structure. Solid-state NMR (SSNMR) measurements of dh-BN with high and low propene surface coverages show four different binding modes. The introduction of defects into h-BN creates regions of electronic deficiency and excess. Density functional theory calculations show that both the alkene and hydrogen-bond order are reduced over four specific defects: boron substitution for nitrogen (B N), vacancies (V B and V N), and Stone–Wales defects. SSNMR and binding-energy calculations show that V N are most likely the catalytically active sites. Our work shows that catalytic sites can be introduced into a material previously thought to be catalytically inactive through the production of defects.« less

Synthesis of N-doped TiO2 Using Guanidine Nitrate: An Excellent Visible Light Photocatalyst

EPA Science Inventory

An excellent visible light active nitrogen-rich TiO2 photocatalyst have been synthesized by using guanidine nitrate as the doping material. The catalytic efficiency of the catalyst has been demonstrated by the decomposition of the dye, methyl orange (MO), and the pollutant, 2,4 d...

Catalytic thermal decomposition of methane to COx-free hydrogen and carbon nanotubes over MgO supported bimetallic group VIII catalysts

NASA Astrophysics Data System (ADS)

Awadallah, A. E.; Aboul-Enein, A. A.; El-Desouki, D. S.; Aboul-Gheit, A. K.

2014-03-01

Bimetallic Ni-Fe, Ni-Co and Fe-Co supported on MgO catalysts with a total metals content of 50 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nanomaterials. The catalytic runs were carried out at 700 °C under atmospheric pressure using fixed bed horizontal flow reactor. The materials were characterized by XRD, TEM, Raman spectroscopy, surface analysis and TGA-DTG. The data showed that the bimetallic 25% Fe-25%Co/MgO catalyst exhibited remarkable higher activity and stability up to ˜10 h time-on-stream with respect to H2 production. However, the catalytic activity and durability was greatly declined after incorporating 25%Ni to either 25%Fe or 25%Co/MgO catalysts at all time on stream. The main reason for the catalytic inhibition of Ni containing catalysts is consuming NiO during the formation of rock-salt MgxNi(1-x)O solid solution. However, the almost complete segregation of Fe2O3 and Co3O4 oxides played an important role for the high activity of the Fe-Co based catalyst. TEM images illustrate that the accumulated carbon over all catalysts are multi-walled carbon nanotubes in nature. The TG data showed that a higher yield of MWCNTs was achieved over bimetallic Fe-Co catalyst compared to the Ni-Fe or Ni-Co containing catalysts.

Size-controllable APTS stabilized ruthenium(0) nanoparticles catalyst for the dehydrogenation of dimethylamine-borane at room temperature.

PubMed

Zahmakıran, Mehmet; Philippot, Karine; Özkar, Saim; Chaudret, Bruno

2012-01-14

Dimethylamine-borane, (CH(3))(2)NHBH(3), has been considered as one of the attractive materials for the efficient storage of hydrogen, which is still one of the key issues in the "Hydrogen Economy". In a recent communication we have reported the synthesis and characterization of 3-aminopropyltriethoxysilane stabilized ruthenium(0) nanoparticles with the preliminary results for their catalytic performance in the dehydrogenation of dimethylamine-borane at room temperature. Herein, we report a complete work including (i) effect of initial [APTS]/[Ru] molar ratio on both the size and the catalytic activity of ruthenium(0) nanoparticles, (ii) collection of extensive kinetic data under non-MTL conditions depending on the substrate and catalyst concentrations to define the rate law of Ru(0)/APTS-catalyzed dehydrogenation of dimethylamine-borane at room temperature, (iii) determination of activation parameters (E(a), ΔH(#) and ΔS(#)) for Ru(0)/APTS-catalyzed dehydrogenation of dimethylamine-borane; (iv) demonstration of the catalytic lifetime of Ru(0)/APTS nanoparticles in the dehydrogenation of dimethylamine-borane at room temperature, (v) testing the bottlability and reusability of Ru(0)/APTS nanocatalyst in the room-temperature dehydrogenation of dimethylamine-borane, (vi) quantitative carbon disulfide (CS(2)) poisoning experiments to find a corrected TTO and TOF values on a per-active-ruthenium-atom basis, (vii) a summary of extensive literature review for the catalysts tested in the catalytic dehydrogenation of dimethylamine-borane as part of the results and discussions.

Metal and Metal Oxide Interactions and Their Catalytic Consequences for Oxygen Reduction Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Qingying; Ghoshal, Shraboni; Li, Jingkun

2017-06-01

Many industrial catalysts are composed of metal particles supported on metal oxides (MMO). It is known that the catalytic activity of MMO materials is governed by metal and metal oxide interactions (MMOI), but how to optimize MMO systems via manipulation of MMOI remains unclear, due primarily to the ambiguous nature of MMOI. Herein, we develop a Pt/NbOx/C system with tunable structural and electronic properties via a modified arc plasma deposition method. We unravel the nature of MMOI by characterizing this system under reactive conditions utilizing combined electrochemical, microscopy, and in situ spectroscopy. We show that Pt interacts with the Nbmore » in unsaturated NbOx owing to the oxygen deficiency in the MMO interface, whereas Pt interacts with the O in nearly saturated NbOx, and further interacts with Nb when the oxygen atoms penetrate into the Pt cluster at elevated potentials. While the Pt–Nb interactions do not benefit the inherent activity of Pt toward oxygen reduction reaction (ORR), the Pt–O interactions improve the ORR activity by shortening the Pt–Pt bond distance. Pt donates electrons to NbOx in both Pt–Nb and Pt–O cases. The resultant electron efficiency stabilizes low-coordinated Pt sites, hereby stabilizing small Pt particles. This determines the two characteristic features of MMO systems: dispersion of small metal particles and high catalytic durability. These findings contribute to our understandings of MMO catalytic systems.« less

Mild Deoxygenation of Sulfoxides over Plasmonic Molybdenum Oxide Hybrid with Dramatic Activity Enhancement under Visible Light.

PubMed

Kuwahara, Yasutaka; Yoshimura, Yukihiro; Haematsu, Kohei; Yamashita, Hiromi

2018-06-17

Harvesting solar light to boost commercially important organic synthesis still remains a challenge. Coupling of conventional noble metal catalysts with plasmonic oxide materials which exhibit intense plasmon absorption in the visible light region is a promising option for efficient solar energy utilization in catalysis. Herein we for the first time demonstrate that plasmonic hydrogen molybdenum bronze coupled with Pt nanoparticles (Pt/H x MoO 3-y ) shows a high catalytic performance in the deoxygenation of sulfoxides with 1 atm H 2 at room temperature, with dramatic activity enhancement under visible light irradiation relative to dark condition. The plasmonic molybdenum oxide hybrids with strong plasmon resonance peaks pinning at around 556 nm are obtained via a facile H-spillover process. Pt/H x MoO 3-y hybrid provides excellent selectivity for the deoxygenation of various sulfoxides as well as pyridine N-oxides, in which drastically improved catalytic efficiencies are obtained under the irradiation of visible light. Comprehensive analyses reveal that oxygen vacancies massively introduced via a H-spillover process are the main active sites, and reversible redox property of Mo atoms and strong plasmonic absorption play key roles in this reaction. The catalytic system works under extremely mild conditions and can boost the reaction by the assist of visible light, offering an ultimately greener protocol to produce sulfides from sulfoxides. Our findings may open up a new strategy for designing plasmon-based catalytic systems that can harness visible light efficiently.

Characterization of calcium oxide catalysts from natural sources and their application in the transesterification of sunflower oil.

PubMed

Correia, Leandro Marques; Saboya, Rosana Maria Alves; Campelo, Natália de Sousa; Cecilia, Juan Antonio; Rodríguez-Castellón, Enrique; Cavalcante, Célio Loureiro; Vieira, Rodrigo Silveira

2014-01-01

The catalytic activities of calcium oxide obtained from natural sources (crab shell and eggshell) were characterized and evaluated in the transesterification of vegetable oil. These catalysts are mainly composed of calcium carbonate, which is partially converted into CaO after calcination (900°C for 2h). The catalysts have some advantages, such as abundant occurrence, low cost, porous structure, and nontoxic. The materials were characterized by XRD, FTIR, TG/DTG, CO2-TPD, XPS, SEM, and BET methods. The thermal treatment produces small particles of CaCO3 and CaO that are responsible for the catalytic activity. The conversion from triglycerides to methyl ester was not observed in transesterification carried out using natural crab shell and eggshell. Under optimized reaction conditions, the conversions to YFAME using the calcined catalysts were: crab shell (83.10±0.27 wt.%) and eggshell (97.75±0.02 wt.%). These results, showed that these materials have promising viability in transesterification for biodiesel production. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis and characterization of Cr-MSU-1 and its catalytic application for oxidation of styrene

NASA Astrophysics Data System (ADS)

Liu, Hong; Wang, Zhigang; Hu, Hongjiu; Liang, Yuguang; Wang, Mengyang

2009-07-01

Chromium-containing mesoporous silica material Cr-MSU-1 was synthesized using lauryl alcohol-polyoxyethylene (23) ether as templating agent under the neutral pH condition by two-step method. The sample was characterized by XRD, TEM, FT-IR, UV-Vis, ESR, ICP-AES and N 2 adsorption. Its catalytic performance for oxidation of styrene was studied. Effects of the solvent used, the styrene/H 2O 2 mole ratio and the reaction temperature and time on the oxidation of styrene over the Cr-MSU-1 catalyst were examined. The results indicate that Cr ions have been successfully incorporated into the framework of MSU-1 and the Cr-MSU-1 material has a uniform worm-like holes mesoporous structure. After Cr-MSU-1 is calcined, most of Cr 3+ is oxidized to Cr 5+ and Cr 6+ in tetrahedral coordination and no extra-framework Cr 2O 3 is formed. The Cr-MSU-1 catalyst is highly active for the selective oxidation of styrene and the main reaction products over Cr-MSU-1 are benzaldehyde and phenylacetaldehyde. Its catalytic performance remains stable within five repeated runs and no leaching is noticed for this chromium-based catalyst.

Nanostructured Catalytic Hybrid Materials for Energy Conversion or Storage

DTIC Science & Technology

2017-08-27

and 6) and characterized them using bomb calorimetry, DSC and XRD. - We are organizing the data to make research articles and patents. [Iron...Unlimited Distribution Figure 4 • Bomb calorimeter (BC) enthalpy plot of Al-encapsulated nanofibers Nanostructured catalytic hybrid materials for energy

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

DOE PAGES

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi; ...

2017-11-13

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from anmore » amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme-packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. As a result, this study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales and exhibits properties and function that arise from the interaction between individual building blocks.« less

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

PubMed Central

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi; Yang, Lin; Yoshimura, Hideyuki; Miettinen, Heini M.; LaFrance, Ben; Patterson, Dustin P.; Schwarz, Benjamin; Karty, Jonathan A.; Prevelige, Peter E.; Lee, Byeongdu; Douglas, Trevor

2018-01-01

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy; the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from an amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles, and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. This study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales, and exhibits properties and function that arise from the interaction between individual building blocks. PMID:29131580

Modular Self-Assembly of Protein Cage Lattices for Multistep Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uchida, Masaki; McCoy, Kimberly; Fukuto, Masafumi

The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here, we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy: the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from anmore » amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme-packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. As a result, this study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales and exhibits properties and function that arise from the interaction between individual building blocks.« less

In Situ Spectroscopy and Mechanistic Insights into CO Oxidation on Transition-Metal-Substituted Ceria Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elias, Joseph S.; Stoerzinger, Kelsey A.; Hong, Wesley T.

Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu0.1Ce0.9O2–x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M0.1Ce0.9O2–x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2– transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu0.1Ce0.9O2–x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) andmore » in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO32– in the absence of O2. We find that CO32– desorbs as CO2 only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O2. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper–oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is rate-determining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (Evac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M0.1Ce0.9O2–x catalysts that spans three orders of magnitude. The applicability of Evac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu0.1La0.1Ce0.8O2–x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO2 materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of substituting metal through the computational screening of Evac.« less

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,...

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica.

PubMed

Ji, Yazhou; Caskey, Christopher; Richards, Ryan M

2015-07-09

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability.

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

PubMed Central

Ji, Yazhou; Caskey, Christopher; Richards, Ryan M.

2015-01-01

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability. PMID:26274058

Novel Catalysis by Gold: A Modern Alchemy

NASA Astrophysics Data System (ADS)

Haruta, Masatake

Gold has long been neglected as a catalyst because of its chemical inertness. However, when gold is deposited as nanoparticles on carbon and polymer materials as well as on base metal oxides and hydroxides, it exhibits unique catalytic properties for many reactions such as CO oxidation at a temperature as low as 200 K, gas phase direct epoxidation of propylene, and aerobic oxidation of glucose to gluconic acid. The structure-catalytic activity correlations are discussed with emphasis on the contact structure, support selection, and the size control of gold particles. Gold clusters with diameters smaller than 2 nm are expected to exhibit novel properties in catalysis, optics, and electronics depending on the size (number of atoms), shape, and the electronic and chemical interaction with the support materials. The above achievements and attempts can be regarded as a modern alchemy that creates valuables by means of the noblest element with little practical use.

CO-oxidation catalysts: Low-temperature CO oxidation over Noble-Metal Reducible Oxide (NMRO) catalysts

NASA Technical Reports Server (NTRS)

Herz, Richard K.

1990-01-01

Oxidation of CO to CO2 is an important reaction technologically and environmentally and a complex and interesting reaction scientifically. In most cases, the reaction is carried out in order to remove CO as an environmental hazard. A major application of heterogeneous catalysts is catalytic oxidation of CO in the exhaust of combustion devices. The reaction over catalysts in exhaust gas is fast and often mass-transfer-limited since exhaust gases are hot and O2/CO ratios are high. The main challenges to catalyst designers are to control thermal sintering and chemical poisoning of the active materials. The effect of the noble metal on the oxide is discussed, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form unique catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

PubMed

Smith, Rodney D L; Prévot, Mathieu S; Fagan, Randal D; Zhang, Zhipan; Sedach, Pavel A; Siu, Man Kit Jack; Trudel, Simon; Berlinguette, Curtis P

2013-04-05

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

Metal oxide composite enabled nanotextured Si photoanode for efficient solar driven water oxidation.

PubMed

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.

A molecular approach to self-supported cobalt-substituted ZnO materials as remarkably stable electrocatalysts for water oxidation.

