Biosynthesis of Pd-Au alloys on carbon fiber paper: Towards an eco-friendly solution for catalysts fabrication

NASA Astrophysics Data System (ADS)

Zhuang, Zechao; Wang, Feifeng; Naidu, Ravendra; Chen, Zuliang

2015-09-01

Bimetallic nanomaterials with enhanced activity and stability have been extensively studied as emerging catalysts for hydrogen evolution reaction (HER). Expensive and environmentally unfriendly chemical synthesis routes inhibit their large-scale applications. In this work, we developed a facile and green synthesis of Pd-Au alloy nanoparticles (NPs) dispersed on carbon fiber paper (CFP) by plant-mediated bioreduction coupled with self-assembly. Engineering the morphology and composition of bimetallic catalysts synthesized by plant extracts on complex substrate is achieved. The resulting NPs are uniform in shape and have a spherical morphology with an average diameter of ∼180 nm, in which the molar ratio of Au/Pd is near 75:25 and the catalysts loading is about 0.5 mg cm-2. The Pd-Au/CFP hybrid electrode exhibits an excellent HER performance with a Tafel slope of 47 mV dec-1 and an exchange current density of 0.256 mA cm-2. Electrochemical stability tests through long-term potential cycles and potentiostatic electrolysis further confirm the high durability of the electrode. This development offers an efficient and eco-friendly catalysts synthesis route for constructing water-splitting cells and other electrocatalytic devices.

Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation.

PubMed

Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

2015-08-07

Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.

One-pot solvothermal synthesis of ordered intermetallic Pt2In3 as stable and efficient electrocatalyst towards direct alcohol fuel cell application

NASA Astrophysics Data System (ADS)

Jana, Rajkumar; Peter, Sebastian C.

2016-10-01

Ordered intermetallic Pt2In3 nanoparticles have been synthesized by superhydride reduction of K2PtCl4 and InCl3.xH2O precursors using facile, one-pot solvothermal method. We report surfactant free solvothermal synthesis of a novel ordered Pt2In3 intermetallic nanoparticles for the first time. The structure and morphology of the catalyst has been confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, energy-dispersive spectrometry and X-ray photoelectron spectroscopy. The electrocatalytic properties of the catalysts have been investigated by cyclic voltammetry and chronoamperometry. The as prepared Pt2In3 catalyst exhibit far superior electrocatalytic activity and stability towards alcohol oxidation over commercial Pt/C. The specific activity of as synthesized catalyst was found to be 3.2 and 2.3 times higher than commercial Pt/C for methanol and ethanol oxidation, respectively. This improved activity and durability of the Pt2In3 nanoparticles can make the catalyst an ideal catalyst candidate for direct alcohol fuel cell.

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 6, October 1--December 31, 1995

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

NONE

1996-12-31

The project involves the construction of an 80,000 gallons per day (260 TPD) methanol unit utilizing coal-derived synthesis gas from Eastman`s integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries, product distillation facilities, and utilities. The technology to be demonstrated is the product of a cooperative development effort by Air Products and DOE in a program that started in 1981. Developed to enhance electric power generation using integrated gasification combined cycle (IGCC) technology, the LPMEOH{trademark} process is ideally suited for directly processing gases produced by modern-day coalmore » gasifiers. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates. At the Eastman complex, the technology will be integrated with existing coal-gasifiers. A carefully developed test plan will allow operations at Eastman to simulate electricity demand load-following in coal-based IGCC facilities. The operations will also demonstrate the enhanced stability and heat dissipation of the conversion process, its reliable on/off operation, and its ability to produce methanol as a clean liquid fuel without additional upgrading. An off-site product testing program will be conducted to demonstrate the suitability of the methanol product as a transportation fuel and as a fuel for stationary applications for small modular electric power generators for distributed power.« less

Facile and gram-scale synthesis of metal-free catalysts: toward realistic applications for fuel cells.

PubMed

Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young; Kim, Min Jeong; Yoo, Ji Mun; Park, Ji Eun; Choe, Heeman; Sung, Yung-Eun

2015-03-02

Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells.

Facile and Gram-scale Synthesis of Metal-free Catalysts: Toward Realistic Applications for Fuel Cells

PubMed Central

Kim, Ok-Hee; Cho, Yong-Hun; Chung, Dong Young; Kim, Min Jeong; Yoo, Ji Mun; Park, Ji Eun; Choe, Heeman; Sung, Yung-Eun

2015-01-01

Although numerous reports on nonprecious metal catalysts for replacing expensive Pt-based catalysts have been published, few of these studies have demonstrated their practical application in fuel cells. In this work, we report graphitic carbon nitride and carbon nanofiber hybrid materials synthesized by a facile and gram-scale method via liquid-based reactions, without the use of toxic materials or a high pressure-high temperature reactor, for use as fuel cell cathodes. The resulting materials exhibited remarkable methanol tolerance, selectivity, and stability even without a metal dopant. Furthermore, these completely metal-free catalysts exhibited outstanding performance as cathode materials in an actual fuel cell device: a membrane electrode assembly with both acidic and alkaline polymer electrolytes. The fabrication method and remarkable performance of the single cell produced in this study represent progressive steps toward the realistic application of metal-free cathode electrocatalysts in fuel cells. PMID:25728910

Cationic Zn-Porphyrin Polymer Coated onto CNTs as a Cooperative Catalyst for the Synthesis of Cyclic Carbonates.

PubMed

Jayakumar, Sanjeevi; Li, He; Chen, Jian; Yang, Qihua

2018-01-24

The development of solid catalysts containing multiple active sites that work cooperatively is very attractive for biomimetic catalysis. Herein, we report the synthesis of bifunctional catalysts by supporting cationic porphyrin-based polymers on carbon nanotubes (CNTs) using the direct reaction of 5,10,15,20-tetrakis(4-pyridyl)porphyrin zinc(II), di(1H-imidazol-1-yl)methane, and 1,4-bis(bromomethyl)benzene in the presence of CNTs. The bifunctional catalysts could efficiently catalyze the cycloaddition reaction of epoxides and CO 2 under solvent-free conditions with porphyrin zinc(II) as the Lewis acid site and a bromine anion as a nucleophilic agent working in a cooperative way. Furthermore, a relative amount of porphyrin zinc(II) and quaternary ammonium bromide could be facilely adjusted for facilitating cooperative behavior. The bifunctional catalyst with a TOF up to 2602 h -1 is much more active than the corresponding homogeneous counterpart and is one of the most active heterogeneous catalysts ever reported under cocatalyst-free conditions. The high activity is mainly attributed to the enhanced cooperation effect of the bifunctional catalyst. With a wide substrate scope, the bifunctional catalyst could be stably recycled. This work demonstrates a new approach for the generation of a cooperative activation effect for solid catalysts.

Heterometallic metal-organic framework-templated synthesis of porous Co3O4/ZnO nanocage catalysts for the carbonylation of glycerol

NASA Astrophysics Data System (ADS)

Lü, Yinyun; Jiang, Yating; Zhou, Qi; Li, Yunmei; Chen, Luning; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

2017-12-01

The efficient synthesis of glycerol carbonate (GLC) has recently received great attention due to its significance in reducing excess glycerol in biodiesel production as well as its promising applications in several industrial fields. However, the achievement of high conversion and high selectivity of GLC from glycerol in heterogeneous catalytic processes remains a challenge due to the absence of high-performance solid catalysts. Herein, highly porous nanocage catalysts composed of well-mixed Co3O4 and ZnO nanocrystals were successfully fabricated via a facile heterometallic metal-organic framework (MOF)-templated synthetic route. Benefiting from a high porosity and the synergistic effect between Co3O4 and ZnO, the as-prepared composite catalysts exhibited a significantly enhanced production efficiency of GLC in the carbonylation reaction of glycerol with urea compared to the single-component counterparts. The yield of GLC over the Co50Zn50-350 catalyst reached 85.2%, with 93.3% conversion and near 91% GLC selectivity, and this catalytic performance was superior to that over most heterogeneous catalysts. More importantly, the proposed templated synthetic strategy of heterometallic MOFs facilitates the regulation of catalyst composition and surface structure and can therefore be potentially extended in the tailoring of other metal oxide composite catalysts.

Facile one-pot synthesis of cellulose nanocrystal-supported hollow CuFe2O4 nanoparticles as efficient catalyst for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Zhang, Sufeng; Zhao, Dongyan; Hou, Chen; Liang, Chen; Li, Hao

2018-06-01

A facile and efficient one-pot method for the synthesis of well-dispersed hollow CuFe2O4 nanoparticles (H-CuFe2O4 NPs) in the presence of cellulose nanocrystals (CNC) as the support was described. Based on the one-pot solvothermal condition control, magnetic H-CuFe2O4 NPs were in-situ grown on the CNC surface uniformly. TEM images indicated good dispersity of H-CuFe2O4 NPs with uniform size of 300 nm. The catalytic activity of H-CuFe2O4/CNC was tested in the catalytic reduction of 4-nitrophenol (4-NP) in aqueous solution. Compared with most CNC-based ferrite catalysts, H-CuFe2O4/CNC catalyst exhibited an excellent catalytic activity toward the reduction of 4-NP. The catalytic performance of H-CuFe2O4/CNC catalyst was remarkably enhanced with the rate constant of 3.24 s-1 g-1, which was higher than H-CuFe2O4 NPs (0.50 s-1 g-1). The high catalytic activity was attributed to the introduction of CNC and the special hollow mesostructure of H-CuFe2O4 NPs. In addition, the H-CuFe2O4/CNC catalyst promised good conversion efficiency without significant decrease even after 10 cycles, confirming relatively high stability. Because of its environmental sustainability and magnetic separability, H-CuFe2O4/CNC catalyst was shown to indicate that the ferrite nanoparticles supported on CNC were acted as a promising catalyst and exhibited potential applications in numerous ferrite based catalytic reactions.

A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

PubMed Central

Denmark, Scott E.; Gould, Nathan D.; Wolf, Larry M.

2011-01-01

Despite over three decades of research into asymmetric phase transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with a libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity oriented approach wherein the tandem inter[4+2]/intra[3+2] cycloaddition of nitroalkenes serves as the key transformation. A two part synthetic strategy comprised of: (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way based on the effective positive potential of the ammonium ion. PMID:21446721

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: aqueous hydration of nitriles to amides.

PubMed

Baig, R B Nasir; Varma, Rajender S

2012-06-25

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe(3)O(4)@SiO(2)) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions.

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.

Facile synthesis of porous Pt-Pd nanospheres supported on reduced graphene oxide nanosheets for enhanced methanol electrooxidation

NASA Astrophysics Data System (ADS)

Li, Shan-Shan; Lv, Jing-Jing; Hu, Yuan-Yuan; Zheng, Jie-Ning; Chen, Jian-Rong; Wang, Ai-Jun; Feng, Jiu-Ju

2014-02-01

In this study, a simple, facile, and effective wet-chemical strategy was developed in the synthesis of uniform porous Pt-Pd nanospheres (Pt-Pd NSs) supported on reduced graphene oxide nanosheets (RGOs) under ambient temperature, where octylphenoxypolye thoxyethanol (NP-40) is used as a soft template, without any seed, organic solvent or special instruments. The as-prepared nanocomposites display enhanced electrocatalytic activity and good stability toward methanol oxidation, compared with commercial Pd/C and Pt/C catalysts. This strategy may open a new route to design and prepare advanced electrocatalysts for fuel cells.

Design of multi-shell Fe2O3@MnOx@CNTs for the selective catalytic reduction of NO with NH3: improvement of catalytic activity and SO2 tolerance

NASA Astrophysics Data System (ADS)

Cai, Sixiang; Hu, Hang; Li, Hongrui; Shi, Liyi; Zhang, Dengsong

2016-02-01

Manganese based catalysts are highly active in the NH3-SCR reaction for NOx removal. Unfortunately, manganese oxides can be easily deactivated by sulfur dioxide in the flow gas, which has become the main obstacle for their practical applications. To address this problem, we presented a green and facile method for the synthesis of multi-shell Fe2O3@MnOx@CNTs. The morphology and structural properties of the catalysts were systematically investigated. The results revealed that the MnOx@CNT core-shell structure was formed during the chemical bath deposition, while the outermost MnOx species were transformed to Fe2O3 after the galvanic replacement reaction. The formation of the multi-shell structure induced the enhancement of the active oxygen species, reducible species as well as adsorption of the reactants, which brought about excellent de-NOx performance. Moreover, the Fe2O3 shell could effectively suppress the formation of the surface sulfate species, leading to the desirable SO2 resistance to the multi-shell catalyst. Hence, the synthesis protocol could provide guidance for the preparation and elevation of manganese based catalysts.Manganese based catalysts are highly active in the NH3-SCR reaction for NOx removal. Unfortunately, manganese oxides can be easily deactivated by sulfur dioxide in the flow gas, which has become the main obstacle for their practical applications. To address this problem, we presented a green and facile method for the synthesis of multi-shell Fe2O3@MnOx@CNTs. The morphology and structural properties of the catalysts were systematically investigated. The results revealed that the MnOx@CNT core-shell structure was formed during the chemical bath deposition, while the outermost MnOx species were transformed to Fe2O3 after the galvanic replacement reaction. The formation of the multi-shell structure induced the enhancement of the active oxygen species, reducible species as well as adsorption of the reactants, which brought about excellent de-NOx performance. Moreover, the Fe2O3 shell could effectively suppress the formation of the surface sulfate species, leading to the desirable SO2 resistance to the multi-shell catalyst. Hence, the synthesis protocol could provide guidance for the preparation and elevation of manganese based catalysts. Electronic supplementary information (ESI) available: Experimental details and catalytic performance of the Fe-Mn@CNTs IM, TEM images of Fe@Mn CNTs, stability and H2O resistance studies of the catalysts. See DOI: 10.1039/c5nr08701e

IRON(III) NITRATE-CATALYZED FACILE SYNTHESIS OF DIPHENYLMETHYL (DPM) ETHERS FROM ALCOHOLS

EPA Science Inventory

Diphenyl methyl (DPM) ethers constitute important structural portion of some pharmaceutical entities and also as protective group for hydroxyl groups in synthetic chemistry. DPM ethers are normally prepared using concentrated acids or base as catalysts, which may result in the fo...

Facile Synthesis of Nanoporous Pt-Y alloy with Enhanced Electrocatalytic Activity and Durability

NASA Astrophysics Data System (ADS)

Cui, Rongjing; Mei, Ling; Han, Guangjie; Chen, Jiyun; Zhang, Genhua; Quan, Ying; Gu, Ning; Zhang, Lei; Fang, Yong; Qian, Bin; Jiang, Xuefan; Han, Zhida

2017-02-01

Recently, Pt-Y alloy has displayed an excellent electrocatalytic activity for oxygen reduction reaction (ORR), and is regarded as a promising cathode catalyst for fuel cells. However, the bulk production of nanoscaled Pt-Y alloy with outstanding catalytic performance remains a great challenge. Here, we address the challenge through a simple dealloying method to synthesize nanoporous Pt-Y alloy (NP-PtY) with a typical ligament size of ~5 nm. By combining the intrinsic superior electrocatalytic activity of Pt-Y alloy with the special nanoporous structure, the NP-PtY bimetallic catalyst presents higher activity for ORR and ethanol oxidation reaction, and better electrocatalytic stability than the commercial Pt/C catalyst and nanoporous Pt alloy. The as-made NP-PtY holds great application potential as a promising electrocatalyst in proton exchange membrane fuel cells due to the advantages of facile preparation and excellent catalytic performance.

Plasma-Assisted Synthesis of Monodispersed and Robust Ruthenium Ultrafine Nanocatalysts for Organosilane Oxidation and Oxygen Evolution Reactions.

PubMed

Gnanakumar, Edwin S; Ng, Wesley; Coşkuner Filiz, Bilge; Rothenberg, Gadi; Wang, Sheng; Xu, Hualong; Pastor-Pérez, Laura; Pastor-Blas, M Mercedes; Sepúlveda-Escribano, Antonio; Yan, Ning; Shiju, N Raveendran

2017-11-23

We report a facile and general approach for preparing ultrafine ruthenium nanocatalysts by using a plasma-assisted synthesis at <100 °C. The resulting Ru nanoparticles are monodispersed (typical size 2 nm) and remain that way upon loading onto carbon and TiO 2 supports. This gives robust catalysts with excellent activities in both organosilane oxidation and the oxygen evolution reaction.

A facile method to synthesize boron-doped Ni/Fe alloy nano-chains as electrocatalyst for water oxidation

NASA Astrophysics Data System (ADS)

Yang, Yisu; Zhuang, Linzhou; Lin, Rijia; Li, Mengran; Xu, Xiaoyong; Rufford, Thomas E.; Zhu, Zhonghua

2017-05-01

We report a novel magnetic field assisted chemical reduction method for the synthesis of boron-doped Ni/Fe nano-chains as promising catalysts for the oxygen evolution reaction (OER). The boron-doped Ni/Fe nano-chains were synthesised in a one step process at room temperature using NaBH4 as a reducing agent. The addition of boron reduced the magnetic moment of the intermediate synthesis products and produced nano-chains with a high specific surface area of 73.4 m2 g-1. The boron-doped Ni/Fe nano-chains exhibited catalytic performance superior to state-of-the-art Ba0.5Sr0.5Co0.8Fe0.2O3-δ perovskite and RuO2 noble metal oxide catalysts. The mass normalized activity of the boron-doped Ni/Fe nano-chains measured at an overpotential of 0.35 V was 64.0 A g-1, with a Tafel slope of only 40 mV dec-1. The excellent performance of the boron-doped Ni/Fe nano-chains can be attributed to the uniform elemental distribution and highly amorphous structure of the B-doped nano-chains. These results provide new insights into the effect of doping transition-metal based OER catalysts with non-metallic elements. The study demonstrates a facile approach to prepare transition metal nano-chains using magnetic field assisted chemical reduction method as cheap and highly active catalysts for electrochemical water oxidation.

Facile and Low-cost Synthesis of Mesoporous Ti-Mo Bi-metal Oxide Catalysts for Biodiesel Production from Esterification of Free Fatty Acids in Jatropha curcas Crude Oil.

PubMed

Zhang, Qiuyun; Li, Hu; Yang, Song

2018-05-01

Mesoporous Ti-Mo bi-metal oxides with various titanium-molybdenum ratios were successfully fabricated via a facile approach by using stearic acid as a low-cost template agent. thermal gravity (TG) /differential scanning calorimetry (DSC) analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption-desorption isotherm, NH 3 temperature-programmed desorption (NH 3 -TPD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements indicated these materials possessing mesoporous structure, sufficient pore size and high acid intensity. The catalytic performance of prepared catalysts was evaluated by esterification of free fatty acids in Jatropha curcas crude oil (JCCO) with methanol. The effects of various parameters on FFA conversion were investigated. The esterification conversion of 87.8% was achieved under the condition of 180°C, 2 h, methanol to JCCO molar ratio of 20:1 and 3.0 wt.% catalyst (relative to the weight of JCCO). The mesoporous catalysts were found to exhibit high activities toward the simultaneous esterification and transesterification of JCCO. Furthermore, the catalyst could be recovered with a good reusability.

Sodium citrate assisted facile synthesis of AuPd alloy networks for ethanol electrooxidation with high activity and durability

NASA Astrophysics Data System (ADS)

Zhai, Yanling; Zhu, Zhijun; Lu, Xiaolin; Zhou, H. Susan

2016-10-01

The direct ethanol fuel cell is an emerging energy conversion device for which palladium is considered as the one of the most effective components for anode catalyst, however, its widespread application has been still limited by the activity and durability of the anode catalyst. In this work, AuPd alloy networks (NWs) are synthesized using H2PdCl4 and HAuCl4 as precursors reduced by NaBH4 in the presence of sodium citrate (SC). The results reveal that SC plays significant role in network structure, resulting in the enhanced electrocatalytic activity of the catalyst. This self-supported AuPd NWs catalyst exhibits much higher electrochemical catalytic activity than commercial Pd/C catalyst toward ethanol electrooxidation in alkaline solution. Significantly, AuPd NWs catalyst shows extremely high durability at the beginning of the chronoamperometry test, and as high as 49% of the mass current density (1.41 A/mgPd) remains after 4000 s current-time test at -0.3 V (vs. Ag/AgCl) in N2-saturated KOH-ethanol solution. This strategy provides a facile method for the preparation of alloy networks with high electrochemical activity, and can be potentially expanded to a variety of electrochemical applications.

Synthesis of an amine-oleate derivative using an ionic catalyst

USDA-ARS?s Scientific Manuscript database

A facile (and environmentally friendly) reaction, between epoxidized methyl oleate and aniline to produce an oleate-aniline adduct, without the formation of fatty amide, was discovered. This reaction was carried out neat, with a catalytic amount of an ionic liquid. No solvent or byproducts were pr...

Study of low-temperature active rare-earth oxide catalysts for automotive exhaust clean-up.

DOT National Transportation Integrated Search

2014-02-01

We report a facile onepot synthesis of CexZr1-xO2 (0x1) solid solution nanocrystals using hydrothermal reactions. A direct formation of oxide solid solutions in aqueous solution under pressure at low temperatures was clearly revealed by X-ra...

Mixing with microwaves: solvent-free and catalyst-free synthesis of pyrazoles and diazepines

EPA Science Inventory

A simple and facile condensation of hydrazines/hydrazides and diamines with 1,3-diketones/β-ketoester leads to the preparation of pyrazoles and diazepines in high yields. This eco-friendly protocol is accelerated by microwave heating and efficiently carried out without any r...

V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-09-01

This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only <20% of its electrochemical surface area as compared to 50% loss exhibited by Pt/C. This study thus demonstrates Pt/V-TiO2 nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

Synthesis of flower-like molybdenum sulfide/graphene hybrid as an efficient oxygen reduction electrocatalyst for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Arunchander, A.; Peera, S. Gouse; Sahu, A. K.

2017-06-01

Nanostructured transition metal chalcogenides (TMCs) have significant interest towards electrochemical devices such as fuel cells, metal-ion batteries, due to their unique physical and electrochemical properties. Herein, we report a facile hydrothermal synthesis of flower-like nanostructured molybdenum sulphide and its incorporation on to graphene as a potential oxygen reduction reaction catalyst in alkaline medium. The phase purity and morphological evolution of MoS2 is systematically studied through X-ray diffraction and scanning electron microscopic techniques. The electronic states of metal and non-metallic species are deeply studied by X-ray photoelectron spectroscopy. The effect of annealing temperatures and TMC concentrations are also investigated by electrochemical techniques such as cyclic and linear sweep voltammograms. The optimised electrocatalyst (MoS2/G-500) delivers significant ORR activity with onset and half-wave potentials of 0.91 and 0.80 V (vs. RHE), respectively. Superior durability compared to state-of-art Pt/C catalyst is ascertained by repeating potential cycles for about 5000 times and also by chronoamperometric technique. Finally, the hybrid catalyst is evaluated in AEMFC as cathode catalyst which delivers peak power density of about 29 mW cm-2 under ambient temperature and pressure. The present findings emphasis that MoS2/G catalyst is promising as cost-effective and alternative to noble metal-based catalysts for fuel cell applications.

Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis

PubMed Central

Blosi, Magda; Ortelli, Simona; Costa, Anna Luisa; Dondi, Michele; Lolli, Alice; Andreoli, Sara; Benito, Patricia; Albonetti, Stefania

2016-01-01

This work deals with the development of a green and versatile synthesis of stable mono- and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP) as the chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were achieved with this method of preparation. All of the materials were tested as effective catalysts in the reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to prepare TiO2- and CeO2-supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural (HMF) to 2,5-furandicarboxylic acid (FDCA). The use of Au/Cu and Au/Pd bimetallic catalysts led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3OCFClCF2Cl to CF3OCF=CF2. The effect of Cu on the hydrogenating properties of Pd was demonstrated. PMID:28773672

Hydrothermal Synthesis of Nanostructured Manganese Oxide as Cathodic Catalyst in a Microbial Fuel Cell Fed with Leachate

PubMed Central

Haoran, Yuan; Lifang, Deng; Tao, Lu; Yong, Chen

2014-01-01

Much effort has been devoted to the synthesis of novel nanostructured MnO2 materials because of their unique properties and potential applications as cathode catalyst in Microbial fuel cell. Hybrid MnO2 nanostructures were fabricated by a simple hydrothermal method in this study. Their crystal structures, morphology, and electrochemical characters were carried out by FESEM, N2-adsorption-desorption, and CV, indicating that the hydrothermally synthesized MnO2 (HSM) was structured by nanorods of high aspect ratio and multivalve nanoflowers and more positive than the naturally synthesized MnO2 (NSM), accompanied by a noticeable increase in oxygen reduction peak current. When the HSM was employed as the cathode catalyst in air-cathode MFC which fed with leachate, a maximum power density of 119.07 mW/m2 was delivered, 64.68% higher than that with the NSM as cathode catalyst. Furthermore, the HSM via a 4-e pathway, but the NSM via a 2-e pathway in alkaline solution, and as 4-e pathway is a more efficient oxygen reduction reaction, the HSM was more positive than NSM. Our study provides useful information on facile preparation of cost-effective cathodic catalyst in air-cathode MFC for wastewater treatment. PMID:24723824

One-pot Catalyst-free Synthesis of β- and γ-Hydroxy Sulfides Using Diaryliodonium Salts and Microwaves

EPA Science Inventory

A facile one-pot high-yield protocol is described for the preparation of β- and γ-hydroxy sulfides directly from diaryliodonium salts, potassium thiocyanate, and ethane-1,2-diol (ethylene glycol)/propane-1,3-diol (β-propylene glycol) without the need for any addit...

Facile synthesis of PdAgTe nanowires with superior electrocatalytic activity

NASA Astrophysics Data System (ADS)

Hong, Wei; Wang, Jin; Wang, Erkang

2014-12-01

In this work, ultrathin Te nanowires (NWs) with high-aspect-ratio are prepared by a simple hydrothermal method. By using Te NWs as the sacrificial template, we demonstrate a facile and efficient method for the synthesis of PdAgTe NWs with high-quality through the partly galvanic replacement between Te NWs and the corresponding noble metal salts precursors in an aqueous solution. The compositions of PdAgTe NWs can be tuned by simply altering the concentration of the precursors. After cyclic voltammetry treatment, multi-component PdAgTe NW with a highly active and stable surface can be obtained. The structure and composition of the as-prepared nanomaterials are analyzed by transmission electron microscope, X-ray diffraction, energy dispersive X-ray spectroscopy, inductively coupled plasma-mass spectroscopy and X-ray photoelectron spectroscopy. Electrochemical catalytic measurement results prove that the as synthesized PdAgTe NWs present superior catalytic activity toward ethanol electrooxidation in alkaline solution than the commercial Pd/C catalyst, which making them can be used as effective catalysts for the direct ethanol fuel cells.

Facile synthesis of PdSx/C porous nanospheres and their applications for ethanol oxidation reaction

NASA Astrophysics Data System (ADS)

Zhang, Qiang; Zhang, Fuhua; Ma, Xuemei; Zheng, Yiqun; Hou, Shifeng

2016-12-01

We report a facile approach for the synthesis of carbon-supported palladium polysulphide porous nanospheres (PdSx/C) and their applications for ethanol oxidation reaction. Typical synthesis started with generation of palladium/poly (3,4-ethylenedioxythiophene)(Pd/PEDOT) nanospheres, followed by a calcination process at an optimized temperature to form PdSx/C, with an average size of 2.47 ± 0.60 and 50 nm of PdSx nanoparticles and carbon porous nanospheres, respectively. Various techniques, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electrochemical techniques were performed to characterize their morphologies, compositions and structures. In contrary to most Pd-based electrochemical catalysts that could be easily poised with trace sulfur during the catalytic oxidation process, the as-prepared PdSx/C porous nanospheres exhibited high electrocatalytic activities and stabilities for the electrochemical catalytic oxidation of ethanol in alkaline medium. In particular, the forward peak current intensity achieved 162.1 mA mg-1 and still maintained at 46.7 mA mg-1 even after 1000 cycles. This current work not only offers a novel type of fuel-cell catalyst for ethanol oxidation reaction, but also provides a possible route for solving the sulfur-poisoning problem in catalysis.

Alternative Fuels Research Laboratory

NASA Technical Reports Server (NTRS)

Surgenor, Angela D.; Klettlinger, Jennifer L.; Nakley, Leah M.; Yen, Chia H.

2012-01-01

NASA Glenn has invested over $1.5 million in engineering, and infrastructure upgrades to renovate an existing test facility at the NASA Glenn Research Center (GRC), which is now being used as an Alternative Fuels Laboratory. Facility systems have demonstrated reliability and consistency for continuous and safe operations in Fischer-Tropsch (F-T) synthesis and thermal stability testing. This effort is supported by the NASA Fundamental Aeronautics Subsonic Fixed Wing project. The purpose of this test facility is to conduct bench scale F-T catalyst screening experiments. These experiments require the use of a synthesis gas feedstock, which will enable the investigation of F-T reaction kinetics, product yields and hydrocarbon distributions. Currently the facility has the capability of performing three simultaneous reactor screening tests, along with a fourth fixed-bed reactor for catalyst activation studies. Product gas composition and performance data can be continuously obtained with an automated gas sampling system, which directly connects the reactors to a micro-gas chromatograph (micro GC). Liquid and molten product samples are collected intermittently and are analyzed by injecting as a diluted sample into designated gas chromatograph units. The test facility also has the capability of performing thermal stability experiments of alternative aviation fuels with the use of a Hot Liquid Process Simulator (HLPS) (Ref. 1) in accordance to ASTM D 3241 "Thermal Oxidation Stability of Aviation Fuels" (JFTOT method) (Ref. 2). An Ellipsometer will be used to study fuel fouling thicknesses on heated tubes from the HLPS experiments. A detailed overview of the test facility systems and capabilities are described in this paper.

Sono-synthesis of solar light responsive S-N-C-tri doped TiO2 photo-catalyst under optimized conditions for degradation and mineralization of Diclofenac.

PubMed

Ramandi, Sara; Entezari, Mohammad H; Ghows, Narjes

2017-09-01

C-N-S-tri doped TiO 2 anatase phase was synthesized using a facile, effective and novel sonochemical method at low frequency (20kHz) and at room temperature. Titanium butoxide as the titanium precursor and thiourea as the dopant source were used in the synthesis of the photo-catalyst. The effects of important parameters such as thiourea/Ti molar ratio, ultrasound intensity, sonication time and temperature were studied on the synthesis of tri-doped TiO 2 . The XPS results confirmed the presence of N, S, and C in the photo-catalyst. The photo-catalytic efficiency of the synthesized catalyst was studied toward the removal of Diclofenac as a model pharmaceutical organic pollutant. The results confirmed that the photo-catalyst synthesized with narrower band gap energy, shorter sonication time and higher ultrasound intensity leads to a rapid removal of Diclofenac. The effect of operational variables on the photo-catalytic activity of C-N-S tri doped TiO 2 nanoparticles was studied and optimized using the Taguchi method as a statistical technique. Additionally, the degradation process followed the pseudo-first-order kinetics model and the highest apparent rate constant of 0.0632min -1 achieved in 90min. Chemical oxygen demand (COD) analysis confirmed that the mineralization took place completely (100%) under the optimized conditions in 180min. Different scavengers were applied during the degradation process and active species such as OH and O 2 - had key roles in the photo-catalytic process. Copyright © 2017 Elsevier B.V. All rights reserved.

Magnetically Recoverable Pd/Fe 3O 4 Core-Shell Nanowire Clusters with Increased Hydrogenation Activity

DOE PAGES

Watt, John; Kotula, Paul G.; Huber, Dale L.

2017-02-06

Core-shell nanostructures are promising candidates for the next generation of catalysts due to synergistic effects which can arise from having two active species in close contact, leading to increased activity. Likewise, catalysts displaying added functionality, such as a magnetic response, can increase their scientific and industrial potential. Here, we synthesize Pd/Fe 3O 4 core-shell nanowire clusters and apply them as hydrogenation catalysts for an industrially important hydrogenation reaction; the conversion of acetophenone to 1-phenylethanol. During synthesis, the palladium nanowires self-assemble into clusters which act as a high surface area framework for the growth of a magnetic iron oxide shell. Wemore » demonstrate excellent catalytic activity due to the presence of palladium while the strong magnetic properties provided by the iron oxide shell enable facile catalyst recovery.« less

Size-controlled synthesis of NiFe2O4 nanospheres via a PEG assisted hydrothermal route and their catalytic properties in oxidation of alcohols by periodic acid

NASA Astrophysics Data System (ADS)

Paul, Bappi; Purkayastha, Debraj Dhar; Dhar, Siddhartha Sankar

2016-05-01

A novel and facile approach for synthesis of spinel nickel ferrites (NiFe2O4) nanoparticles (NPs) employing homogeneous chemical precipitation followed by hydrothermal heating is reported. The synthesis involves use of tributylamine (TBA) as a hydroxylating agent in synthesis of nickel ferrites. Polyethylene glycol (PEG) 4000 was used as surfactant. As-synthesized NiFe2O4 NPs were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption-desorption isotherm (BET) and vibrating sample magnetometry (VSM). The XRD pattern revealed formation of cubic face-centered NiFe2O4 and TEM image showed spherical particles of sizes 2-10 nm. These NiFe2O4 NPs were used as magnetically recoverable catalyst in oxidation of cyclic alcohols to their corresponding aldehydes by periodic acid. This eco-friendly procedure affords products in very high yield and selectivity. The reusability of the catalyst is proved to be noteworthy as the material exhibits no significant changes in its catalytic activity even after five cycles of reuse.

Carbon-embedded Ni nanocatalysts derived from MOFs by a sacrificial template method for efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol.

PubMed

Su, Yanping; Chen, Chun; Zhu, Xiaoguang; Zhang, Yong; Gong, Wanbing; Zhang, Haimin; Zhao, Huijun; Wang, Guozhong

2017-05-16

We report a fast and simple method for the synthesis of Ni-based metal-organic-frameworks (Ni-MOFs). Due to the existence of nickel ions and an organic ligand, the MOFs are employed as a sacrificial template for the facile preparation of carbon-embedded Ni (Ni/C) catalysts by a direct thermal decomposition method. The obtained Ni/C catalysts exhibit excellent catalytic activity for selectively transforming furfural (FAL) to tetrahydrofurfuryl alcohol (THFOL) due to the Ni nanoparticles (NPs) embedded uniformly in the ligand-derived carbon. The exemplified results illustrate that the catalytic performance of the Ni/C catalyst is greatly affected by the calcination conditions (temperature and time), composition of the Ni-MOF precursor and the catalysis conditions. The conversion of FAL and selectivity of THFOL both reached 100% under the conditions of 120 °C, 1 MPa H 2 pressure and 120 min of hydrogenation over the Ni/C-500 catalyst, derived from the pyrolysis of Ni-MOFs (Ni : BTC mole ratio of 1.0) at 500 °C for 120 min, which exhibits an average nanoparticle size of ∼14 nm and uniform dispersion, and the highest BET surface area (∼92 m 2 g -1 ) among all investigated Ni/C catalysts. This facilely prepared heterogeneous catalyst would be very promising for the replacement of noble metal catalysts for the efficient catalytic conversion of biomass-derived feedstocks into value-added chemicals.

On the Synthesis of Carbon Nanotubes from Waste Solid Hydrocarbons

NASA Astrophysics Data System (ADS)

Zhuo, Chuanwei

Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. They consist of coaxial tubular graphene sheets, with diameters in the order of nanometers (1 x 10-9 m) and lengths in the order of micrometers (1 x 10-6 m). The latter can now be extended into the order of meters. Carbon nanotubes (CNTs) have been studied for more than 20 years. CNTs possess superior electrical, mechanical, thermal, chemical, and structural properties, which make their potential applications nowadays overwhelmingly widespread. Now entering into the growth phase of product life cycle, increasing usage of CNTs in commercial products is part of the beginning of the nano-technological revolution. Expanding markets for CNTs' large volume applications place ever-increasing demands on lowering their production costs to the level acceptable by the end-user applications. It is estimated that the mass application of CNTs will be facilitated only when the price of CNTs approaches that of conductive carbon black. The synthesis of CNTs involves three elements: the carbonaceous feedstocks (raw materials), the catalysts, and the necessary process power consumption. Therefore, they jointly contribute to the major operation expenditures in CNT synthesis/production. Current technologies for large-scale production of CNTs (either chemical vapor deposition, CVD, or combustion synthesis) require intensive consumption of premium feedstocks and catalysts, and the CVD process requires high energy consumption. Therefore, there is a pressing need for resource-benign and energy-benign, cost-effective nano-manufacturing processes. In the search for sustainable alternatives, it would be prudent to explore renewable and/or replenishable low-cost feedstocks, such as those found in municipal, industrial, and agricultural recycling streams. In the search for low cost catalysts, stainless steels have been proposed as cost-effective dual purpose substrates and catalysts, as they contain transition metals (iron, nickel, etc.) which are well-documented to be effective catalysts for CNT growth. In this doctoral dissertation, the feasibility of utilizing municipal / industrial / agriculture wastes as carbon sources for CNTs has been examined and proven. It was also found that the effluents of the CNT synthesis process can also serve as gaseous fuels for "clean" power production, which can then be used for energy self-sustaining CNT synthesis. Besides, a facile catalyst pre-treatment has been developed to activate stainless steel based substrate/catalyst for efficient CNT growth. Finally, the efforts of CO2 on the pyrolyzate gases and on the CNT co-generation were also investigated.

Facile solvothermal synthesis of highly active and robust Pd1.87Cu0.11Sn electrocatalyst towards direct ethanol fuel cell applications

NASA Astrophysics Data System (ADS)

Jana, Rajkumar; Dhiman, Shikha; Peter, Sebastian C.

2016-08-01

Ordered intermetallic Pd1.87Cu0.11Sn ternary electrocatalyst has been synthesized by sodium borohydride reduction of precursor salts Pd(acac)2, CuCl2.2H2O and SnCl2 using one-pot solvothermal synthesis method at 220 °C with a reaction time of 24 h. To the best of our knowledge, here for the first time we report surfactant free synthesis of a novel ordered intermetallic ternary Pd1.87Cu0.11Sn nanoparticles. The ordered structure of the catalyst has been confirmed by powder x-ray diffraction, transmission electron microscopy (TEM). Composition and morphology of the nanoparticles have been confirmed through field emission scanning electron microscopy, energy-dispersive spectrometry and TEM. The electrocatalytic activity and stability of the ternary electrocatalyst towards ethanol oxidation in alkaline medium was investigated by cyclic voltammetry and chronoamperometry techniques. The catalyst is proved to be highly efficient and stable upto 500th cycle and even better than commercially available Pd/C (20 wt%) electrocatalysts. The specific and mass activity of the as synthesized ternary catalyst are found to be ∼4.76 and ∼2.9 times better than that of commercial Pd/C. The enhanced activity and stability of the ordered ternary Pd1.87Cu0.11Sn catalyst can make it as a promising candidate for the alkaline direct ethanol fuel cell application.

Facile synthesis of highly active reduced graphene oxide-CuI catalyst through a simple combustion method for photocatalytic reduction of CO2 to methanol

NASA Astrophysics Data System (ADS)

Zhang, Wenjun; Li, Yingjie; Zhang, Xiaoxiong; Li, Cuiluo

2017-09-01

We report a facile combustion method synthesis of reduced graphene oxide/CuI composites as a photocatalyst, in which CuI nanoparticles were homogeneously distributed on the surface of reduced graphene oxide (rGO), showing a good visible light response. The rGO-supported and unsupported CuI hybrids were tested over the photocatalytic reduction of CO2 for methanol evolution in visible light. In the current study rGO-CuI composites have shown excellent yields (19.91 μmol g-cat-1). rGO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the CuI nanoparticles.

In situ synthesis and catalytic application of reduced graphene oxide supported cobalt nanowires

NASA Astrophysics Data System (ADS)

Xu, Zhiqiang; Long, Qin; Deng, Yi; Liao, Li

2018-05-01

Controlled synthesis of magnetic nanocomposite with outstanding catalytic performances is a promising strategy in catalyst industry. We proposed a novel concept for fabrication of reduced graphene oxide-supported cobalt nanowires (RGO/Co-NWs) nanocomposite as high-efficient magnetic catalyst. Unlike the majority of experiments necessitating harsh synthesis conditions such as high-pressure, high-temperature and expensive template, here the RGO/Co-NWs were successfully prepared in aqueous solution under mild conditions with the assistance of external magnetic field. The synthetic process was facile and external magnetic force was adopted to induce the unidirectional self-assembly of cobalt crystals on graphene oxide to form RGO/Co-NWs. The possible formation mechanism laid on the fact that the dipole magnetic moments of the nanoparticles were aligned along the magnetic induction lines with the external magnetic field direction resulting in the formation of nanowires elongating in the direction of the magnetization axis. Simultaneously, a series of controlled reactions were conducted to illuminate the effect of graphene oxide, external magnetic field and PVP on the morphology and size of RGO/Co-NWs in the present approach. More importantly, the nanocomposite exhibited a high catalytic performance towards ammonia borane. Hence the novel nanocomposite holds a great potential for technological applications such as catalyst industry.

Magnetic porous Fe3O4/carbon octahedra derived from iron-based metal-organic framework as heterogeneous Fenton-like catalyst

NASA Astrophysics Data System (ADS)

Li, Wenhui; Wu, Xiaofeng; Li, Shuangde; Tang, Wenxiang; Chen, Yunfa

2018-04-01

The synthesis of effective and recyclable Fenton-like catalyst is still a key factor for advanced oxidation processes. Herein, magnetic porous Fe3O4/carbon octahedra were constructed by a two-step controlled calcination of iron-based metal organic framework. The porous octahedra were assembled by interpenetrated Fe3O4 nanoparticles coated with graphitic carbon layer, offering abundant mesoporous channels for the solid-liquid contact. Moreover, the oxygen-containing functional groups on the surface of graphitic carbon endow the catalysts with hydrophilic nature and well-dispersion into water. The porous Fe3O4/carbon octahedra show efficiently heterogeneous Fenton-like reactions for decomposing the organic dye methylene blue (MB) with the help of H2O2, and nearly 100% removal efficiency within 60 min. Furthermore, the magnetic catalyst retains the activity after ten cycles and can be easily separated by external magnetic field, indicating the long-term catalytic durability and recyclability. The good Fenton-like catalytic performance of the as-synthesized Fe3O4/carbon octahedra is ascribed to the unique mesoporous structure derived from MOF-framework, as well as the sacrificial role and stabilizing effect of graphitic carbon layer. This work provides a facile strategy for the controllable synthesis of integrated porous octahedral structure with graphitic carbon layer, and thereby the catalyst holds significant potential for wastewater treatment.

Facile Fabrication of Composition-Tuned Ru-Ni Bimetallics in Ordered Mesoporous Carbon for Levulinic Acid Hydrogenation

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

Yang, Ying; Gao, Guang; Zhang, Xin

Bimetallic catalysts are of great importance due to their unique catalytic properties. However, their conventional synthesis requires tedious multistep procedures and prolonged synthetic time, and the resulting bimetallics usually disperse unevenly and show poor stability. It is challenging to develop a facile and step-economic synthetic methodology for highly efficient bimetallic catalysts. In this study, we report an elegant metal complex-involved multicomponent assembly route to highly efficient Ru–Ni bimetallics in ordered mesoporous carbons (OMC). The fabrication of composition-tuned Ru–Ni bimetallics in OMC (Ru xNi 1–x–OMC, x = 0.5–0.9) was facilely realized via in situ construction of CTAB-directed cubic Ia3d chitosan-ruthenium–nickel–silica mesophasemore » before pyrolysis and silica removal. The resulting Ru xNi 1–x–OMC materials are in-depth characterized with X-ray diffraction, N 2 adsorption–desorption, transmission electron microscopy, infrared spectrum, and X-ray absorption fine structure. This facile fabrication method renders homogeneously dispersed Ru–Ni bimetallics embedded in the mesoporous carbonaceous framework and creates a highly active and stable Ru 0.9Ni 0.1–OMC catalyst for the hydrogenation of levulinic acid (LA) to prepare γ-valerolactone (GVL), a biomass-derived platform molecule with wide application in the preparation of renewable chemicals and liquid transportation fuels. A high TOF (>2000 h –1) was obtained, and the Ru 0.9Ni 0.1–OMC catalyst could be used at least 15 times without obvious loss of its catalytic performance.« less

Preparation and characterization of V/TiO{sub 2} nanocatalyst with magnetic nucleus of iron

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

Feyzi, Mostafa; Rafiee, Hamid Reza, E-mail: rafieehr@yahoo.com; Ranjbar, Shahram

2013-11-15

Graphical abstract: - Highlights: • Fe-V/TiO{sub 2} nanocatalyst is prepared. • Combination of sol–gel and wetness impregnation methods. • Facile separation of catalyst from medium by magnet. - Abstract: A magnetic composite containing V/TiO{sub 2} was prepared by combination of sol–gel and wetness impregnation methods. The effects of synthesis temperature, different weight percents of Fe supported on TiO{sub 2}, vanadium loading and the heating rate of calcination on the structure and morphology of nanocatalyst were investigated. The optimum conditions for synthesized catalyst were 40 wt.% of Fe, 15 wt.% of V and synthesis temperature equal to 30 °C. Characterization ofmore » catalyst is carried out using XRD, TGA, DSC, SEM, FTIR and N{sub 2} physisorption measurements. The magnetic character of nanocatalyst was measured using VSM, which showed the typical paramagnetic behavior of sample at room temperature with a saturation magnetization value equal to 8.283 emu/g. The nanocatalyst has a particle size about 56 nm and can easily be separated from medium by a magnet.« less

Synthesis of vertical MnO2 wire arrays on hemp-derived carbon for efficient and robust green catalysts

NASA Astrophysics Data System (ADS)

Yang, MinHo; Kim, Dong Seok; Sim, Jae-Wook; Jeong, Jae-Min; Kim, Do Hyun; Choi, Jae Hyung; Kim, Jinsoo; Kim, Seung-Soo; Choi, Bong Gill

2017-06-01

Three-dimensional (3D) carbon materials derived from waste biomass have been attracted increasing attention in catalysis and materials science because of their great potential of catalyst supports with respect to multi-functionality, unique structures, high surface area, and low cost. Here, we present a facile and efficient way for preparing 3D heterogeneous catalysts based on vertical MnO2 wires deposited on hemp-derived 3D porous carbon. The 3D porous carbon materials are fabricated by carbonization and activation processes using hemp (Cannabis Sttiva L.). These 3D porous carbon materials are employed as catalyst supports for direct deposition of vertical MnO2 wires using a one-step hydrothermal method. The XRD and XPS results reveal the crystalline structure of α-MnO2 wires. The resultant composites are further employed as a catalyst for glycolysis of poly(ethylene terephthalate) (PET) with high conversion yield of 98%, which is expected to be expressly profitable for plastics recycling industry.

One-Pot Polyol Synthesis of Pt/CeO2 and Au/CeO2 Nanopowders as Catalysts for CO Oxidation.

PubMed

Pilger, Frank; Testino, Andrea; Lucchini, Mattia Alberto; Kambolis, Anastasios; Tarik, Mohammed; El Kazzi, Mario; Arroyo, Yadira; Rossell, Marta D; Ludwig, Christian

2015-05-01

The facile one-pot synthesis of CeO2-based catalysts has been developed to prepare a relatively large amount of nanopowders with relevant catalytic activity towards CO oxidation. The method consists of a two-steps process carried out in ethylene glycol: in the first step, 5 nm well-crystallized pure CeO2 is prepared. In a subsequent second step, a salt of a noble metal is added to the CeO2 suspension and the deposition of the noble metal on the nanocrystalline CeO2 is induced by heating. Two catalysts were prepared: Pt/CeO2 and Au/CeO2. The as-prepared catalysts, the thermally treated catalysts, as well as the pure CeO2, are characterized by XRD, TGA, XPS, FTIR, HR-TEM, STEM, particle size distribution, and N2-physisorption. In spite of the identical preparation protocol, Au and Pt behave in a completely different way: Au forms rather large particles, most of them with triangular shape, easily identifiable and dispersed in the CeO2 matrix. In contrast, Pt was not identified as isolated particles. The high resolution X-ray diffraction carried out on the Pt/CeO2 thermally treated sample (500 degrees C for 1 h) shows a significant CeO2 lattice shrinkage, which can be interpreted as an at least partial incorporation of Pt into the CeO2 crystal lattice. Moreover, only Pt2+ and Pt4+ species were identified by XPS. In literature, the incorporation of Pt into the CeO2 lattice is supported by first-principle calculations and experimentally demonstrated only by combustion synthesis methods. To the best of our knowledge this is the first report where ionically dispersed Pt into the CeO2 lattice is obtained via a liquid synthesis method. The thermally treated Pt/CeO2 sample revealed good activity with 50% CO conversion at almost room temperature.

Lewis Acid Catalyzed Asymmetric Three-Component Coupling Reaction: Facile Synthesis of α-Fluoromethylated Tertiary Alcohols.

PubMed

Aikawa, Kohsuke; Kondo, Daisuke; Honda, Kazuya; Mikami, Koichi

2015-12-01

A chiral dicationic palladium complex is found to be an efficient Lewis acid catalyst for the synthesis of α-fluoromethyl-substituted tertiary alcohols using a three-component coupling reaction. The reaction transforms three simple and readily available components (terminal alkyne, arene, and fluoromethylpyruvate) to valuable chiral organofluorine compounds. This strategy is completely atom-economical and results in perfect regioselectivities and high enantioselectivities of the corresponding tertiary allylic alcohols in good to excellent yields. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Merging gold and organocatalysis: a facile asymmetric synthesis of annulated pyrroles.

PubMed

Hack, Daniel; Loh, Charles C J; Hartmann, Jan M; Raabe, Gerhard; Enders, Dieter

2014-04-01

The combination of cinchona-alkaloid-derived primary amine and Au(I) -phosphine catalysts allowed the selective C-H functionalization of two adjacent carbon atoms of pyrroles under mild reaction conditions. This sequential dual activation provides seven-membered-ring-annulated pyrrole derivatives in excellent yields and enantioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pd@Pt Core–Shell Nanoparticles with Branched Dandelion-like Morphology as Highly Efficient Catalysts for Olefin Reduction

EPA Science Inventory

A facile synthesis based on the addition of ascorbic acid to a mixture of Na2PdCl4, K2PtCl6, and Pluronic P123 results in highly branched core–shell nanoparticles (NPs) with a micro–mesoporous dandelion-like morphology comprising Pd core and Pt shell. The slow reduction kinetics ...

Investigation of syngas interaction in alcohol synthesis catalysts. Quarterly technical progress report, September 1, 1993--January 31, 1994

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

Not Available

1994-02-10

The project establishes the necessary experiment and laboratory facilities at Xavier University. This phase of the work has taken a considerable amount of time, due to the limited laboratory space and the involved administrative policies and procedures in procuring the necessary chemicals, glassware and auxiliary supplies. Though there still remain some minor problems with space, the laboratory is now equipped for preparation of catalysts. During this period, the authors focused their attention toward analyzing the magnetic nature of extensively used trimetallic catalyst system Cu-Co-Cr for the production of higher alcohols. The authors decided to investigate the effect of method ofmore » preparation and intermetallic ratio on the magnetic behavior of the system.« less

ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

NASA Astrophysics Data System (ADS)

Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

2018-04-01

Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

Ultrasound mediated catalyst free synthesis of 6H-1-benzopyrano[4,3-b]quinolin-6-ones leading to novel quinoline derivatives: their evaluation as potential anti-cancer agents.

PubMed

Mulakayala, Naveen; Rambabu, D; Raja, Mohan Rao; M, Chaitanya; Kumar, Chitta Suresh; Kalle, Arunasree M; Rama Krishna, G; Malla Reddy, C; Basaveswara Rao, M V; Pal, Manojit

2012-01-15

A facile and catalyst free synthesis of 6H-1-benzopyrano[4,3-b]quinolin-6-ones has been accomplished via the reaction of 4-chloro-2-oxo-2H-chromene-3-carbaldehyde with various aromatic amines in the presence of ultrasound. Some of these compounds were converted to the corresponding 2-(3-(hydroxymethyl)quinolin-2-yl)phenols and further structure elaboration of a representative quinoline derivative is presented. Molecular structure of two representative compounds was confirmed by single crystal X-ray diffraction study. Many of these compounds were evaluated for their anti-proliferative properties in vitro against four cancer cell lines and several compounds were found to be active. Further in vitro studies indicated that inhibition of sirtuins could be the possible mechanism of action of these molecules. Copyright © 2011 Elsevier Ltd. All rights reserved.

Heavily Graphitic-Nitrogen Self-doped High-porosity Carbon for the Electrocatalysis of Oxygen Reduction Reaction

NASA Astrophysics Data System (ADS)

Feng, Tong; Liao, Wenli; Li, Zhongbin; Sun, Lingtao; Shi, Dongping; Guo, Chaozhong; Huang, Yu; Wang, Yi; Cheng, Jing; Li, Yanrong; Diao, Qizhi

2017-11-01

Large-scale production of active and stable porous carbon catalysts for oxygen reduction reaction (ORR) from protein-rich biomass became a hot topic in fuel cell technology. Here, we report a facile strategy for synthesis of nitrogen-doped porous nanocarbons by means of a simple two-step pyrolysis process combined with the activation of zinc chloride and acid-treatment process, in which kidney bean via low-temperature carbonization was preferentially adopted as the only carbon-nitrogen sources. The results show that this carbon material exhibits excellent ORR electrocatalytic activity, and higher durability and methanol-tolerant property compared to the state-of-the-art Pt/C catalyst for the ORR, which can be mainly attributed to high graphitic-nitrogen content, high specific surface area, and porous characteristics. Our results can encourage the synthesis of high-performance carbon-based ORR electrocatalysts derived from widely-existed natural biomass.

Theophylline-assisted, eco-friendly synthesis of PtAu nanospheres at reduced graphene oxide with enhanced catalytic activity towards Cr(VI) reduction.

PubMed

Hu, Ling-Ya; Chen, Li-Xian; Liu, Meng-Ting; Wang, Ai-Jun; Wu, Lan-Ju; Feng, Jiu-Ju

2017-05-01

Theophylline as a naturally alkaloid is commonly employed to treat asthma and chronic obstructive pulmonary disorder. Herein, a facile theophylline-assisted green approach was firstly developed for synthesis of PtAu nanospheres/reduced graphene oxide (PtAu NSs/rGO), without any surfactant, polymer, or seed involved. The obtained nanocomposites were applied for the catalytic reduction and removal of highly toxic chromium (VI) using formic acid as a model reductant at 50°C, showing the significantly enhanced catalytic activity and improved recyclability when compared with commercial Pt/C (50%) and home-made Au nanocrystals supported rGO (Au NCs/rGO). It demonstrates great potential applications of the catalyst in wastewater treatment and environmental protection. The eco-friendly route provides a new platform to fabricate other catalysts with enhanced catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Greener Route for Synthesis of aryl and alkyl-14H-dibenzo [a.j] xanthenes using Graphene Oxide-Copper Ferrite Nanocomposite as a Recyclable Heterogeneous Catalyst

NASA Astrophysics Data System (ADS)

Kumar, Aniket; Rout, Lipeeka; Achary, Lakkoji Satish Kumar; Dhaka, Rajendra. S.; Dash, Priyabrat

2017-02-01

A facile, efficient and environmentally-friendly protocol for the synthesis of xanthenes by graphene oxide based nanocomposite (GO-CuFe2O4) has been developed by one-pot condensation route. The nanocomposite was designed by decorating copper ferrite nanoparticles on graphene oxide (GO) surface via a solution combustion route without the use of template. The as-synthesized GO-CuFe2O4 composite was comprehensively characterized by XRD, FTIR, Raman, SEM, EDX, HRTEM with EDS mapping, XPS, N2 adsorption-desorption and ICP-OES techniques. This nanocomposite was then used in an operationally simple, cost effective, efficient and environmentally benign synthesis of 14H-dibenzo xanthene under solvent free condition. The present approach offers several advantages such as short reaction times, high yields, easy purification, a cleaner reaction, ease of recovery and reusability of the catalyst by a magnetic field. Based upon various controlled reaction results, a possible mechanism for xanthene synthesis over GO-CuFe2O4 catalyst was proposed. The superior catalytic activity of the GO-CuFe2O4 nanocomposite can be attributed to the synergistic interaction between GO and CuFe2O4 nanoparticles, high surface area and presence of small sized CuFe2O4 NPs. This versatile GO-CuFe2O4 nanocomposite synthesized via combustion method holds great promise for applications in wide range of industrially important catalytic reactions.

Facile Synthesis of Single Crystal Vanadium Disulfide Nanosheets by Chemical Vapor Deposition for Efficient Hydrogen Evolution Reaction.