PubMed

Pfrommer, Johannes; Lublow, Michael; Azarpira, Anahita; Göbel, Caren; Lücke, Marcel; Steigert, Alexander; Pogrzeba, Martin; Menezes, Prashanth W; Fischer, Anna; Schedel-Niedrig, Thomas; Driess, Matthias

2014-05-12

In regard to earth-abundant cobalt water oxidation catalysts, very recent findings show the reorganization of the materials to amorphous active phases under catalytic conditions. To further understand this concept, a unique cobalt-substituted crystalline zinc oxide (Co:ZnO) precatalyst has been synthesized by low-temperature solvolysis of molecular heterobimetallic Co(4-x)Zn(x) O4 (x = 1-3) precursors in benzylamine. Its electrophoretic deposition onto fluorinated tin oxide electrodes leads after oxidative conditioning to an amorphous self-supported water-oxidation electrocatalyst, which was observed by HR-TEM on FIB lamellas of the EPD layers. The Co-rich hydroxide-oxidic electrocatalyst performs at very low overpotentials (512 mV at pH 7; 330 mV at pH 12), while chronoamperometry shows a stable catalytic current over several hours. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution

DOE PAGES

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

Nanoscale octahedral molecular sieves: Syntheses, characterization, and applications

NASA Astrophysics Data System (ADS)

Liu, Jia

The major part of this research consists of studies on novel synthesis methods, characterization, and catalytic applications of nanoscale manganese oxide octahedral molecular sieves. The second part involves studies of new applications of bulk porous molecular sieve and layered materials (MSLM), zeolites, and inorganic powder materials for diminishing wound bleeding. Manganese oxide octahedral molecular sieves (OMS) are very important microporous materials. They have been used widely as bulk materials in catalysis, separations, chemical sensors, and batteries, due to their unique tunnel structures and useful properties. Novel methods have been developed to synthesize novel nanoscale octahedral molecular sieve manganese oxides (OMS) and metal-substituted OMS materials in order to modify their physical and chemical properties and to improve their catalytic applications. Different synthetic routes were investigated to find better, faster, and cheaper pathways to produce nanoscale or metal-substituted OMS materials. In the synthetic study of nanosize OMS materials, a combination of sol-gel synthesis and hydrothermal reaction was used to prepare pure crystalline nanofibrous todorokite-type (OMS-1) and cryptomelane-typed (OMS-2) manganese oxides using four alkali cations (Li+, K+, Na +, Rb+) and NH4+ cations. In the synthesis study of nanoscale and metal-substituted OMS materials, a combination of sol-gel synthesis and solid-state reaction was used to prepare transition metal-substituted OMS-2 nanorods, nanoneedles, and nanowires. Preparative parameters of syntheses, such as cation templates, heating temperature and time, were investigated in these syntheses of OMS-1 and OMS-2 materials. The catalytic activities of the novel synthetic nanoscale OMS materials has been evaluated on green oxidation of alcohols and toluene and were found to be much higher than their correspondent bulk materials. New applications of bulk manganese oxide molecular sieve and layered materials (MSLM), zeolites, and several inorganic powder materials have also been studied for diminishing bleeding via in vitro tests using horse blood and in vivo tests on rat organs. MSLM, as well as several types of zeolite, and several inorganic compounds, have been found to have excellent ability to clot blood and arrest wound bleeding. Effects of properties of these porous materials on the efficiency of blood coagulation have been discussed.

Decomposition of energetic molecules by interfacing with a catalytic oxide: opportunities and challenges

NASA Astrophysics Data System (ADS)

Wang, Fenggong; Tsyshevsky, Roman; Zverev, Anton; Mitrofanov, Anatoly; Kuklja, Maija

Organic-inorganic interfaces provide both intrigues and opportunities for designing systems that possess properties and functionalities inaccessible by each individual component. In particular, mixing with a photocatalyst may significantly affect the adsorption, decomposition, and photoresponse of organic molecules. Here, we choose the formulation of TiO2 and trinitrotoluene (TNT), a highly catalytic oxide and a prominent explosive, as a prototypical example to explore the interaction at the interface on the photosensitivity of energetic materials. We show that, whether or not a catalytic oxide additive can help molecular decompositions under light illumination depends largely on the band alignment between the oxide surface and the energetic molecule. Furthermore, an oxygen vacancy can lead to the electron density transfer from the surface to the energetic molecules, causing an enhancement of the bonding between molecules and surface and a reduction of the molecular decomposition activation barriers.

Bioinspired construction of multi-enzyme catalytic systems.

PubMed

Shi, Jiafu; Wu, Yizhou; Zhang, Shaohua; Tian, Yu; Yang, Dong; Jiang, Zhongyi

2018-06-18

Enzyme catalysis, as a green, efficient process, displays exceptional functionality, adaptivity and sustainability. Multi-enzyme catalysis, which can accomplish the tandem synthesis of valuable materials/chemicals from renewable feedstocks, establishes a bridge between single-enzyme catalysis and whole-cell catalysis. Multi-enzyme catalysis occupies a unique and indispensable position in the realm of biological reactions for energy and environmental applications. Two complementary strategies, i.e., compartmentalization and substrate channeling, have been evolved by living organisms for implementing the complex in vivo multi-enzyme reactions (MERs), which have been applied to construct multi-enzyme catalytic systems (MECSs) with superior catalytic activity and stabilities in practical biocatalysis. This tutorial review aims to present the recent advances and future prospects in this burgeoning research area, stressing the features and applications of the two strategies for constructing MECSs and implementing in vitro MERs. The concluding remarks are presented with a perspective on the construction of MECSs through rational combination of compartmentalization and substrate channeling.

The Non-innocent Phenalenyl Unit: An Electronic Nest to Modulate the Catalytic Activity in Hydroamination Reaction

PubMed Central

Mukherjee, Arup; Sen, Tamal K.; Ghorai, Pradip Kr; Mandal, Swadhin K.

2013-01-01

The phenalenyl unit has played intriguing role in different fields of research spanning from chemistry, material chemistry to device physics acting as key electronic reservoir which has not only led to the best organic single component conductor but also created the spin memory device of next generation. Now we show the non-innocent behaviour of phenalenyl unit in modulating the catalytic behaviour in a homogeneous organic transformation. The present study establishes that the cationic state of phenalenyl unit can act as an organic Lewis acceptor unit to influence the catalytic outcome of intermolecular hydroamination reaction of carbodiimides. For the present study, we utilized organoaluminum complexes of phenalenyl ligands in which the phenalenyl unit maintains the closed shell electronic state. The DFT calculation reveals that the energy of LUMO of the catalyst is mainly controlled by phenalenyl ligands which in turn determines the outcome of the catalysis. PMID:24084653

Catalytic effect of different reactor materials under subcritical water conditions: decarboxylation of cysteic acid into taurine

NASA Astrophysics Data System (ADS)

Faisal, M.

2018-03-01

In order to understand the influence of reactor materials on the catalytic effect for a particular reaction, the decomposition of cysteic acid from Ni/Fe-based alloy reactors under subcritical water conditions was examined. Experiments were carried out in three batch reactors made of Inconel 625, Hastelloy C-22 and SUS 316 over temperatures of 200 to 300 °C. The highest amount of eluted metals was found for SUS 316. The results demonstrated that reactor materials contribute to the resulting product. Under the tested conditions, cysteic acid decomposes readily with SUS 316. However, the Ni-based materials (Inconel 625 and Hastelloy C-22) show better resistance to metal elution. It was found that among the materials used in this work, SUS 316 gave the highest reaction rate constant of 0.1934 s‑1. The same results were obtained at temperatures of 260 and 300 °C. Investigation of the Arrhenius activation energy revealed that the highest activation energy was for Hastelloy C-22 (109 kJ/mol), followed by Inconel 625 (90 kJ/mol) and SUS 316 (70 kJ/mol). The decomposition rate of cysteic acid was found to follow the results for the trend of the eluted metals. Therefore, it can be concluded that the decomposition of cysteic acid was catalyzed by the elution of heavy metals from the surface of the reactor. The highest amount of taurine from the decarboxylation of cysteic acid was obtained from SUS 316.

Catalysis by metal-organic frameworks: fundamentals and opportunities.

PubMed

Ranocchiari, Marco; van Bokhoven, Jeroen Anton

2011-04-14

Crystalline porous materials are extremely important for developing catalytic systems with high scientific and industrial impact. Metal-organic frameworks (MOFs) show unique potential that still has to be fully exploited. This perspective summarizes the properties of MOFs with the aim to understand what are possible approaches to catalysis with these materials. We categorize three classes of MOF catalysts: (1) those with active site on the framework, (2) those with encapsulated active species, and (3) those with active sites attached through post-synthetic modification. We identify the tunable porosity, the ability to fine tune the structure of the active site and its environment, the presence of multiple active sites, and the opportunity to synthesize structures in which key-lock bonding of substrates occurs as the characteristics that distinguish MOFs from other materials. We experience a unique opportunity to imagine and design heterogeneous catalysts, which might catalyze reactions previously thought impossible.

Solid State Carbon Monoxide Sensor

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Wood, George M. (Inventor); Schryer, David R. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); DAmbrosia, Christine M. (Inventor)

1999-01-01

A means for detecting carbon monoxide which utilizes an un-heated catalytic material to oxidize carbon monoxide at ambient temperatures. Because this reaction is exothermic, a thermistor in contact with the catalytic material is used as a sensing element to detect the heat evolved as carbon monoxide is oxidized to carbon dioxide at the catalyst surface, without any heaters or external heating elements for the ambient air or catalytic element material. Upon comparison to a reference thermistor, relative increases in the temperature of the sensing thermistor correspond positively with an increased concentration of carbon monoxide in the ambient medium and are thus used as an indicator of the presence of carbon monoxide.

Influence of physicochemical treatments on iron-based spent catalyst for catalytic oxidation of toluene.

PubMed

Kim, Sang Chai; Shim, Wang Geun

2008-06-15

The catalytic oxidation of toluene was studied over an iron-based spent and regenerated catalysts. Air, hydrogen, or four different acid solutions (oxalic acid (C2H2O4), citric acid (C6H8O7), acetic acid (CH3COOH), and nitric acid (HNO3)) were employed to regenerate the spent catalyst. The properties of pretreated spent catalyst were characterized by the Brunauer Emmett Teller (BET), inductively coupled plasma (ICP), temperature programmed reduction (TPR), and X-ray diffraction (XRD) analyses. The air pretreatment significantly enhanced the catalytic activity of the spent catalyst in the pretreatment temperature range of 200-400 degrees C, but its catalytic activity diminished at the pretreatment temperature of 600 degrees C. The catalytic activity sequence with respect to the air pretreatment temperatures was 400 degrees C>200 degrees C>parent>600 degrees C. The TPR results indicated that the catalytic activity was correlated with both the oxygen mobility and the amount of available oxygen on the catalyst. In contrast, the hydrogen pretreatment had a negative effect on the catalytic activity, and toluene conversion decreased with increasing pretreatment temperatures (200-600 degrees C). The XRD and TPR results confirmed the formation of metallic iron which had a negative effect on the catalytic activity with increasing pretreatment temperature. The acid pretreatment improved the catalytic activity of the spent catalyst. The catalytic activity sequence with respect to different acids pretreatment was found to be oxalic acid>citric acid>acetic acid>or=nitric acid>parent. The TPR results of acid pretreated samples showed an increased amount of available oxygen which gave a positive effect on the catalytic activity. Accordingly, air or acid pretreatments were more promising methods of regenerating the iron-based spent catalyst. In particular, the oxalic acid pretreatment was found to be most effective in the formation of FeC2O4 species which contributed highly to the catalytic combustion of toluene.

Ceo2 Based Catalysts for the Treatment of Propylene in Motorcycle’s Exhaust Gases

PubMed Central

Pham, Phuong Thi Mai; Le Minh, Thang; Nguyen, Tien The; Van Driessche, Isabel

2014-01-01

In this work, the catalytic activities of several single metallic oxides were studied for the treatment of propylene, a component in motorcycles’ exhaust gases, under oxygen deficient conditions. Amongst them, CeO2 is one of the materials that exhibit the highest activity for the oxidation of C3H6. Therefore, several mixtures of CeO2 with other oxides (SnO2, ZrO2, Co3O4) were tested to investigate the changes in catalytic activity (both propylene conversion and CO2 selectivity). Ce0.9Zr0.1O2, Ce0.8Zr0.2O2 solid solutions and the mixtures of CeO2 and Co3O4 was shown to exhibit the highest propylene conversion and CO2 selectivity. They also exhibited good activities when tested under oxygen sufficient and excess conditions and with the presence of co-existing gases (CO, H2O). PMID:28788253

Studies on the photo-catalytic activity of semiconductor nanostructures and their gold core-shell on the photodegradation of malathion.

PubMed

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.

Ce(III, IV)-MOF electrocatalyst as signal-amplifying tag for sensitive electrochemical aptasensing.

PubMed

Yu, Hua; Han, Jing; An, Shangjie; Xie, Gang; Chen, Sanping

2018-06-30

Metal-organic frameworks (MOFs) as a new class of porous materials have attracted increasing attention in the field of biomimetic catalysis. This study firstly reports a mixed valence state Ce-MOF possessing intrinsic catalytic activity towards thionine (Thi), and its application in constructing an amplified electrochemical aptasensor for thrombin detection. As noticed, the novel catalytic process combines the advantages of 3D infinite extension of the Ce(III, IV)-MOF skeleton containing large amounts of catalytic sites and spontaneous recycling of the Ce(III)/Ce(IV) for electrochemical reduction of Thi, thereby presenting amplified electrochemical signals. To further improve the aptasensor performance, the high selectivity of proximity binding-induced DNA strand displacement and high efficiency of exonuclease III-assisted recycling amplification were incorporated into the assay. The aptasensor was employed to detect thrombin in complex serum samples, which shows high sensitivity, specificity, stability and reproducibility. This work offers an opportunity to develop MOF-based electrocatalyst as signal-amplifying tag for versatile bioassays and catalytic applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Fundamentals and Catalytic Applications of CeO2-Based Materials.

PubMed

Montini, Tiziano; Melchionna, Michele; Monai, Matteo; Fornasiero, Paolo

2016-05-25

Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40(th) anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are deepening our understanding of these materials, helping us to predict their behavior and application potential. This review has a wide view on all those aspects related to ceria which promise to produce an important impact on our life, encompassing fundamental knowledge of CeO2 and its properties, characterization toolbox, emerging features, theoretical studies, and all the catalytic applications, organized by their degree of establishment on the market.

Novel techniques for the synthesis of three-way catalytic converter support materials

NASA Astrophysics Data System (ADS)

Anyaba, Prince Nwabueze

Current automobiles use catalytic converters, consisting of noble metals on an oxide support, to convert noxious engine exhaust pollutants into less harmful species. The development of mesoporous oxide supports with optimal pore geometries could enable these devises to decrease in size and weight and significantly reduce the metal loadings required to achieve optimal performance. Thus, in this work, I investigated a wide range of techniques for the synthesis of mesoporous oxides to determine if they could be adapted to ceria-zirconia-yttria mixed oxide (CZY) systems, which are the industry standard for the optimal oxide support for catalytic converter applications. Additionally, I compared and critically evaluated the catalytic performance of the CZY mixed oxides, which were synthesized from the various templating techniques. The catalytic performance test was broken up into two: catalyst activity test which was determined based on the light-off temperatures at which 50% conversion of the reacting species have been converted; and resistance to surface area loss under accelerated aging at heating rate of 20°C/min form 700 to 1000°C, with the final temperature being held fixed for 4 h. To date, the most cost effective methods for preparing mesoporous materials are via techniques that employ templates or structure directing agents. These templates can be divided into two groups: endo-templates (i.e., soft templates, such as surfactants, dendrimers, and block copolymers) and exo-templates (i.e., hard templates, such as porous carbons and resins). The soft templating techniques generally involve both sol-gel and templating methods, while the hard templates required no sol-gel chemistry to achieve the desired templating effect. The precursors for ceria, zirconia, and yttria used were cerium (III) nitrate hexahydrate, zirconyl nitrate, and yttrium nitrate hexahydrate, respectively. The mesoporous CZY materials that were synthesized had surface area values that were between 40 and 120 m2/g and pore diameters that range from 2.2 to 9.0 nm after calcination in air from ambient temperature to 600°C at heating rates varied from 1 to 20°C/min, with the final temperature being maintained for 4 h. The novel CZY oxides that were prepared from the different templating techniques were characterized using nitrogen physisorption to determine the Brunauer--Emmett--Teller (BET) surface area and the Barrett--Joyner--Halenda (BJH) pore size distribution. Samples that showed some promise were further examined by transmission electron microscopy (TEM) to study the morphology of the structure; scanning electron microscopy (SEM) to study the bulk surface structure; thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) to determine physical and chemical changes occurring during calcination; elemental analysis to determine composition; powder X-ray diffraction (PXD) to determine the existence of crystalline structure; and small angle X-ray diffraction (SAXD) to determine the occurrence of mesoscale ordering of repeating units. Finally, selected samples underwent catalytic testing under simulated exhaust conditions. The results of the tests showed that CZY materials synthesized using sol-gel methods with the Pluronic P123 soft template were the most active (i.e., had the lowest light off temperature), while CZY material with least loss of surface area after accelerated aging from 700 to 1000°C was the polymeric resin templated CZY materials.

Preparation and properties of plate-like titanate (PLT)/calcia-doped ceria (CDC) composites by sol-gel coating method.

PubMed

Liu, Xiangwen; Liu, Jingxiao; Dong, Xiaoli; Yin, Shu; Sato, Tsugio

2009-08-01

In order to obtain UV-shielding materials with good comfort, higher safety and effective UV-shielding ability, lepidocrocite type plate-like titanate (K(0.8)Li(0.27)Ti(1.73)O(4), donated as: PLT)/calcia-doped ceria (donated as: CDC) composites were synthesized by a sol-gel method. After dissolving Ce(NO(3))(3).6H(2)O and Ca(NO(3))(2).4H(2)O into absolute ethanol at 40 degrees C, glacial acetic acid (HAc) and PLT particles dispersed into absolute ethanol were added. Then, the solution was heated at 60 degrees C to get gel-like substance. This gel was dried in a vacuum oven at 333 K for 5 h, and then, the product was collected and ground in an agate mortar followed by calcination at 1073 K for 2 h to form PLT/CDC composites. By optimization, 20 mass% of CDC was coated by one operation. PLT/CDC composites with higher CDC content were obtained by repeating the coating process. The morphology, catalytic activity for the oxidation of organic material, UV-shielding ability and dynamic friction coefficient of as-obtained PLT/CDC composites were characterized. As a result, broad-spectrum UV-shielding composite materials with good comfort and low oxidation catalytic activity were successfully synthesized.

Process of making porous ceramic materials with controlled porosity

DOEpatents

Anderson, Marc A.; Ku, Qunyin

1993-01-01

A method of making metal oxide ceramic material is disclosed by which the porosity of the resulting material can be selectively controlled by manipulating the sol used to make the material. The method can be used to make a variety of metal oxide ceramic bodies, including membranes, but also pellets, plugs or other bodies. It has also been found that viscous sol materials can readily be shaped by extrusion into shapes typical of catalytic or adsorbent bodies used in industry, to facilitate the application of such materials for catalytic and adsorbent applications.

Reactive Distillation and Air Stripping Processes for Water Recycling and Trace Contaminant Control

NASA Technical Reports Server (NTRS)

Boul, Peter J.; Lange, Kevin E.; Conger, Bruce; Anderson, Molly

2009-01-01

Reactive distillation designs are considered to reduce the presence of volatile organic compounds in the purified water. Reactive distillation integrates a reactor with a distillation column. A review of the literature in this field has revealed a variety of functional reactive columns in industry. Wastewater may be purified by a combination of a reactor and a distiller (e.g., the EWRS or VPCAR concepts) or, in principle, through a design which integrates the reactor with the distiller. A review of the literature in reactive distillation has identified some different designs in such combinations of reactor and distiller. An evaluation of reactive distillation and reactive air stripping is presented with regards to the reduction of volatile organic compounds in the contaminated water and air. Among the methods presented, an architecture is presented for the evaluation of the simultaneous oxidation of organics in air and water. These and other designs are presented in light of potential improvements in power consumptions and air and water purities for architectures which include catalytic activity integrated into the water processor. In particular, catalytic oxidation of organics may be useful as a tool to remove contaminants that more traditional distillation and/or air stripping columns may not remove. A review of the current leading edge at the commercial level and at the research frontier in catalytically active materials is presented. Themes and directions from the engineering developments in catalyst design are presented conceptually in light of developments in the nanoscale chemistry of a variety of catalyst materials.

Support effects in catalysis studied by in-situ sum frequency generation vibrational spectroscopy and in-situ x-ray spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, Griffin John

Here, kinetic measurements are paired with in-situ spectroscopic characterization tools to investigate colloidally based, supported Pt catalytic model systems in order to elucidate the mechanisms by which metal and support work in tandem to dictate activity and selectivity. The results demonstrate oxide support materials, while inactive in absence of Pt nanoparticles, possess unique active sites for the selective conversion of gas phase molecules when paired with an active metal catalyst.

Sustainable resource recovery and energy conversion processes using microbial electrochemical technologies

NASA Astrophysics Data System (ADS)

Yates, Matthew D.

Microbial Electrochemical Technologies (METs) are emerging technological platforms for the conversion of waste into usable products. METs utilize naturally occurring bacteria, called exoelectrogens, capable of transferring electrons to insoluble terminal electron acceptors. Electron transfer processes in the exoelectrogen Geobacter sulfurreducens were exploited here to develop sustainable processes for synthesis of industrially and socially relevant end products. The first process examined was the removal of soluble metals from solution to form catalytic nanoparticles and nanoporous structures. The second process examined was the biocatalytic conversion of electrons into hydrogen gas using electrons supplied directly to an electrode. Nanoparticle formation is desirable because materials on the nanoscale possess different physical, optical, electronic, and mechanical properties compared to bulk materials. In the first process, soluble palladium was used to form catalytic palladium nanoparticles using extracellular electron transfer (EET) processes of G. sulfurreducens, typically the dominant member of mixedculture METs. Geobacter cells reduced the palladium extracellularly using naturally produced pili, which provided extracellular adsorption and reduction sites to help delay the diffusion of soluble metals into the cell. The extracellular reduction prevented cell inactivation due to formation of intracellular particles, and therefore the cells could be reused in multiple palladium reduction cycles. A G. sulfurreducens biofilm was next investigated as a biotemplate for the formation of a nanoporous catalytic palladium structure. G. sulfurreducens biofilms have a dense network of pili and extracellular cytochromes capable of high rates of electron transfer directly to an electrode surface. These pili and cytochromes provide a dense number of reduction sites for nanoparticle formation without the need for any synthetic components. The cells within the biofilm also can act as natural agents for preventing agglomeration of nanoparticles, and subsequent decrease of active surface area, on the electrode surface. The cell template was carbonized and removed via thermal treatments, leaving a catalytically active mesoporous palladium structure. The biotemplated mesoporous structure had a high surface area composed of nanoparticles, and a high pore volume and surface area. The biotemplated porous structure also exhibited an increased catalytic activity compared to an electroplated palladium electrode and an electrode coated with synthetically produced palladium nanoparticles attached to the surface with a Nafion binder. The biotemplated mesoporous structure was found to be an alternative process to form a porous structure directly on an electrode using only materials and processes that naturally occur in G. sulfurreducens biofilms. Biotemplated catalytic structures are an alternative method to form a porous structure with high catalytic activity without using any synthetic compounds. However, their uses in large scale processes require that the catalyst layer be durable. The electrochemical and mechanical stability of biotemplated mesoporous structures was tested on different support materials (polished graphite, carbon paper, carbon cloth, and stainless steel) subjected to electrochemical and/or mechanical stress. Carbon paper was found to withstand the most electrochemical and mechanical stress of the four different support materials tested. Polished graphite was able to withstand electrochemical stress, but deteriorated under a combination of electrochemical and mechanical stress. Different readily available and inexpensive polymers (polyaniline and polydimethylsiloxane) were also tested against a widely used polymer (NafionRTM) to stabilize the palladium catalyst on the polished graphite surface. The polyaniline was the most effective binder because it enhanced the catalytic activity and could be electropolymerized around the catalyst, giving the greatest amount of control over the thickness of the polymer layer. The second process studied used exoelectrogenic bacteria in METs for the conversion of electrons to hydrogen via water electrolysis in a biocathodic system. Naturally occurring biocatalytic cell material on the cathode surface was used to lower the cathode overpotential. Different cell cultures ( G. sulfurreducens, Methanosarcina barkeri, and Escherichia coli) were tested for their effect on hydrogen formation using electrons supplied to an insoluble electrode. The mode of hydrogen production was investigated by monitoring hydrogen production over three to five months using G. sulfurreducens biofilms (pregrown under anodic conditions with acetate) that were: (1) not supplied with an organic carbon source for cell growth and maintenance, (2) killed with ethanol, or (3) supplied with lactate, an organic carbon source and electron donor for G. sulfurreducens. Hydrogen was produced at a rate 10--20 times higher over five months in reactors that were either not given organic carbon or killed with ethanol, compared to reactors with lactate added. The methanogen, M. barkeri, was also tested as a biocatalyst because it is able to grow autotrophically. However, M. barkeri cells did not grow in the reactor with the electrode potential poised, based on the lack of evidence for methane production. Despite the lack of cell activity, the rate of hydrogen production with M. barkeri was similar to the rate observed in killed G. sulfurreducens reactors. The addition of E. coli, a non-exoelectrogenic bacteria, resulted in an initial elevated hydrogen gas production, but hydrogen production rates similar to background levels after three months. No cells were detected on the electrode surfaces after five months using scanning electron microscopy and unique metals, such as iron, nickel, cobalt, and zinc, were detected on the electrode surfaces exposed to cells. The identifiable peptides extracted from the electrodes were found to be derived primarily from metalloproteins produced by G. sulfurreducens and M. barkeri cells. These findings show that hydrogen can be produced in a biocathodic system by abiotic cell material attached to a graphite electrode surface and that it does not require electron uptake by living cells.

The Synthesis of Photocatalyst Material ZnO using the Simple Sonication Method

NASA Astrophysics Data System (ADS)

Faradis, R.; Azizah, E. N.; Marella, S. D.; Aini, N.; Prasetyo, A.

2018-03-01

ZnO is well known as photocatalyst material therefore potentially to applied in many purposes. The particle size of photocatalyst material influenced the catalytic activities. In this research, ZnO was synthesized using the simple sonication method to obtain the the smaller particle with sonication time variation respectively: 30, 60, 160, 360 minute. X-ray diffraction data showed that the synthesized material have wurtzite structure with space group P63 mc. The synthesized ZnO with 30 minutes sonication time produced the smallest particle size and have the lowest band gap energy (2.79 eV). The photocatalytic test at methylene blue also showed that the optimum activity was gained from ZnO which synthesized at 30 minute sonication time (degradation percentage of metylene blue is 77.93%).

Discovery of Novel NOx Catalysts for CIDI Applications by High-throughput Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blint, Richard J.

DOE project DE-PS26-00NT40758 has developed very active, lean exhaust, NOx reduction catalysts that have been tested on the discovery system, laboratory reactors and engine dynamometer systems. The goal of this project is the development of effective, affordable NOx reduction catalysts for lean combustion engines in the US light duty vehicle market which can meet Tier II emission standards with hydrocarbons based reductants for reducing NOx. General Motors (prime contractor) along with subcontractors BASF (Engelhard) (a catalytic converter developer) and ACCELRYS (an informatics supplier) carried out this project which began in August of 2002. BASF (Engelhard) has run over 16,000 testsmore » of 6100 possible catalytic materials on a high throughput discovery system suitable for automotive catalytic materials. Accelrys developed a new database informatics system which allowed material tracking and data mining. A program catalyst was identified and evaluated at all levels of the program. Dynamometer evaluations of the program catalyst both with and without additives show 92% NOx conversions on the HWFET, 76% on the US06, 60% on the cold FTP and 65% on the Set 13 heavy duty test using diesel fuel. Conversions of over 92% on the heavy duty FTP using ethanol as a second fluid reductant have been measured. These can be competitive with both of the alternative lean NOx reduction technologies presently in the market. Conversions of about 80% were measured on the EUDC for lean gasoline applications without using active dosing to adjust the C:N ratio for optimum NOx reduction at all points in the certification cycle. A feasibility analysis has been completed and demonstrates the advantages and disadvantages of the technology using these materials compared with other potential technologies. The teaming agreements among the partners contain no obstacles to commercialization of new technologies to any potential catalyst customers.« less

Boosting ORR Catalytic Activity by Integrating Pyridine-N Dopants, a High Degree of Graphitization, and Hierarchical Pores into a MOF-Derived N-Doped Carbon in a Tandem Synthesis.

PubMed

Liu, Dandan; Li, Liangjun; Xu, Huanfei; Dai, Pengcheng; Wang, Ying; Gu, Xin; Yan, Liting; Zhao, Guoming; Zhao, Xuebo

2018-05-18

N-doped carbon materials represent promising metal-free electrocatalysts for the oxygen reduction reaction (ORR), the cathode reaction in fuel cells, metal-air batteries, and so on. A challenge for optimizing the ORR catalytic activities of these electrocatalysts is to tune their local structures and chemical compositions in a rational and controlled way that can achieve the synergistic function of each factor. Herein, we report a tandem synthetic strategy that integrates multiple contributing factors into an N-doped carbon. With an N-containing MOF (ZIF-8) as the precursor, carbonization at higher temperatures leads to a higher degree of graphitization. Subsequent NH 3 etching of this highly graphitic carbon enabled the introduction of a higher content of pyridine-N sites and higher porosity. By optimizing these three factors, the resultant carbon materials displayed ORR activity that was far superior to that of carbon derived from a one-step pyrolysis. The onset potential of 0.955 V versus a reversible hydrogen electrode (RHE) and the half-wave potential of 0.835 V versus RHE are among the top ranks of metal-free ORR catalysts and are comparable to commercial Pt/C (20 wt %) catalysts. Kinetic studies revealed lower H 2 O 2 yields, higher electron-transfer numbers, and lower Tafel slopes for these carbon materials compared with that derived from a one-step carbonization. These findings verify the effectiveness of this tandem synthetic strategy to enhance the ORR activity of N-doped carbon materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Modifications during a Catalytic Reaction: A Combined APT and FIB/SEM Analysis of Surface Segregation

DOE PAGES

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

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

PubMed Central

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

2013-01-01

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

Catalytic behavior of ‘Pt-atomic chain encapsulated gold nanotube’: A density functional study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nigam, Sandeep, E-mail: snigam@barc.gov.in; Majumder, Chiranjib

2016-05-23

With an aim to design novel material and explore its catalytic performance towards CO oxidation, Pt atomic chain was introduced inside gold nanotube (Au-NT). Theoretical calculations at the level of first principles formalism was carried out to investigate the atomic and electronic properties of the composite. Geometrically Pt atoms prefer to align in zig-zag fashion. Significant electronic charge transfer from inside Pt atoms to the outer wall Au atoms is observed. Interaction of O{sub 2} with Au-NT wall follows by injection of additional electronic charge in the anti-bonding orbital of oxygen molecule leading to activation of the O-O bond. Furthermore » interaction of CO molecule with the activated oxygen molecule leads to spontaneous oxidation reaction and formation of CO{sub 2}.« less