PubMed

Yuan, Jiangtan; Wu, Jingjie; Hardy, Will J; Loya, Philip; Lou, Minhan; Yang, Yingchao; Najmaei, Sina; Jiang, Menglei; Qin, Fan; Keyshar, Kunttal; Ji, Heng; Gao, Weilu; Bao, Jiming; Kono, Junichiro; Natelson, Douglas; Ajayan, Pulickel M; Lou, Jun

2015-10-07

A facile chemical vapor deposition method to prepare single-crystalline VS2 nanosheets for the hydrogen evolution reaction is reported. The electrocatalytic hydrogen evolution reaction (HER) activities of VS2 show an extremely low overpotential of -68 mV at 10 mA cm(-2), small Tafel slopes of ≈34 mV decade(-1), as well as high stability, demonstrating its potential as a candidate non-noble-metal catalyst for the HER. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

PubMed Central

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-01-01

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology. PMID:27340940

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst.

PubMed

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-06-08

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm(2)), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

Rapid synthesis of Fe-doped CuO-Ce0.8Zr0.2O2 catalysts for CO preferential oxidation in H2-rich streams: Effect of iron source and the ratio of Fe/Cu

NASA Astrophysics Data System (ADS)

Wang, Jing; Han, Caiyun; Gao, Xiaoya; Lu, Jichang; Wan, Gengpin; He, Dedong; Chen, Ran; Chen, Kezhen; He, Sufang; Luo, Yongming

2017-03-01

A facile route (urea grind combustion method) is described for the rapid synthesis of Fe-doped Cu-Ce-Zr catalysts within 30 min through simple grinding and combustion. The effects of iron source and Fe/Cu mass ratio on the performances of the catalysts for CO preferential oxidation (CO-PROX) are evaluated. The influences of H2O, CO2, and their mixture on the activity as well as stability of the catalysts are also investigated. The samples are characterized by XRD, N2 adsorption-desorption, H2-TPR, TEM, Raman and XPS. Fe(NO3)3 is found to be superior to FeCl3 and Fe2(SO4)3 as the iron source for Fe-CuCZ catalyst. Among the different synthesized catalysts, 1/10Fe(N)-CuCZ is found to be the most active catalyst, indicating that the optimal Fe/Cu mass ratio is 1/10. The influences of H2O, CO2, and H2O + CO2 on the catalytic performance of 1/10Fe(N)-CuCZ are in the order of CO2 < CO2 + H2O < H2O. 1/10Fe(N)-CuCZ exhibits excellent stability during a 228 h time-on-stream test. 1/10Fe(N)-CuCZ shows the highest catalytic activity and excellent stability even in the presence of H2O and CO2. The excellent catalytic performance can be attributed to the synergy between the highly dispersed copper species and ceria, as well as the formation of more oxygen vacancies and reduced copper species.

MIL-100 derived nitrogen-embodied carbon shells embedded with iron nanoparticles

NASA Astrophysics Data System (ADS)

Mao, Chengyu; Kong, Aiguo; Wang, Yuan; Bu, Xianhui; Feng, Pingyun

2015-06-01

The use of metal-organic frameworks (MOFs) as templates and precursors to synthesize new carbon materials with controllable morphology and pre-selected heteroatom doping holds promise for applications as efficient non-precious metal catalysts. Here, we report a facile pyrolysis pathway to convert MIL-100 into nitrogen-doped carbon shells encapsulating Fe nanoparticles in a comparative study involving multiple selected nitrogen sources. The hierarchical porous architecture, embedded Fe nanoparticles, and nitrogen decoration endow this composite with a superior oxygen reduction activity. Furthermore, the excellent durability and high methanol tolerance even outperform the commercial Pt-C catalyst.The use of metal-organic frameworks (MOFs) as templates and precursors to synthesize new carbon materials with controllable morphology and pre-selected heteroatom doping holds promise for applications as efficient non-precious metal catalysts. Here, we report a facile pyrolysis pathway to convert MIL-100 into nitrogen-doped carbon shells encapsulating Fe nanoparticles in a comparative study involving multiple selected nitrogen sources. The hierarchical porous architecture, embedded Fe nanoparticles, and nitrogen decoration endow this composite with a superior oxygen reduction activity. Furthermore, the excellent durability and high methanol tolerance even outperform the commercial Pt-C catalyst. Electronic supplementary information (ESI) available: Material synthesis and elemental analysis, electrochemistry measurements, and additional figures. See DOI: 10.1039/c5nr02346g

Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

DOEpatents

Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

1998-01-01

The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

Facile Synthesis of Defect-Rich and S/N Co-Doped Graphene-Like Carbon Nanosheets as an Efficient Electrocatalyst for Primary and All-Solid-State Zn-Air Batteries.

PubMed

Zhang, Jian; Zhou, Huang; Zhu, Jiawei; Hu, Pei; Hang, Chao; Yang, Jinlong; Peng, Tao; Mu, Shichun; Huang, Yunhui

2017-07-26

Developing facile and low-cost porous graphene-based catalysts for highly efficient oxygen reduction reaction (ORR) remains an important matter for fuel cells. Here, a defect-enriched and dual heteroatom (S and N) doped hierarchically porous graphene-like carbon nanomaterial (D-S/N-GLC) was prepared by a simple and scalable strategy, and exhibits an outperformed ORR activity and stability as compared to commercial Pt/C catalyst in an alkaline condition (its half-wave potential is nearly 24 mV more positive than Pt/C). The excellent ORR performance of the catalyst can be attributed to the synergistic effect, which integrates the novel graphene-like architectures, 3D hierarchically porous structure, superhigh surface area, high content of active dopants, and abundant defective sites in D-S/N-GLC. As a result, the developed catalysts are used as the air electrode for primary and all-solid-state Zn-air batteries. The primary batteries demonstrate a higher peak power density of 252 mW cm -2 and high voltage of 1.32 and 1.24 V at discharge current densities of 5 and 20 mA cm -2 , respectively. Remarkably, the all-solid-state battery also exhibits a high peak power density of 81 mW cm -2 with good discharge performance. Moreover, such catalyst possesses a comparable ORR activity and higher stability than Pt/C in acidic condition. The present work not only provides a facile but cost-efficient strategy toward preparation of graphene-based materials, but also inspires an idea for promoting the electrocatalytic activity of carbon-based materials.

Catalyst for selective conversion of synthesis gas and method of making the catalyst

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald

1986-01-01

A Fischer-Tropsch (F-T) catalyst, a method of making the catalyst and an F-T process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range. In general, the selective and notably stable catalyst, consists of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of an F-T metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

A novel copper complex supported on magnetic reduced graphene oxide: an efficient and green nanocatalyst for the synthesis of 1-amidoalkyl-2-naphthol derivatives

NASA Astrophysics Data System (ADS)

Kooti, M.; Karimi, M.; Nasiri, E.

2018-02-01

A new Cu(II) complex supported on magnetic reduced graphene oxide was prepared and characterized by various techniques, such as FT-IR, XRD, SEM, EDX, TEM, TGA, BET, ICP, and VSM. The synthesized nanocomposite, which has size distribution of 25-30 nm, was employed as catalyst in one-pot synthesis of 1-amidoalkyl-2-naphthols via three-component condensation reaction of amides, aromatic aldehydes, and 2-naphthol, under solvent-free conditions. The introduced catalysis procedure for the synthesis of 1-amidoalkyl-2-naphthol derivatives offers several advantages namely, short reaction times, high yields, facile recyclability, and cost effectiveness. [Figure not available: see fulltext.

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

One-pot solvothermal synthesis of ordered intermetallic Pt{sub 2}In{sub 3} as stable and efficient electrocatalyst towards direct alcohol fuel cell application

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

Jana, Rajkumar; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

Ordered intermetallic Pt{sub 2}In{sub 3} nanoparticles have been synthesized by superhydride reduction of K{sub 2}PtCl{sub 4} and InCl{sub 3}.xH{sub 2}O precursors using facile, one-pot solvothermal method. We report surfactant free solvothermal synthesis of a novel ordered Pt{sub 2}In{sub 3} intermetallic nanoparticles for the first time. The structure and morphology of the catalyst has been confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, energy-dispersive spectrometry and X-ray photoelectron spectroscopy. The electrocatalytic properties of the catalysts have been investigated by cyclic voltammetry and chronoamperometry. The as prepared Pt{sub 2}In{sub 3} catalyst exhibit far superior electrocatalytic activity andmore » stability towards alcohol oxidation over commercial Pt/C. The specific activity of as synthesized catalyst was found to be ~3.2 and ~2.3 times higher than commercial Pt/C for methanol and ethanol oxidation, respectively. This improved activity and durability of the Pt{sub 2}In{sub 3} nanoparticles can make the catalyst an ideal catalyst candidate for direct alcohol fuel cell. - Graphical abstract: The ordered structure of Pt{sub 2}In{sub 3} nanoparticles synthesized by solvothermal method has confirmed through XRD and TEM. Cyclic voltametry and chronoamperometry showed improved catalytic activity and stability compared to commercial Pt/C. - Highlights: • Ordered Pt{sub 2}In{sub 3} nanoparticles were synthesized by solvothermal method. • Electrooxidation of alcohols on Pt{sub 2}In{sub 3} catalyst was investigated in acidic medium. • Pt{sub 2}In{sub 3} catalyst has superior catalytic activity compared to commercial Pt/C. • Pt{sub 2}In{sub 3} catalyst exhibited much higher stability than commercial Pt/C.« less

Theoretical study of methanol synthesis from CO2 and CO hydrogenation on the surface of ZrO2 supported In2O3 catalyst

NASA Astrophysics Data System (ADS)

Dou, Maobin; Zhang, Minhua; Chen, Yifei; Yu, Yingzhe

2018-06-01

The interactions between ZrO2 support and In2O3 catalyst play pivotal role in the catalytic conversion of CO2 to methanol. Herein, a density functional theory study has been conducted to research the mechanism of methanol synthesis from CO2 and CO hydrogenation on the defective ZrO2 supported In2O3(110) surface (D surface). The calculations reveal that methanol is produced mainly via the HCOO reaction pathway from CO2 hydrogenation on D surface, and the hydrogenation of HCOO to form H2COO species with an activation barrier of 1.21 eV plays the rate determining step for the HCOO reaction pathway. The direct dissociation of CO2 to CO on D surface is kinetically and energetically prohibited. Methanol synthesis from CO hydrogenation on D surface is much facile comparing with the elementary steps involved in CO2 hydrogenation. The rate determining step of CO hydrogenation to methanol is the formation of H3CO species on the vacancy site with a barrier of 0.51 eV. ZrO2 support has significant effect on the suppressing of the dissociation of CO2 and stabilization of H2COO species on the surface of In2O3 catalyst.

Electroless plating of Ni-B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

NASA Astrophysics Data System (ADS)

Wen, Xiao-Ping; Dai, Hong-Bin; Wu, Lin-Song; Wang, Ping

2017-07-01

Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni-B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni-B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

Facile synthesis of palladium nanoparticles supported on multi-walled carbon nanotube for efficient hydrogenation of biomass-derived levulinic acid

NASA Astrophysics Data System (ADS)

Yan, Kai; Lafleur, Todd; Liao, Jiayou

2013-09-01

Different loading of palladium (Pd) nanoparticles were successfully fabricated on multi-walled carbon nanotubes using Pd acetylacetonate as the precursor via a simple liquid impregnation method. The crystal phase, morphology, textural structure and the chemical state of the resulting Pd nanoparticles (Pd/CNT) catalysts were studied and the characterization results indicated that the uniform dispersion of small Pd nanoparticles with the size range of 1.0-4.5 nm was achieved. The synthesized Pd/CNT catalysts exhibited efficient performance for the catalytic hydrogenation of biomass-derived levulinic acid into biofuel γ-valerolactone. In comparison with the commercial 5 wt% Pd/C and the 5 wt% Pd/CNT catalyst prepared by Pd nitrate precursor, much higher activities were achieved, whereas the biofuel γ-valerolactone was highly produced with 56.3 % yield at 57.6 % conversion of levulinic acid on the 5 wt% Pd/CNT catalyst under mild conditions. The catalyst developed in this work may be a good candidate for the wide applications in the hydrogenation.

Automated synthesis of a 96 product-sized library of triazole derivatives using a solid phase supported copper catalyst.

PubMed

Jlalia, Ibtissem; Beauvineau, Claire; Beauvière, Sophie; Onen, Esra; Aufort, Marie; Beauvineau, Aymeric; Khaba, Eihab; Herscovici, Jean; Meganem, Faouzi; Girard, Christian

2010-04-28

This article deal with the parallel synthesis of a 96 product-sized library using a polymer-based copper catalyst that we developed which can be easily separated from the products by simple filtration. This gave us the opportunity to use this catalyst in an automated chemical synthesis station (Chemspeed ASW-2000). Studies and results about the preparation of the catalyst, its use in different solvent systems, its recycling capabilities and its scope and limitations in the synthesis of this library will be addressed. The synthesis of the triazole library and the very good results obtained will finally be discussed.

Fenton-like degradation of Methylene Blue using paper mill sludge-derived magnetically separable heterogeneous catalyst: Characterization and mechanism.

PubMed

Zhou, Guoqiang; Chen, Ziwen; Fang, Fei; He, Yuefeng; Sun, Haili; Shi, Huixiang

2015-09-01

For the paper industry, the disposal and management of the yielded sludge are a considerable challenge. In our work, the paper mill sludge-derived magnetically separable heterogeneous catalyst (PMS-Fe-380) was prepared easily through a facile synthesis method. The morphology and structure of PMS-Fe-380 were fully characterized by means of X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and Brunauer-Emmet-Teller analysis. The catalytic activity of PMS-Fe-380 was evaluated by degradation of Methylene Blue (MB). The reusability and stability of PMS-Fe-380 were evaluated in five repeated runs, which suggested that PMS-Fe-380 manifested excellent stability of catalytic activity. Moreover, leaching tests indicated that the leached iron is negligible (<0.5mg/L). This study provides an alternative environmentally friendly reuse method for paper mill sludge and a novel catalyst PMS-Fe-380 that can be considered as a promising heterogeneous Fenton-like catalyst. Copyright © 2015. Published by Elsevier B.V.

Sustainable utility of magnetically recyclable nano-catalysts in water: Applications in organic synthesis

EPA Science Inventory

Magnetically recyclable nano-catalysts and their use in aqueous media is a perfect combination for the development of greener sustainable methodologies in organic synthesis. It is well established that magnetically separable nano-catalysts avoid waste of catalysts or reagents and...

Towards Stable CuZnAl Slurry Catalysts for the Synthesis of Ethanol from Syngas

NASA Astrophysics Data System (ADS)

Dong, Weibing; Gao, Zhihua; Zhang, Qian; Huang, Wei

2018-07-01

A stable CuZnAl slurry catalyst for the synthesis of ethanol from syngas has been developed by adjusting the heat treatment conditions of the complete liquid-phase method. The activity evaluation results showed that the CuZnAl catalyst, when heat-treated under a high pressure and temperature, was a stable catalyst for the synthesis of ethanol. The selectivity of ethanol using the CuZnAl slurry catalyst, which was heat-treated at 553 K under 4.0 MPa, increased continuously with time and was stable at approximately 26.00% after 144 h. The characterization results indicated that the CuZnAl slurry catalyst heat-treated under high pressure conditions could facilitate the formation of a more perfect structure with a larger specific surface area. The prepared catalyst contained a balance of strong and weak acid sites, an appropriate form of Cu2O and a high Cu/Zn atomic ratio at the catalyst surface, providing its stability in ethanol synthesis from syngas.

One-Step Facile Synthesis of Cobalt Phosphides for Hydrogen Evolution Reaction Catalysts in Acidic and Alkaline Medium.

PubMed

Sumboja, Afriyanti; An, Tao; Goh, Hai Yang; Lübke, Mechthild; Howard, Dougal Peter; Xu, Yijie; Handoko, Albertus Denny; Zong, Yun; Liu, Zhaolin

2018-05-09

Catalysts for hydrogen evolution reaction are in demand to realize the efficient conversion of hydrogen via water electrolysis. In this work, cobalt phosphides were prepared using a one-step, scalable, and direct gas-solid phosphidation of commercially available cobalt salts. It was found that the effectiveness of the phosphidation reaction was closely related to the state of cobalt precursors at the reaction temperature. For instance, a high yield of cobalt phosphides obtained from the phosphidation of cobalt(II) acetate was related to the good stability of cobalt salt at the phosphidation temperature. On the other hand, easily oxidizable salts (e.g., cobalt(II) acetylacetonate) tended to produce a low amount of cobalt phosphides and a large content of metallic cobalt. The as-synthesized cobalt phosphides were in nanostructures with large catalytic surface areas. The catalyst prepared from phosphidation of cobalt(II) acetate exhibited an improved catalytic activity as compared to its counterpart derived from phosphidation of cobalt(II) acetylacetonate, showing an overpotential of 160 and 175 mV in acidic and alkaline electrolytes, respectively. Both catalysts also displayed an enhanced long-term stability, especially in the alkaline electrolyte. This study illustrates the direct phosphidation behavior of cobalt salts, which serve as a good vantage point in realizing the large-scale synthesis of transition-metal phosphides for high-performance electrocatalysts.

Technology development for cobalt F-T catalysts. Quarterly technical progress report number 10, January 1--March 31, 1995

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

Singleton, A.H.

1995-06-28

The goal of this project is the development of a commercially-viable, cobalt-based Fischer-Tropsch (F-T) catalyst for use in a slurry bubble column reactor. The major objectives of this work are (1) to develop a cobalt-based F-T catalyst with low (< 5%) methane selectivity, (2) to develop a cobalt-based F-T catalyst with water-gas shift activity, and (3) to combine both these improvements into one catalyst. The project consists of five major tasks: catalyst development; catalyst testing; catalyst reproducibility tests; catalyst aging tests; and preliminary design and cost estimate for a demonstrate scale catalyst production facility. Technical accomplishments during this reporting periodmore » include the following. It appears that the higher activity obtained for the catalysts prepared using an organic solution and reduced directly without prior calcination was the result of higher dispersions obtained under such pretreatment. A Ru-promoted Co catalyst on alumina with 30% Co loading exhibited a 4-fold increase in dispersion and a 2-fold increase in activity in the fixed-bed reactor from that obtained with the non-promoted catalyst. Several reactor runs have again focused on pushing conversion to higher levels. The maximum conversion obtained has been 49.7% with 26g catalyst. Further investigations of the effect of reaction temperature on the performance of Co catalysts during F-T synthesis were started using a low activity catalyst and one of the most active catalysts. The three 1 kg catalyst batches prepared by Calsicat for the reproducibility and aging studies were tested in both the fixed-bed and slurry bubble column reactors under the standard reaction conditions. The effects of adding various promoters to some cobalt catalysts have also been addressed. Results are presented and discussed.« less

Effect of nitrogen doping on the microstructure and visible light photocatalysis of titanate nanotubes by a facile cohydrothermal synthesis via urea treatment

NASA Astrophysics Data System (ADS)

Hu, Cheng-Ching; Hsu, Tzu-Chien; Lu, Shan-Yu

2013-09-01

A facile one-step cohydrothermal synthesis via urea treatment has been adopted to prepare a series of nitrogen-doped titanate nanotubes with highly efficient visible light photocatalysis of rhodamine B, in an effect to identify the effect of nitrogen doping on the photodegradation efficiency. The morphology and microstructure of the thus-prepared N-doped titanates were characterized by nitrogen adsorption/desorption isotherms, transmission electron microscopy, and scanning electron microscopy. With increasing urea loadings, the N-doped titanates change from a porous multi-layer and nanotube-shaped to a dense and aggregated particle-shaped structure, accompanied with reduced specific surface area and pore volume and enhanced pore diameter. Interstitial linkage to titanate via Tisbnd Osbnd N and Tisbnd Nsbnd O is confirmed by X-ray photoelectron spectroscopy. Factors governing the photocatalytic degradation such as the specific surface area of the catalyst and the degradation pathway are analyzed, a mechanistic illustration on the photodegradation is provided, and a 3-stage degradation mechanism is identified. The synergistic contribution due to the enhanced deethylation and chromophore cleavage on rhodamine B molecules and the reduced band gap on the catalyst TiO2 by interstitial nitrogen-doping has been accounted for the high photodegradation efficiency of the N-doped titanate nanotubes.

FeF(3) catalyzed cascade C-C and C-N bond formation: synthesis of differentially substituted triheterocyclic benzothiazole functionalities under solvent-free condition.

PubMed

Atar, Amol B; Jeong, Yeon Tae

2014-05-01

A series of diverse polyfunctionalized triheterocyclic benzothiazoles were easily prepared in excellent yields via the Biginelli reaction of 2-aminobenzothiazole with substituted benzaldehydes and α-methylene ketones using FeF(3) as an expeditious catalyst under solvent-free conditions. The protocol provides a practical and straightforward approach toward highly functionalized triheterocyclic benzothiazole derivatives in excellent yields. The reaction was conveniently promoted by FeF(3) and the catalyst could be recovered easily after the reaction and reused without any loss of its catalytic activity. The advantageous features of this methodology are high atom economy, operational simplicity, shorter reaction time, convergence, and facile automation.

Processes and catalysts for conducting fischer-tropsch synthesis in a slurry bubble column reactor

DOEpatents

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

1999-01-01

Processes and catalysts for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor (SBCR). One aspect of the invention involves the use of cobalt catalysts without noble metal promotion in an SBCR. Another aspect involves using palladium promoted cobalt catalysts in an SBCR. Methods for preparing noble metal promoted catalysts via totally aqueous impregnation and procedures for producing attrition resistant catalysts are also provided.

Oxygen-promoted catalyst sintering influences number density, alignment, and wall number of vertically aligned carbon nanotubes

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

Shi, Wenbo; Li, Jinjing; Polsen, Erik S.

A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. In this paper, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs. In particular, single- or few-walled CNT forests were achieved at very low oxygen loading, with single-to-multi-walled CNT diameters ranging from 4.8 ±more » 1.3 nm to 6.4 ± 1.1 nm over 0–800 ppm O 2, and an expected variation in alignment, where both were related to the annealed catalyst morphology. Morphological differences were not the result of subsurface diffusion, but instead occurred via Ostwald ripening under several hundred ppm O 2, and this effect was mitigated by high H 2 concentrations and not due to water vapor (as confirmed in O 2-free water addition experiments), supporting the importance of O 2 specifically. Further characterization of the interface between the Fe catalyst and Al 2O 3 support revealed that either oxygen-deficit metal oxide or oxygen-adsorption on metals could be functional mechanisms for the observed catalyst nanoparticle evolution. Finally, taken as a whole, our results suggest that the impacts of O 2 and H 2 on the catalyst evolution have been underappreciated and underleveraged in CNT synthesis, and these could present a route toward facile manipulation of CNT forest morphology through control of the reactive gaseous atmosphere alone.« less

Oxygen-promoted catalyst sintering influences number density, alignment, and wall number of vertically aligned carbon nanotubes.

PubMed

Shi, Wenbo; Li, Jinjing; Polsen, Erik S; Oliver, C Ryan; Zhao, Yikun; Meshot, Eric R; Barclay, Michael; Fairbrother, D Howard; Hart, A John; Plata, Desiree L

2017-04-20

A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. Here, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs. In particular, single- or few-walled CNT forests were achieved at very low oxygen loading, with single-to-multi-walled CNT diameters ranging from 4.8 ± 1.3 nm to 6.4 ± 1.1 nm over 0-800 ppm O 2 , and an expected variation in alignment, where both were related to the annealed catalyst morphology. Morphological differences were not the result of subsurface diffusion, but instead occurred via Ostwald ripening under several hundred ppm O 2 , and this effect was mitigated by high H 2 concentrations and not due to water vapor (as confirmed in O 2 -free water addition experiments), supporting the importance of O 2 specifically. Further characterization of the interface between the Fe catalyst and Al 2 O 3 support revealed that either oxygen-deficit metal oxide or oxygen-adsorption on metals could be functional mechanisms for the observed catalyst nanoparticle evolution. Taken as a whole, our results suggest that the impacts of O 2 and H 2 on the catalyst evolution have been underappreciated and underleveraged in CNT synthesis, and these could present a route toward facile manipulation of CNT forest morphology through control of the reactive gaseous atmosphere alone.

Oxygen-promoted catalyst sintering influences number density, alignment, and wall number of vertically aligned carbon nanotubes

DOE PAGES

Shi, Wenbo; Li, Jinjing; Polsen, Erik S.; ...

2017-04-11

A lack of synthetic control and reproducibility during vertically aligned carbon nanotube (CNT) synthesis has stifled many promising applications of organic nanomaterials. Oxygen-containing species are particularly precarious in that they have both beneficial and deleterious effects and are notoriously difficult to control. In this paper, we demonstrated diatomic oxygen's ability, independent of water, to tune oxide-supported catalyst thin film dewetting and influence nanoscale (diameter and wall number) and macro-scale (alignment and density) properties for as-grown vertically aligned CNTs. In particular, single- or few-walled CNT forests were achieved at very low oxygen loading, with single-to-multi-walled CNT diameters ranging from 4.8 ±more » 1.3 nm to 6.4 ± 1.1 nm over 0–800 ppm O 2, and an expected variation in alignment, where both were related to the annealed catalyst morphology. Morphological differences were not the result of subsurface diffusion, but instead occurred via Ostwald ripening under several hundred ppm O 2, and this effect was mitigated by high H 2 concentrations and not due to water vapor (as confirmed in O 2-free water addition experiments), supporting the importance of O 2 specifically. Further characterization of the interface between the Fe catalyst and Al 2O 3 support revealed that either oxygen-deficit metal oxide or oxygen-adsorption on metals could be functional mechanisms for the observed catalyst nanoparticle evolution. Finally, taken as a whole, our results suggest that the impacts of O 2 and H 2 on the catalyst evolution have been underappreciated and underleveraged in CNT synthesis, and these could present a route toward facile manipulation of CNT forest morphology through control of the reactive gaseous atmosphere alone.« less

Synthesis, characterization, and photocatalytic properties of core/shell mesoporous silica nanospheres supporting nanocrystalline titania

NASA Astrophysics Data System (ADS)

Cendrowski, K.; Chen, X.; Zielinska, B.; Kalenczuk, R. J.; Rümmeli, M. H.; Büchner, B.; Klingeler, R.; Borowiak-Palen, E.

2011-11-01

The facile bulk synthesis of silica nanospheres makes them an attractive support for the transport of chemical compounds such as nanocrystalline titanium dioxide. In this contribution we present a promising route for the synthesis of mesoporous silica nanospheres (m-SiO2) with diameter in range 200 nm, which are ideal supports for nanocrystalline titanium dioxide (TiO2). The detailed microscopic and spectroscopic characterizations of core/shell structure (m-SiO2/TiO2) were conducted. Moreover, the photocatalytic potential of the nanostructures was investigated via phenol decomposition and hydrogen generation. A clear enhancement of photoactivity in both reactions as compared to commercial TiO2-Degussa P25 catalyst is detected.

Processes and catalysts for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor

DOEpatents

Singleton, A.H.; Oukaci, R.; Goodwin, J.G.

1999-08-17

Processes and catalysts are disclosed for conducting Fischer-Tropsch synthesis in a slurry bubble column reactor (SBCR). One aspect of the invention involves the use of cobalt catalysts without noble metal promotion in an SBCR. Another aspect involves using palladium promoted cobalt catalysts in an SBCR. Methods for preparing noble metal promoted catalysts via totally aqueous impregnation and procedures for producing attrition resistant catalysts are also provided. 1 fig.

Precursor-Based Synthesis of Porous Colloidal Particles towards Highly Efficient Catalysts.

PubMed

Zheng, Yun; Geng, Hongbo; Zhang, Yufei; Chen, Libao; Li, Cheng Chao

2018-04-02

In recent years, porous colloidal particles have found promising applications in catalytic fields, such as photocatalysis, electrocatalysis, industrial and automotive byproducts removal, as well as biomass upgrading. These applications are critical for alleviating the energy crisis and environmental pollution. Porous colloidal particles have remarkable specific areas and abundant reactive sites, which can significantly improve the mass/charge transport and reaction rate in catalysis. Precursor-based synthesis is among the most facile and widely-adopted methods to achieve monodisperse and homogeneous porous colloidal particles. In the current review, we briefly introduce the general catalytic applications of porous colloidal particles. The conventional precursor-based methods are reviewed to design state-of-the-art porous colloidal particles as highly efficient catalysts. The recent development of porous colloidal particles derived from metal-organic frameworks (MOFs), glycerates, carbonate precursors, and ion exchange methods are reviewed. In the end, the current concerns and future development of porous colloidal particles are outlined. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size and morphology controlled NiSe nanoparticles as efficient catalyst for the reduction reactions

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

Subbarao, Udumula; Marakatti, Vijaykumar S.; Amshumali, Mungalimane K.