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

PubMed

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

2013-05-28

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO4 material phase transformations in direct methanol synthesis from methane

NASA Astrophysics Data System (ADS)

Dasireddy, Venkata D. B. C.; Khan, Faiza B.; Hanzel, Darko; Bharuth-Ram, Krish; Likozar, Blaž

2017-11-01

The effect of the FePO4 material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O2, H2O and N2O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO4 (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe2P2O7, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

Novel Fe-Pd/SiO2 catalytic materials for degradation of chlorinated organic compounds in water

EPA Science Inventory

Novel reactive materials for catalytic degradation of chlorinated organic compounds in water at ambient conditions have been prepared on the basis of silica-supported Pd-Fe nanoparticles. Nanoscale Fe-Pd particles were synthesized inside porous silica supports using (NH₄

Rational design and synthesis of efficient Carbon and/or Silica functional nanomaterials for electrocatalysis and nanomedicine

NASA Astrophysics Data System (ADS)

Da Silva, Rafael

In nanomaterials there is a strong correlation between structure and properties. Thus, the design and synthesis of nanomaterials with well-defined structures and morphology is essential in order to produce materials with not only unique but also tailorable properties. The unique properties of nanomaterials in turn can be taken advantage of to create materials and nanoscale devices that can help address important societal issues, such as meeting renewable energy sources and efficient therapeutic and diagnostic methods to cure a range of diseases. In this thesis, the different synthetic approaches I have developed to produce functional nanomaterials composed of earth-abundant elements (mainly carbon and silica) at low cost in a very sustainable manner are discussed. In Chapter 1, the fundamental properties of nanomaterials and their properties and potential applications in many areas are introduced. In chapter 2, a novel synthetic method that allows polymerization of polyaniline (PANI), a conducting polymer, inside cylindrical channel pores of nanoporous silica (SBA-15) is discussed. In addition, the properties of the III resulting conducting polymer in the confined nanochannel spaces of SBA-15, and more importantly, experimental demonstration of the use of the resulting hybrid material (PANI/SBA-15 material) as electocatalyst for electrooxidation reactions with good overpotential, close to zero, are detailed. In chapter 3, the synthetic approach discussed in Chapter 2 is further extended to afford nitrogen- and oxygen-doped mesoporous carbons. This is possible by pyrolysis of the PANI/SBA-15 composite materials under inert atmosphere, followed by etching away their silica framework. The high catalytic activity of resulting carbon-based materials towards oxygen reduction reaction despite they do not possess any metal dopants is also included. The potential uses of nanomaterials in areas such as nanomedicine need deep understanding of the biocompatibility/ toxicity of the materials. In Chapter 4, comparative in vitro and in vivo assessments of the biological properties and murine lung toxicity (biocompatibility) of the carbon-based nanomaterials synthesized above and in core-shell architectures containing carbon, silica and cobalt is presented. The results indicate that silica shell is essential for biocompatibility. Furthermore, cobalt oxide is the preferred phase over the zero valent Co(0) phase to impart biocompatibility to cobalt-based nanoparticles. This study is a result of collaboration between Asefa's research group at Rutgers University and Souid's research group at United Arab Emirates University. In Chapter 5, a new synthetic method to carbon nanoneedles (or a new class of carbon nanomaterials with high aspect ratios) is presented. In the work, cellulose nanocrystals are prepared and used as precursor for carbon nanostructures. Unlike other types of carbon nanomaterials, carbon IV nanoneedles possess high surface area and large proportion of edge planes, which have outstanding charge transfer and catalytic properties. The resulting metal-free, carbon nanoneedles are shown to serve as effective electrocatalysts for oxidation of hydrazine. In Chapter 6, the synthesis of amorphous carbon nanoneedles containing cobalt and their catalytic activities for oxygen reduction reaction is discussed. Even though the activity of the materials is lower than the one discussed in Chapter 3 for polyaniline-derived mesoporous carbons, the result and discussion in this chapter provides new insights on the effects and advantages of carbon nanoneedles on the electrocatalytic activity of the materials. In addition, the effects of cobalt content and nanoneedles' structures on the catalytic activity of the materials are described. In chapter 7, the synthesis of very small Au nanoparticles within SBA-15 mesoporous silica host materials by galvanic exchange reactions is described. The resulting Au/SBA-15 materials with different size Au nanoparticles are shown to have very interesting surface plasmon resonance (SPR) activity as a result of the confinement of large numbers of Au nanoparticles side-to-side in a row within the cylindrical channel pores of SBA-15 and the many SPR hot spots they formed. The surface enhanced Raman scattering (SERS) property of the materials in form of powder, showing reasonably high SERS enhancement factor for analytes is discussed. Finally in Chapter 8, Conclusions and Future Prospects are discussed.

Physicochemical characteristics and desulphurization activity of pyrolusite-blended activated coke.

PubMed

Yang, Lin; Jiang, Xia; Huang, Tian; Jiang, Wenju

2015-01-01

In this study, a novel activated coke (AC-P) was prepared by the blending method using bituminous coal as the raw material and pyrolusite as the catalyst. The physicochemical properties of prepared activated coke (AC) were characterized by BET, Fourier-Transform Infrared Spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The results indicated that the blended pyrolusite had a slight effect on the structural properties of AC, while the oxygenated functional groups on AC were increased and MnO2 and Fe2O3 in pyrolusite were reduced to MnO and Fe on the AC-P samples, respectively. All the AC-P samples significantly improved the removal of SO2, with the highest sulphur capacity (153 mg/g) for the AC blended with 8 wt% pyrolusite, which was 57.7% higher than that of the blank activated cock. This could be mainly attributed to the change in surface chemical properties of the AC-P samples and the active catalytic components in pyrolusite for the catalytic oxidation of SO2 in desulphurization process.

Enhancing the photocatalytic degradation of Fe-Ti over SiO2 nanocomposite material for paraquat removal

NASA Astrophysics Data System (ADS)

Kruanetr, Senee; Wanchanthuek, Ratchaneekorn

2018-05-01

The effect of Fe and Ti loaded over SiO2 (called FeTi/SiO2) in paraquat degradation was studied for both the catalytic activity and the catalyst surface properties. Sufficient characterization techniques were used to obtain the physical and chemical properties of the FeTi/SiO2 system, such as the adsorption-desorption isotherm, surface area and porous structure, XRD diffraction, FTIR spectroscopy, UV–vis diffuse reflection spectrometry and XPS spectroscopy. The catalytic activity in paraquat degradation studies showed that the bimetallic Fe-Ti over SiO2 had higher activity than the monometallic of either Fe or Ti over SiO2 and also the order of the Fe and Ti loading was the significant parameter affecting the activity. The XPS showed that the level of Fe3+ over the catalyst was related to the obtained activity. Moreover, the optimum Fe:Ti ratio in the FeTi/SiO2 system was 1:1 (by weight). Finally, the effect of the support pretreatment (SiO2 pretreatment) was studied and showed a negative effect on the expressed activity.

Highly active non-PGM catalysts prepared from metal organic frameworks

DOE PAGES

Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; ...

2015-06-11

Finding inexpensive alternatives to platinum group metals (PGMs) is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs). Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/N x/C) prepared from iron doped zeolitic imidazolate frameworks (ZIFs) are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/N x/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR) electrocatalytic activity mustmore » be demonstrated in membrane-electrode assemblies (MEAs) of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.« less

North Carolina Biomolecular Engineering and Materials Applications Center (NC-BEMAC).

DTIC Science & Technology

1987-12-29

enzyme has been replaced with cobalt(II). A further objective was to investigate Co2 activation by low molecular weight transition metal complexes as...Characterization of Low Molecular Weight Metal Complexes as Potential Models for IBio-Catalytic Processes. A number of transit ion met~~il oom~pi cxe; hive...binding, the enzyme suffered loss of activity during radiation polymerization. When covalent binding was u:sed it was necessary to introduce suitably

MEMS-based fuel cells with integrated catalytic fuel processor and method thereof

DOEpatents

Jankowski, Alan F [Livermore, CA; Morse, Jeffrey D [Martinez, CA; Upadhye, Ravindra S [Pleasanton, CA; Havstad, Mark A [Davis, CA

2011-08-09

Described herein is a means to incorporate catalytic materials into the fuel flow field structures of MEMS-based fuel cells, which enable catalytic reforming of a hydrocarbon based fuel, such as methane, methanol, or butane. Methods of fabrication are also disclosed.

Apparatus for the investigation of high-temperature, high-pressure gas-phase heterogeneous catalytic and photo-catalytic materials.

PubMed

Alvino, Jason F; Bennett, Trystan; Kler, Rantej; Hudson, Rohan J; Aupoil, Julien; Nann, Thomas; Golovko, Vladimir B; Andersson, Gunther G; Metha, Gregory F

2017-05-01

A high-temperature, high-pressure, pulsed-gas sampling and detection system has been developed for testing new catalytic and photocatalytic materials for the production of solar fuels. The reactor is fitted with a sapphire window to allow the irradiation of photocatalytic samples from a lamp or solar simulator light source. The reactor has a volume of only 3.80 ml allowing for the investigation of very small quantities of a catalytic material, down to 1 mg. The stainless steel construction allows the cell to be heated to 350 °C and can withstand pressures up to 27 bar, limited only by the sapphire window. High-pressure sampling is made possible by a computer controlled pulsed valve that delivers precise gas flow, enabling catalytic reactions to be monitored across a wide range of pressures. A residual gas analyser mass spectrometer forms a part of the detection system, which is able to provide a rapid, real-time analysis of the gas composition within the photocatalytic reaction chamber. This apparatus is ideal for investigating a number of industrially relevant reactions including photocatalytic water splitting and CO 2 reduction. Initial catalytic results using Pt-doped and Ru nanoparticle-doped TiO 2 as benchmark experiments are presented.

Influence of the interfacial peptide organization on the catalysis of hydrogen evolution.

PubMed

Doneux, Th; Dorcák, V; Palecek, E

2010-01-19

The hydrogen evolution reaction is catalyzed by peptides and proteins adsorbed on electrode materials with high overpotentials for this reaction, such as mercury. The catalytic response characteristics are known to be very sensitive to the composition and structure of the investigated biomolecule, opening the way to the implementation of a label-free, reagentless electroanalytical method in protein analysis. Herein, it is shown using the model peptide Cys-Ala-Ala-Ala-Ala-Ala that the interfacial organization significantly influences the catalytic behavior. This peptide forms at the electrode two distinct films, depending on the concentration and accumulation time. The low-coverage film, composed of flat-lying molecules (area per molecule of approximately 250-290 A(2)), yields a well-defined catalytic peak at potentials around -1.75 V. The high-coverage film, made of upright-oriented peptides (area per molecule of approximately 43 A(2)), is catalytically more active and the peak is observed at potentials less negative by approximately 0.4 V. The higher activity, evidenced by constant-current chronopotentiometry and cyclic voltammetry, is attributed to an increase in the acid dissociation constant of the amino acid residues as a result of the low permittivity of the interfacial region, as inferred from impedance measurements. An analogy is made to the known differences in acidic-basic behaviors of solvent-exposed and hydrophobic domains of proteins.

Effects of copper-precursors on the catalytic activity of Cu/graphene catalysts for the selective catalytic oxidation of ammonia

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.

Defects Engineered Monolayer MoS 2 for Improved Hydrogen Evolution Reaction

DOE PAGES

Ye, Gonglan; Gong, Yongji; Lin, Junhao; ...

2016-01-13

MoS 2 is a promising, low-cost material for electrochemical hydrogen production due to its high activity and stability during the reaction. Our work represents an easy method to increase the hydrogen production in electrochemical reaction of MoS 2 via defect engineering, and helps to understand the catalytic properties of MoS 2.

Regulation of Catalytic and Non-catalytic Functions of the Drosophila Ste20 Kinase Slik by Activation Segment Phosphorylation.

PubMed

Panneton, Vincent; Nath, Apurba; Sader, Fadi; Delaunay, Nathalie; Pelletier, Ariane; Maier, Dominic; Oh, Karen; Hipfner, David R

2015-08-21

Protein kinases carry out important functions in cells both by phosphorylating substrates and by means of regulated non-catalytic activities. Such non-catalytic functions have been ascribed to many kinases, including some members of the Ste20 family. The Drosophila Ste20 kinase Slik phosphorylates and activates Moesin in developing epithelial tissues to promote epithelial tissue integrity. It also functions non-catalytically to promote epithelial cell proliferation and tissue growth. We carried out a structure-function analysis to determine how these two distinct activities of Slik are controlled. We find that the conserved C-terminal coiled-coil domain of Slik, which is necessary and sufficient for apical localization of the kinase in epithelial cells, is not required for Moesin phosphorylation but is critical for the growth-promoting function of Slik. Slik is auto- and trans-phosphorylated in vivo. Phosphorylation of at least two of three conserved sites in the activation segment is required for both efficient catalytic activity and non-catalytic signaling. Slik function is thus dependent upon proper localization of the kinase via the C-terminal coiled-coil domain and activation via activation segment phosphorylation, which enhances both phosphorylation of substrates like Moesin and engagement of effectors of its non-catalytic growth-promoting activity. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Analysis of in vitro evolution reveals the underlying distribution of catalytic activity among random sequences.

PubMed

Pressman, Abe; Moretti, Janina E; Campbell, Gregory W; Müller, Ulrich F; Chen, Irene A

2017-08-21

The emergence of catalytic RNA is believed to have been a key event during the origin of life. Understanding how catalytic activity is distributed across random sequences is fundamental to estimating the probability that catalytic sequences would emerge. Here, we analyze the in vitro evolution of triphosphorylating ribozymes and translate their fitnesses into absolute estimates of catalytic activity for hundreds of ribozyme families. The analysis efficiently identified highly active ribozymes and estimated catalytic activity with good accuracy. The evolutionary dynamics follow Fisher's Fundamental Theorem of Natural Selection and a corollary, permitting retrospective inference of the distribution of fitness and activity in the random sequence pool for the first time. The frequency distribution of rate constants appears to be log-normal, with a surprisingly steep dropoff at higher activity, consistent with a mechanism for the emergence of activity as the product of many independent contributions. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Facile construction of vertically aligned EuS-ZnO hybrid core shell nanorod arrays for visible light driven photocatalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ranjith, K. S.; Kumar, D. Ranjith; Kumar, R. T. Rajendra, E-mail: rtrkumar@buc.edu.in

2015-06-24

We demonstrated the development of coupled semiconductor in the form of hybrid heterostructures for significant advancement in catalytic functional materials. In this article, we report the preparation of vertically aligned core shell ZnO-EuS nanorod photocatalyst arrays by a simple chemical solution process followed by sulfudation process. The XRD pattern confirmed formation of the hexagonal wurtzite structure of ZnO and cubic nature of the EuS. Cross sectional FESEM images show vertical rod array structure, and the size of the nanorods ranges from 80 to 120 nm. UV-Vis DRS spectra showed that the optical absorption of ZnO was significantly enhanced to the visiblemore » region by modification with EuS surfaces. TEM study confirmed that the surface of ZnO was drastically improved by the modification with EuS nanoparticle. The catalytic activity of EuS−ZnO core shell nanorod arrays were evaluated by the photodegradation of Methylene Blue (MB) dye under visible irradiation. The results revealed that the photocatalytic activity of EuS−ZnO was much higher than that of ZnO under natural sunlight. EuS−ZnO was found to be stable and reusable without appreciable loss of catalytic activity up to four consecutive cycles.« less

Submicron sized water-stable metal organic framework (bio-MOF-11) for catalytic degradation of pharmaceuticals and personal care products.

PubMed

Azhar, Muhammad Rizwan; Vijay, Periasamy; Tadé, Moses O; Sun, Hongqi; Wang, Shaobin

2018-04-01

Water-stable and active metal organic frameworks (MOFs) are important materials for mitigation of water contaminants via adsorption and catalytic reactions. In this study, a highly water-stable Co-based MOF, namely bio-MOF-11-Co, was synthesized by a simplified benign method. Moreover, it was used as a catalyst in successful activation of peroxymonsulfate for catalytic degradation of sulfachloropyradazine (SCP) and para-hydroxybenzoic acid (p-HBA) as representatives of pharmaceuticals and personal care products, respectively. The bio-MOF-11-Co showed rapid degradation of both p-HBA and SCP and could be reused multiple times without losing the activity by simply water washing. The effects of catalyst and PMS loadings as well as temperature were further studied, showing that high catalyst and PMS loadings as well as temperature produced faster kinetic degradation of p-HBA and SCP. The generation of highly reactive and HO radicals during the degradation was investigated by quenching tests and electron paramagnetic resonance. A plausible degradation mechanism was proposed based on the functionalities in the bio-MOF-11-Co. The availability of electron rich nucleobase adenine reinforced the reaction kinetics by electron donation along with cobalt atoms in the bio-MOF-11-Co structure. Copyright © 2017 Elsevier Ltd. All rights reserved.

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna-Reactor Plasmonic Photocatalysis.

PubMed

Li, Kun; Hogan, Nathaniel J; Kale, Matthew J; Halas, Naomi J; Nordlander, Peter; Christopher, Phillip

2017-06-14

Efficient photocatalysis requires multifunctional materials that absorb photons and generate energetic charge carriers at catalytic active sites to facilitate a desired chemical reaction. Antenna-reactor complexes are an emerging multifunctional photocatalytic structure where the strong, localized near field of the plasmonic metal nanoparticle (e.g., Ag) is coupled to the catalytic properties of the nonplasmonic metal nanoparticle (e.g., Pt) to enable chemical transformations. With an eye toward sustainable solar driven photocatalysis, we investigate how the structure of antenna-reactor complexes governs their photocatalytic activity in the light-limited regime, where all photons need to be effectively utilized. By synthesizing core@shell/satellite (Ag@SiO 2 /Pt) antenna-reactor complexes with varying Ag nanoparticle diameters and performing photocatalytic CO oxidation, we observed plasmon-enhanced photocatalysis only for antenna-reactor complexes with antenna components of intermediate sizes (25 and 50 nm). Optimal photocatalytic performance was shown to be determined by a balance between maximized local field enhancements at the catalytically active Pt surface, minimized collective scattering of photons out of the catalyst bed by the complexes, and minimal light absorption in the Ag nanoparticle antenna. These results elucidate the critical aspects of local field enhancement, light scattering, and absorption in plasmonic photocatalyst design, especially under light-limited illumination conditions.

Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

PubMed

Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

2013-08-20

Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is a standard catalyst for reactions such as CO oxidation and the water-gas shift (WGS). This metal serves as an ideal replacement for other noble metals that are neither abundant nor cost effective. To prepare the inverse system we deposited nanoparticles (2-20 nm) of cerium oxide onto the Cu(111) surface. During this process, the Cu(111) surface grows an oxide layer that is characteristic of Cu₂O (Cu¹⁺). This oxide can influence the growth of ceria nanoparticles. Evidence suggests triangular-shaped CeO₂(111) grows on Cu₂O(111) surfaces while rectangular CeO₂(100) grows on Cu₄O₃(111) surfaces. We used the CeOx/Cu₂O/Cu(111) inverse system to study two catalytic processes: the WGS (CO + H₂O → CO₂ + H₂) and CO oxidation (2CO + O₂ → 2CO₂). We discovered that the addition of small amounts of ceria nanoparticles can activate the Cu(111) surface and achieve remarkable enhancement of catalytic activity in the investigated reactions. In the case of the WGS, the CeOx nanoparticle facilitated this process by acting at the interface with Cu to dissociate water. In the CO oxidation case, an enhancement in the dissociation of O₂ by the nanoparticles was a key factor. The strong interaction between CeOx nanoparticles and Cu(111) when preoxidized and reduced in CO resulted in a massive surface reconstruction of the copper substrate with the introduction of microterraces that covered 25-35% of the surface. This constitutes a new mechanism for surface reconstruction not observed before. These microterraces helped to facilitate a further enhancement of activity towards the WGS by opening an additional channel for the dissociation of water. In summary, inverse catalysts of CeOx/Cu(111) and CeO₂/Cu₂O/Cu(111) demonstrate the versatility of a model system to obtain insightful knowledge of catalytic processes. These systems will continue to offer a unique opportunity to probe key catalytic components and elucidate the relationship between structure and reactivity of novel materials and reactions in the future.

Vanadium Oxide Deposited on Strontium Titanate and Related Supports: Structural, Redox, and Catalytic Properties in Oxidative Dehydrogenation Reactions

NASA Astrophysics Data System (ADS)

McCarthy, James A.

The field of heterogeneous catalysis has advanced largely through the understanding of structure-function relationships, and novel support materials constitute one possible strategy to further this knowledge through the determination of support effects. To this end, the synthesis, characterization, and reactivity of a new catalytic system are reported herein. Vanadium oxide supported on SrTiO3 (VOx/STO) was prepared by atomic layer deposition, and its activity was investigated in various oxidative dehydrogenation (ODH) reactions. In cyclohexane and propane ODH experiments at 500 °C, selectivity toward COx was found to decrease with greater VOx density and minimal STO surface exposure. This indicates that the support itself is an effective total oxidation catalyst, which complicates VOx performance measurements. In the propane studies, VOx/STO achieved lower turnover frequency (TOF) and propylene yield compared to conventional supported VO x materials. The lower activity of VOx/STO catalysts was correlated with their VOx species being less easily reducible, as determined by temperature-programmed reduction (TPR). The suppressed reducibility is attributed to the stronger surface basicity of STO, which is induced by the presence of relatively electropositive Sr2+ within the perovskite lattice. Studies of cyclohexene ODH at 300 °C were conducted to minimize intrinsic conversion from the supports. The VOx/STO catalysts were mostly found to be less active than VOx/TiO2 and VOx/Al 2O3, in accordance with reducibility measurements. However, one sample containing 0.75% vanadium on STO was particularly active, achieving a TOF greater than 0.01 s-1, while maintaining almost 90% dehydrogenation selectivity. In general, VOx/STO materials were found to be more selective for 1,3-cyclohexadiene compared to traditional catalysts. Other titanates of the form A2+TiO3 were also investigated as supports, and the reducibility of VOx was found to trend with the electronegativity of the A-site cation and the basicity of the titanate. When applied to cyclohexene ODH however, no discernable relationship between reducibility and TOF could be observed, implying that other factors play a major role in this reaction. Through this work, a deeper understanding has been developed concerning the impact of titanate supports on VOx redox and catalytic properties. These findings demonstrate the ability of novel support materials to reveal new insights into structure-function relationships.

ROLE OF TUNGSTEN IN THE AQUEOUS PHASE HYDRODEOXYGENATION OF ETHYLENE GLYCOL ON TUNGSTATED ZIRCONIA SUPPORTED PALLADIUM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marin-Flores, Oscar G.; Karim, Ayman M.; Wang, Yong

2014-11-15

The focus of the present work was specifically on the elucidation of the role played by tungsten on the catalytic activity and selectivity of tungstated zirconia supported palladium (Pd-mWZ) for the aqueous phase hydrodeoxygenation (APHDO) of ethylene glycol (EG). Zirconia supported palladium (Pd-mZ) was used as reference. The catalysts were prepared via incipient wet impregnation and characterized using X-ray diffraction (XRD), temperature-programmed reduction (TPR), CO pulse chemisorption, CO-DRIFTS, ammonia temperature-programmed desorption (NH3-TPD) and pyridine adsorption. The presence of W results in larger Pd particles on supported Pd catalysts, i.e., 0.9 and 6.1 nm Pd particles are for Pd-mZ and Pd-mWZ,more » respectively. For comparison purposes, the activity of the catalytic materials used in this work was obtained using a well-defined set of operating conditions. The catalytic activity measurements show that the overall intrinsic activity of Pd particles on mWZ is 1.9 times higher than on mZ. APHDO process appears to be highly favored on Pd-mWZ whereas Pd-mZ exhibits a higher selectivity for reforming. This difference in terms of selectivity seems to be related to the high concentration of Brønsted acid sites and electron-deficient Pd species present on Pd-mWZ.« less

Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)-Oxo Sites in Magnesium-Diluted Fe2(dobdc).

PubMed

Verma, Pragya; Vogiatzis, Konstantinos D; Planas, Nora; Borycz, Joshua; Xiao, Dianne J; Long, Jeffrey R; Gagliardi, Laura; Truhlar, Donald G

2015-05-06

The catalytic properties of the metal-organic framework Fe2(dobdc), containing open Fe(II) sites, include hydroxylation of phenol by pure Fe2(dobdc) and hydroxylation of ethane by its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc). In earlier work, the latter reaction was proposed to occur through a redox mechanism involving the generation of an iron(IV)-oxo species, which is an intermediate that is also observed or postulated (depending on the case) in some heme and nonheme enzymes and their model complexes. In the present work, we present a detailed mechanism by which the catalytic material, Fe0.1Mg1.9(dobdc), activates the strong C-H bonds of ethane. Kohn-Sham density functional and multireference wave function calculations have been performed to characterize the electronic structure of key species. We show that the catalytic nonheme-Fe hydroxylation of the strong C-H bond of ethane proceeds by a quintet single-state σ-attack pathway after the formation of highly reactive iron-oxo intermediate. The mechanistic pathway involves three key transition states, with the highest activation barrier for the transfer of oxygen from N2O to the Fe(II) center. The uncatalyzed reaction, where nitrous oxide directly oxidizes ethane to ethanol is found to have an activation barrier of 280 kJ/mol, in contrast to 82 kJ/mol for the slowest step in the iron(IV)-oxo catalytic mechanism. The energetics of the C-H bond activation steps of ethane and methane are also compared. Dehydrogenation and dissociation pathways that can compete with the formation of ethanol were shown to involve higher barriers than the hydroxylation pathway.

Interplay between the spin-selection rule and frontier orbital theory in O2 activation and CO oxidation by single-atom-sized catalysts on TiO2(110).

PubMed

Li, Shunfang; Zhao, Xingju; Shi, Jinlei; Jia, Yu; Guo, Zhengxiao; Cho, Jun-Hyung; Gao, Yanfei; Zhang, Zhenyu

2016-09-28

Exploration of the catalytic activity of low-dimensional transition metal (TM) or noble metal catalysts is a vital subject of modern materials science because of their instrumental role in numerous industrial applications. Recent experimental advances have demonstrated the utilization of single atoms on different substrates as effective catalysts, which exhibit amazing catalytic properties such as more efficient catalytic performance and higher selectivity in chemical reactions as compared to their nanostructured counterparts; however, the underlying microscopic mechanisms operative in these single atom catalysts still remain elusive. Based on first-principles calculations, herein, we present a comparative study of the key kinetic rate processes involved in CO oxidation using a monomer or dimer of two representative TMs (Pd and Ni) on defective TiO2(110) substrates (TMn@TiO2(110), n = 1, 2) to elucidate the underlying mechanism of single-atom catalysis. We reveal that the O2 activation rates of the single atom TM catalysts deposited on TiO2(110) are governed cooperatively by the classic spin-selection rule and the well-known frontier orbital theory (or generalized d-band picture) that emphasizes the energy gap between the frontier orbitals of the TM catalysts and O2 molecule. We further illuminate that the subsequent CO oxidation reactions proceed via the Langmuir-Hinshelwood mechanism with contrasting reaction barriers for the Pd monomer and dimer catalysts. These findings not only provide an explanation for existing observations of distinctly different catalytic activities of Pd@TiO2(110) and Pd2@TiO2(110) [Kaden et al., Science, 2009, 326, 826-829] but also shed new insights into future utilization and optimization of single-atom catalysis.

Bi2S3microspheres grown on graphene sheets as low-cost counter-electrode materials for dye-sensitized solar cells.

PubMed

Li, Guang; Chen, Xiaoshuang; Gao, Guandao

2014-03-21

In this work, we synthesized 3D Bi2S3 microspheres comprised of nanorods grown along the (211) facet on graphene sheets by a solvothermal route, and investigated its catalytic activities through I-V curves and conversion efficiency tests as the CE in DSSCs. Although the (211) facet has a large band gap for a Bi2S3 semiconductor, owing to the introduction of graphene into the system, its short-circuit current density, open-circuit voltage, fill factor, and efficiency were Jsc = 12.2 mA cm(-2), Voc = 0.75 V, FF = 0.60, and η = 5.5%, respectively. By integrating it with graphene sheets, our material achieved the conversion efficiency of 5.5%, which is almost triple the best conversion efficiency value of the DSSCs with (211)-faceted 3D Bi2S3 without graphene (1.9%) reported in the latest literature. Since this conversion-efficient 3D material grown on the graphene sheets significantly improves its catalytic properties, it paves the way for designing and applying low-cost Pt-free CE materials in DSSC from inorganic nanostructures.

Catalytic thermal barrier coatings

DOEpatents

Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh

2009-06-02

A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammells, Anthony F.

2005-09-27

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammels, Anthony F.

2000-01-01

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

Preparation, characterization and catalytic application of CoFe2O4 nanoparticles in the synthesis of benzimidazoles

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.

Catalytic synthesis of ammonia-a "never-ending story"?

PubMed

Schlögl, Robert

2003-05-09

Nitrogen atoms are essential for the function of biological molecules and thus are and important component of fertilizers and medicaments. Bonds to nitrogen also find nonbiological uses in dyes, explosives, and resins. The synthesis of all these materials requires ammonia as an activated nitrogen building block. This situation is true for natural processes and the chemical industry. Knowledge of the various techniques for the preparation of ammonia is thus of fundamental importance for chemistry. The Haber-Bosch synthesis was the first heterogeneous catalytic system employed in the chemical industry and is still in use today. Understanding the mechanism and the translation of the knowledge into technical perfection has become a fundamental criterion for scientific development in catalysis research.