Facile and efficient ball milling and polyol methods were employed for the synthesis of nickel selenide (NiSe) nanoparticle. The particle size of the NiSe nanoparticle has been controlled mechanically by varying the ball size in the milling process. The role of the surfactants in the formation of various morphologies was studied. The compounds were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray energy dispersive spectroscopy (EDS). The efficiency of the NiSe nanoparticle as a catalyst was tested for the reduction of para-nitroaniline (PNA) to para-phenyldiamine (PPD) and para-nitrophenol (PNP) to para-aminophenol (PAP)more » using NaBH{sub 4} as the reducing agent. Particle size, morphology and the presence of surfactant played a crucial role in the reduction process. - Graphical abstract: NiSe nanoparticles in different size and morphology were synthesized using facile ball milling and polyol methods. Particle size, morphology and the presence of surfactant in these materials played a crucial role in the hydrogenation of PNA and PNP. - Highlights: • NiSe nanoparticles synthesized using ball milling and solution phase methods. • NiSe nanoparticle is an efficient catalyst for the reduction of PNA and PNP. • NiSe is found to be better than the best reported noble metal catalysts.« less

Flexible nitrogen-doped graphene/carbon nanotube/Co3O4 paper and its oxygen reduction activity

NASA Astrophysics Data System (ADS)

Li, Shan-Shan; Cong, Huai-Ping; Wang, Ping; Yu, Shu-Hong

2014-06-01

Due to the demand of an efficient, inexpensive and scalable synthesis of oxygen reduction reaction (ORR) catalyst for practical application in fuel cell, we demonstrate a facile strategy to fabricate the flexible nitrogen-doped graphene/carbon nanotube/Co3O4 (NG/CNT/Co3O4) paper catalyst. In the hydrothermal process, the in situ formation of Co3O4 nanoparticles, reduction of GO and doping of nitrogen species occur simultaneously in the assembled paper in ammonia solution. Because of the synergistic effects of three active components and the spacing effect of CNTs and Co3O4 nanoparticles on avoiding the re-aggregation of assembled graphene nanosheets, the free-standing NG/CNT/Co3O4 paper exhibits an enhanced ORR catalytic performance with stable durability and strong methanol-tolerant capability, indicating promising potential as ORR electrocatalyst in practical applications.Due to the demand of an efficient, inexpensive and scalable synthesis of oxygen reduction reaction (ORR) catalyst for practical application in fuel cell, we demonstrate a facile strategy to fabricate the flexible nitrogen-doped graphene/carbon nanotube/Co3O4 (NG/CNT/Co3O4) paper catalyst. In the hydrothermal process, the in situ formation of Co3O4 nanoparticles, reduction of GO and doping of nitrogen species occur simultaneously in the assembled paper in ammonia solution. Because of the synergistic effects of three active components and the spacing effect of CNTs and Co3O4 nanoparticles on avoiding the re-aggregation of assembled graphene nanosheets, the free-standing NG/CNT/Co3O4 paper exhibits an enhanced ORR catalytic performance with stable durability and strong methanol-tolerant capability, indicating promising potential as ORR electrocatalyst in practical applications. Electronic supplementary information (ESI) available: XRD patterns, elemental mapping images, DSC-TGA curves and XPS spectrum of NG/CNT/Co3O4 paper; SEM images and XPS spectra of NG/Co3O4 paper; RDE curves and corresponding K-L plots of different catalysts. See DOI: 10.1039/c4nr02101k

Facile synthesis of bacitracin-templated palladium nanoparticles with superior electrocatalytic activity

NASA Astrophysics Data System (ADS)

Li, Yanji; Wang, Zi; Li, Xiaoling; Yin, Tian; Bian, Kexin; Gao, Faming; Gao, Dawei

2017-02-01

Palladium nanomaterials have attracted great attention on the development of electrocatalysts for fuel cells. Herein, we depicted a novel strategy in the synthesis of palladium nanoparticles with superior electrocatalytic activity. The new approach, based on the self-assembly of bacitracin biotemplate and palladium salt for the preparation of bacitracin-palladium nanoparticles (Bac-PdNPs), was simple, low-cost, and green. The complex, composed by a series of spherical Bac-PdNPs with a diameter of 70 nm, exhibited a chain-liked morphology in TEM and a face-centered cubic crystal structure in X-Ray diffraction and selected area electron diffraction. The palladium nanoparticles were mono-dispersed and stable in aqueous solution as shown in TEM and zeta potential. Most importantly, compared to the commercial palladium on carbon (Pd/C) catalyst (8.02 m2 g-1), the Bac-PdNPs showed a larger electrochemically active surface area (47.57 m2 g-1), which endowed the products an excellent electrocatalytic activity for ethanol oxidation in alkaline medium. The strategy in synthesis of Bac-PdNPs via biotemplate approach might light up new ideas in anode catalysts for direct ethanol fuel cells.

Two-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds

PubMed Central

Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

2015-01-01

Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold–gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon–hydrogen bonds with molecular oxygen. PMID:25902034

Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds.

PubMed

Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

2015-04-22

Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold-gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon-hydrogen bonds with molecular oxygen.

Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds

NASA Astrophysics Data System (ADS)

Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

2015-04-01

Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold-gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon-hydrogen bonds with molecular oxygen.

Stereodivergent Aminocatalytic Synthesis of Z- and E-Trisubstituted Double Bonds from Alkynals.

PubMed

Marzo, Leyre; Luis-Barrera, Javier; Mas-Ballesté, Rubén; Ruano, José Luis García; Alemán, José

2016-11-07

A highly diastereoselective synthesis of trisubstituted Z- or E-enals, which are important intermediates in organic synthesis, as well as being present in natural products, is described using different alkynals and nucleophiles as starting materials. Diastereocontrol is mainly governed by the appropriate catalyst. Therefore, those reactions controlled by steric effects, such as the Jørgensen-Hayashi's catalyst, give access to E isomers, and those catalysts that facilitate hydrogen bonding, such as tetrazol-pyrrolidine Ley's catalyst, allow the synthesis of Z isomers. A stereochemical model based on DFT calculations is proposed. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Helical Carbon Fibers and Related Materials: A Review on the Past and Recent Developments

PubMed Central

Raghubanshi, Himanshu; Dikio, Ezekiel Dixon

2015-01-01

Helical carbon fibers (HCFs) have been widely studied due to their unique helical morphology and superior properties, which make them efficient materials for several potential applications. This review summarizes the past and current advancement on the synthesis of HCFs. The review focuses and discusses synthesis strategies and effect of experimental parameters on the growth of HCFs. The effect of preparation method of catalyst, catalyst nature, catalyst composition, catalyst size, catalyst initial and final shape, reaction temperature, reaction time, carbon source, impurities, and electromagnetic field on the growth of HCFs is reviewed. We also discuss the growth mechanism for HCFs and the synthesis of HCFs related materials. Finally, we conclude with a brief summary and an outlook on the challenges and future prospects of HCFs. PMID:28347045

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion

PubMed Central

2017-01-01

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer–Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters. PMID:28824820

Magnetically retrievable catalysts for organic synthesis

EPA Science Inventory

The use of magnetic nanoparticles (MNPs) as a catalyst in organic synthesis has become a subject of intense investigation. The recovery of expensive catalysts after catalytic reaction and reusing it without losing its activity is an important feature in the sustainable process de...

Design and Stereoselective Preparation of a New Class of Chiral Olefin Metathesis Catalysts and Application to Enantioselective Synthesis of Quebrachamine: Catalyst Development Inspired by Natural Product Synthesis

PubMed Central

Sattely, Elizabeth S.; Meek, Simon J.; Malcolmson, Steven J.; Schrock, Richard R.; Hoveyda, Amir H.

2010-01-01

A total synthesis of the Aspidosperma alkaloid quebrachamine in racemic form is first described. A key catalytic ring-closing metathesis of an achiral triene is used to establish the all-carbon quaternary stereogenic center and the tetracyclic structure of the natural product; the catalytic transformation proceeds with reasonable efficiency through the use of existing achiral Ru or Mo catalysts. Ru- or Mo-based chiral olefin metathesis catalysts have proven to be inefficient and entirely nonselective in cases where the desired product is observed. In the present study, the synthesis route thus serves as a platform for the discovery of new olefin metathesis catalysts that allow for efficient completion of an enantioselective synthesis of quebrachamine. Accordingly, on the basis of mechanistic principles, stereogenic-at-Mo complexes bearing only monodentate ligands have been designed. The new catalysts provide significantly higher levels of activity than observed with the previously reported Ru- or Mo-based complexes. Enantiomerically enriched chiral alkylidenes are generated through diastereoselective reactions involving achiral Mo-based bispyrrolides and enantiomerically pure silyl-protected binaphthols. Such chiral catalysts initiate the key enantioselective ring-closing metathesis step in the total synthesis of quebrachamine efficiently (1 mol % loading, 22 °C, 1 h, >98% conversion, 84% yield) and with high selectivity (98:2 er, 96% ee). PMID:19113867

Hierarchical Mesoporous NiO/MnO2@PANI Core-Shell Microspheres, Highly Efficient and Stable Bifunctional Electrocatalysts for Oxygen Evolution and Reduction Reactions.

PubMed

He, Junkai; Wang, Mingchao; Wang, Wenbo; Miao, Ran; Zhong, Wei; Chen, Sheng-Yu; Poges, Shannon; Jafari, Tahereh; Song, Wenqiao; Liu, Jiachen; Suib, Steven L

2017-12-13

We report on the new facile synthesis of mesoporous NiO/MnO 2 in one step by modifying inverse micelle templated UCT (University of Connecticut) methods. The catalyst shows excellent electrocatalytic activity and stability for both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline media after further coating with polyaniline (PANI). For electrochemical performance, the optimized catalyst exhibits a potential gap, ΔE, of 0.75 V to achieve a current of 10 mA cm -2 for the OER and -3 mA cm -2 for the ORR in 0.1 M KOH solution. Extensive characterization methods were applied to investigate the structure-property of the catalyst for correlations with activity (e.g., XRD, BET, SEM, HRTEM, FIB-TEM, XPS, TGA, and Raman). The high electrocatalytic activity of the catalyst closely relates to the good electrical conductivity of PANI, accessible mesoporous structure, high surface area, as well as the synergistic effect of the specific core-shell structure. This work opens a new avenue for the rational design of core-shell structure catalysts for energy conversion and storage applications.

Analysis of the critical step in catalytic carbodiimide transformation: proton transfer from amines, phosphines, and alkynes to guanidinates, phosphaguanidinates, and propiolamidinates with Li and Al catalysts.

PubMed

Rowley, Christopher N; Ong, Tiow-Gan; Priem, Jessica; Richeson, Darrin S; Woo, Tom K

2008-12-15

While lithium amides supported by tetramethylethylenediamine (TMEDA) are efficient catalysts in the synthesis of substituted guanidines via the guanylation of an amine with carbodiimide, as well as the guanylation of phosphines and conversion of alkynes into propiolamidines, aluminum amides are only efficient catalysts for the guanylation of amides. Density functional theory (DFT) calculations were used to explain this difference in activity. The origin of this behavior is apparent in the critical step where a proton is transferred from the substrate to a metal guanidinate. The activation energies of these steps are modest for amines, phosphines, and alkynes when a lithium catalyst was used, but are prohibitively high for the analogous reactions with phosphines and alkynes for aluminum amide catalysts. Energy decomposition analysis (EDA) indicates that these high activations energies are due to the high energetic cost of the detachment of a chelating guanidinate nitrogen from the aluminum in the proton transfer transition state. Amines are able to adopt an ideal geometry for facile proton transfer to the aluminum guanidinate and concomitant Al-N bond formation, while phosphines and alkynes are not.

Recent developments on ultrasound assisted catalyst-free organic synthesis.

PubMed

Banerjee, Bubun

2017-03-01

Mother Nature needs to be protected from ever increasing chemical pollutions associated with synthetic organic processes. The fundamental challenge for today's methodologists is to make their protocols more environmentally benign and sustainable by avoiding the extensive use of hazardous reagents and solvents, harsh reaction conditions, and toxic metal catalysts. However, the people of the twenty-first century are well aware about the side effects of those hazardous substances used and generated by the chemical processes. As a result, the last decade has seen a tremendous outburst in modifying chemical processes to make them 'sustainable' for the betterment of our environment. Catalysts play a crucial role in organic synthesis and thus they find huge applications and uses. Scientists' continuously trying to modify the catalysts to reduce their toxicity level, but the most benign way is to design an organic reaction without catalyst(s), if possible. It is worthy to mention that the involvement of ultrasound in organic synthesis is sometimes fulfilling this goal. In many occasions the applications of ultrasound can avoid the use of catalysts in organic reactions. Such beneficial features as a whole have motivated the organic chemists to apply ultrasonic irradiation in more heights and as a results, in recent past, there were immense applications of ultrasound in organic reactions for the synthesis of diverse organic scaffolds under catalyst-free condition. The present review summarizes the latest developments on ultrasound assisted catalyst-free organic synthesis reported so far. Copyright © 2016 Elsevier B.V. All rights reserved.

Pt based PEMFC catalysts prepared from colloidal particle suspensions--a toolbox for model studies.

PubMed

Speder, Jozsef; Altmann, Lena; Roefzaad, Melanie; Bäumer, Marcus; Kirkensgaard, Jacob J K; Mortensen, Kell; Arenz, Matthias

2013-03-14

A colloidal synthesis approach is presented that allows systematic studies of the properties of supported proton exchange membrane fuel cell (PEMFC) catalysts. The applied synthesis route is based on the preparation of monodisperse nanoparticles in the absence of strong binding organic stabilizing agents. No temperature post-treatment of the catalyst is required rendering the synthesis route ideally suitable for comparative studies. We report work concerning a series of catalysts based on the same colloidal Pt nanoparticle (NP) suspension, but with different high surface area (HSA) carbon supports. It is shown that for the prepared catalysts the carbon support has no catalytic co-function, but carbon pre-treatment leads to enhanced sticking of the Pt NPs on the support. An unwanted side effect, however, is NP agglomeration during synthesis. By contrast, enhanced NP sticking without agglomeration can be accomplished by the addition of an ionomer to the NP suspension. The catalytic activity of the prepared catalysts for the oxygen reduction reaction is comparable to industrial catalysts and no influence of the particle size is found in the range of 2-5 nm.

Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst

DOE PAGES

Lu, Yongwu; Yu, Fei; Hu, Jin; ...

2012-04-12

Zn-Mn promoted Cu-Fe based catalyst was synthesized by the co-precipitation method. Mixed alcohols synthesis from syngas was studied in a half-inch tubular reactor system after the catalyst was reduced. Zn-Mn promoted Cu-Fe based catalyst was characterized by SEM-EDS, TEM, XRD, and XPS. The liquid phase products (alcohol phase and hydrocarbon phase) were analyzed by GC-MS and the gas phase products were analyzed by GC. The results showed that Zn-Mn promoted Cu-Fe based catalyst had high catalytic activity and high alcohol selectivity. The maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons were also very high. Cumore » (111) was the active site for mixed alcohols synthesis, Fe 2C (101) was the active site for olefin and paraffin synthesis. The reaction mechanism of mixed alcohols synthesis from syngas over Zn-Mn promoted Cu-Fe based catalyst was proposed. Here, Zn-Mn promoted Cu-Fe based catalyst can be regarded as a potential candidate for catalytic conversion of biomass-derived syngas to mixed alcohols.« less

Supported fischer-tropsch catalyst and method of making the catalyst

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

1987-01-01

A Fischer-Tropsch catalyst and a method of making the catalyst for a Fischer-Tropsch process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas, is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Nano-catalysts with Magnetic Core: Sustainable Options for Greener Synthesis

EPA Science Inventory

Author’s perspective on nano-catalysts with magnetic core is summarized with recent work from his laboratory. Magnetically recyclable nano-catalysts and their use in benign media is an ideal blend for the development of sustainable methodologies in organic synthesis. Water or pol...

Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

NASA Astrophysics Data System (ADS)

Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

2018-06-01

Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

O-nitroso aldol synthesis: Catalytic enantioselective route to α-aminooxy carbonyl compounds via enamine intermediate

PubMed Central

Momiyama, Norie; Torii, Hiromi; Saito, Susumu; Yamamoto, Hisashi

2004-01-01

The approach using pyrrolidine enamine as substrate has been studied for this synthesis, and an important catalyst structural feature has been developed. After survey of pyrrolidine-based Brønsted acid catalyst, tetrazole catalyst (3f) was found to be optimal in synthesis of aminooxy carbonyl compounds in high yields, with complete enantioselectivity not only for aldehydes but also for ketones. PMID:15067138

Magnetic nanoparticle supported phosphotungstic acid: An efficient catalyst for the synthesis of xanthene derivatives

NASA Astrophysics Data System (ADS)

Patel, Nipun; Katheriya, Deepak; Dadhania, Harsh; Dadhania, Abhishek

2018-05-01

Magnetic nanoparticle supported phosphotungstic acid (Fe3O4@SiO2-HPW) was applied as a highly efficient catalyst for the synthesis of 14H-dibenzoxanthene derivatives via condensation reaction of 2-naphthol and aryl aldehydes. The catalyst was found highly efficient for the synthesis of xanthene derivatives under solvent free condition. The catalyst showed high activity and stability during the reaction and provided excellent yield of the corresponding products in short reaction time. All the synthesized compounds were characterized through FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. Furthermore, the catalyst is magnetically recoverable and can be reused several times without significant loss of its catalytic activity.

Catalyst and process for converting synthesis gas to liquid motor fuels

DOEpatents

Coughlin, Peter K.

1987-01-01

The addition of an inert metal component, such as gold, silver or copper, to a Fischer-Tropsch catalyst comprising cobalt enables said catalyst to convert synthesis gas to liquid motor fuels at about 240.degree.-370.degree. C. with advantageously reduced selectivity of said cobalt for methane in said conversion. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.

Catalyst for converting synthesis gas to liquid motor fuels

DOEpatents

Coughlin, Peter K.

1986-01-01

The addition of an inert metal component, such as gold, silver or copper, to a Fischer-Tropsch catalyst comprising cobalt enables said catalyst to convert synthesis gas to liquid motor fuels at about 240.degree.-370.degree. C. with advantageously reduced selectivity of said cobalt for methane in said conversion. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.

Synthesis of 6-alkyluridines from 6-cyanouridine via zinc(II) chloride-catalyzed nucleophilic substitution with alkyl Grignard reagents.

PubMed

Shih, Yu-Chiao; Yang, Ya-Ying; Lin, Chun-Chi; Chien, Tun-Cheng

2013-04-19

6-Cyanouracil derivatives underwent a direct nucleophilic substitution reaction with alkyl Grignard reagents in the presence of zinc(II) chloride as a catalyst to form the corresponding 6-alkyluracils. This methodology is applicable to sugar-protected 6-cyanouridine and 6-cyano-2'-deoxyuridine without the protection at the N(3)-imide and provides a facile and general access to versatile 6-alkyluracil and 6-alkyluridine derivatives.

Exploiting basic principles to control the selectivity of the vapor phase catalytic oxidative cross-coupling of primary alcohols over nanoporous gold catalysts

DOE PAGES

Wang, Lu-Cun; Stowers, Kara J.; Zugic, Branko; ...

2015-05-20

It is important to achieve high selectivity for high volume chemical synthesis in order to lower energy consumption through reduction in waste. Here, we report the selective synthesis of methyl esters—methyl acetate and methyl butyrate—through catalytic O 2-assisted cross-coupling of methanol with ethanol or 1-butanol using activated, support-free nanoporous gold (npAu). Both well-controlled studies on ingots in UHV and experiments under ambient pressure catalytic conditions on both ingots and microspherical hollow shell catalysts reveal guiding principles for controlling selectivity. Under UHV conditions, the ester products of the cross-coupling of methanol with both ethanol and 1-butanol evolve near room temperature inmore » temperature-programmed reaction studies, indicating that the reactions occur facilely. Furthermore, under steady-state catalytic operation, high stable activity was observed for cross-coupling in flowing gaseous reactant mixtures at atmospheric pressure and 423 K with negligible combustion. Optimum selectivity for cross-coupling is obtained in methanol-rich mixtures due to a combination of two factors: (1) the relative coverage of the respective alkoxys and (2) the relative facility of their β-H elimination. The relative coverage of the alkoxys is governed by van der Waal’s interactions between the alkyl groups and the surface; here, we demonstrate the importance of these weak interactions in a steady-state catalytic process.« less

Development of highly active and stable hybrid cathode catalyst for PEMFCs

NASA Astrophysics Data System (ADS)

Jung, Won Suk

Polymer electrolyte membrane fuel cells (PEMFCs) are attractive power sources of the future for a variety of applications including portable electronics, stationary power, and automobile application. However, sluggish cathode kinetics, high Pt cost, and durability issues inhibit the commercialization of PEMFCs. To overcome these drawbacks, research has been focused on alloying Pt with transition metals since alloy catalysts show significantly improved catalytic properties like high activity, selectivity, and durability. However, Pt-alloy catalysts synthesized using the conventional impregnation method exhibit uneven particle size and poor particle distribution resulting in poor performance and/or durability in PEMFCs. In this dissertation, a novel catalyst synthesis methodology is developed and compared with catalysts prepared using impregnation method and commercial catalysts. Two approaches are investigated for the catalyst development. The catalyst durability was studied under U. S. DRIVE Fuel Cell Tech Team suggested protocols. In the first approach, the carbon composite catalyst (CCC) having active sites for oxygen reduction reaction (ORR) is employed as a support for the synthesis of Pt/CCC catalyst. The structural and electrochemical properties of Pt/CCC catalyst are investigated using high-resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, while RDE and fuel cell testing are carried out to study the electrochemical properties. The synergistic effect of CCC and Pt is confirmed by the observed high activity towards ORR for the Pt/CCC catalyst. The second approach is the synthesis of Co-doped hybrid cathode catalysts (Co-doped Pt/CCC) by diffusing the Co metal present within the CCC support into the Pt nanoparticles during heat-treatment. The optimized Co-doped Pt/CCC catalyst performed better than the commercial catalysts and the catalyst prepared using the impregnation method in PEMFCs and showed high stability under 30,000 potential cycles between 0.6 and 1.0 V. To further increase the stability of the catalyst at high potential cycles (1.0-1.5 V), high temperature treatment is used to obtain graphitized carbon having optimum BET surface area. The novel catalyst synthesis procedure developed in this study was successfully applied for the synthesis of Co-doped Pt catalysts supported on the graphitized carbon which showed high activity and enhanced stability at high potentials.

Magnetic silica supported palladium catalyst: synthesis of allyl aryl ethers in water

EPA Science Inventory

A simple and benign procedure for the synthesis of aryl allyl ethers has been developed using phenols, allyl acetates and magnetically recyclable silica supported palladium catalyst in water; performance of reaction in air and easy separation of the catalyst using an external mag...

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1991-02-12

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.-), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1990-01-01

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Redox Switchable Coordination Catalysis: An Advanced Tool for Catalyst Control and Tailored Polyolefin Synthesis

DTIC Science & Technology

2017-06-18

olefins at a much slower rate than its non -reduced analogue which can be harnessed to control polyolefin comonomer incorporation percentages and thus its...opportunities for mechanistic understanding, catalyst control , and polyolefin synthesis that are impossible using heterogeneous 1. REPORT DATE (DD-MM...Advanced Tool for Catalyst Control and Tailored Polyolefin Synthesis The views, opinions and/or findings contained in this report are those of the

Fe3O4@SiO2@KIT-6 as an Efficient and Reusable Catalyst for the Synthesis of Novel Derivatives of 3,3'-((Aryl-1-phenyl-1H-pyrazol-4- yl)methylene)bis (1H-indole).

PubMed

Nikpassand, Mohammad; Fekri, Leila Zare; Nabatzadeh, Mozhdeh

2017-01-01

Korea advanced institute of science and technology cubic ordered mesoporous silica (KIT-6 mesoporous) silica coated magnetite nanoparticles, is an effective, ecobenign and recyclable catalyst for the electrophilic substitution reactions of indoles with various synthetized aldehydes to afford the corresponding novel diindolylmethanes in high yields and short reaction times. The catalyst can be recovered and reused without loss of activity. The work-up of the reaction consists of a simple separation, followed by concentration of the crude product and purification. The present methodology offers several advantages such as aqueous media, excellent yields, simple procedure, mild conditions and reduced environmental consequences. All of synthesized compounds are new and were characterized by IR, NMR and elemental analyses. A mixture of synthetized pyrazolecarbaldehydes [24] (2.0mmol), indole (4.0mmol) and Fe3O4@SiO2@KIT-6 (0.04mmol) and H2O (10mL) were stirred at room temperature for the required reaction time according to Table 2. After completion of the reaction, the product was solved in CHCl3 (3×10 mL) and insoluble catalyst was removed by filtration in the presence of an efficient magnetic bar. The organic phase including the product and CHCl3 was evaporated under vacuum. The resulting crude material was purified by recrystallization from EtOH to afford pure products. As part of our on interest for the development of efficient and environmentally friendly procedures for the synthesis of heterocyclic and pharmaceutical compounds, an efficient, facile and aqueous media was introduced for the synthesis of novel derivatives of diindolylmethanes containing pyrazole moiety. A variety of synthetized aldehyde compounds reacted smoothly with indoles to produce diindolylmethanes under these reaction conditions. The electron deficiency and the nature of the substituents on the aromatic ring show some effects on this conversion. All the reactions were run with catalytic amounts of catalysts. The best results gained with 0.04mmol of Fe3O4@SiO2@KIT-6 as a strong Lewis acid at room temperature in aqueous media. In conclusion, we have investigated the synthesized KIT-6 mesoporous silica coated magnetite nanoparticles (MMNPs) as a mild and efficient catalyst for the synthesis of novel diindolylmethanes coupled with pyrazole moiety in aqua media. The simplicity, easy workup together with the use of inexpensive, environmentally friendly and reusable catalyst, is the notable features of this catalytic procedure. To the best of our knowledge, this is the first report for the synthesis of a new library of diindolylmethane compound bearing pyrazole moiety that enhance the biological and pharmacological activity. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Oxygenates vs. synthesis gas

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

Kamil Klier; Richard G. Herman; Alessandra Beretta

1999-04-01

Methanol synthesis from H{sub 2}/CO has been carried out at 7.6 MPa over zirconia-supported copper catalysts. Catalysts with nominal compositions of 10/90 mol% and 30/70 mol% Cu/ZrO{sub 2} were used in this study. Additionally, a 3 mol% cesium-doped 10/90 catalyst was prepared to study the effect of doping with heavy alkali, and this promoter greatly increased the methanol productivity. The effects of CO{sub 2} addition, water injection, reaction temperature, and H{sub 2}/C0 ratio have been investigated. Both CO{sub 2} addition to the synthesis gas and cesium doping of the catalyst promoted methanol synthesis, while inhibiting the synthesis of dimethyl ether.more » Injection of water, however, was found to slightly suppress methanol and dimethyl ether formation while being converted to CO{sub 2} via the water gas shift reaction over these catalysts. There was no clear correlation between copper surface area and catalyst activity. Surface analysis of the tested samples revealed that copper tended to migrate and enrich the catalyst surface. The concept of employing a double-bed reactor with a pronounced temperature gradient to enhance higher alcohol synthesis was explored, and it was found that utilization of a Cs-promoted Cu/ZnO/Cr{sub 2}O{sub 3} catalyst as a first lower temperature bed and a Cs-promoted ZnO/Cr{sub 2}O{sub 3} catalyst as a second high-temperature bed significantly promoted the productivity of 2-methyl-1-propanol (isobutanol) from H{sub 2}/CO synthesis gas mixtures. While the conversion of CO to C{sub 2+} oxygenates over the double-bed configuration was comparable to that observed over the single Cu-based catalyst, major changes in the product distribution occurred by the coupling to the zinc chromite catalyst; that is, the productivity of the C{sub 1}-C{sub 3} alcohols decreased dramatically, and 2-methyl branched alcohols were selectively formed. The desirable methanol/2-methyl oxygenate molar ratios close to 1 were obtained in the present double-bed system that provides the feedstock for the synthesis of high octane and high cetane ethers, where the isobutanol productivity was as high as 139 g/kg cat/hr. Higher alcohol synthesis has been investigated over a Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst at temperatures higher (up to 703K) than those previously utilized, and no sintering of the catalyst was observed during the short-term testing. However, the higher reaction temperatures led to lower CO conversion levels and lower yield of alcohols, especially of methanol, because of equilibrium limitations. With the double catalyst bed configuration, the effect of pressure in the range of 7.6--12.4 MPa on catalyst activity and selectivity was studied. The upper bed was composed of the copper-based catalyst at 598K, and the lower bed consisted of a copper-free Cs-ZnO/Cr{sub 2}O{sub 3} catalyst at a high temperature of 678K. High pressure was found to increase CO conversion to oxygenated products, although the increase in isobutanol productivity did not keep pace with that of methanol. It was also shown that the Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalyst could be utilized to advantage as the second-bed catalyst at 613--643K instead of the previously used copper-free Cs-ZnO/ Cr{sub 2}O{sub 3} catalyst at higher temperature, With double Cs/Cu/ZnO/Cr{sub 2}O{sub 3} catalysts, high space time yields of up to 202 g/kg cat/hr, with high selectivity to isobutanol, were achieved.« less

Functionalized carbon dot adorned coconut shell char derived green catalysts for the rapid synthesis of amidoalkyl naphthols.