Catalytic hollow spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1989-01-01

The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Catalytic hollow spheres

NASA Technical Reports Server (NTRS)

Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

1986-01-01

The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation

PubMed Central

2011-01-01

Highly dispersed cobalt-silicon mixed oxide [Co-SiO2] nanosphere was successfully prepared with a modified reverse-phase microemulsion method. This material was characterized in detail by X-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance spectra, X-ray absorption spectroscopy near-edge structure, and N2 adsorption-desorption measurements. High valence state cobalt could be easily obtained without calcination, which is fascinating for the catalytic application for its strong oxidation ability. In the selective oxidation of cyclohexane, Co-SiO2 acted as an efficient catalyst, and good activity could be obtained under mild conditions. PMID:22067075

Photochemical Water Oxidation Using {PMo12O40@Mo72Fe30}n Based Soft Oxometalate

NASA Astrophysics Data System (ADS)

Das, Santu; Roy, Soumyajit

Finding an alternative energy resource which can produce clean energy at a low cost is one of the major concerns of our times. The conversion of light energy into chemical energy is one key step forward in the direction. With that end in view photochemical water oxidation to produce oxygen plays a crucial role. In the present paper we have synthesized a soft oxometalate {PMo12O40@Mo72Fe30}n(1) from its well-known precursor polyoxometalate constituent [Muller et al., Chem. Commun. 1, 657 (2001)]. It is known that in the matter of catalysis, high surface area, possibility of heterogenization, recoverability makes soft oxometalates (SOMs) attractive as catalytic materials. Here we exploit such advantages of SOMs. The SOM based material acts as an active catalyst for photochemical water oxidation reaction with a maximum turnover number of 20256 and turnover frequency of 24.11min-1. The catalyst material is stable under photochemical reaction conditions and therefore can be reused for multiple photo catalytic water oxidation reaction cycles.

Inclusion of Ti and Zr species on clay surfaces and their effect on the interaction with organic molecules

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.

Transition-metal-free catalysts for the sustainable epoxidation of alkenes: from discovery to optimisation by means of high throughput experimentation.

PubMed

Lueangchaichaweng, Warunee; Geukens, Inge; Peeters, Annelies; Jarry, Benjamin; Launay, Franck; Bonardet, Jean-Luc; Jacobs, Pierre A; Pescarmona, Paolo P

2012-02-01

Transition-metal-free oxides were studied as heterogeneous catalysts for the sustainable epoxidation of alkenes with aqueous H₂O₂ by means of high throughput experimentation (HTE) techniques. A full-factorial HTE approach was applied in the various stages of the development of the catalysts: the synthesis of the materials, their screening as heterogeneous catalysts in liquid-phase epoxidation and the optimisation of the reaction conditions. Initially, the chemical composition of transition-metal-free oxides was screened, leading to the discovery of gallium oxide as a novel, active and selective epoxidation catalyst. On the basis of these results, the research line was continued with the study of structured porous aluminosilicates, gallosilicates and silica-gallia composites. In general, the gallium-based materials showed the best catalytic performances. This family of materials represents a promising class of heterogeneous catalysts for the sustainable epoxidation of alkenes and offers a valid alternative to the transition-metal heterogeneous catalysts commonly used in epoxidation. High throughput experimentation played an important role in promoting the development of these catalytic systems.

A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide

PubMed Central

Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush

2018-01-01

Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil–5 (ZSM-5), TiO2, and Al2O3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir–Hinshelwood or Eley–Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH3 catalyst are suggested. PMID:29600136

A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide.

PubMed

Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush; Mohamed, Abdul Rahman Bin

2018-01-01

Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil-5 (ZSM-5), TiO 2 , and Al 2 O 3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir-Hinshelwood or Eley-Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH 3 catalyst are suggested.

Synthesis and study of electrolytic materials with a high-energy defect structure and a developed surface

NASA Astrophysics Data System (ADS)

Gryzunova, N. N.; Vikarchuk, A. A.; Tyur'kov, M. N.

2016-10-01

The defect structure of the electrolytic copper coatings formed upon mechanical activation of a cathode is described. These coatings are shown to have a fragmented structure containing disclination-type defects, namely, terminating dislocation, disclination and twin boundaries; partial disclinations, misorientation bands; and twin layers. They have both growth and deformation origins. The mechanisms of formation of the structural defects are discussed. It is experimentally proved that part of the elastic energy stored in the crystal volume during electrocrystallization can be converted into surface energy. As a result, catalytically active materials with a large developed surface can be synthesized.

Surface Structure Dependent Electrocatalytic Activity of Co3O4 Anchored on Graphene Sheets toward Oxygen Reduction Reaction

PubMed Central

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

Optimal levels of oxygen deficiency in the visible light photocatalyst TiO2-x and long-term stability of catalytic performance

NASA Astrophysics Data System (ADS)

Nakano, Takuma; Ito, Ryosuke; Kogoshi, Sumio; Katayama, Noboru

2016-11-01

The dependence of the visible light-responsive photocatalytic activity of oxygen deficient TiO2 (TiO2-x) prepared by Ar/H2 plasma surface treatment on the degree of oxygen deficiency (x) was assessed to determine the deficiency region associated with highest performance. The highest activity was obtained at x=0.06 (TiO1.94). The maximum visible light activity for this material, estimated from the formaldehyde (HCHO) removal rate, was three times higher than that exhibited by nitrogen-doped TiO2 (TiO2-xNx). The catalytic ability was found to decrease over the first week after fabrication of the material, after which it became stable, and the performance of TiO2-x at this point was found to be nearly equal to that of TiO2-xNx. The results of ab initio calculations of density of states for TiO2-x suggest that new oxygen deficiency states emerge at almost the exact center between the valence and conduction bands when x>0.06, which increases the recombination rate between electrons and holes. Therefore the declining performance of TiO2-x at larger x values is attributed to the emergence of new oxygen deficient states.

Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmed, Nesreen S.; Surface Chemistry and Catalytic Studies Group, King Abdulaziz University; Menzel, Robert

Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%,more » respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH. - Graphical abstract: CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary, two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. - Highlights: • CuAl LDH/GO and CoAl LDH/GO hybrid materials with different LDH compositions were prepared. • Hybrids were fully characterised and their catalytic efficiency over the Classic Ullman Reaction was studied. • CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) in 25 min reaction times. • GO provides a light-weight, charge complementary, two-dimensional material that interacts effectively with the 2D LDHs. • After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.« less

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.

Rational approach to polymer-supported catalysts: synergy between catalytic reaction mechanism and polymer design.

PubMed

Madhavan, Nandita; Jones, Christopher W; Weck, Marcus

2008-09-01

Supported catalysis is emerging as a cornerstone of transition metal catalysis, as environmental awareness necessitates "green" methodologies and transition metal resources become scarcer and more expensive. Although these supported systems are quite useful, especially in their capacity for transition metal catalyst recycling and recovery, higher activity and selectivity have been elusive compared with nonsupported catalysts. This Account describes recent developments in polymer-supported metal-salen complexes, which often surpass nonsupported analogues in catalytic activity and selectivity, demonstrating the effectiveness of a systematic, logical approach to designing supported catalysts from a detailed understanding of the catalytic reaction mechanism. Over the past few decades, a large number of transition metal complex catalysts have been supported on a variety of materials ranging from polymers to mesoporous silica. In particular, soluble polymer supports are advantageous because of the development of controlled and living polymerization methods that are tolerant to a wide variety of functional groups, including controlled radical polymerizations and ring-opening metathesis polymerization. These methods allow for tuning the density and structure of the catalyst sites along the polymer chain, thereby enabling the development of structure-property relationships between a catalyst and its polymer support. The fine-tuning of the catalyst-support interface, in combination with a detailed understanding of catalytic reaction mechanisms, not only permits the generation of reusable and recyclable polymer-supported catalysts but also facilitates the design and realization of supported catalysts that are significantly more active and selective than their nonsupported counterparts. These superior supported catalysts are accessible through the optimization of four basic variables in their design: (i) polymer backbone rigidity, (ii) the nature of the linker, (iii) catalyst site density, and (iv) the nature of the catalyst attachment. Herein, we describe the design of polymer supports tuned to enhance the catalytic activity or decrease, or even eliminate, decomposition pathways of salen-based transition metal catalysts that follow either a monometallic or a bimetallic reaction mechanism. These findings result in the creation of some of the most active and selective salen catalysts in the literature.

Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution

NASA Astrophysics Data System (ADS)

Liu, Yuanyue; Wu, Jingjie; Hackenberg, Ken P.; Zhang, Jing; Wang, Y. Morris; Yang, Yingchao; Keyshar, Kunttal; Gu, Jing; Ogitsu, Tadashi; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M.; Wood, Brandon C.; Yakobson, Boris I.

2017-09-01

Low-cost, layered transition-metal dichalcogenides (MX2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. The catalysts reach 10 mA cm-2 current density at an overpotential of ˜50-60 mV with a loading of 10-55 μg cm-2, surpassing other reported MX2 candidates without any performance-enhancing additives.

Synthesis of hierarchical Co3O4@NiO core-shell nanotubes with a synergistic catalytic activity for peroxidase mimicking and colorimetric detection of dopamine.

PubMed

Zhu, Yun; Yang, Zezhou; Chi, Maoqiang; Li, Meixuan; Wang, Ce; Lu, Xiaofeng

2018-05-01

Fabrication of core-shell nanostructured catalyst is a promising way for tuning its catalytic performance due to the highly active interface and rich redox properties. In this work, hierarchical Co 3 O 4 @NiO core-shell nanotubes are fabricated by the deposition of NiO shells via a chemical bath treatment using electrospun Co-C composite nanofibers as templates, followed by a calcination process in air. The as-prepared Co 3 O 4 @NiO core-shell nanotubes exhibit a uniform and novel hollow structure with Co 3 O 4 nanoparticles attached to the inner wall of NiO nanotubes and excellent catalytic activity toward the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H 2 O 2 . Due to the synergistic effect, the peroxidase-like activity of the Co 3 O 4 @NiO core-shell nanotubes is much higher than that of individual Co 3 O 4 and NiO components. Owing to the superior peroxidase-like activity, a simple and rapid colorimetric approach for the detection of dopamine with a detection limit of 1.21µM and excellent selectivity has been developed. It is anticipated that the prepared Co 3 O 4 @NiO core-shell nanotubes are promising materials applied for biomedical analysis and environmental monitoring. Copyright © 2018 Elsevier B.V. All rights reserved.

Organoelement chemistry: promising growth areas and challenges

NASA Astrophysics Data System (ADS)

Abakumov, G. A.; Piskunov, A. V.; Cherkasov, V. K.; Fedushkin, I. L.; Ananikov, V. P.; Eremin, D. B.; Gordeev, E. G.; Beletskaya, I. P.; Averin, A. D.; Bochkarev, M. N.; Trifonov, A. A.; Dzhemilev, U. M.; D'yakonov, V. A.; Egorov, M. P.; Vereshchagin, A. N.; Syroeshkin, M. A.; Jouikov, V. V.; Muzafarov, A. M.; Anisimov, A. A.; Arzumanyan, A. V.; Kononevich, Yu N.; Temnikov, M. N.; Sinyashin, O. G.; Budnikova, Yu H.; Burilov, A. R.; Karasik, A. A.; Mironov, V. F.; Storozhenko, P. A.; Shcherbakova, G. I.; Trofimov, B. A.; Amosova, S. V.; Gusarova, N. K.; Potapov, V. A.; Shur, V. B.; Burlakov, V. V.; Bogdanov, V. S.; Andreev, M. V.

2018-05-01

The chemistry of organoelement compounds is now one of the most rapidly developing fields of research, regarding both fundamental science and solution of applied problems. This review covers a variety of classes of organoelement compounds, ranging from molecules with highly labile carbon–element bonds to compounds with stable bonds that form the basis of novel structural materials and demonstrates their role in scientific research and industrial production. The use of Grignard reagents in modern organic synthesis and application of catalytic cyclomagnesiation and cycloalumination reactions for the preparation of difficult-to-access metallacycles are considered. The electron transfer processes in redox-active derivatives of Group 14 elements and the role of radical ions in these processes are discussed. Considerable attention is paid to organometallic compounds, first of all, as catalysts; the dynamic nature of catalysis with these compounds is noted. Unusual strained metallacycles of high thermal stability, zirconacyclocumulenes, which also exhibit catalytic activity, are described. Complexes with redox-active ligands that substantially affect the reactivity of the metal centre and directly participate in reactions with various substrates as well as organometallic compounds of lanthanides are considered. Modern environmentally benign methods for the synthesis of organosilicon compounds and production of unique materials based on them are discussed. Particular Sections are devoted to organophosphorus compounds, including those exhibiting therapeutic properties and possessing unusual optical characteristics, and organic chalcogen compounds, which find use as ligands and biologically active molecules. The bibliography includes 1045 references.

Textile/metal-organic-framework composites as self-detoxifying filters for chemical-warfare agents.

PubMed

López-Maya, Elena; Montoro, Carmen; Rodríguez-Albelo, L Marleny; Aznar Cervantes, Salvador D; Lozano-Pérez, A Abel; Cenís, José Luis; Barea, Elisa; Navarro, Jorge A R

2015-06-01

The current technology of air-filtration materials for protection against highly toxic chemicals, that is, chemical-warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self-cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal-organic framework (MOF) materials to develop advanced self-detoxifying adsorbents of chemical-warfare agents containing hydrolysable P-F, P-O, and C-Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air-permeation properties of the textiles with the self-detoxifying properties of the MOF material. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Covalent triazine framework supported non-noble metal nanoparticles with superior activity for catalytic hydrolysis of ammonia borane: from mechanistic study to catalyst design† †Electronic supplementary information (ESI) available: 11B NMR spectra, XRD patterns, results of BET and ICP, XPS spectra, TOF values and activation energies E a of the non-noble metal catalysts, time versus volume of H2, catalytic activities and TEM images of 5% Co/CNT, 3% Co/CNT, 1% Co/CNT, the plot of hydrogen generation rate versus the concentration of Co and AB, kinetic isotope effect and TEM image of 5% Co/CTF-1 after reaction. See DOI: 10.1039/c6sc02456d Click here for additional data file.

PubMed Central

Li, Zhao; Liu, Lin; Chen, Weidong; Zhang, Miao; Wu, Guotao; Chen, Ping

2017-01-01

Development of non-noble metal catalysts with similar activity and stability to noble metals is of significant importance in the conversion and utilization of clean energy. The catalytic hydrolysis of ammonia borane (AB) to produce 3 equiv. of H2, as an example of where noble metal catalysts significantly outperform their non-noble peers, serves as an excellent test site for the design and optimization of non-noble metal catalysts. Our kinetic isotopic effect measurements reveal, for the first time, that the kinetic key step of the hydrolysis is the activation of H2O. Deducibly, a transition metal with an optimal electronic structure that bonds H2O and –OH in intermediate strengths would favor the hydrolysis of AB. By employing a covalent triazine framework (CTF), a newly developed porous material capable of donating electrons through the lone pairs on N, the electron densities of nano-sized Co and Ni supported on CTF are markedly increased, as well as their catalytic activities. Specifically, Co/CTF exhibits a total turnover frequency of 42.3 molH2 molCo –1 min–1 at room temperature, which is superior to all peer non-noble metal catalysts ever reported and even comparable to some noble metal catalysts. PMID:28451227

Perspective: Size selected clusters for catalysis and electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halder, Avik; Curtiss, Larry A.; Fortunelli, Alessandro

We report that size-selected clusters containing a handful of atoms may possess noble catalytic properties different from nano-sized or bulk catalysts. Size- and composition-selected clusters can also serve as models of the catalytic active site, where an addition or removal of a single atom can have a dramatic effect on their activity and selectivity. In this Perspective, we provide an overview of studies performed under both ultra-high vacuum and realistic reaction conditions aimed at the interrogation, characterization and understanding of the performance of supported size-selected clusters in heterogeneous and electrochemical reactions, which address the effects of cluster size, cluster composition,more » cluster-support interactions and reaction conditions, the key parameters for the understanding and control of catalyst functionality. Computational modelling based on density functional theory sampling of local minima and energy barriers or ab initio Molecular Dynamics simulations is an integral part of this research by providing fundamental understanding of the catalytic processes at the atomic level, as well as by predicting new materials compositions which can be validated in experiments. Lastly, we discuss approaches which aim at the scale up of the production of well-defined clusters for use in real world applications.« less

Selective hydrogenation of phenol to cyclohexanone over Pd@CN (N-doped porous carbon): Role of catalyst reduction method

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.