PubMed

Narayanan, Divya P; Cherikallinmel, Sudha Kochiyil; Sankaran, Sugunan; Narayanan, Binitha N

2018-06-15

A one pot synthesis of carbon dot incorporated porous coconut shell char derived sulphonated catalyst is reported here for the first time and is effectively used in the multicomponent synthesis of amidoalkyl naphthol. Macroporous nature of the char is revealed from scanning electron microscopic (SEM) analysis, whereas the dispersion of carbon dots (CDs) on the porous coconut shell char is confirmed from the high resolution transmission electron microscopic (HRTEM) analysis. Fluorescence emission spectrum further confirmed the presence of CDs in the catalyst. Fourier-transform infrared (FTIR) spectral analysis of the materials indicated that sulphonation occurred both to the CD and to the porous char. X-ray photo electron spectroscopic (XPS) analysis of the most active catalyst confirmed the presence of both sulphonic acid and carboxylic acid groups in the catalyst. The coconut shell char derived materials prepared by varying the amount of H 2 SO 4 are successfully utilized as efficient alternative green catalysts for the multicomponent reaction, where excellent activity in amidoalkyl naphthol synthesis is obtained within short periods under solvent free reaction conditions. A maximum yield of 98% is obtained in the synthesis of N-[Phenyl-(2-hydroxy-naphthalen-1-yl)-methyl]-benzamide, the representative amidoalkyl naphthol, with the best catalyst within 3 min of reaction. The catalyst is highly active for the reactions carried out with varieties of aldehydes and amides with a product yield in the range of 88-98%. The best catalyst system retained more than 90% of its initial activity even upto 6 th repeated run. Copyright © 2018 Elsevier Inc. All rights reserved.

Catalytic evaluation on liquid phase oxidation of vanillyl alcohol using air and H2O2 over mesoporous Cu-Ti composite oxide

NASA Astrophysics Data System (ADS)

Saha, Subrata; Hamid, Sharifah Bee Abd; Ali, Tammar Hussein

2017-02-01

A mesoporous, highly crystalline Cu-Ti composite oxide catalyst was prepared via facile, simple and modified solution method varying Cu and Ti ratio for selective liquid phase oxidation of vanillyl alcohol. Various spectroscopic procedures were employed to systematically characterize the catalyst structural and physicochemical properties. The defect chemistry of the catalyst was confirmed from the presence of surface defects revealed through HRTEM imagery between the TiO2 (101) and Cu3TiO4 (012) planes, complemented by the XRD profiling. Further, presence of oxygen vacancy evidenced by O 1s XPS spectra were observed on the catalyst surface. Moreover, the stoichiometry of Cu and Ti in the catalyst synthesis protocol was notably found to be the vital determinant to alter the redox properties of Cu-Ti composite oxide catalyst supported by H2-TPR. O2-TPD analysis. Moreover, a rational investigation was done using different oxidants such as air and H2O2 with variables reaction conditions. The catalyst was active for liquid phase oxidation of vanillyl alcohol to vanillin with performance of 66% conversion and 71% selectivity using H2O2 in base free condition. And also, catalytic activity was significantly improved by 94% conversion with 86% selectivity to vanillin in liquid phase aerobic oxidation at the optimum reaction conditions. To expand the superiority of the catalyst, three times reusability study was also examined with appreciable catalytic activity.

Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis

PubMed Central

Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S.; Schrock, Richard R.; Hoveyda, Amir H.

2009-01-01

Discovery of efficient catalysts is one of the most compelling objectives of modern chemistry. Chiral catalysts are in particularly high demand, as they facilitate synthesis of enantiomerically enriched small molecules that are critical to developments in medicine, biology and materials science1. Especially noteworthy are catalysts that promote—with otherwise inaccessible efficiency and selectivity levels—reactions demonstrated to be of great utility in chemical synthesis. Here we report a class of chiral catalysts that initiate alkene metathesis1 with very high efficiency and enantioselectivity. Such attributes arise from structural fluxionality of the chiral catalysts and the central role that enhanced electronic factors have in the catalytic cycle. The new catalysts have a stereogenic metal centre and carry only monodentate ligands; the molybdenum-based complexes are prepared stereoselectively by a ligand exchange process involving an enantiomerically pure aryloxide, a class of ligands scarcely used in enantioselective catalysis2,3. We demonstrate the application of the new catalysts in an enantioselective synthesis of the Aspidosperma alkaloid, quebrachamine, through an alkene metathesis reaction that cannot be promoted by any of the previously reported chiral catalysts. PMID:19011612

Anh To | NREL

Science.gov Websites

pyrolysis vapors Catalytic depolymerization of biomass Process scale-up for catalyst synthesis and testing continuous flow reactors (gas & liquid phases) Catalyst synthesis: zeolites, supported metals, and

Synthesis of borasiloxanes by oxidative hydrolysis of silanes and pinacolborane using Cu3(BTC)2 as a solid catalyst.

PubMed

Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; Concepcion, Patricia; Garcia, Hermenegildo

2017-09-05

A convenient method for the synthesis of borasiloxanes from silanes and pinacolboranes using Cu 3 (BTC) 2 as a heterogeneous catalyst in acetonitrile at 70 °C is reported. This procedure is more convenient than Ru and Pd based homogeneous catalysts because it avoids the use of noble metals, easy handling of starting materials and the catalyst can be reused.

Activation of catalysts for synthesizing methanol from synthesis gas

DOEpatents

Blum, David B.; Gelbein, Abraham P.

1985-01-01

A method for activating a methanol synthesis catalyst is disclosed. In this method, the catalyst is slurried in an inert liquid and is activated by a reducing gas stream. The activation step occurs in-situ. That is, it is conducted in the same reactor as is the subsequent step of synthesizing methanol from a methanol gas stream catalyzed by the activated catalyst still dispersed in a slurry.

Fischer–Tropsch Synthesis: Characterization Rb Promoted Iron Catalyst

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

Sarkar,A.; Jacobs, G.; Ji, Y.

Rubidium promoted iron Fischer-Tropsch synthesis (FTS) catalysts were prepared with two Rb/Fe atomic ratios (1.44/100 and 5/100) using rubidium nitrate and rubidium carbonate as rubidium precursors. Results of catalytic activity and deactivation studies in a CSTR revealed that rubidium promoted catalysts result in a steady conversion with a lower deactivation rate than that of the corresponding unpromoted catalyst although the initial activity of the promoted catalyst was almost half that of the unpromoted catalyst. Rubidium promotion results in lower methane production, and higher CO2, alkene and 1-alkene fraction in FTS products. M{umlt o}ssbauer spectroscopic measurements of CO activated and workingmore » catalyst samples indicated that the composition of the iron carbide phase formed after carbidization was -Fe5 C2 for both promoted and unpromoted catalysts. However, in the case of the rubidium promoted catalyst, '-Fe2.2C became the predominant carbidic phase as FTS continued and the overall catalyst composition remained carbidic in nature. In contrast, the carbide content of the unpromoted catalyst was found to decline very quickly as a function of synthesis time. Results of XANES and EXAFS measurements suggested that rubidium was present in the oxidized state and that the compound most prevalent in the active catalyst samples closely resembled that of rubidium carbonate.« less

Synthesis and Stabilization of Supported Metal Catalysts by Atomic Layer Deposition

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

Lu, Junling; Elam, Jeffrey W.; Stair, Peter C.

2013-03-12

Supported metal nanoparticles are among the most important cata-lysts for many practical reactions, including petroleum refining, automobile exhaust treatment, and Fischer–Tropsch synthesis. The catalytic performance strongly depends on the size, composition, and structure of the metal nanoparticles, as well as the underlying support. Scientists have used conventional synthesis methods including impregnation, ion exchange, and deposition–precipitation to control and tune these factors, to establish structure–performance relationships, and to develop better catalysts. Meanwhile, chemists have improved the stability of metal nanoparticles against sintering by the application of protective layers, such as polymers and oxides that encapsulate the metal particle. This often leadsmore » to decreased catalytic activity due to a lack of precise control over the thickness of the protective layer. A promising method of catalyst synthesis is atomic layer deposition (ALD). ALD is a variation on chemical vapor deposition in which metals, oxides, and other materials are deposited on surfaces by a sequence of self-limiting reactions. The self-limiting character of these reactions makes it possible to achieve uniform deposits on high-surface-area porous solids. Therefore, design and synthesis of advanced catalysts on the nanoscale becomes possible through precise control over the structure and composition of the underlying support, the catalytic active sites, and the protective layer. In this Account, we describe our advances in the synthesis and stabilization of supported metal catalysts by ALD. After a short introduction to the technique of ALD, we show several strategies for metal catalyst synthesis by ALD that take advantage of its self-limiting feature. Monometallic and bimetallic catalysts with precise control over the metal particle size, composition, and structure were achieved by combining ALD sequences, surface treatments, and deposition temperature control. Next, we describe ALD oxide overcoats applied with atomically precise thickness control that stabilize metal catalysts while preserving their catalytic function. We also discuss strategies for generation and control over the porosity of the overcoats that allow the embedded metal particles to remain accessible by reactants, and the details for ALD alumina overcoats on metal catalysts. Moreover, using methanol decomposition and oxidative dehydrogenation of ethane as probe reactions, we demonstrate that selectively blocking low coordination metal sites by oxide overcoats can provide another strategy to enhance both the durability and selectivity of metal catalysts.« less

A Facile Synthesis of Nitrogen-Doped Highly Porous Carbon Nanoplatelets: Efficient Catalysts for Oxygen Electroreduction

NASA Astrophysics Data System (ADS)

Zhang, Yaqing; Zhang, Xianlei; Ma, Xiuxiu; Guo, Wenhui; Wang, Chunchi; Asefa, Tewodros; He, Xingquan

2017-02-01

The oxygen reduction reaction (ORR) is of great importance for various renewable energy conversion technologies such as fuel cells and metal-air batteries. Heteroatom-doped carbon nanomaterials have proven to be robust metal-free electrocatalysts for ORR in the above-mentioned energy devices. Herein, we demonstrate the synthesis of novel highly porous N-doped carbon nanoplatelets (N-HPCNPs) derived from oatmeal (or a biological material) and we show the materials’ high-efficiency as electrocatalyst for ORR. The obtained N-HPCNPs hybrid materials exhibit superior electrocatalytic activities towards ORR, besides excellent stability and good methanol tolerance in both basic and acidic electrolytes. The unique nanoarchitectures with rich micropores and mesopores, as well as the high surface area-to-volume ratios, present in the materials significantly increase the density of accessible catalytically active sites in them and facilitate the transport of electrons and electrolyte within the materials. Consequently, the N-HPCNPs catalysts hold a great potential to serve as low-cost and highly efficient cathode materials in direct methanol fuel cells (DMFCs).

Synthesis, characterization and photocatalytic performance of self-assembled mesoporous TiO₂ nanoparticles.

PubMed

Lin, Yuan-Chung; Liu, Shou-Heng; Syu, Han-Ren; Ho, Tsung-Han

2012-09-01

A facile synthesis route is reported for preparation of mesoporous TiO(2) nanoparticles (MT-x) through evaporation induced self-assembly by using Pluronic F127, titanium isopropoxide, and various amounts of ethanol as templating agents, titanium sources and solvents, respectively. A variety of different spectroscopic and analytical techniques, such as small- and large-angle powder X-ray diffraction (XRD), N(2) adsorption-desorption isotherms, transmission electron microscopy (TEM), Raman and Fourier transform infrared (FTIR) spectroscopies were used to characterize the physicochemical properties of various MT-x catalysts. Among the catalysts, MT-20 was found to have better mesostructures formed by the arrangement of anatase TiO(2) nanoparticles of ca. 17.3 nm with broad interparticle pore size distribution. Hydrogen generation from water splitting on MT-20 using visible light was enhanced by at least 8.7 times if compared with the conventional TiO(2) photocatalyst. The superior photocatalytic performances observed for the synthesized MT-20 may be attributed to the presence of unique nanostructures in the TiO(2) photocatalysts. Copyright © 2012 Elsevier B.V. All rights reserved.

Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

NASA Astrophysics Data System (ADS)

Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

2016-08-01

Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

A facile one-pot solvothermal method for synthesis of magnetically recoverable Pd-Fe3O4 hybrid nanocatalysts for the Mizoroki-Heck reaction

NASA Astrophysics Data System (ADS)

Zhen, Fangchen; Ran, Maofei; Chu, Wei; Jiang, Chengfa; Sun, Wenjing

2018-03-01

Pd-Fe3O4 hybrid nanostructures were prepared using a simple one-pot hydrothermal method. The prepared materials were characterized by Fourier transform-infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma, N2 adsorption-desorption, and vibrating sample magnetometry. This self-assembled nanosystem acted as an efficient magnetically recyclable noble metal-based multi-functional nanocatalyst. It showed excellent catalytic activity and stability for the Heck reaction of iodobenzene and styrene under mild conditions. The methods used to prepare the Pd-Fe3O4 catalysts were simple and low-cost, which will be useful for the large-scale development and application of a magnetically recoverable Pd catalyst.

Copper-catalyzed domino cycloaddition/C-N coupling/cyclization/(C-H arylation): an efficient three-component synthesis of nitrogen polyheterocycles.

PubMed

Qian, Wenyuan; Wang, Hao; Allen, Jennifer

2013-10-11

A cat of all trades: A single copper catalyst promoted up to three reaction steps with separate catalytic cycles in a domino sequence (azide-alkyne cycloaddition/Goldberg amidation/Camps cyclization/(CH arylation)) for the rapid construction of complex heterocycles from three simple components under mild conditions. Facile cleavage of the triazole ring enables further elaboration of the condensation products. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Subeutectic Synthesis of Epitaxial Si-NWs with Diverse Catalysts Using a Novel Si Precursor

PubMed Central

2010-01-01

The applicability of a novel silicon precursor with respect to reasonable nanowire (NW) growth rates, feasibility of epitaxial NW growth and versatility with respect to diverse catalysts was investigated. Epitaxial growth of Si-NWs was achieved using octochlorotrisilane (OCTS) as Si precursor and Au as catalyst. In contrast to the synthesis approach with SiCl4 as precursor, OCTS provides Si without the addition of H2. By optimizing the growth conditions, effective NW synthesis is shown for alternative catalysts, in particular, Cu, Ag, Ni, and Pt with the latter two being compatible to complementary metal-oxide-semiconductor technology. As for these catalysts, the growth temperatures are lower than the lowest liquid eutectic; we suggest that the catalyst particle is in the solid state during NW growth and that a solid-phase diffusion process, either in the bulk, on the surface, or both, must be responsible for NW nucleation. PMID:20843058

Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Yang, Wen; Feng, Yan-Yan; Jiang, Cheng-Fa; Chu, Wei

2014-12-01

The CoMgO and CoMnMgO catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes (CNTs) through the catalytic chemical vapor deposition (CCVD). The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction (TPR) and X-ray diffraction (XRD) techniques, and the synthesized carbon materials are characterized by transmission electron microscopy (TEM) and thermo gravimetric analysis (TG). TEM measurement indicates that the catalyst CoMgO enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the CoMnMgO catalyst has a higher selectivity for CNTs than CoMgO. Meanwhile, different diameters of CNTs are synthesized by CoMnMgO catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution. The CoMnMgO catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.

Hydrocarbon synthesis catalyst and method of preparation

DOEpatents

Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

1983-08-02

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint. 9 figs.

Hydrocarbon synthesis catalyst and method of preparation

DOEpatents

Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

1983-08-02

A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint.

A facile approach towards synthesis, characterization, single crystal structure, and DFT study of 5-bromosalicylalcohol

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

Rastogi, Rupali, E-mail: rastogirupali@ymail.com; Tarannum, Nazia; Butcher, R. J.

2016-03-15

5-Bromosalicylalcohol was prepared by the interaction of NaBH{sub 4} and 5-bromosalicylaldehyde. The use of sodium borohydride makes the reaction easy, facile, economic and does not require any toxic catalyst. The compound is characterized by FTIR, {sup 1}H NMR, {sup 13}C NMR, TEM and ESI-mass spectra. Crystal structure is determined by single crystal X-ray analysis. Quantum mechanical calculations of geometries, energies and thermodynamic parameters are carried out using density functional theory (DFT/B3LYP) method with 6-311G(d,p) basis set. The optimized geometrical parameters obtained by B3LYP method show good agreement with experimental data.

Fischer-Tropsch activity for non-promoted cobalt-on-alumina catalysts

DOEpatents

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2001-01-01

Cobalt catalysts, and processes employing these inventive catalysts, for hydrocarbon synthesis. The inventive catalyst comprises cobalt on an alumina support and is not promoted with any noble or near noble metals. In one aspect of the invention, the alumina support preferably includes a dopant in an amount effective for increasing the activity of the inventive catalyst. The dopant is preferably a titanium dopant. In another aspect of the invention, the cobalt catalyst is preferably reduced in the presence of hydrogen at a water vapor partial pressure effective to increase the activity of the cobalt catalyst for hydrocarbon synthesis. The water vapor partial pressure is preferably in the range of from 0 to about 0.1 atmospheres.

VQS (vapor-quasiliquid-solid, vapor-quasisolid-solid) mechanism presents a unified foundation for the syntheses of nanotubes, primarily carbon nanotubes

NASA Astrophysics Data System (ADS)

Mohammad, S. Noor

2017-09-01

Nanotubes are synthesized almost entirely by metal-catalyst-free and metal-catalyst-mediated non-eutectic mechanism(s). An investigation has been carried out to understand the basics of this mechanism. Various possible chemical and physical processes involved in nanotube synthesis have been researched. Various components and attributes of nanotube synthesis have been evaluated. Phase transitions, alloy formation, porosity, carrier transport and the fundamentals underlying them have been examined. Nanoparticle surfaces conducive to nanotube synthesis have been examined. The role of surface treatment, which includes oxidation, oxygenation, acid treatment, plasma treatment, water treatment, sputtering, etc in creating such surfaces, has been investigated. The role of surface treatment and phase transitions as functions of temperature, pressure, ambient, contaminants, surface amorphicity, etc in creating diffusion paths for the diffusion of growth species for supersaturation and nucleation has been explored. Interdiffusion of catalyst and source materials, and hence exchange of materials, on the nanoparticle surface, have been elucidated. This exchange of materials on catalyst surface appears to add a new dimension to the synthesis kinetics. Integrated together, they reveal a general mechanism for probably all metal-catalyst-free and metal-catalyst-mediated non-eutectic nanotube synthesis. Available experiments strongly support the proposed mechanism; they suggest that this mechanism has a broad appeal.

Facile Synthesis of Highly Efficient Amorphous Mn-MIL-100 Catalysts: Formation Mechanism and Structure Changes during Application in CO Oxidation.

PubMed

Zhang, Xiaodong; Li, Hongxin; Lv, Xutian; Xu, Jingcheng; Wang, Yuxin; He, Chi; Liu, Ning; Yang, Yiqiong; Wang, Yin

2018-06-21

A comprehensive study was carried out on amorphous metal-organic frameworks Mn-MIL-100 as efficient catalysts for CO oxidation. This study focused on explaining the crystalline-amorphous-crystalline transformations during thermolysis of Mn-MIL-100 and studying the structure changes during the CO oxidation reaction. A possible formation mechanism of amorphous Mn-MIL-100 was proposed. Amorphous Mn-MIL-100 obtained by calcination at 250 °C (a-Mn-250) showed a smaller specific surface area (4 m 2  g -1 ) but high catalytic activity. Furthermore, the structure of amorphous Mn-MIL-100 was labile during the reaction. When a-Mn-250 was treated with reaction atmosphere at high temperature (giving used-a-Mn-250-S), the amorphous catalysts transformed into Mn 2 O 3 . Meanwhile, the BET surface area (164 m 2  g -1 ) and catalytic performance both sharply increased. In addition, used-a-Mn-250-S catalyst transformed from Mn 2 O 3 into Mn 3 O 4 , and this resulted in a slight decrease of catalytic activity in the presence of 1 vol % water vapor in the feed stream. A schematic mechanism of the structure changes during the reaction process was proposed. The success of the synthesis relies on the increase in BET surface area by using CO as retreatment atmosphere, and the enhanced catalytic activity was attributed to the unique structure, a large quantity of surface active oxygen species, oxygen vacancies, and good low-temperature reduction behavior. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemicals from ethanol: the acetone synthesis from ethanol employing Ce0.75Zr0.25O2, ZrO2 and Cu/ZnO/Al2O3.

PubMed

Rodrigues, Clarissa Perdomo; Zonetti, Priscila da Costa; Appel, Lucia Gorenstin

2017-04-04

Acetone is an important solvent and widely used in the synthesis of drugs and polymers. Currently, acetone is mainly generated by the Cumene Process, which employs benzene and propylene as fossil raw materials. Phenol is a co-product of this synthesis. However, this ketone can be generated from ethanol (a renewable feedstock) in one-step. The aim of this work is to describe the influence of physical-chemical properties of three different catalysts on each step of this reaction. Furthermore, contribute to improve the description of the mechanism of this synthesis. The acetone synthesis from ethanol was studied employing Cu/ZnO/Al 2 O 3 , Ce 0.75 Zr 0.25 O 2 and ZrO 2 . It was verified that the acidity of the catalysts needs fine-tuning in order to promote the oxygenate species adsorption and avoid the dehydration of ethanol. The higher the reducibility and the H 2 O dissociation activity of the catalysts are, the higher the selectivity to acetone is. In relation to the oxides, these properties are associated with the presence of O vacancies. The H 2 generation, which occurs during the TPSR, indicates the redox character of this synthesis. The main steps of the acetone synthesis from ethanol are the generation of acetaldehyde, the oxidation of this aldehyde to acetate species (which reduces the catalyst), the H 2 O dissociation, the oxidation of the catalyst producing H 2 , and, finally, the ketonization reaction. These pieces of information will support the development of active catalysts for not only the acetone synthesis from ethanol, but also the isobutene and propylene syntheses in which this ketone is an intermediate. Graphical abstract Acetone from ethanol.

Synthesis of carbon nanotubes using green plant extract as catalyst: unconventional concept and its realization

NASA Astrophysics Data System (ADS)

Tripathi, Nishant; Pavelyev, Vladimir; Islam, S. S.

2017-11-01

Green catalyst derived from plants, a cheap and abundant natural source, is used for the synthesis of multi-walled carbon nanotubes (MWNTs). The concept is unconventional and practically realized into existence by simple CVD growth while keeping away the potential hazards caused by metal catalyst on environment and living organisms. The notable points to mention of such growth are: (1) grown CNTs are free from toxic metal catalyst, (2) low growth temperature (575 °C) required and produced high yield vis-à-vis any other catalyst used so far reported, and (3) no need of expensive and complex systems for its synthesis. Besides, growth of SWNT as well as carbon nano-belts with hollow rectangular cross-section is observed when growth temperature increased to 800 °C, specifically, for the wall-nut extract. The samples were characterized by microscopic and spectroscopic analysis and the results verified our study. The present work provides innovative technique and may open up new avenues for CNTs synthesis and its applications.

Gram-level synthesis of core-shell structured catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Luo, Mingchuan; Wei, Lingli; Wang, Fanghui; Han, Kefei; Zhu, Hong

2014-12-01

Over the past decade, Pt based core-shell structured alloys have been studied extensively as oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs) because of their distinctive electrochemical performance and low Pt loading. In this paper, a facile route based on microwave-assisted polyol method and chemical dealloying process is proposed to synthesize carbon supported core-shell structured nanoparticles (NPs) in gram-level for ORR electrocatalysis in PEMFCs. The obtained samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). These physical characterization indicate that the final synthesized NPs are highly dispersed on the carbon support, and in a core-shell structure with CuPt alloy as the core and Pt as the shell. Electrochemical measurements, conducted by cyclic voltammetry (CV) and rotating disk electrode (RDE) tests, show the core-shell structured catalyst exhibit a 3× increase in mass activity and a 2× increase in specific activity over the commercial Pt/C catalyst, respectively. These results demonstrate that this route can be a reliable way to synthesize low-Pt catalyst in large-scale for PEMFCs.

Influence of various carbon nano-forms as supports for Pt catalyst on proton exchange membrane fuel cell performance

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-08-01

In this study, we discuss the influence of various carbon supports for Pt on proton exchange membrane (PEM) fuel cell performance. Here, Pt supported on various carbon nano-forms [Pt/carbon black (Pt/CB), Pt/single-walled carbon nanotubes (Pt/SWCNT), Pt/multi-walled carbon nanotubes (Pt/MWCNT) and Pt/graphene (Pt/G)] are synthesized by a facile, single step, microwave-assisted, modified chemical reduction route. Their physical, chemical and electrochemical characteristics pertaining to oxygen reduction reaction (ORR) catalytic activity and stability in PEM fuel cell are studied in detail by various techniques and compared. The study shows that the different carbon supports does not significantly affect the Pt particle size during synthesis, but leads to different amount of defective sites in the carbon framework which influence both the availability of active metal nano-catalysts and metal-support interaction. In-situ electrochemical investigations reveal that the different carbon supports influence both ORR catalytic activity and stability of the catalyst. This is further corroborated by the demonstration of varying polarization characteristics on PEM fuel cell performance by different carbon supported Pt catalysts. This study reveals MWCNT as the most suitable carbon support for Pt catalyst, exhibiting high activity and stability for ORR in PEM fuel cell.

Synthesis of Pt/rGO catalysts with two different reducing agents and their methanol electrooxidation activity

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

Vu, Thu Ha Thi, E-mail: ptntd2004@yahoo.fr; Tran, Thanh Thuy Thi, E-mail: tranthithanhthuygl@gmail.com; Le, Hong Ngan Thi

2016-01-15

Highlights: • Pt/rGO catalysts were successfully synthesized using either NaBH{sub 4} or ethylene glycol. • Synthesis using NaBH{sub 4} could improve electrocatalytic towards methanol oxidation of Pt/rGO catalyst. • 40%Pt/rGO synthesized using NaBH{sub 4} showed the best electrocatalytic performance. - Abstract: The synthesis processes of Platinum (Pt) on reduced graphene oxide (rGO) catalysts from graphene oxide (GO) using two reducing agents including sodium borohydride and ethylene glycol is reported. Structure and morphology of Pt/rGO catalysts are characterized by X-ray powder diffraction, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrocatalytic methanol oxidation properties of these catalysts are evaluated bymore » cyclic voltammetry and chronoamperometry. The results show that catalyst synthesized using sodium borohydride has a higher metallic Pt content and an improved catalytic performance in comparison to catalyst synthesized using ethylene glycol. Moreover, effect of Pt loading amount on electrocatalytic methanol oxidation performance of catalysts synthesized using sodium borohydride is systematically investigated. The optimal Pt loading amount on graphene is determined to be 40%.« less

A facile synthesis for cauliflower like CeO2 catalysts from Ce-BTC precursor and their catalytic performance for CO oxidation

NASA Astrophysics Data System (ADS)

Zhang, Xiaodong; Hou, Fulin; Yang, Yang; Wang, Yuxin; Liu, Ning; Chen, Dan; Yang, Yiqiong

2017-11-01

The paper presents a novel and facile method for preparing cauliflowerlike CeO2 through direct decomposition of cerium based metal-organic framework (MOF) Ce-BTC (BTC = 1,3,5-benzenetricarboxylic acid) straw in air. Several analytical tools such as Scanning electron microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric (TG), N2 adsorption-desorption, Temperature programmed reduction (TPR), Raman, X-ray photoelectron spectroscopic (XPS) and Photoluminescence (PL) have been used to characterize Ce-BTC and CeO2. The Ce-BTC calcined at 500 °C (CeO2-500) maintains the morphology of its template ;Ce-BTC; and forms a special cauliflower-like structure. XRD patterns showed that the catalyst has a perfect CeO2 crystal structure and has a smaller particle size. The prepared CeO2 cauliflowers exhibit excellent catalytic activities, long-term stability, and cycling stability for CO oxidation. The improved catalytic activities could be attributed to porous nanorods of CeO2 cauliflowers, which provide more active sites and oxygen vacancy for CO oxidation.

Facile synthesis of porous graphene-like carbon nitride nanosheets with high surface area and enhanced photocatalytic activity via one-step catalyst-free solution self-polymerization

NASA Astrophysics Data System (ADS)

Wu, Shikai; Wen, Shengwu; Xu, Xinmei; Huang, Guozhi; Cui, Yifan; Li, Jinyu; Qu, Ailan

2018-04-01

Porous graphite carbon nitride nanosheets (g-C3N4) are achieved via one-step catalyst-free solution self-polymerization from a single melamine precursor. The resultant porous g-C3N4 nanosheets with the best photodegradation capacity provided the surface area of 669.15 m2/g, which is superior to the surface area of any other porous g-C3N4 reported. Results showed enhanced adsorption and degradation capacity of methyl orange (MO) under UV-visible light irradiation (λ > 350 nm) compared to bulk g-C3N4. The MO oxidation of the porous g-C3N4 nanosheets is driven mostly by the participation of holes, and secondly by rad O2- and rad OH radicals. This approach shed lights on porous g-C3N4 production simply by self-polycondensation of single functional monomer. It also provided a low-cost and eco-friendly method to facilely mass-produce g-C3N4 nanosheets with high surface area for many potential applications.

Enhanced catalyst for converting synthesis gas to liquid motor fuels

DOEpatents

Coughlin, Peter K.

1986-01-01

The conversion of synthesis gas to liquid molar fuels by means of a cobalt Fischer-Tropsch catalyst composition is enhanced by the addition of molybdenum, tungsten or a combination thereof as an additional component of said composition. The presence of the additive component increases the olefinic content of the hydrocarbon products produced. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.

Synthesis-Structure-Activity Relationships in Co3O4 Catalyzed CO Oxidation

NASA Astrophysics Data System (ADS)

Mingle, Kathleen; Lauterbach, Jochen

2018-05-01

In this work, a statistical design and analysis platform was used to develop cobalt oxide based oxidation catalysts prepared via one pot metal salt reduction. An emphasis was placed upon understanding the effects of synthesis conditions, such as heating regimen and Co2+ concentration on the metal salt reduction mechanism, the resultant nanomaterial properties (i.e. size, crystal structure, and crystal faceting), and the catalytic activity in CO oxidation. This was accomplished by carrying out XRD, TEM, and FTIR studies on synthesis intermediates and products. Additionally, high-throughput experimentation was employed to study the performance of Co3O4 oxidation catalysts over a wide range of reaction conditions using a 16-channel fixed bed reactor equipped with a parallel infrared imaging system. Specifically, Co3O4 nanomaterials of varying properties were evaluated for their performance as CO oxidation catalysts. Figure-of-merits including light-off temperatures and activation energies were measured and mapped back to the catalyst properties and synthesis conditions. Statistical analysis methods were used to elucidate significant property-activity relationships as well as the design rules relevant in the synthesis of active catalysts. It was found that CO oxidation light off temperatures could be decreased to <90°C by utilizing the discovered synthesis-structure-activity relationships.

A facile approach towards increasing the nitrogen-content in nitrogen-doped carbon nanotubes via halogenated catalysts

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

Ombaka, L.M.; Ndungu, P.G.; Department of Applied Chemistry, Doornfontein Campus, University of Johannesburg, P.O. Box 17011, Johannesburg 2028

Nitrogen-doped carbon nanotubes (N-CNTs) have been synthesized at 850 °C via a CVD deposition technique by use of three ferrocenyl derivative catalysts, i.e. para-CN, -CF{sub 3} and -Cl substituted-phenyl rings. The synthesized catalysts have been characterized by NMR, IR, HR-MS and XRD. The XRD analysis of the para-CF{sub 3} catalyst indicates that steric factors influence the X-ray structure of 1,1′-ferrocenylphenyldiacrylonitriles. Acetonitrile or pyridine was used as carbon and nitrogen sources to yield mixtures of N-CNTs and carbon spheres (CS). The N-CNTs obtained from the para-CF{sub 3} catalysts, in pyridine, have the highest nitrogen-doping level, show a helical morphology and aremore » less thermally stable compared with those synthesized by use of the para-CN and -Cl as catalyst. This suggests that fluorine heteroatoms enhance nitrogen-doping in N-CNTs and formation of helical-N-CNTs (H-N-CNTs). The para-CF{sub 3} and para-Cl catalysts in acetonitrile yielded iron-filled N-CNTs, indicating that halogens promote encapsulation of iron into the cavity of N-CNT. The use of acetonitrile, as carbon and nitrogen source, with the para-CN and -Cl as catalysts also yielded a mixture of N-CNTs and carbon nanofibres (CNFs), with less abundance of CNFs in the products obtained using para-Cl catalysts. However, para-CF{sub 3} catalyst in acetonitrile gave N-CNTs as the only shaped carbon nanomaterials. - Graphical abstract: Graphical abstract showing the synthesis of N-CNTs using halogenated-ferrocenyl derivatives as catalyst with pyridine or acetonitrile as nitrogen and carbon sources via the chemical vapour deposition technique. - Highlights: • N-CNTs were synthesized from halogenated ferrocenyl catalysts. • Halogenated catalysts promote nitrogen-doping and pyridinic nitrogen in N-CNTs. • Halogenated catalysts facilitate iron filling of N-CNTs.« less

Highly efficient water-mediated approach to access benzazoles: metal catalyst and base-free synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles.

PubMed

Bala, Manju; Verma, Praveen Kumar; Sharma, Deepika; Kumar, Neeraj; Singh, Bikram

2015-05-01

An efficient water-catalyzed method has been developed for the synthesis of 2-substituted benzimidazoles, benzoxazoles, and benzothiazoles in one step. The present method excludes the usage of toxic metal catalysts and bases to produce benzazoles in good to excellent yields. An efficient and versatile water-mediated method has been established for the synthesis of various 2-arylbenzazoles. The present protocol excludes the usage of any catalyst and additive provided excellent selectivities and yields with high functional group tolerance for the synthesis of 2-arylated benzimidazoles, benzoxazoles, and benzothiazoles. Benzazolones were also synthesized using similar reaction protocol.

Porous Nanocrystalline Silicon Supported Bimetallic Pd-Au Catalysts: Preparation, Characterization, and Direct Hydrogen Peroxide Synthesis

PubMed Central

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-01-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterized by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt (DCS) single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 mol gPd-1 h-1 at selectivity of 50% and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at −10°C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability, and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process. PMID:29637068

Porous nanocrystalline silicon supported bimetallic Pd-Au catalysts: preparation, characterization and direct hydrogen peroxide synthesis

NASA Astrophysics Data System (ADS)

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-03-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterised by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 at selectivity of 50 % and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at -10 °C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process.

Monodisperse Ultrasmall Manganese-Doped Multimetallic Oxysulfide Nanoparticles as Highly Efficient Oxygen Reduction Electrocatalyst.

PubMed

Zhang, Yingying; Wang, Xiang; Hu, Dandan; Xue, Chaozhuang; Wang, Wei; Yang, Huajun; Li, Dongsheng; Wu, Tao

2018-04-25

The highly efficient and cheap non-Pt-based electrocatalysts such as transition-based catalysts prepared via facile methods for oxygen reduction reaction (ORR) are desirable for large-scale practical industry applications in energy conversion and storage systems. Herein, we report a straightforward top-down synthesis of monodisperse ultrasmall manganese-doped multimetallic (ZnGe) oxysulfide nanoparticles (NPs) as an efficient ORR electrocatalyst by simple ultrasonic treatment of the Mn-doped Zn-Ge-S chalcogenidometalate crystal precursors in H 2 O/EtOH for only 1 h at room temperature. Thus obtained ultrasmall monodisperse Mn-doped oxysulfide NPs with ultralow Mn loading level (3.92 wt %) not only exhibit comparable onset and half-wave potential (0.92 and 0.86 V vs reversible hydrogen electrode, respectively) to the commercial 20 wt % Pt/C but also exceptionally high metal mass activity (189 mA/mg at 0.8 V) and good methanol tolerance. A combination of transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and electrochemical analysis demonstrated that the homogenous distribution of a large amount of Mn(III) on the surface of NPs mainly accounts for the high ORR activity. We believe that this simple synthesis of Mn-doped multimetallic (ZnGe) oxysulfide NPs derived from chalcogenidometalates will open a new route to explore the utilization of discrete-cluster-based chalcogenidometalates as novel non-Pt electrocatalysts for energy applications and provide a facile way to realize the effective reduction of the amount of catalyst while keeping desired catalytic performances.

Microwave irradiation for the facile synthesis of transition-metal nanoparticles (NPs) in ionic liquids (ILs) from metal-carbonyl precursors and Ru-, Rh-, and Ir-NP/IL dispersions as biphasic liquid-liquid hydrogenation nanocatalysts for cyclohexene.

PubMed

Vollmer, Christian; Redel, Engelbert; Abu-Shandi, Khalid; Thomann, Ralf; Manyar, Haresh; Hardacre, Christopher; Janiak, Christoph

2010-03-22

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M-NPs) have been reproducibly obtained by facile, rapid (3 min), and energy-saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal-carbonyl precursors [M(x)(CO)(y)] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF(4)]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180-250 degrees C, 6-12 h) of [M(x)(CO)(y)] in ILs. The MWI-obtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long-term stable M-NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)(-1) h(-1) and 884 (mol product) (mol Rh)(-1) h(-1) and give almost quantitative conversion within 2 h at 10 bar H(2) and 90 degrees C. Catalyst poisoning experiments with CS(2) (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru-NPs.

Synthesis, characterisation and applications of coiled carbon nanotubes.

PubMed

Hanus, Monica J; Harris, Andrew T

2010-04-01

Coiled carbon nanotubes are helical carbon structures formed when heptagonal and pentagonal rings are inserted into the hexagonal backbone of a 'straight' nanotube. Coiled carbon nanotubes have been reported with both regular and irregular helical structures. In this work the structure, growth mechanism(s), synthesis, properties and potential applications of coiled carbon nanotubes are reviewed. Published data suggests that coiled carbon nanotube synthesis occurs due to nonuniform extrusion of carbon from a catalyst surface. To date, coiled carbon nanotubes have been synthesised using catalyst modification techniques including: (i) the addition of S or P containing compounds during synthesis; (ii) the use of binary or ternary metal catalysts; (iii) the use of microwaves to create a local temperature gradient around individual catalyst particles and; (iv) the use of pH control during catalyst preparation. In most instances coiled carbon nanotubes are produced as a by-product; high yield and/or large-scale synthesis of coiled carbon nanotubes remains problematic. The qualitative analysis of coiled carbon nanotubes is currently hindered by the absence of specific characterisation data in the literature, e.g., oxidation profiles measured by thermogravimetric analysis and Raman spectra of pure coiled carbon nanotube samples.

Ordered micro/macro porous K-OMS-2/SiO2 nanocatalysts: Facile synthesis, low cost and high catalytic activity for diesel soot combustion

PubMed Central

Yu, Xuehua; Zhao, Zhen; Wei, Yuechang; Liu, Jian

2017-01-01

A series of novel oxide catalysts, which contain three-dimensionally ordered macroporous (3DOM) and microporous structure, were firstly designed and successfully synthesized by simple method. In the as-prepared catalysts, 3DOM SiO2 is used as support and microporous K-OMS-2 oxide nanoparticles are supported on the wall of SiO2. 3DOM K-OMS-2/SiO2 oxide catalysts were firstly used in soot particle oxidation reaction and they show very high catalytic activities. The high activities of K-OMS-2/SiO2 oxide catalysts can be assigned to three possible reasons: macroporous effect of 3DOM structure for improving contact between soot and catalyst, microporous effect of K-OMS-2 for adsorption of small gas molecules and interaction of K and Mn for activation of gas molecules. The catalytic activities of catalysts are comparable to or even higher than noble metal catalyst in the medium and high temperature range. For example, the T50 of K-OMS-2/SiO2-50, 328 °C, is much lower than those of Pt/Al2O3 and 3DOM Au/LaFeO3, 464 and 356 °C,respectively. Moreover, catalysts exhibited high catalytic stability. It is attributed to that the K+ ions are introduced into the microporous structure of OMS-2 and stabilized in the catalytic reaction. Meanwhile, the K+ ions play an important role in templating and stabilizing the tunneled framework of OMS-2. PMID:28443610

Facile synthesis of a platinum-lead oxide nanocomposite catalyst with high activity and durability for ethanol electrooxidation.

PubMed

Yang, Wei-Hua; Wang, Hong-Hui; Chen, De-Hao; Zhou, Zhi-You; Sun, Shi-Gang

2012-12-21

Aimed at searching for highly active and stable nano-scale Pt-based catalysts that can improve significantly the energy conversion efficiency of direct ethanol fuel cells (DEFCs), a novel Pt-PbO(x) nanocomposite (Pt-PbO(x) NC) catalyst with a mean size of 3.23 nm was synthesized through a simple wet chemistry method without using a surfactant, organometallic precursors and high temperature. Electrocatalytic tests demonstrated that the as-prepared Pt-PbO(x) NC catalyst possesses a much higher catalytic activity and a longer durability than Pt nanoparticles (nm-Pt) and commercial Pt black catalysts for ethanol electrooxidation. For instance, Pt-PbO(x) NC showed an onset potential that was 30 mV and 44 mV less positive, together with a peak current density 1.7 and 2.6 times higher than those observed for nm-Pt and Pt black catalysts in the cyclic voltammogram tests. The ratio of current densities per unit Pt mass on Pt-PbO(x) NC, nm-Pt and Pt black catalysts is 27.3 : 3.4 : 1 for the long-term (2 hours) chronoamperometric experiments measured at -0.4 V (vs. SCE). In situ FTIR spectroscopic studies revealed that the activity of breaking C-C bonds of ethanol of the Pt-PbO(x) NC is as high as 5.17 times that of the nm-Pt, which illustrates a high efficiency of ethanol oxidation to CO(2) on the as-prepared Pt-PbO(x) NC catalyst.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1993-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Enhanced catalyst and process for converting synthesis gas to liquid motor fuels

DOEpatents

Coughlin, Peter K.

1986-01-01

The conversion of synthesis gas to liquid molar fuels by means of a cobalt Fischer-Tropsch catalyst composition is enhanced by the addition of molybdenum, tungsten or a combination thereof as an additional component of said composition. The presence of the additive component increases the olefinic content of the hydrocarbon products produced. The catalyst composition can advantageously include a support component, such as a molecular sieve, co-catalyst/support component or a combination of such support components.

Immobilization of isolated FI catalyst on polyhedral oligomeric silsesquioxane-functionalized silica for the synthesis of weakly entangled polyethylene.

PubMed

Li, Wei; Yang, Huaqin; Zhang, Jingjing; Mu, Jingshan; Gong, Dirong; Wang, Xiaodong

2016-09-25

Polyhedral oligomeric silsesquioxanes (POSSs) were adsorbed on methylaluminoxane-activated silica for the immobilization of fluorinated bis(phenoxyimine)Ti complexes (FI catalyst). These POSSs have been characterized as horizontal spacers isolating the active sites and hindering the chain overlap in polymerization. The heterogeneous catalyst exhibits considerable activity in the synthesis of weakly entangled polyethylene.

Synthesis of solid catalyst from egg shell waste and clay for biodiesel production

NASA Astrophysics Data System (ADS)

Setiadji, S.; Sundari, C. D. D.; Munir, M.; Fitriyah, S.

2018-05-01

Until now, energy consumption in Indonesia is almost entirely fulfilled by fossil fuels, thus, its availability will be limited and continue to decrease. To overcome these problems, development and utilization of renewable energy are required, one of which is biodiesel. Biodiesel can be prepared through transesterification reaction of vegetable oil using catalyst. In this research, a solid catalyst for biodiesel synthesis was prepared from chicken egg shell waste and clay. Optimization of the transesterification reaction of coconut (Cocos nucifera) oil to obtain biodiesel was also carried out. The formation of CaO/kaolin catalyst was confirmed based on the results of XRD and SEM-EDS. This catalyst is suitable for biodiesel synthesis from vegetable oils with lower FFA (free fatty acid) levels, i.e. coconut oil with FFA level of 0.18%. Based on FTIR result, FFA level and flame tests, it was found that biodiesel was successfully formed. Synthesis of biodiesel has the optimum conditions on reaction time of 16 hours and temperature of 64 °C, with oil: methanol ratio of 1: 15 and CaO/kaolin catalyst concentration of 0.9% in a reflux system.

Open-cage fullerene-like graphitic carbons as catalysts for oxidative dehydrogenation of isobutane.

PubMed

Liang, Chengdu; Xie, Hong; Schwartz, Viviane; Howe, Jane; Dai, Sheng; Overbury, Steven H

2009-06-10

We report herein a facile synthesis of fullerene-like cages, which can be opened and closed through simple thermal treatments. A glassy carbon with enclosed fullerene-like cages of 2-3 nm was synthesized through a soft-template approach that created open mesopores of 7 nm. The open mesopores provided access to the fullerene-like cages, which were opened and closed through heat treatments in air and inert gas at various temperatures. Catalytic measurements showed that the open cages displayed strikingly higher activity for the oxidative dehydrogenation of isobutane in comparison to the closed ones. We anticipate that this synthesis approach could unravel an avenue for pursuing fundamental understanding of the unique catalytic properties of graphitic carbon nanostructures.

Process for the synthesis of aliphatic alcohol-containing mixtures

DOEpatents

Greene, Marvin I.; Gelbein, Abraham P.

1984-01-01

A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

Process for the synthesis of aliphatic alcohol-containing mixtures

DOEpatents

Greene, M.I.; Gelbein, A.P.

1984-10-16

A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

Sodium hydroxide catalyzed monodispersed high surface area silica nanoparticles.

PubMed

Bhakta, Snehasis; Dixit, Chandra K; Bist, Itti; Jalil, Karim Abdel; Suib, Steven L; Rusling, James F

2016-07-01

Understanding of the synthesis kinetics and our ability to modulate medium conditions allowed us to generate nanoparticles via an ultra-fast process. The synthesis medium is kept quite simple with tetraethyl orthosilicate (TEOS) as precursor and 50% ethanol and sodium hydroxide catalyst. Synthesis is performed under gentle conditions at 20 °C for 20 min Long synthesis time and catalyst-associated drawbacks are most crucial in silica nanoparticle synthesis. We have addressed both these bottlenecks by replacing the conventional Stober catalyst, ammonium hydroxide, with sodium hydroxide. We have reduced the overall synthesis time from 20 to 1/3 h, ~60-fold decrease, and obtained highly monodispersed nanoparticles with 5-fold higher surface area than Stober particles. We have demonstrated that the developed NPs with ~3-fold higher silane can be used as efficient probes for biosensor applications.

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

Underwood, R.P.

As part of the DOE-sponsored contract Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas'' experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al[sub 2]O[sub 3] methanol synthesis catalyst, developed in Air Products' laboratories, has the highest performance in terms of rate and selectivity for C[sub 2+]-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

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

Underwood, R.P.

As part of the DOE-sponsored contract ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas`` experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst, developed in Air Products` laboratories, has the highest performance in terms of rate and selectivity for C{sub 2+}-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

Enhanced metal loading in SBA-15-type catalysts facilitated by salt addition. Synthesis, characterization and catalytic epoxide alcoholysis activity of molybdenum incorporated porous silica

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

Budhi, Sridhar; Peeraphatdit, Chorthip; Pylypenko, Svitlana

2014-02-07

We report a novel method to increase the metal loading in SBA-15 silica matrix via direct synthesis. It was demonstrated through the synthesis and characterization of a series of molybdenum containing SBA-15 mesoporous silica catalysts prepared with and without diammonium hydrogen phosphate (DHP) as an additive. Catalysts prepared with DHP show a 2–3 times increase in incorporation of molybdenum in the silica matrix and pore size enlargement. The synthesized catalysts were characterized using nitrogen sorption, X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma–optical emission spectroscopy (ICP–OES). Themore » catalytic activity of catalysts prepared with DHP for alcoholysis of epoxides was superior than the catalyst prepared without DHP. Alcoholysis of epoxides was demonstrated for a range of alcohols and epoxides under ambient conditions in as little as 30 min with high selectivity.« less

Size and morphology controlled NiSe nanoparticles as efficient catalyst for the reduction reactions

NASA Astrophysics Data System (ADS)

Subbarao, Udumula; Marakatti, Vijaykumar S.; Amshumali, Mungalimane K.; Loukya, B.; Singh, Dheeraj Kumar; Datta, Ranjan; Peter, Sebastian C.

2016-12-01

Facile and efficient ball milling and polyol methods were employed for the synthesis of nickel selenide (NiSe) nanoparticle. The particle size of the NiSe nanoparticle has been controlled mechanically by varying the ball size in the milling process. The role of the surfactants in the formation of various morphologies was studied. The compounds were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray energy dispersive spectroscopy (EDS). The efficiency of the NiSe nanoparticle as a catalyst was tested for the reduction of para-nitroaniline (PNA) to para-phenyldiamine (PPD) and para-nitrophenol (PNP) to para-aminophenol (PAP) using NaBH4 as the reducing agent. Particle size, morphology and the presence of surfactant played a crucial role in the reduction process.

Sub-micron Cu/SSZ-13: Synthesis and application as selective catalytic reduction (SCR) catalysts

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

Prodinger, Sebastian; Derewinski, Miroslaw A.; Wang, Yilin

For the first time, sub-micron Cu/SSZ-13, obtained by modifying an existing synthesis procedure, was shown to be an effective and stable catalyst for selective catalytic reduction reactions, such as NO reduction. Characterization of the materials with X-ray diffraction, N2-physisorption and 27Al MAS NMR shows that hydrothermal aging, simulating SCR reaction conditions, is more destructive in respect to dealumination for smaller particles prior to Cu-exchange. However, the catalytic performance and hydrothermal stability for Cu/SSZ-13 is independent of the particle size. In particular, the stability of tetrahedral framework Al is improved in the sub-micron Cu/SSZ-13 catalysts of comparable Cu loading. This indicatesmore » that variations in the Al distribution for different SSZ-13 synthesis procedures have a more critical influence on stabilizing isolated Cu-ions during harsh hydrothermal aging than the particle size. This study is of high interest for applications in vehicular DeNOx technologies where high loadings of active species on wash coats can be achieved by using sub-micron Cu/SSZ-13. The authors would like to thank B. W. Arey and J. J. Ditto for performing electron microscope imaging. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. S. P and M. A. D also acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under the Laboratory Directed Research & Development Program at PNNL. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.« less

Synthesis of carbon nanomaterials from different pyrolysis techniques: a review

NASA Astrophysics Data System (ADS)

Umer Zahid, Muhammad; Pervaiz, Erum; Hussain, Arshad; Shahzad, Muhammad Imran; Niazi, Muhammad Bilal Khan

2018-05-01

In the current age, the significance of carbon-based nanomaterials for many applications has made the efforts for the facile synthesis methods from abundantly available wastes in a cost-effective way. Pyrolysis in a broad spectrum is commonly employed for the synthesis of carbon nanostructures by thermally treating the organic waste. The mechanism of growth of the nanoparticles determines the functional distribution of nanoparticles based on the growing size, medium, and physio-chemical properties. Carbon nanomaterial’s growth is a complicated process which is profoundly influenced by temperature, catalyst, and type of precursor. Nowadays, significant progress has been made in improving nanomaterial’s growth techniques, opening new paths for commercial production of carbon-based nanomaterials. The most promising are the methods involving hydrocarbon-rich organic waste as the feed source. In this review, synthesis of carbon-based nanomaterials, specifically carbon nanotubes (CNTs), Carbon nanofibers (CNFs) and Graphene (G) are discussed by different pyrolysis techniques. Furthermore, the review explores recent advancements made in the context of pyrolysis.

Catalytic Production of Ethanol from Biomass-Derived Synthesis Gas

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

Trewyn, Brian G.; Smith, Ryan G.

2016-06-01

Heterogeneous catalysts have been developed for the conversion of biomass-derived synthetic gas (syngas) to ethanol. The objectives of this project were to develop a clean synthesis gas from biomass and develop robust catalysts with high selectivity and lifetime for C 2 oxygenate production from biomass-derived syngas and surrogate syngas. During the timeframe for this project, we have made research progress on the four tasks: (1) Produce clean bio-oil generated from biomass, such as corn stover or switchgrass, by using fast pyrolysis system, (2) Produce clean, high pressure synthetic gas (syngas: carbon monoxide, CO, and hydrogen, H 2) from bio-oil generatedmore » from biomass by gasification, (3) Develop and characterize mesoporous mixed oxide-supported metal catalysts for the selective production of ethanol and other alcohols, such as butanol, from synthesis gas, and (4) Design and build a laboratory scale synthesis gas to ethanol reactor system evaluation of the process. In this final report, detailed explanations of the research challenges associated with this project are given. Progress of the syngas production from various biomass feedstocks and catalyst synthesis for upgrading the syngas to C 2-oxygenates is included. Reaction properties of the catalyst systems under different reaction conditions and different reactor set-ups are also presented and discussed. Specifically, the development and application of mesoporous silica and mesoporous carbon supports with rhodium nanoparticle catalysts and rhodium nanoparticle with manganese catalysts are described along with the significant material characterizations we completed. In addition to the synthesis and characterization, we described the activity and selectivity of catalysts in our micro-tubular reactor (small scale) and fixed bed reactor (larger scale). After years of hard work, we are proud of the work done on this project, and do believe that this work will provide a solid foundation for the future production of syngas from biomass and the development of heterogeneous catalysts for the syngas to C 2-oxygenate process and for the commercialization of this process. Potential future directions for this research are also discussed within the report.« less

Different routes to methanol: Inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts

DOE PAGES

Kandemir, Timur; Friedrich, Matthias; Parker, Stewart F.; ...

2016-04-14

We have investigated methanol synthesis with model supported copper catalysts, Cu/ZnO and Cu/MgO, using CO/H 2 and CO 2/H 2 as feedstocks. Under CO/H 2 both catalysts show chemisorbed methoxy as a stable intermediate, the Cu/MgO catalyst also shows hydroxyls on the support. Under CO 2/H 2 the catalysts behave differently, in that formate is also seen on the catalyst. For the Cu/ZnO catalyst hydroxyls are present on the metal whereas for the Cu/MgO hydroxyls are found on the support. Furthermore, these results are consistent with a recently published model for methanol synthesis and highlight the key role of ZnOmore » in the process.« less

Multistep continuous-flow synthesis of (R)- and (S)-rolipram using heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Tsubogo, Tetsu; Oyamada, Hidekazu; Kobayashi, Shū

2015-04-01

Chemical manufacturing is conducted using either batch systems or continuous-flow systems. Flow systems have several advantages over batch systems, particularly in terms of productivity, heat and mixing efficiency, safety, and reproducibility. However, for over half a century, pharmaceutical manufacturing has used batch systems because the synthesis of complex molecules such as drugs has been difficult to achieve with continuous-flow systems. Here we describe the continuous-flow synthesis of drugs using only columns packed with heterogeneous catalysts. Commercially available starting materials were successively passed through four columns containing achiral and chiral heterogeneous catalysts to produce (R)-rolipram, an anti-inflammatory drug and one of the family of γ-aminobutyric acid (GABA) derivatives. In addition, simply by replacing a column packed with a chiral heterogeneous catalyst with another column packed with the opposing enantiomer, we obtained antipole (S)-rolipram. Similarly, we also synthesized (R)-phenibut, another drug belonging to the GABA family. These flow systems are simple and stable with no leaching of metal catalysts. Our results demonstrate that multistep (eight steps in this case) chemical transformations for drug synthesis can proceed smoothly under flow conditions using only heterogeneous catalysts, without the isolation of any intermediates and without the separation of any catalysts, co-products, by-products, and excess reagents. We anticipate that such syntheses will be useful in pharmaceutical manufacturing.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, R.