Perspective: Size selected clusters for catalysis and electrochemistry

DOE PAGES

Halder, Avik; Curtiss, Larry A.; Fortunelli, Alessandro; ...

2018-03-15

We report that size-selected clusters containing a handful of atoms may possess noble catalytic properties different from nano-sized or bulk catalysts. Size- and composition-selected clusters can also serve as models of the catalytic active site, where an addition or removal of a single atom can have a dramatic effect on their activity and selectivity. In this Perspective, we provide an overview of studies performed under both ultra-high vacuum and realistic reaction conditions aimed at the interrogation, characterization and understanding of the performance of supported size-selected clusters in heterogeneous and electrochemical reactions, which address the effects of cluster size, cluster composition,more » cluster-support interactions and reaction conditions, the key parameters for the understanding and control of catalyst functionality. Computational modelling based on density functional theory sampling of local minima and energy barriers or ab initio Molecular Dynamics simulations is an integral part of this research by providing fundamental understanding of the catalytic processes at the atomic level, as well as by predicting new materials compositions which can be validated in experiments. Lastly, we discuss approaches which aim at the scale up of the production of well-defined clusters for use in real world applications.« less

Perspective: Size selected clusters for catalysis and electrochemistry

NASA Astrophysics Data System (ADS)

Halder, Avik; Curtiss, Larry A.; Fortunelli, Alessandro; Vajda, Stefan

2018-03-01

Size-selected clusters containing a handful of atoms may possess noble catalytic properties different from nano-sized or bulk catalysts. Size- and composition-selected clusters can also serve as models of the catalytic active site, where an addition or removal of a single atom can have a dramatic effect on their activity and selectivity. In this perspective, we provide an overview of studies performed under both ultra-high vacuum and realistic reaction conditions aimed at the interrogation, characterization, and understanding of the performance of supported size-selected clusters in heterogeneous and electrochemical reactions, which address the effects of cluster size, cluster composition, cluster-support interactions, and reaction conditions, the key parameters for the understanding and control of catalyst functionality. Computational modeling based on density functional theory sampling of local minima and energy barriers or ab initio molecular dynamics simulations is an integral part of this research by providing fundamental understanding of the catalytic processes at the atomic level, as well as by predicting new materials compositions which can be validated in experiments. Finally, we discuss approaches which aim at the scale up of the production of well-defined clusters for use in real world applications.

Bifunctional catalysts for upgrading of biomass-derived oxygenates: A review

DOE PAGES

Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

2016-06-21

Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the differentmore » types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. Finally, these studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.« less

Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability.

PubMed

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.

Synthesis and Catalytic Applications of Multi-Walled Carbon Nanotube-Polyamidoamine Dendrimer Hybrids.

PubMed

Desmecht, Antonin; Steenhaut, Timothy; Pennetreau, Florence; Hermans, Sophie; Riant, Olivier

2018-06-20

Polyamidoamine (PAMAM) dendrimers were covalently immobilized on multi-walled carbon nanotubes (MWNT) via two 'grafting to' strategies. We demonstrate the existence of non-covalent interactions between the two components but outline the superiority of our two grafting approaches, namely xanthate and click chemistry. MWNT surfaces were functionalized with activated ester and propargylic moieties prior to their reaction with PAMAM or azido-PAMAM dendrimers, respectively. The grafting of PAMAM generations 0 to 3 was evaluated with X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). The versatility of our hybrids was demonstrated by post-functionalization sequences involving copper alkyne-azide cycloaddition (CuAAC). We synthesized homogeneous supported iridium complexes at the extremities of the dendrimers. In addition, our materials were used as template for the encapsulation of Pd nanoparticles (NP), validating our nanocomposites for catalytic applications. The palladium-based catalyst was active for carbonylative coupling during 5 consecutive runs without loss of activity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic activity in lithium-treated core–shell MoO x/MoS 2 nanowires

DOE PAGES

Cummins, Dustin R.; Martinez, Ulises; Kappera, Rajesh; ...

2015-09-22

Significant interest has grown in the development of earth-abundant and efficient catalytic materials for hydrogen generation. Layered transition metal dichalcogenides present opportunities for efficient electrocatalytic systems. Here, we report the modification of 1D MoO x/MoS 2 core–shell nanostructures by lithium intercalation and the corresponding changes in morphology, structure, and mechanism of H 2 evolution. The 1D nanowires exhibit significant improvement in H 2 evolution properties after lithiation, reducing the hydrogen evolution reaction (HER) onset potential by ~50 mV and increasing the generated current density by ~600%. The high electrochemical activity in the nanowires results from disruption of MoS 2 layersmore » in the outer shell, leading to increased activity and concentration of defect sites. This is in contrast to the typical mechanism of improved catalysis following lithium exfoliation, i.e., crystal phase transformation. As a result, these structural changes are verified by a combination of Raman and X-ray photoelectron spectroscopy (XPS).« less

Preparation of mesoporous Cs-POM@MOF-199@MCM-41 under two different synthetic methods for a highly oxidesulfurization of dibenzothiophene.

PubMed

Li, Si-Wen; Li, Jia-Rong; Jin, Qi-Ping; Yang, Zhi; Zhang, Rong-Lan; Gao, Rui-Min; Zhao, Jian-She

2017-09-05

Two different synthetic methods, the direct method and the substitution method, were used to synthesize the Cs-POM@MOF-199@MCM-41 (Cs-PMM), in which the modified heteropolyacid with cesium salt has been encapsulated into the pores with the mixture of MOF and MCM-41. The structural properties of the as-prepared catalysts were characterized using various analytical techniques: powder X-ray diffraction, FT-IR, SEM, TEM, XPS and BET, confirming that the Cs-POM active species retained its Keggin structure after immobilization. The substitution method of Cs-PMM exhibited more excellent catalytic performance for oxidative desulfurization of dibenzothiophene in the presence of oxygen. Under optimal conditions, the DBT conversion rate reached up to 99.6% and could be recycled 10 times without significant loss of catalytic activity, which is mainly attributed to the slow leaching of the active heteropolyacid species from the strong fixed effect of the mixture porous materials. Copyright © 2017. Published by Elsevier B.V.

Dehalogenation and coupling of a polycyclic hydrocarbon on an atomically thin insulator.

PubMed

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.

Inhibition effect of graphene oxide on the catalytic activity of acetylcholinesterase enzyme.

PubMed

Wang, Yong; Gu, Yao; Ni, Yongnian; Kokot, Serge

2015-11-01

Variations in the enzyme activity of acetylcholinesterase (AChE) in the presence of the nano-material, graphene oxide (GO), were investigated with the use of molecular spectroscopy UV-visible and fluorescence methods. From these studies, important kinetic parameters of the enzyme were extracted; these were the maximum reaction rate, Vm , and the Michaelis constant, Km . A comparison of these parameters indicated that GO inhibited the catalytic activity of the AChE because of the presence of the AChE-GO complex. The formation of this complex was confirmed with the use of fluorescence data, which was resolved with the use of the MCR-ALS chemometrics method. Furthermore, it was found that the resonance light-scattering (RLS) intensity of AChE changed in the presence of GO. On this basis, it was demonstrated that the relationship between AChE and GO was linear and such models were used for quantitative analyses of GO. Copyright © 2015 John Wiley & Sons, Ltd.

Enzyme leaps fuel antichemotaxis

PubMed Central

Jee, Ah-Young; Dutta, Sandipan; Cho, Yoon-Kyoung

2018-01-01

There is mounting evidence that enzyme diffusivity is enhanced when the enzyme is catalytically active. Here, using superresolution microscopy [stimulated emission-depletion fluorescence correlation spectroscopy (STED-FCS)], we show that active enzymes migrate spontaneously in the direction of lower substrate concentration (“antichemotaxis”) by a process analogous to the run-and-tumble foraging strategy of swimming microorganisms and our theory quantifies the mechanism. The two enzymes studied, urease and acetylcholinesterase, display two families of transit times through subdiffraction-sized focus spots, a diffusive mode and a ballistic mode, and the latter transit time is close to the inverse rate of catalytic turnover. This biochemical information-processing algorithm may be useful to design synthetic self-propelled swimmers and nanoparticles relevant to active materials. Executed by molecules lacking the decision-making circuitry of microorganisms, antichemotaxis by this run-and-tumble process offers the biological function to homogenize product concentration, which could be significant in situations when the reactant concentration varies from spot to spot. PMID:29255047

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.

Preparation and photo-catalytic activities of FeOOH/ZnO/MMT composite

NASA Astrophysics Data System (ADS)

Zhou, Yao; Liu, Fusheng; Yu, Shitao

2015-11-01

Montmorillonite (MMT) was used as the carrier for synthesis of FeOOH and FeOOH/ZnO nano-material. FeOOH and FeOOH/ZnO were synthesized by the aqueous solutions of Fe(NO3)3-HNO3 and Zn(NO3)2-NaOH/Fe(NO3)3-HNO3 with the carrier of montmorillonite respectively. Transmission electron-microscopy (TEM) and X-ray diffraction (XRD) were used to study the morphology form and structure of the nano-materials. TEM was also used to demonstrate that FeOOH/ZnO can be formed with the appropriate interface. According to UV-vis absorption spectra, FeOOH/ZnO has a better response to visible light than FeOOH and ZnO, which indicates there is some coupling effect between FeOOH and ZnO. Pentachlorophenol (PCP) was used as a representative organic pollutant to evaluate the photo-catalytic efficiency of the FeOOH/ZnO and FeOOH catalysts in visible light (λ > 400 nm). The photo-catalytic efficiency of FeOOH/ZnO/MMT is better than FeOOH/MMT. According to FTIR, changes of pH and TOC, the degradation mechanism was also discussed. PCP was degraded to aromatic ketone and chloro-hydrocarbon compounds and then to H2O, CO2 and HCl.

Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

DOE PAGES

Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; ...

2016-06-08

Nanoscale carbons are typically synthesized by thermal decomposition of a hydrocarbon at the surface of a metal catalyst. Whereas the use of silicon as an alternative to metal catalysts could unlock new techniques to seamlessly couple carbon nanostructures and semiconductor materials, stable carbide formation renders bulk silicon incapable of the precipitation and growth of graphitic structures. In this article, we provide evidence supported by comprehensive in situ Raman experiments that indicates nanoscale grains of silicon in porous silicon (PSi) scaffolds act as catalysts for hydrocarbon decomposition and growth of few-layered graphene at temperatures as low as 700 K. Self-limiting growthmore » kinetics of graphene with activation energies measured between 0.32–0.37 eV elucidates the formation of highly reactive surface-bound Si radicals that aid in the decomposition of hydrocarbons. Nucleation and growth of graphitic layers on PSi exhibits striking similarity to catalytic growth on nickel surfaces, involving temperature dependent surface and subsurface diffusion of carbon. Lastly, this work elucidates how the nanoscale properties of silicon can be exploited to yield catalytic properties distinguished from bulk silicon, opening an important avenue to engineer catalytic interfaces combining the two most technologically important materials for modern applications—silicon and nanoscale carbons.« less

Carbon dioxide conversion over carbon-based nanocatalysts.

PubMed

Khavarian, Mehrnoush; Chai, Siang-Piao; Mohamed, Abdul Rahman

2013-07-01

The utilization of carbon dioxide for the production of valuable chemicals via catalysts is one of the efficient ways to mitigate the greenhouse gases in the atmosphere. It is known that the carbon dioxide conversion and product yields are still low even if the reaction is operated at high pressure and temperature. The carbon dioxide utilization and conversion provides many challenges in exploring new concepts and opportunities for development of unique catalysts for the purpose of activating the carbon dioxide molecules. In this paper, the role of carbon-based nanocatalysts in the hydrogenation of carbon dioxide and direct synthesis of dimethyl carbonate from carbon dioxide and methanol are reviewed. The current catalytic results obtained with different carbon-based nanocatalysts systems are presented and how these materials contribute to the carbon dioxide conversion is explained. In addition, different strategies and preparation methods of nanometallic catalysts on various carbon supports are described to optimize the dispersion of metal nanoparticles and catalytic activity.

Takovite-aluminosilicate-Cr materials prepared by adsorption of Cr3+ from industrial effluents as catalysts for hydrocarbon oxidation reactions.

PubMed

Ciuffi, Katia J; de Faria, Emerson H; Marçal, Liziane; Rocha, Lucas A; Calefi, Paulo S; Nassar, Eduardo J; Pepe, Iuri; da Rocha, Zênis N; Vicente, Miguel A; Trujillano, Raquel; Gil, Antonio; Korili, Sophia A

2012-05-01

The catalytic efficiency of takovite-aluminosilicate-chromium catalysts obtained by adsorption of Cr(3+) ions from aqueous solutions by a takovite-aluminosilicate nanocomposite adsorbent is reported. The adsorbent was synthesized by the coprecipitation method. The catalytic activity of the final Cr-catalysts depended on the amount of adsorbed chromium. (Z)-cyclooctene conversion up to 90% with total selectivity for the epoxide was achieved when the oxidation was carried out with hydrogen peroxide, at room temperature. After five consecutive runs, the catalysts maintained high activity, although after the sixth reuse, the epoxide yields strongly decreased to 35%. The catalysts were also efficient for cyclohexane oxidation, reaching up to 18% conversion, with cyclohexanone/cyclohexanol selectivity close to 1.2. On the whole, their use as catalysts gives a very interesting application for the solids obtained by adsorption of a contaminant cation such as Cr(3+).

Tandem Nitrogen Functionalization of Porous Carbon: Toward Immobilizing Highly Active Palladium Nanoclusters for Dehydrogenation of Formic Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhangpeng; Yang, Xinchun; Tsumori, Nobuko

2017-03-10

Highly dispersed palladium nanoclusters (Pd NCs) immobilized by a nitrogen (N)-functionalized porous carbon support (N-MSC-30) are synthesized by a wet chemical reduction method, wherein the N-MSC-30 prepared by a tandem low temperature heat-treatment approach proved to be a distinct support for stabilizing the Pd NCs. The prepared Pd/N-MSC-30 shows extremely high catalytic activity and recyclability for the dehydrogenation of formic acid (FA), affording the highest turnover frequency (TOF = 8414 h -1) at 333 K, which is much higher than that of the Pd catalyst supported on the N-MSC-30 prepared via a one-step process. This tandem heat treatment strategy providesmore » a facile and effective synthetic methodology to immobilize ultrafine metal NPs on N-functionalized carbon materials, which have tremendous application prospects in various catalytic fields.« less

Enzyme Technology of Peroxidases: Immobilization, Chemical and Genetic Modification

NASA Astrophysics Data System (ADS)

Longoria, Adriana; Tinoco, Raunel; Torres, Eduardo

An overview of enzyme technology applied to peroxidases is made. Immobilization on organic, inorganic, and hybrid supports; chemical modification of amino acids and heme group; and genetic modification by site-directed and random mutagenesis are included. Different strategies that were carried out to improve peroxidase performance in terms of stability, selectivity, and catalytic activity are analyzed. Immobilization of peroxidases on inorganic and organic materials enhances the tolerance of peroxidases toward the conditions normally found in many industrial processes, such as the presence of an organic solvent and high temperature. In addition, it is shown that immobilization helps to increase the Total Turnover Number at levels high enough to justify the use of a peroxidase-based biocatalyst in a synthesis process. Chemical modification of peroxidases produces modified enzymes with higher thermostability and wider substrate variability. Finally, through mutagenesis approaches, it is possible to produce modified peroxidases capable of oxidizing nonnatural substrates with high catalytic activity and affinity.