1985-04-02

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

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

NONE

The objective of Task 1 is to prepare and evaluate catalysts and to develop efficient reactor systems for the selective conversion of hydrogen-lean synthesis gas to alcohol fuel extender and octane enhancers. Task 1 is subdivided into three separate subtasks: laboratory and equipment setup; catalysis research; and reaction engineering and modeling. Research at West Virginia University (WVU) is focused on molybdenum-based catalysts for higher alcohol synthesis. Parallel research carried out at Union Carbide Corporation (UCC) is focused on transition-metal-oxide catalysts. During this time period, at WVU, we tried several methods to eliminate problems related to condensation of heavier products whenmore » reduced Mo-Ni-K/C materials were used as catalysts. We then resumed our kinetic study on the reduced Mo-Ni-K/C materials were used as catalysts. We then resumed our kinetic study on the reduced Mo-Ni-K/C catalysts. We have also obtained same preliminary results in our attempts to analyze quantitatively the temperature-programmed reduction spectra for C- supported Mo-based catalysts. We have completed the kinetic study for the sulfided Co-K-MoS{sub 2}/C catalyst. We have compared the results of methanol synthesis using the membrane reactor with those using a simple plug-flow reactor. At UCC, the complete characterization of selected catalysts has been completed. The results suggest that catalyst pretreatment under different reducing conditions yield different surface compositions and thus different catalytic reactivities.« less

In situ Generated Ruthenium Catalyst Systems Bearing Diverse N-Heterocyclic Carbene Precursors for Atom-Economic Amide Synthesis from Alcohols and Amines.

PubMed

Cheng, Hua; Xiong, Mao-Qian; Cheng, Chuan-Xiang; Wang, Hua-Jing; Lu, Qiang; Liu, Hong-Fu; Yao, Fu-Bin; Chen, Cheng; Verpoort, Francis

2018-02-16

The transition-metal-catalyzed direct synthesis of amides from alcohols and amines is herein demonstrated as a highly environmentally benign and atom-economic process. Among various catalyst systems, in situ generated N-heterocyclic carbene (NHC)-based ruthenium (Ru) halide catalyst systems have been proven to be active for this transformation. However, these existing catalyst systems usually require an additional ligand to achieve satisfactory results. In this work, through extensive screening of a diverse variety of NHC precursors, we discovered an active in situ catalyst system for efficient amide synthesis without any additional ligand. Notably, this catalyst system was found to be insensitive to the electronic effects of the substrates, and various electron-deficient substrates, which were not highly reactive with our previous catalyst systems, could be employed to afford the corresponding amides efficiently. Furthermore, mechanistic investigations were performed to provide a rationale for the high activity of the optimized catalyst system. NMR-scale reactions indicated that the rapid formation of a Ru hydride intermediate (signal at δ=-7.8 ppm in the 1 H NMR spectrum) after the addition of the alcohol substrate should be pivotal in establishing the high catalyst activity. Besides, HRMS analysis provided possible structures of the in situ generated catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A catalytic tethering strategy: simple aldehydes catalyze intermolecular alkene hydroaminations.

PubMed

MacDonald, Melissa J; Schipper, Derek J; Ng, Peter J; Moran, Joseph; Beauchemin, André M

2011-12-21

Herein we describe a catalytic tethering strategy in which simple aldehyde precatalysts enable, through temporary intramolecularity, room-temperature intermolecular hydroamination reactivity and the synthesis of vicinal diamines. The catalyst allows the formation of a mixed aminal from an allylic amine and a hydroxylamine, resulting in a facile intramolecular hydroamination event. The promising enantioselectivities obtained with a chiral aldehyde also highlight the potential of this catalytic tethering approach in asymmetric catalysis and demonstrate that efficient enantioinduction relying only on temporary intramolecularity is possible. © 2011 American Chemical Society

Green heterogeneous Pd(II) catalyst produced from chitosan-cellulose micro beads for green synthesis of biaryls.

PubMed

Baran, Talat; Sargin, Idris; Kaya, Murat; Menteş, Ayfer

2016-11-05

In green catalyst systems, both the catalyst and the technique should be environmentally safe. In this study we designed a green palladium(II) catalyst for microwave-assisted Suzuki CC coupling reactions. The catalyst support was produced from biopolymers; chitosan and cellulose. The catalytic activity of the catalyst was tested on 16 substrates in solvent-free media and compared with those of commercial palladium salts. Reusability tests were done. The catalyst was also used in conventional reflux-heating system to demonstrate the efficiency of microwave heating method. We recorded high activity, selectivity and excellent TONs (6600) and TOFs (82500) just using a small catalyst loading (1.5×10(-3)mol%) in short reaction time (5min). The catalyst exhibited a long lifetime (9 runs). The findings indicated that both green chitosan/cellulose-Pd(II) catalyst and the microwave heating are suitable for synthesis of biaryl compounds by using Suzuki CC coupling reactions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Remarkably selective iridium catalysts for the elaboration of aromatic C-H bonds.

PubMed

Cho, Jian-Yang; Tse, Man Kin; Holmes, Daniel; Maleczka, Robert E; Smith, Milton R

2002-01-11

Arylboron compounds have intriguing properties and are important building blocks for chemical synthesis. A family of Ir catalysts now enables the direct synthesis of arylboron compounds from aromatic hydrocarbons and boranes under "solventless" conditions. The Ir catalysts are highly selective for C-H activation and do not interfere with subsequent in situ transformations, including Pd-mediated cross-couplings with aryl halides. By virtue of their favorable activities and exceptional selectivities, these Ir catalysts impart the synthetic versatility of arylboron reagents to C-H bonds in aromatic and heteroaromatic hydrocarbons.

Synthesis and characterization of gold graphene composite with dyes as model substrates for decolorization: A surfactant free laser ablation approach

NASA Astrophysics Data System (ADS)

Sai Siddhardha, R. S.; Lakshman Kumar, V.; Kaniyoor, Adarsh; Sai Muthukumar, V.; Ramaprabhu, S.; Podila, Ramakrishna; Rao, A. M.; Ramamurthy, Sai Sathish

2014-12-01

A facile surfactant free laser ablation mediated synthesis (LAMS) of gold-graphene composite is reported here. The material was characterized using transmission electron microscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, powdered X-ray diffraction, Raman spectroscopy, Zeta potential measurements and UV-Visible spectroscopic techniques. The as-synthesized gold-graphene composite was effectively utilized as catalyst for decolorization of 4 important textile and laser dyes. The integration of gold nanoparticles (AuNPs) with high surface area graphene has enhanced the catalytic activity of AuNPs. This enhanced activity is attributed to the synergistic interplay of pristine gold's electronic relay and π-π stacking of graphene with the dyes. This is evident when the Rhodamine B (RB) reduction rate of the composite is nearly twice faster than that of commercial citrate capped AuNPs of similar size. In case of Methylene blue (MB) the rate of reduction is 17,000 times faster than uncatalyzed reaction. This synthetic method opens door to laser ablation based fabrication of metal catalysts on graphene for improved performance without the aid of linkers and surfactants.

Facile synthesis of graphene by pyrolysis of poly(methyl methacrylate) on nickel particles in the confined microzones

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

Hong, Ningning; Yang, Wei; Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute of University of Science and Technology of China, Suzhou, Jiangsu, 215123

2012-12-15

Graphical abstract: Display Omitted Highlights: ► The GNWs with few defects were synthesized by pyrolyzing PMMA on nickel particles. ► PMMA as carbon source was easily prepared and safe to handle. ► Nickel microparticles were directly used as catalysts without any pre-treatment. ► The method can be used for the low cost and bulk production of graphene. -- Abstract: In this work, multi-layer graphene has been prepared by pyrolyzing poly(methyl methacrylate) (PMMA) on nickel microparticles in the confined microzones formed by organophilic montmorillonite (OMT). Gram-scale of product can be obtained per day by using this method. The obtained graphene wasmore » evaluated by scanning and transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. Pyrolytic conditions such as the system composition of the composites, reaction temperature and the size of catalyst are important parameters affecting the morphology and yield of the final product. Based on the experimental observations and reported literatures, a possible formation process is discussed. The synthesis method of graphene is simple, low-cost, and scalable, which is promising for the application in many fields.« less

Hydrazine Catalyst Production: Sustaining S-405 Technology

NASA Technical Reports Server (NTRS)

Wucherer, E. J.; Cook, Timothy; Stiefel, Mark; Humphries, Randy, Jr.; Parker, Janet

2003-01-01

The development of the iridium-based Shell 405 catalyst for spontaneous decomposition of hydrazine was one of the key enabling technologies for today's spacecraft and launch vehicles. To ensure that this crucial technology was not lost when Shell elected to exit the business, Aerojet, supported by NASA, has developed a dedicated catalyst production facility that will supply catalyst for future spacecraft and launch vehicle requirements. We have undertaken a program to transfer catalyst production from Shell Chemical USA (Houston, TX) to Aerojet's Redmond, WA location. This technology transition was aided by Aerojet's 30 years of catalyst manufacturing experience and NASA diligence and support in sustaining essential technologies. The facility has produced and tested S-405 catalyst to existing Shell 405 specifications and standards. Our presentation will describe the technology transition effort including development of the manufacturing facility, capture of the manufacturing process, test equipment validation, initial batch build and final testing.

Carbon-Encapsulated WOx Hybrids as Efficient Catalysts for Hydrogen Evolution.

PubMed

Jing, Shengyu; Lu, Jiajia; Yu, Guangtao; Yin, Shibin; Luo, Lin; Zhang, Zengsong; Ma, Yanfeng; Chen, Wei; Shen, Pei Kang

2018-05-29

Developing non-noble metal catalysts as Pt substitutes, with good activity and stability, remains a great challenge for cost-effective electrochemical evolution of hydrogen. Herein, carbon-encapsulated WO x anchored on a carbon support (WO x @C/C) that has remarkable Pt-like catalytic behavior for the hydrogen evolution reaction (HER) is reported. Theoretical calculations reveal that carbon encapsulation improves the conductivity, acting as an electron acceptor/donor, and also modifies the Gibbs free energy of H* values for different adsorption sites (carbon atoms over the W atom, O atom, WO bond, and hollow sites). Experimental results confirm that WO x @C/C obtained at 900 °C with 40 wt% metal loading has excellent HER activity regarding its Tafel slope and overpotential at 10 and 60 mA cm -2 , and also has outstanding stability at -50 mV for 18 h. Overall, the results and facile synthesis method offer an exciting avenue for the design of cost-effective catalysts for scalable hydrogen generation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A facile, efficient, and sustainable chitosan/CaHAp catalyst and one-pot synthesis of novel 2,6-diamino-pyran-3,5-dicarbonitriles.

PubMed

Maddila, Suresh; Gangu, Kranthi Kumar; Maddila, Surya Narayana; Jonnalagadda, Sreekantha B

2017-02-01

A simple and versatile one-pot three-component synthetic protocol is devised for heterocycles, viz. 2,6-diamino-4-substituted-4H-pyran-3,5-dicarbonitrile derivatives, in short reaction times ([Formula: see text]30 min) at room temperature using ethanol as a solvent. This method involves the three-component reaction of malononitrile, substituted aldehydes, and cyanoacetamide catalyzed by chitosan-doped calcium hydroxyapatites (CS/CaHAps) giving good to excellent yields (86-96%). Twelve new pyran derivatives (4a-l) were synthesized and their structures were established and confirmed by different spectroscopic methods ([Formula: see text]H NMR, [Formula: see text]C NMR, [Formula: see text]N NMR, and HRMS). The heterogeneous catalyst, CS/CaHAp, was characterized by various instrumental techniques including XRD, TEM, SEM, and FT-IR and TGA spectroscopies. The catalyst was easily separable and reusable for up to six runs without any apparent loss of activity. The reported protocol has many benefits, such as ease of preparation, use of a green solvent, reduced reaction times, excellent product yields, and operational simplicity.

Flower-Like ZnO-Assisted One-Pot Encapsulation of Noble Metal Nanoparticles Supported Catalysts with ZIFs

NASA Astrophysics Data System (ADS)

Lin, Lu; Liu, Haiou; Zhang, Xiongfu

2018-03-01

Rational design of efficient approaches to fabricate MOFs-coated core-shell composites is promising but challenging. We report here the encapsulation of Pd nanoparticles (Pd NPs) supported flower-like ZnO (F-ZnO) microspheres with ZIF-8 shell through a facile strategy, in which the formation and immobilization of Pd NPs on F-ZnO supports and the subsequent growth of ZIF-8 shells over them are effectively integrated into one-pot synthetic route. Importantly, the utilization of ZnO both as support of Pd NPs and Zn2+ source of ZIF-8 is favorable for the implement of one-pot synthesis, due to its functions in anchoring Pd NPs and inducing ZIF-8 formation. Further insights into the morphological influence of zinc oxide particles on the resulting materials indicate that the flower-like microspheres with 2D nanosheets as subunits also benefit the coating of Pd NPs supported cores with ZIF-8, resulting in a well-defined core-shell catalyst. The achieved catalyst deliveries remarkable performance in terms of selectivity, anti-poisoning and recyclability in the liquid hydrogenations of alkenes.

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

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

DOEpatents

Schrodi, Yann [Agoura Hills, CA

2011-11-29

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

DOEpatents

Schrodi, Yann

2013-07-09

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

DOEpatents

Schrodi, Yann

2016-02-09

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

DOEpatents

Schrodi, Yann

2015-09-22

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Attrition resistant catalysts for slurry-phase Fischer-Tropsch process

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

K. Jothimurugesan

1999-11-01

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T because they are relatively inexpensive and possess reasonable activity for F-T synthesis (FTS). Their most advantages trait is their high water-gas shift (WGS) activity compared to their competitor, namely cobalt. This enables Fe F-T catalysts to process lowmore » H{sub 2}/CO ratio synthesis gas without an external shift reaction step. However, a serious problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, make the separation of catalyst from the oil/wax product very difficult if not impossible, an d result in a steady loss of catalyst from the reactor. The objectives of this research were to develop a better understanding of the parameters affecting attrition of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance.« less

hcp-Co nanowires grown on metallic foams as catalysts for the Fischer-Tropsch synthesis.

PubMed

Soulantica, Katerina; Harmel, Justine; Peres, Laurent; Estrader, Marta; Berliet, Adrien; Maury, Sylvie; Fécant, Antoine; Chaudret, Bruno; Serp, Philippe

2018-06-12

The possibility to control the structural characteristics of the active phase of supported catalysts offers the opportunity to improve catalyst performance, especially in structure sensitive catalytic reactions. In parallel, heat management is of critical importance for the catalytic performance in highly endo- or exothermic reactions. The Fisher-Tropsch synthesis (FTS) is a structure sensitive exothermic reaction, which enables catalytic transformation of syngas to high quality liquid fuels. We have elaborated monolithic cobalt based heterogeneous catalysts through a wet chemistry approach that allows control over nanocrystal shape and crystallographic phase, while at the same time enables heat management. Copper and nickel foams have been employed as supports for the epitaxial growth of hcp-Co nanowires, directly from a solution containing a coordination compound of cobalt and stabilizing ligands. The Co/Cufoam catalyst has been tested for the Fischer-Tropsch synthesis in fixed bed reactor, showing stability, and significantly superior activity and selectivity towards C5+ compared to a Co/SiO2-Al2O3 reference catalyst under the same conditions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fischer–Tropsch synthesis: Effect of ammonia on supported cobalt catalysts

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

Pendyala, Venkat Ramana Rao; Jacobs, Gary; Bertaux, Clement

The effect of ammonia in syngas on the performance of various supported cobalt catalysts (i.e., Al 2O 3, TiO 2 and SiO 2) was investigated during Fischer-Tropsch synthesis (FTS) using a continuously stirred tank reactor (CSTR). The addition of ammonia (10 ppmv NH 3) caused a significant deactivation for all supported cobalt catalysts, but the rate of deactivation was higher for the silica-supported catalysts relative to the alumina and titania-supported catalysts used in this work. Ammonia addition had a positive effect on product selectivity (i.e., lower light gas products and higher C 5+) for alumina and titania-supported catalysts compared tomore » ammonia free conditions, whereas, the addition of ammonia increased lighter hydrocarbon (C 1-C 4) products and decreased higher hydrocarbon (C 5+) selectivity compared to ammonia-free synthesis conditions for the silica-supported catalyst. For alumina and titania-supported catalysts, the activity almost recovered with mild in-situ hydrogen treatment of the ammonia exposed catalysts. For the silica-supported catalyst, the loss of activity is somewhat irreversible (i.e., cannot be regained after the mild hydrogen treatment). Addition of ammonia led to a significant loss in BET surface area and changes in pore diameter (consistent with pore collapse of a fraction of pores into the microporous range as described in the literature), as well as formation of catalytically inactive cobalt support compounds for the silica-supported catalyst. On the other hand, the pore characteristics of alumina and titania-supported catalysts were not significantly changed. In conclusion, XANES results of the ammonia exposed silica-supported catalysts further confirm the formation of cobalt-support compounds (cobalt silicates).« less

Fischer–Tropsch synthesis: Effect of ammonia on supported cobalt catalysts

DOE PAGES

Pendyala, Venkat Ramana Rao; Jacobs, Gary; Bertaux, Clement; ...

2016-02-22

The effect of ammonia in syngas on the performance of various supported cobalt catalysts (i.e., Al 2O 3, TiO 2 and SiO 2) was investigated during Fischer-Tropsch synthesis (FTS) using a continuously stirred tank reactor (CSTR). The addition of ammonia (10 ppmv NH 3) caused a significant deactivation for all supported cobalt catalysts, but the rate of deactivation was higher for the silica-supported catalysts relative to the alumina and titania-supported catalysts used in this work. Ammonia addition had a positive effect on product selectivity (i.e., lower light gas products and higher C 5+) for alumina and titania-supported catalysts compared tomore » ammonia free conditions, whereas, the addition of ammonia increased lighter hydrocarbon (C 1-C 4) products and decreased higher hydrocarbon (C 5+) selectivity compared to ammonia-free synthesis conditions for the silica-supported catalyst. For alumina and titania-supported catalysts, the activity almost recovered with mild in-situ hydrogen treatment of the ammonia exposed catalysts. For the silica-supported catalyst, the loss of activity is somewhat irreversible (i.e., cannot be regained after the mild hydrogen treatment). Addition of ammonia led to a significant loss in BET surface area and changes in pore diameter (consistent with pore collapse of a fraction of pores into the microporous range as described in the literature), as well as formation of catalytically inactive cobalt support compounds for the silica-supported catalyst. On the other hand, the pore characteristics of alumina and titania-supported catalysts were not significantly changed. In conclusion, XANES results of the ammonia exposed silica-supported catalysts further confirm the formation of cobalt-support compounds (cobalt silicates).« less

Open-cage Fullerene-like Graphitic Carbons as Catalysts for Oxidative Dehydrogenation of Isobutane

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

Liang, Chengdu; Xie, Hong; Schwartz, Viviane

We report herein a facile synthesis of fullerene-like cages, which can be opened and closed through simple thermal treatments. A glassy carbon with enclosed fullerene-like cages of 2-3 nm was synthesized through a soft-template approach that created open mesopores of 7 nm. The open mesopores provided access to the fullerene-like cages, which were opened and closed through heat treatments in air and inert gas at various temperatures. Catalytic measurements showed that the open cages displayed strikingly higher activity for the oxidative dehydrogenation of isobutane in comparison to the close ones. We anticipate that this synthesis approach could unravel an avenuemore » for pursuing fundamental understanding of the unique catalytic properties of graphitic carbon nanostructures.« less

[Pd(μ-Cl)Cl(IPr*)]2: a highly hindered pre-catalyst for the synthesis of tetra-ortho-substituted biaryls via Grignard reagent cross-coupling.

PubMed

Lesieur, Mathieu; Slawin, Alexandra M Z; Cazin, Catherine S J

2014-08-14

The new well-defined catalyst [Pd(μ-Cl)Cl(IPr*)]2 enables the efficient Grignard reagent cross-coupling for the synthesis of tetra-ortho-substituted biaryls. The high reactivity of the complex is associated with the important bulkiness of the IPr* ligand. The dimer represents the most efficient catalyst reported to date for this challenging transformation.

Fe-based Fischer Tropsch Synthesis of biomass-derived syngas: Effect of synthesis method

Treesearch

Khiet Mai; Thomas Elder; Les Groom; James J. Spivey

2015-01-01

Two 100Fe/4Cu/4K/6Zn catalysts were prepared using two different methods: coprecipitation or impregnation methods. The effect of the preparation methods on the catalyst structure, catalytic properties, and the conversion of biomass-derived syngas via Fischer–Tropsch synthesis was investigated. Syngas was derived from gasifying Southern pine woodchips and had the...

Nitrogen-doped graphene catalysts: High energy wet ball milling synthesis and characterizations of functional groups and particle size variation with time and speed

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

Zhuang, Shiqiang; Nunna, Bharath Babu; Boscoboinik, Jorge Anibal

Nitrogen-doped graphene (N-G) catalyst emerges as one of the promising non-platinum group metal (non-PGM) catalysts with the advantages of low cost, high oxygen reduction reaction (ORR) activity, stability, and selectivity to replace expensive PGM catalysts in electrochemical systems. This research investigated nanoscale high energy wet (NHEW) ball milling for the synthesis of N-G catalysts to make conventional problems such as sintering or localized overheating issues negligible. The successful synthesis of N-G catalysts with comparable catalytic performance to 10 wt% Pt/C by using this method has been published. This paper focuses on understanding the effect of grinding speed and grinding timemore » on the particle size and chemical state of N-G catalysts through the physical and chemical characterization. The research result shows that (1) the final particle size, nitrogen doping percentage, and nitrogen bonding composition of synthesized N-G catalysts are predictable and controllable by adjusting the grinding time, the grinding speed, and other relative experimental parameters; (2) the final particle size of N-G catalysts could be estimated from the derived relation between the cracking energy density and the particle size of ground material in the NHEW ball milling process with specified experimental parameters; and (3) the chemical composition of N-G catalysts synthesized by NHEW ball milling is controllable by adjusting the grinding time and grinding speed.« less

Nitrogen-doped graphene catalysts: High energy wet ball milling synthesis and characterizations of functional groups and particle size variation with time and speed

DOE PAGES

Zhuang, Shiqiang; Nunna, Bharath Babu; Boscoboinik, Jorge Anibal; ...

2017-07-26

Nitrogen-doped graphene (N-G) catalyst emerges as one of the promising non-platinum group metal (non-PGM) catalysts with the advantages of low cost, high oxygen reduction reaction (ORR) activity, stability, and selectivity to replace expensive PGM catalysts in electrochemical systems. This research investigated nanoscale high energy wet (NHEW) ball milling for the synthesis of N-G catalysts to make conventional problems such as sintering or localized overheating issues negligible. The successful synthesis of N-G catalysts with comparable catalytic performance to 10 wt% Pt/C by using this method has been published. This paper focuses on understanding the effect of grinding speed and grinding timemore » on the particle size and chemical state of N-G catalysts through the physical and chemical characterization. The research result shows that (1) the final particle size, nitrogen doping percentage, and nitrogen bonding composition of synthesized N-G catalysts are predictable and controllable by adjusting the grinding time, the grinding speed, and other relative experimental parameters; (2) the final particle size of N-G catalysts could be estimated from the derived relation between the cracking energy density and the particle size of ground material in the NHEW ball milling process with specified experimental parameters; and (3) the chemical composition of N-G catalysts synthesized by NHEW ball milling is controllable by adjusting the grinding time and grinding speed.« less

Facile synthesis of high surface area molybdenum nitride and carbide

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

Roy, Aaron; Serov, Alexey; Artyushkova, Kateryna

2015-08-15

The synthesis of high surface area γ-Mo{sub 2}N and α-Mo{sub 2}C is reported (116 and 120 m{sup 2}/g) without the temperature programmed reduction of MoO{sub 3}. γ-Mo{sub 2}N was prepared in an NH{sub 3}-free synthesis using forming gas (7 at% H{sub 2}, N{sub 2}-balance) as the reactive atmosphere. Three precursors were studied ((NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}·4H{sub 2}O, (NH{sub 4}){sub 2} Mg(MoO{sub 4}){sub 2}, and MgMoO{sub 4}) along with the sacrificial support method (SSM) as a means of reducing the particle size of Mo{sub 2}N and Mo{sub 2}C. In situ X-ray diffraction (XRD) studies were carried out to identify reactionmore » intermediates, the temperature at which various intermediates form, and the average domain size of the Mo{sub 2}N products. Materials were synthesized in bulk and further characterized by XRD, HRTEM, XPS, and BET. - Highlights: • Facile synthesis of γ-Mo2N and α-Mo2C with surface area exceeding 100 m{sup 2}/g. • Sacrificial support method was used to achieve these high surface areas. • Materials can serve as catalysts or supports in (electro)chemical processes.« less

Heterogeneous catalytic process for alcohol fuels from syngas

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

Minahan, D.M.; Nagaki, D.A.

1995-12-31

This project is focused on the discovery and evaluation of novel heterogeneous catalyst for the production of oxygenated fuel enhancers from synthesis gas. Catalysts have been studied and optimized for the production of methanol and isobutanol mixtures which may be used for the downstream synthesis of MTBE or related oxygenates. Higher alcohols synthesis (HAS) from syngas was studied; the alcohols that are produced in this process may be used for the downstream synthesis of MTBE or related oxygenates. This work has resulted in the discovery of a catalyst system that is highly selective for isobutanol compared with the prior art.more » The catalysts operate at high temperature (400{degrees}C), and consist of a spinel oxide support (general formula AB{sub 2}O{sub 4}, where A=M{sup 2+} and B = M{sup 3+}), promoted with various other elements. These catalysts operate by what is believed to be an aldol condensation mechanism, giving a product mix of mainly methanol and isobutanol. In this study, the effect of product feed/recycle (methanol, ethanol. n-propanol, isopropanol, carbon dioxide and water) on the performance of 10-DAN-55 (spinel oxide based catalyst) at 400{degrees}C, 1000 psi, GHSV = 12,000 and syngas (H{sub 2}/CO) ratio = 1:2 (alcohol addition) and 1:1 (carbon dioxide and water addition) was studied. The effect of operation at high temperatures and pressures on the performance of an improved catalyst formulation was also examined.« less

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-24

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste

PubMed Central

Liu, Wu-Jun; Tian, Ke; Jiang, Hong; Yu, Han-Qing

2013-01-01

In this work, sawdust, a biomass waste, is converted into a magnetic porous carbonaceous (MPC) solid acid catalyst by an integrated fast pyrolysis–sulfonation process. The resultant magnetic solid acid has a porous structure with high surface area of 296.4 m2 g−1, which can be attributed to the catalytic effect of Fe. The catalytic activity and recyclability of the solid acid catalyst are evaluated during three typical acid-catalyzed reactions: esterification, dehydration, and hydrolysis. The favorable catalytic performance in all three reactions is attributed to the acid's high strength with 2.57 mmol g−1 of total acid sites. Moreover, the solid acid can be reused five times without a noticeable decrease in catalytic activity, indicating the stability of the porous carbon (PC)–sulfonic acid group structure. The findings in the present work offer effective alternatives for environmentally friendly utilization of abundant biomass waste. PMID:23939253

High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

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

Duan, Haohong; Li, Dongguo; Tang, Yan

2017-04-05

The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermostmore » atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.« less

High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

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

Duan, Haohong; Li, Dongguo; Tang, Yan

2017-04-05

Search for active, stable and cost-efficient electrocatalysts for hydrogen production via water splitting could make substantial impact to the energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high surface area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) compared to Rh/C and Pt/C catalysts. The atomic structure of the rhodium phosphide nanocubes was directly observed by annular dark-field scanning transmission electron microscopy (ADF-STEM),more » which revealed phosphorous-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorous plays crucial role in determining the robust catalyst properties.« less

Highly efficient hydrogen evolution based on Ni3S4@MoS2 hybrids supported on N-doped reduced graphene oxide

NASA Astrophysics Data System (ADS)

Xu, Xiaobing; Zhong, Wei; Wu, Liqian; Sun, Yuan; Wang, Tingting; Wang, Yuanqi; Du, Youwei

2018-01-01

Hydrogen evolution reaction (HER) through water splitting at low overpotential is an appealing technology to produce renewable energy, wherein the design of stable electrocatalysts is very critical. To achieve optimal electrochemical performance, a highly efficient and stable noble-metal-free HER catalyst is synthesized by means of a facile hydrothermal co-synthesis. It consists of Ni3S4 nanosheets and MoS2 nanolayers supported on N-doped reduced graphene oxide (Ni3S4/MoS2@N-rGO). The optimized sample provides a large amount of active sites that benefit electron transfer in 3D conductive networks. Thanks to the strong synergistic effect in the catalyst network, we achieved a low overpotential of 94 mV, a small Tafel slope of 56 mV/dec and remarkable durability in an acidic medium.

Hierarchical Pd-Sn alloy nanosheet dendrites: an economical and highly active catalyst for ethanol electrooxidation.