Development of Inorganic Nanomaterials as Photocatalysts for the Water Splitting Reaction

NASA Astrophysics Data System (ADS)

Frame, Fredrick Andrew

The photochemical water splitting reaction is of great interest for converting solar energy into usable fuels. This dissertation focuses on the development of inorganic nanoparticle catalysts for solar energy driven conversion of water into hydrogen and oxygen. The results from these selected studies have allowed greater insight into nanoparticle chemistry and the role of nanoparticles in photochemical conversion of water in to hydrogen and oxygen. Chapter 2 shows that CdSe nanoribbons have photocatalytic activity for hydrogen production from water in the presence of Na2S/Na2SO 3 as sacrificial electron donors in both UV and visible light. Quantum confinement of this material leads to an extended bandgap of 2.7 eV and enables the photocatalytic activity of this material. We report on the photocatalytic H2 evolution, and its dependence on platinum co-catalysts, the concentration of the electron donor, and the wavelength of incident radiation. Transient absorption measurements reveal decay of the excited state on multiple timescales, and an increase of lifetimes of trapped electrons due to the sacrificial electron donors. In chapter 3, we explore the catalytic activity of citrate-capped CdSe quantum dots. We show that the process is indeed catalytic for these dots in aqueous 0.1 M Na2S:Na2SO3, but not in pure water. Furthermore, optical spectroscopy was used to report electronic transitions in the dots and electron microscopy was used to obtain morphology of the catalyst. Interestingly, an increasing catalytic rate is noted for undialyzed catalyst. Dynamic light scattering experiments show an increased hydrodynamic radius in the case of undialyzed CdSe dots in donor solution. In chapter 4 we show that CdSe:MoS2 nanoparticle composites with improved catalytic activity can be assembled from CdSe and MoS2 nanoparticle building units. We report on the photocatalytic H 2 evolution, quantum efficiency using LED irriadiation, and its dependence on the co-catalyst loading. Furthermore, optical spectroscopy, cyclic voltammetry, and electron microscopy were used to obtain morphology, optical properties, and electronic structure of the catalysts. In chapter 5, illumination with visible light (lambda > 400 nm) photoconverts a red V2O5 gel in aqueous methanol solution into a green VO2 gel. The presence of V(4+) in the green VO2 gel is supported by Electron Energy Loss Spectra. High-resolution electron micrographs, powder X-ray diffraction, and selective area electron diffraction (SAED) data show that the crystalline structure of the V2O5 gel is retained upon reduction. After attachment of colloidal Pt nanoparticles, H2 evolution proceeds catalytically on the VO2 gel. The Pt nanoparticles reduce the H2 evolution overpotential. However, the activity of the new photocatalyst remains limited by the VO2 conduction band edge just below the proton reduction potential. Chapter 6 studies the ability of IrO2 to evolve oxygen from aqueous solutions under UV irradiation. We show that visible illumination (lambda > 400 nm) of iridium dioxide (IrO2) nanocrystals capped in succinic acid in aqueous sodium persulfate solution leads to catalytic oxygen evolution. While the majority of catalytic hydrogen evolution comes from UV light, the process can still be driven with visible light. Morphology, optical properties, surface photovoltage measurements, and oxygen evolution rates are discussed.

Piloted rich-catalytic lean-burn hybrid combustor

DOEpatents

Newburry, Donald Maurice

2002-01-01

A catalytic combustor assembly which includes, an air source, a fuel delivery means, a catalytic reactor assembly, a mixing chamber, and a means for igniting a fuel/air mixture. The catalytic reactor assembly is in fluid communication with the air source and fuel delivery means and has a fuel/air plenum which is coated with a catalytic material. The fuel/air plenum has cooling air conduits passing therethrough which have an upstream end. The upstream end of the cooling conduits is in fluid communication with the air source but not the fuel delivery means.

A comparative theoretical study of the catalytic activities of Au2(-) and AuAg(-) dimers for CO oxidation.

PubMed

Liu, Peng; Song, Ke; Zhang, Dongju; Liu, Chengbu

2012-05-01

The detailed mechanisms of catalytic CO oxidation over Au(2)(-) and AuAg(-) dimers, which represent the simplest models for monometal Au and bimetallic Au-Ag nanoparticles, have been studied by performing density functional theory calculations. It is found that both Au(2)(-) and AuAg(-) dimers catalyze the reaction according to the similar mono-center Eley-Rideal mechanism. The catalytic reaction is of the multi-channel and multi-step characteristic, which can proceed along four possible pathways via two or three elementary steps. In AuAg(-), the Au site is more active than the Ag site, and the calculated energy barrier values for the rate-determining step of the Au-site catalytic reaction are remarkably smaller than those for both the Ag-site catalytic reaction and the Au(2)(-) catalytic reaction. The better catalytic activity of bimetallic AuAg(-) dimer is attributed to the synergistic effect between Au and Ag atom. The present results provide valuable information for understanding the higher catalytic activity of Au-Ag nanoparticles and nanoalloys for low-temperature CO oxidation than either pure metallic catalyst.

Metabolic Noise, Vestigial Metabolites or the Raw Material of Ecological Adaptation? Opportunitistic Enzymes, Catalytic Promiscuity and the Evolution of Chemodiversity in Nature (2010 JGI User Meeting)

ScienceCinema

Noel, Joseph

2018-04-26

Joseph Noel from the Salk Institute on "Metabolic Noise, Vestigial Metabolites or the Raw Material of Ecological Adaptation? Enzymes, Catalytic Promiscuity and the Evolution of Chemodiversity in Nature" on March 26, 2010 at the 5th Annual DOE JGI User Meeting.

Predicting Catalytic Activity of Nanoparticles by a DFT-Aided Machine-Learning Algorithm.

PubMed

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.

Investigating the Hydrolysis of Starch Using "a"-Amylase Contained in Dishwashing Detergent and Human Saliva

ERIC Educational Resources Information Center

Munegumi, Toratane; Inutsuka, Masato; Hayafuji, Yukitaka

2016-01-01

Although saliva has commonly been used to teach about digestion by organisms, the phenomenon of digestion is actually caused by enzymes as catalytic substances. This activity explores the hydrolysis of starch by "a"-amylase in cleaning materials as well as a comparison with the similar reaction using human saliva. The fact that the…

A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

PubMed Central

Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

2017-01-01

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C–O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven. PMID:28621710

A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

PubMed

Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

2017-06-16

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K₂CO₃ base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.

Catalytic nanoporous membranes

DOEpatents

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.

In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.

PubMed

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.

Molecular Self-Assembly Strategy for Generating Catalytic Hybrid Polypeptides

PubMed Central

Ikezoe, Yasuhiro; Pike, Douglas H.; Nanda, Vikas; Matsui, Hiroshi

2016-01-01

Recently, catalytic peptides were introduced that mimicked protease activities and showed promising selectivity of products even in organic solvents where protease cannot perform well. However, their catalytic efficiency was extremely low compared to natural enzyme counterparts presumably due to the lack of stable tertiary fold. We hypothesized that assembling these peptides along with simple hydrophobic pockets, mimicking enzyme active sites, could enhance the catalytic activity. Here we fused the sequence of catalytic peptide CP4, capable of protease and esterase-like activities, into a short amyloidogenic peptide fragment of Aβ. When the fused CP4-Aβ construct assembled into antiparallel β-sheets and amyloid fibrils, a 4.0-fold increase in the hydrolysis rate of p-nitrophenyl acetate (p-NPA) compared to neat CP4 peptide was observed. The enhanced catalytic activity of CP4-Aβ assembly could be explained both by pre-organization of a catalytically competent Ser-His-acid triad and hydrophobic stabilization of a bound substrate between the triad and p-NPA, indicating that a design strategy for self-assembled peptides is important to accomplish the desired functionality. PMID:27116246

Molecular self-assembly strategy for generating catalytic hybrid polypeptides

DOE PAGES

Maeda, Yoshiaki; Fang, Justin; Ikezoe, Yasuhiro; ...

2016-04-26

Recently, catalytic peptides were introduced that mimicked protease activities and showed promising selectivity of products even in organic solvents where protease cannot perform well. However, their catalytic efficiency was extremely low compared to natural enzyme counterparts presumably due to the lack of stable tertiary fold. We hypothesized that assembling these peptides along with simple hydrophobic pockets, mimicking enzyme active sites, could enhance the catalytic activity. Here we fused the sequence of catalytic peptide CP4, capable of protease and esterase-like activities, into a short amyloidogenic peptide fragment of Aβ. When the fused CP4-Aβ construct assembled into antiparallel β- sheets and amyloidmore » fibrils, a 4.0-fold increase in the hydrolysis rate of p-nitrophenyl acetate (p-NPA) compared to neat CP4 peptide was observed. Furthermore, the enhanced catalytic activity of CP4-Aβ assembly could be explained both by pre-organization of a catalytically competent Ser-His-acid triad and hydrophobic stabilization of a bound substrate between the triad and p-NPA, indicating that a design strategy for self-assembled peptides is important to accomplish the desired functionality.« less

Carbon nanotube synthesis with different support materials and catalysts

NASA Astrophysics Data System (ADS)

Gümüş, Fatih; Yuca, Neslihan; Karatepe, Nilgün

2013-09-01

Having remarkable characteristics, carbon nanotubes (CNTs) have attracted a lot of interest. Their mechanical, electrical, thermal and chemical properties make CNTs suitable for several applications such as electronic devices, hydrogen storage, textile, drug delivery etc. CNTs have been synthesized by various methods, such as arc discharge, laser ablation and catalytic chemical vapor deposition (CCVD). In comparison with the other techniques, CCVD is widely used as it offers a promising route for mass production. High capability of decomposing hydrocarbon formation is desired for the selected catalysts. Therefore, transition metals which are in the nanometer scale are the most effective catalysts. The common transition metals that are being used are Fe, Co, Ni and their binary alloys. The impregnation of the catalysts over the support material has a crucial importance for the CNT production. In this study, the influence of the support materials on the catalytic activity of metals was investigated. CNTs have been synthesized over alumina (Al2O3), silica (SiO2) and magnesium oxide (MgO) supported Fe, Co, Fe-Co catalysts. Catalyst - support material combinations have been investigated and optimum values for each were compared. Single walled carbon nanotubes (SWCNTs) were produced at 800°C. The duration of synthesis was 30 minutes for all support materials. The synthesized materials were characterized by thermal gravimetric analysis (TGA), Raman spectroscopy and transmission electron microscopy.

Voltage-dependent motion of the catalytic region of voltage-sensing phosphatase monitored by a fluorescent amino acid

PubMed Central

Sakata, Souhei; Jinno, Yuka; Kawanabe, Akira; Okamura, Yasushi

2016-01-01

The cytoplasmic region of voltage-sensing phosphatase (VSP) derives the voltage dependence of its catalytic activity from coupling to a voltage sensor homologous to that of voltage-gated ion channels. To assess the conformational changes in the cytoplasmic region upon activation of the voltage sensor, we genetically incorporated a fluorescent unnatural amino acid, 3-(6-acetylnaphthalen-2-ylamino)-2-aminopropanoic acid (Anap), into the catalytic region of Ciona intestinalis VSP (Ci-VSP). Measurements of Anap fluorescence under voltage clamp in Xenopus oocytes revealed that the catalytic region assumes distinct conformations dependent on the degree of voltage-sensor activation. FRET analysis showed that the catalytic region remains situated beneath the plasma membrane, irrespective of the voltage level. Moreover, Anap fluorescence from a membrane-facing loop in the C2 domain showed a pattern reflecting substrate turnover. These results indicate that the voltage sensor regulates Ci-VSP catalytic activity by causing conformational changes in the entire catalytic region, without changing their distance from the plasma membrane. PMID:27330112

Voltage-dependent motion of the catalytic region of voltage-sensing phosphatase monitored by a fluorescent amino acid.

PubMed

Sakata, Souhei; Jinno, Yuka; Kawanabe, Akira; Okamura, Yasushi

2016-07-05

The cytoplasmic region of voltage-sensing phosphatase (VSP) derives the voltage dependence of its catalytic activity from coupling to a voltage sensor homologous to that of voltage-gated ion channels. To assess the conformational changes in the cytoplasmic region upon activation of the voltage sensor, we genetically incorporated a fluorescent unnatural amino acid, 3-(6-acetylnaphthalen-2-ylamino)-2-aminopropanoic acid (Anap), into the catalytic region of Ciona intestinalis VSP (Ci-VSP). Measurements of Anap fluorescence under voltage clamp in Xenopus oocytes revealed that the catalytic region assumes distinct conformations dependent on the degree of voltage-sensor activation. FRET analysis showed that the catalytic region remains situated beneath the plasma membrane, irrespective of the voltage level. Moreover, Anap fluorescence from a membrane-facing loop in the C2 domain showed a pattern reflecting substrate turnover. These results indicate that the voltage sensor regulates Ci-VSP catalytic activity by causing conformational changes in the entire catalytic region, without changing their distance from the plasma membrane.

Sc-substituted La0.6Sr0.4FeO3-δ mixed conducting oxides as promising electrodes for symmetrical solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Liu, Xuejiao; Han, Da; Zhou, Yucun; Meng, Xie; Wu, Hao; Li, Junliang; Zeng, Fanrong; Zhan, Zhongliang

2014-01-01

The main barrier to symmetrical solid oxide fuel cells (SOFCs), where the same catalytic materials are used simultaneously as the anodes and the cathodes, is to identify a redox-stable catalyst that exhibits superior catalytic activities for both fuel oxidation and oxygen reduction reactions. Here we report a Sc-substituted La0.6Sr0.4FeO3-δ oxide, La0.6Sr0.4Fe0.9Sc0.1O3-δ, that shows great promise as a new symmetrical electrode material with good structural stability and reasonable conductivities in air and hydrogen. We further demonstrate that nano-scale La0.6Sr0.4Fe0.9Sc0.1O3-δ catalysts impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ backbones exhibit good catalytic activities for oxygen reduction and hydrogen oxidation reactions and thereby yield low polarization resistances, e.g., 0.015 Ω cm2 in air and 0.29 Ω cm2 in hydrogen with appropriate current collection at 800 °C. Thin La0.9Sr0.1Ga0.8Mg0.2O3-δ electrolyte fuel cells with such symmetrical La0.6Sr0.4Fe0.9Sc0.1O3-δ catalysts showed maximum power densities of 0.56 and 0.32 W cm-2 when operating on 97% H2-3% H2O at 800 and 700 °C, respectively.