PubMed

Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

2013-01-01

Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures.

Nitrogen-doped micropore-dominant carbon derived from waste pine cone as a promising metal-free electrocatalyst for aqueous zinc/air batteries

NASA Astrophysics Data System (ADS)

Lei, Xiaoke; Wang, Mengran; Lai, Yanqing; Hu, Langtao; Wang, Hao; Fang, Zhao; Li, Jie; Fang, Jing

2017-10-01

The exploitation for highly effective and low-cost metal-free catalysts with facile and environmental friendly method for oxygen reduction reaction is still a great challenge. To find an effective method for catalyst synthesis, in this manuscript, waste biomass pine cone is employed as raw material and nitrogen-doped micropore-dominant carbon material with excellent ORR catalytic activity is successfully synthesized. The as-prepared N-doped micropore-dominant carbon possesses a high surface area of 1556 m2 g-1. In addition, this carbon electrocatalyst loaded electrode exhibits a high discharge voltage 1.07 V at the current density of 50 mA cm-2, which can be ascribed to the rich micropores and high content of pyridinic N of the prepared carbon, indicative of great potential in the application of zinc/air batteries.

Hierarchical Pd-Sn Alloy Nanosheet Dendrites: An Economical and Highly Active Catalyst for Ethanol Electrooxidation

PubMed Central

Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

2013-01-01

Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures. PMID:23383368

Catalyst-Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β-Keto Sulfides and Sulfones.

PubMed

Wang, Huamin; Wang, Guangyu; Lu, Qingquan; Chiang, Chien-Wei; Peng, Pan; Zhou, Jiufu; Lei, Aiwen

2016-10-04

Difunctionalization of activated alkenes, a powerful strategy in chemical synthesis, has been accomplished for direct synthesis of a series of β-keto sulfides and β-keto sulfones. The transformation, mediated by O2 , proceeds smoothly in water and without any catalyst. Prominent advantages of this method include mild reaction conditions, purification simplicity, and gram-scale synthesis, underlining the practical utility of this methodology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward chemical propulsion: synthesis of ROMP-propelled nanocars.

PubMed

Godoy, Jazmin; Vives, Guillaume; Tour, James M

2011-01-25

The synthesis and ring-opening metathesis polymerization (ROMP) activity of two nanocars functionalized with an olefin metathesis catalyst is reported. The nanocars were attached to a Hoveyda-Grubbs first- or second-generation metathesis catalyst via a benzylidene moiety. The catalytic activity of these nanocars toward ROMP of 1,5-cyclooctadiene was similar to that of their parent catalysts. The activity of the Hoveyda-Grubbs first-generation catalyst-functionalized nanocar was further tested with polymerization of norbornene. Hence, the prospect is heightened for a ROMP process to propel nanocars across a surface by providing the translational force.

Fischer-Tropsch process

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

1987-01-01

A Fischer-Tropsch process utilizing a product selective and stable catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Diastereoselective auxiliary- and catalyst-controlled intramolecular aza-Michael reaction for the elaboration of enantioenriched 3-substituted isoindolinones. Application to the synthesis of a new pazinaclone analogue

PubMed Central

Sallio, Romain; Lebrun, Stéphane; Capet, Frédéric; Agbossou-Niedercorn, Francine

2018-01-01

A new asymmetric organocatalyzed intramolecular aza-Michael reaction by means of both a chiral auxiliary and a catalyst for stereocontrol is reported for the synthesis of optically active isoindolinones. A selected cinchoninium salt was used as phase-transfer catalyst in combination with a chiral nucleophile, a Michael acceptor and a base to provide 3-substituted isoindolinones in good yields and diastereomeric excesses. This methodology was applied to the asymmetric synthesis of a new pazinaclone analogue which is of interest in the field of benzodiazepine-receptor agonists. PMID:29623121

The Heck Reaction: A Microscale Synthesis Using a Palladium Catalyst

NASA Astrophysics Data System (ADS)

Martin, William B.; Kateley, Laura J.

2000-06-01

Palladium catalysts are central to a large variety of modern organic syntheses. Heck reactions use palladium acetate as the preferred precatalyst to effect vinylic substitutions involving haloarenes and haloalkenes. The microscale synthesis described uses a reaction between a bromoiodobenzene and acrylic acid to produce a bromocinnamic acid. Structure verification for the product uses IR and 1H NMR spectroscopy. This experiment is appropriate for a second-semester introductory organic chemistry laboratory or an intermediate-level organic synthesis laboratory. It could be adapted as a project for two or three students, with each member of the group preparing a different isomer or using a different catalyst source.

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

White, Curt M.; Quiring, Michael S.; Jensen, Karen L.; Hickey, Richard F.; Gillham, Larry D.

1998-10-27

In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by slurring them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation.

Catalyst and process development for synthesis gas conversion to isobutylene. Quarterly report, October 1, 1992--December 31, 1992

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

Anthony, R.G.; Akgerman, A.

1993-02-01

The objectives of this project are to develop a new catalyst, the kinetics for this catalyst, reactor models for trickle bed, slurry and fixed bed reactors, and simulate the performance of fixed bed trickle flow reactors, slurry flow reactors, and fixed bed gas phase reactors for conversion of a hydrogen lean synthesis gas to isobutylene. The goals for the quarter include: (1) Conduct experiments using a trickle bed reactor to determine the effect of reactor type on the product distribution. (2) Use spherical pellets of silica as a support for zirconia for the purpose of increasing surface, area and performancemore » of the catalysts. (3) Conduct exploratory experiments to determine the effect of super critical drying of the catalyst on the catalyst surface area and performance. (4) Prepare a ceria/zirconia catalyst by the precipitation method.« less

Direct Routes from Synthesis Gas to Ethylene Glycol.

ERIC Educational Resources Information Center

Dombek, B. D.

1986-01-01

Discusses the synthesis of ethylene glycol from carbon monoxide and hydrogen using bimetallic catalysts. Although this technology has not been implemented, it illustrates two important future trends, namely, use of bimetallic catalysts and use of coal-derived carbon monoxide and hydrogen as a new feed stock. (JN)

A modified preparation procedure for carbon nanotube-confined Nd/Na heterobimetallic catalyst for anti-selective catalytic asymmetric nitroaldol reactions.

PubMed

Sureshkumar, Devarajulu; Hashimoto, Kazuki; Kumagai, Naoya; Shibasaki, Masakatsu

2013-11-15

A recyclable asymmetric metal-based catalyst is a rare entity among the vast collection of asymmetric catalysts developed so far. Recently we found that the combination of a self-assembling metal-based asymmetric catalyst and multiwalled carbon nanotubes (MWNTs) produced a highly active and recyclable catalyst in which the catalytically active metal complex was dispersed in the MWNT network. Herein we describe an improved preparation procedure and full details of a Nd/Na heterobimetallic complex confined in MWNTs. Facilitated self-assembly of the catalyst with MWNTs avoided the sacrificial use of excess chiral ligand for the formation of the heterobimetallic complex, improving the loading ratio of the catalyst components. Eighty-five percent of the catalyst components were incorporated onto MWNTs to produce the confined catalyst, which was a highly efficient and recyclable catalyst for the anti-selective asymmetric nitroaldol reaction. The requisite precautions for the catalyst preparation to elicit reproducible catalytic performance are summarized. Superior catalytic profiles over the prototype catalyst without MWNTs were revealed in the synthesis of optically active 1,2-nitroalkanols, which are key intermediates for the synthesis of therapeutics.

Synthesis of renewable diesel through hydrodeoxygenation reaction from nyamplung oil (Calophyllum Inophyllum oil) using NiMo/Z and NiMo/C catalysts with rapid heating and cooling method

NASA Astrophysics Data System (ADS)

Susanto, B. H.; Prakasa, M. B.; Shahab, M. H.

2016-11-01

The synthesis of metal nanocrystal was conducted by modification preparation from simple heating method which heating and cooling process run rapidly. The result of NiMo/Z 575 °C characterizations are 33.73 m2/gram surface area and 31.80 nm crystal size. By used NiMo/C 700 °C catalyst for 30 minutes which had surface area of 263.21 m2/gram, had 31.77 nm crystal size, and good morphology, obtained catalyst with high activity, selectivity, and stability. After catalyst activated, synthesis of renewable diesel performed in hydrogenation reactor at 375 °C, 12 bar, and 800 rpm. The result of conversion was 81.99%, yield was 68.08%, and selectivity was 84.54%.

Facile hydrothermal synthesis of Fe3O4@cellulose aerogel nanocomposite and its application in Fenton-like degradation of Rhodamine B.

PubMed

Jiao, Yue; Wan, Caichao; Bao, Wenhui; Gao, He; Liang, Daxin; Li, Jian

2018-06-01

A magnetic cellulose aerogel-supported Fe 3 O 4 nanoparticles composite was designed as a highly efficient and eco-friendly catalyst for Fenton-like degradation of Rhodamine B (RhB). The composite (coded as Fe 3 O 4 @CA) was formed by embedding well-dispersed Fe 3 O 4 nanoparticles into the 3D structure of cellulose aerogels by virtue of a facile and cheap hydrothermal method. Comparative studies indicate that the RhB decolorization ratio is much higher in co-presence of Fe 3 O 4 and H 2 O 2 than that in presence of Fe 3 O 4 or H 2 O 2 only, revealing that the Fe 3 O 4 @CA-catalyzed Fenton-like reaction governed the RhB decolorization process. It was also found that almost 100% RhB removal was achieved in the Fenton-like system. Moreover, the composite exhibited higher catalytic activity than that of the individual Fe 3 O 4 particles. In addition, the Fe 3 O 4 @CA catalyst retained ∼97% of its ability to degrade RhB after the six successive degradation experiments, suggesting its excellent reusability. All these merits indicate that the green and low-cost catalyst with strong magnetic responsiveness possesses good potential for H 2 O 2 -driven Fenton-like treatment of organic dyestuff wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Attrition Resistant Iron-Based Fischer-Tropsch Catalysts

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

Jothimurugesan, K.; Goodwin, J.G.; Spivey, J.J.

1997-03-26

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRS) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modem coal gasifiers. This is because in addition to reasonable F-T activity, the FT catalysts also possess high water gas shift (WGS) activity. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.« less

Attrition Resistant Iron-Based Fischer-Tropsch Catalysts.

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

Jothimurugesan, K.; Goodwin, J.S.; Spivey, J.J.

1997-09-22

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO and H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a seriousmore » problem with the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity.« less

Facile purification and click labeling with 2-[ 18F]fluoroethyl azide using solid phase extraction cartridges

DOE PAGES

Zhou, Dong; Chu, Wenhua; Peng, Xin; ...

2014-11-04

In this paper, a facile method was developed to purify 2-[ 18F]fluoroethyl azide ([ 18F]FEA) using a C18 cartridge and an Oasis® HLB cartridge in series, in which [18F]FEA was exclusively trapped on the HLB cartridge. [ 18F]FEA can be eluted for reactions in solution; alternatively click labeling can be carried out on the HLB cartridge itself by loading an alkyne substrate and copper (I) catalyst dissolved in DMF onto the cartridge. Finally, this solid phase extraction methodology for purification and click labeling with [ 18F]FEA, either in solution or on the cartridge, is safe, simple, reproducible in high yield,more » and compatible with automated synthesis of 18F-labeled PET tracers.« less

Effect of different catalysts on urea-formaldehyde resin synthesis

Treesearch

Qi-Ning Sun; Chung-Yun Hse; Todd F. Shupe

2014-01-01

Four catalysts (H2SO4, HCl, H3PO4, and NaOH/NH4OH) were studied in the preparation of melamine modified urea– formaldehyde (UFM) resins. 13C-nuclear magnetic resonance spectroscopic analysis of the UFM resins at different synthesis stages revealed the...

Modified chiral triazolium salts for enantioselective benzoin cyclization of enolizable keto-aldehydes: synthesis of (+)-sappanone B.

PubMed

Takikawa, Hiroshi; Suzuki, Keisuke

2007-07-05

Asymmetric synthesis of (+)-sappanone B (1), a natural product with a 3-hydroxy chromanone structure, was achieved via enantioselective benzoin cyclization by using a modified Rovis catalyst and triethylamine. This catalyst enabled the successful benzoin cyclization of readily enolizable keto-aldehydes.

MESOPOROUS IRON PHOSPHATE AS AN ACTIVE, SELECTIVE AND RECYCLABLE CATALYST FOR THE SYNTHESIS OF NOPOL BY PRINS CONDENSATION

EPA Science Inventory

Mesoporous iron phosphate is found to be a highly active and recyclable heterogeneous catalyst for the selective synthesis of nopol by Prins condensation of ?-pinene and paraformaldehyde in acetonitrile at 80 oC.

Benign by design: catalyst-free in-water, on-water green chemical methodologies in organic synthesis

EPA Science Inventory

The development of organic synthesis under sustainable conditions is a primary goal of practicing green chemists who want to prevent pollution and design safer pathways. Although, it is challenging to avoid the use of catalysts, or solvents in all the organic reactions but progre...

Novel nanodispersed coal liquefaction catalysts: Molecular design via microemulsion-based synthesis. Final technical report, October 1990--December 1994

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

Osseo-Asare, K.; Boakye, E.; Vittal, M.

1995-04-01

This report described the synthesis of Molybdenum Sulfides in microemulsions by acidification of ammonium tetrathiomolybdate. Molybdenum Sulfides have been shown to be potential coal liquefaction catalysts. The importance of particle size, temperature effects, and coal surface chemistry to impregnation are discussed.

A Facile Molecular Precursor Route to Metal Phosphide Nanoparticles and Their Evaluation as Hydrodeoxygenation Catalysts

DOE PAGES

Habas, Susan E.; Baddour, Frederick G.; Ruddy, Daniel A.; ...

2015-11-05

Metal phosphides have been identified as a promising class of materials for the catalytic upgrading of bio-oils, which are renewable and potentially inexpensive sources for liquid fuels. Herein, we report the facile synthesis of a series of solid, phase-pure metal phosphide nanoparticles (NPs) (Ni 2P, Rh 2P, and Pd 3P) utilizing commercially available, air-stable metal–phosphine complexes in a one-pot reaction. This single-source molecular precursor route provides an alternative method to access metal phosphide NPs with controlled phases and without the formation of metal NP intermediates that can lead to hollow particles. The formation of the Ni 2P NPs was shownmore » to proceed through an amorphous Ni–P intermediate, leading to the desired NP morphology and metal-rich phase. This low-temperature, rapid route to well-defined metal NPs is expected to have broad applicability to a variety of readily available or easily synthesized metal–phosphine complexes with high decomposition temperatures. Hydrodeoxygenation of acetic acid, an abundant bio-oil component, was performed to investigate H 2 activation and deoxygenation pathways under conditions that are relevant to ex situ catalytic fast pyrolysis (high temperatures, low pressures, and near-stoichiometric H 2 concentrations). The catalytic performance of the silica-supported metal phosphide NPs was compared to the analogous incipient wetness (IW) metal and metal phosphide catalysts over the range 200–500 °C. Decarbonylation was the primary pathway for H 2 incorporation in the presence of all of the catalysts except NP-Pd 3P, which exhibited minimal productive activity, and IW-Ni, which evolved H 2. The highly controlled NP-Ni2P and NP-Rh2P catalysts, which were stable under these conditions, behaved comparably to the IW-metal phosphides, with a slight shift to higher product onset temperatures, likely due to the presence of surface ligands. Most importantly, the NP-Ni 2P catalyst exhibited H 2 activation and incorporation, in contrast to IW-Ni, indicating that the behavior of the metal phosphide is significantly different from that of the parent metal, and more closely resembles that of noble metal catalysts.« less

Water-soluble metal nanoparticles stabilized by plant polyphenols for improving the catalytic properties in oxidation of alcohols

NASA Astrophysics Data System (ADS)

Mao, H.; Liao, Y.; Ma, J.; Zhao, S. L.; Huo, F. W.

2015-12-01

Plant polyphenols extracted from plants are one of the most abundant biomasses in nature, which are typical water soluble natural polymers. Herein, we reported a facile approach for the synthesis of platinum nanoparticle (PtNP) aqueous colloid by utilizing black wattle tannin (BWT, a typical plant polyphenol) as amphiphilic stabilizer. The phenolic hydroxyls of BWT provide the PtNPs with enough hydrophilicity, and their reduction ability could protect the PtNPs from deactivation caused by oxygen atmosphere. Additionally, the hydrophilic nature of BWT could efficiently promote the oxidation of alcohols in water, meanwhile, the hydrophobic and rigid backbones of plant polyphenols are able to suppress the PtNPs from aggregating, thus ensuring the high dispersion of the PtNPs during reactions. Under mild aerobic conditions, the as-prepared BWT-Pt colloid catalyst exhibited high activity in a series of biphasic oxidation of aromatic alcohols and aliphatic alcohols. As for the cycling stability, the BWT-Pt catalyst showed no obvious decrease during the 7 cycles, revealing superior cycling stability as compared with the counterparts using PVP or PEG as the stabilizer.Plant polyphenols extracted from plants are one of the most abundant biomasses in nature, which are typical water soluble natural polymers. Herein, we reported a facile approach for the synthesis of platinum nanoparticle (PtNP) aqueous colloid by utilizing black wattle tannin (BWT, a typical plant polyphenol) as amphiphilic stabilizer. The phenolic hydroxyls of BWT provide the PtNPs with enough hydrophilicity, and their reduction ability could protect the PtNPs from deactivation caused by oxygen atmosphere. Additionally, the hydrophilic nature of BWT could efficiently promote the oxidation of alcohols in water, meanwhile, the hydrophobic and rigid backbones of plant polyphenols are able to suppress the PtNPs from aggregating, thus ensuring the high dispersion of the PtNPs during reactions. Under mild aerobic conditions, the as-prepared BWT-Pt colloid catalyst exhibited high activity in a series of biphasic oxidation of aromatic alcohols and aliphatic alcohols. As for the cycling stability, the BWT-Pt catalyst showed no obvious decrease during the 7 cycles, revealing superior cycling stability as compared with the counterparts using PVP or PEG as the stabilizer. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07897k

Development of GREET Catalyst Module

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

Wang, Zhichao; Dunn, Jennifer B.; Cronauer, Donald C.

2014-09-01

Catalysts are critical inputs for many pathways that convert biomass into biofuels. Energy consumption and greenhouse gas (GHG) emissions during the production of catalysts and chemical inputs influence the life-cycle energy consumption, and GHG emissions of biofuels and need to be considered in biofuel life-cycle analysis (LCA). In this report, we develop energy and material flows for the production of three different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5]) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™)more » catalyst module. They were selected because they are consumed in existing U.S. Department of Energy (DOE) analyses of biofuel processes. For example, a thermochemical ethanol production pathway (indirect gasification and mixed alcohol synthesis) developed by the National Renewable Energy Laboratory (NREL) uses olivine, DEPG, and tar reforming and alcohol synthesis catalysts (Dutta et al., 2011). ZSM-5 can be used in biofuel production pathways such as catalytic upgrading of sugars into hydrocarbons (Biddy and Jones, 2013). Other uses for these compounds and catalysts are certainly possible. In this report, we document the data sources and methodology we used to develop material and energy flows for the catalysts and compounds in the GREET catalyst module. In Section 2 we focus on compounds used in the model Dutta et al. (2011) developed. In Section 3, we report material and energy flows associated with ZSM-5 production. Finally, in Section 4, we report results.« less

Silver-palladium catalysts for the direct synthesis of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Khan, Zainab; Dummer, Nicholas F.; Edwards, Jennifer K.

2017-11-01

A series of bimetallic silver-palladium catalysts supported on titania were prepared by wet impregnation and assessed for the direct synthesis of hydrogen peroxide, and its subsequent side reactions. The addition of silver to a palladium catalyst was found to significantly decrease hydrogen peroxide productivity and hydrogenation, but crucially increase the rate of decomposition. The decomposition product, which is predominantly hydroxyl radicals, can be used to decrease bacterial colonies. The interaction between silver and palladium was characterized using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The results of the TPR and XPS indicated the formation of a silver-palladium alloy. The optimal 1% Ag-4% Pd/TiO2 bimetallic catalyst was able to produce approximately 200 ppm of H2O2 in 30 min. The findings demonstrate that AgPd/TiO2 catalysts are active for the synthesis of hydrogen peroxide and its subsequent decomposition to reactive oxygen species. The catalysts are promising for use in wastewater treatment as they combine the disinfectant properties of silver, hydrogen peroxide production and subsequent decomposition. This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

Easy solid-phase synthesis of pH-insensitive heterogeneous CNTs/FeS Fenton-like catalyst for the removal of antibiotics from aqueous solution.

PubMed

Ma, Jie; Yang, Mingxuan; Yu, Fei; Chen, Junhong

2015-04-15

We report a facile solid method to synthesize efficient carbon-based Fenton-like catalyst (CNTs/FeS) using as-prepared carbon nanotubes (APCNTs), which makes full use of the iron nanoparticles in APCNTs without needless purification. Furthermore, the CNTs/FeS was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric (TG) and other analysis techniques, and then the CNTs/FeS was used as a Fenton-like catalyst for removing ciprofloxacin from aqueous solution. Response Surface Methodology (RSM) was applied to find the effect of the reaction parameter and the optimum operating condition. Results shows the catalytic reaction had better suitability than previous studies in a wide range of pH values (pH 3-8) and the Fenton-like catalyst CNTs/FeS exhibits good catalytic activity for removing of antibiotic, which be attributed to the synergistic effect of adsorption-advanced oxidation and significantly improves efficiency of advanced oxidation. More importantly, the CNTs/FeS catalyst exhibit good regeneration performance and retains a high catalytic capacity (>75%) even after four reaction cycles. The catalytic mechanism were also studied further, the removal mechanism of ciprofloxacin by a CNTs/FeS heterogeneous Fenton-like process primarily involves three removal pathways occurring simultaneously: (a) adsorption removal by CNTs, (b) Fenton-like degradation catalyzed by FeS, (c) catalytic degradation by CNTs catalyst. And these actions also have synergistic effects for ciprofloxacin removal. Copyright © 2014 Elsevier Inc. All rights reserved.

Benzylation of Nitroalkanes Using Copper-Catalyzed Thermal Redox Catalysis: Toward the Facile C-Alkylation of Nitroalkanes

PubMed Central

Gildner, Peter G.; Gietter, Amber A. S.; Cui, Di; Watson, Donald A.

2012-01-01

The C-alkylation of nitroalkanes under mild conditions has been a significant challenge in organic synthesis for more than a century. Herein, we report a simple Cu(I) catalyst, generated in situ, that is highly effective for C-benzylation of nitroalkanes using abundant benzyl bromides and related heteroaromatic compounds. This process, which we believe proceeds via a thermal redox mechanism, allows access to a variety of complex nitroalkanes under mild reaction conditions and represents the first step towards developing a general catalytic system for the alkylation of nitroalkanes. PMID:22691127

Synthesis of coiled carbon nanotubes on Co/Al2O3 catalysts in a fluidised-bed

NASA Astrophysics Data System (ADS)

Liu, Jun; Harris, Andrew T.

2010-02-01

Mixtures of regularly coiled and straight multi-walled carbon nanotubes (MWNTs) were synthesised on alumina supported Co catalysts prepared by pH controlled, wet impregnation. The synthesis reaction was performed under C2H2:H2:N2 at 750 °C in a fluidised-bed for 30 min. Scanning electron microscopy/energy dispersive X-ray spectroscopy shows good distribution of the active Co particles on the surface of the alumina support. Determined from 10 individual SEM images from the same product batch, the CNTs present are typically from 10 to 40 nm in diameter. Thermogravimetric analysis (TGA) and Raman spectroscopy indicate the total oxidative weight loss is independent of pH during catalyst preparation. This study is the first to report the use of a fluidised-bed for the synthesis of coiled MWNTs, using alumina supported Co catalysts.

Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Hata, Kenji; Futaba, Don N.; Mizuno, Kohei; Namai, Tatsunori; Yumura, Motoo; Iijima, Sumio

2004-11-01

We demonstrate the efficient chemical vapor deposition synthesis of single-walled carbon nanotubes where the activity and lifetime of the catalysts are enhanced by water. Water-stimulated enhanced catalytic activity results in massive growth of superdense and vertically aligned nanotube forests with heights up to 2.5 millimeters that can be easily separated from the catalysts, providing nanotube material with carbon purity above 99.98%. Moreover, patterned, highly organized intrinsic nanotube structures were successfully fabricated. The water-assisted synthesis method addresses many critical problems that currently plague carbon nanotube synthesis.

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide.

PubMed

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-11-16

The effect of oxide coating on the activity of a copper-zinc oxide-based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO₂ conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides.

Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide

PubMed Central

Umegaki, Tetsuo; Kojima, Yoshiyuki; Omata, Kohji

2015-01-01

The effect of oxide coating on the activity of a copper-zinc oxide–based catalyst for methanol synthesis via the hydrogenation of carbon dioxide was investigated. A commercial catalyst was coated with various oxides by a sol-gel method. The influence of the types of promoters used in the sol-gel reaction was investigated. Temperature-programmed reduction-thermogravimetric analysis revealed that the reduction peak assigned to the copper species in the oxide-coated catalysts prepared using ammonia shifts to lower temperatures than that of the pristine catalyst; in contrast, the reduction peak shifts to higher temperatures for the catalysts prepared using L(+)-arginine. These observations indicated that the copper species were weakly bonded with the oxide and were easily reduced by using ammonia. The catalysts prepared using ammonia show higher CO2 conversion than the catalysts prepared using L(+)-arginine. Among the catalysts prepared using ammonia, the silica-coated catalyst displayed a high activity at high temperatures, while the zirconia-coated catalyst and titania-coated catalyst had high activity at low temperatures. At high temperature the conversion over the silica-coated catalyst does not significantly change with reaction temperature, while the conversion over the zirconia-coated catalyst and titania-coated catalyst decreases with reaction time. From the results of FTIR, the durability depends on hydrophilicity of the oxides. PMID:28793674

Synthesis of Large and Few Atomic Layers of Hexagonal Boron Nitride on Melted Copper

PubMed Central

Khan, Majharul Haque; Huang, Zhenguo; Xiao, Feng; Casillas, Gilberto; Chen, Zhixin; Molino, Paul J.; Liu, Hua Kun

2015-01-01

Hexagonal boron nitride nanosheets (h-BNNS) have been proposed as an ideal substrate for graphene-based electronic devices, but the synthesis of large and homogeneous h-BNNS is still challenging. In this contribution, we report a facile synthesis of few-layer h-BNNS on melted copper via an atmospheric pressure chemical vapor deposition process. Comparative studies confirm the advantage of using melted copper over solid copper as a catalyst substrate. The former leads to the formation of single crystalline h-BNNS that is several microns in size and mostly in mono- and bi-layer forms, in contrast to the polycrystalline and mixed multiple layers (1–10) yielded by the latter. This difference is likely to be due to the significantly reduced and uniformly distributed nucleation sites on the smooth melted surface, in contrast to the large amounts of unevenly distributed nucleation sites that are associated with grain boundaries and other defects on the solid surface. This synthesis is expected to contribute to the development of large-scale manufacturing of h-BNNS/graphene-based electronics. PMID:25582557

Caffeine-catalyzed gels.

PubMed

DiCiccio, Angela M; Lee, Young-Ah Lucy; Glettig, Dean L; Walton, Elizabeth S E; de la Serna, Eva L; Montgomery, Veronica A; Grant, Tyler M; Langer, Robert; Traverso, Giovanni

2018-07-01

Covalently cross-linked gels are utilized in a broad range of biomedical applications though their synthesis often compromises easy implementation. Cross-linking reactions commonly utilize catalysts or conditions that can damage biologics and sensitive compounds, producing materials that require extensive post processing to achieve acceptable biocompatibility. As an alternative, we report a batch synthesis platform to produce covalently cross-linked materials appropriate for direct biomedical application enabled by green chemistry and commonly available food grade ingredients. Using caffeine, a mild base, to catalyze anhydrous carboxylate ring-opening of diglycidyl-ether functionalized monomers with citric acid as a tri-functional crosslinking agent we introduce a novel poly(ester-ether) gel synthesis platform. We demonstrate that biocompatible Caffeine Catalyzed Gels (CCGs) exhibit dynamic physical, chemical, and mechanical properties, which can be tailored in shape, surface texture, solvent response, cargo release, shear and tensile strength, among other potential attributes. The demonstrated versatility, low cost and facile synthesis of these CCGs renders them appropriate for a broad range of customized engineering applications including drug delivery constructs, tissue engineering scaffolds, and medical devices. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Synthesis of large and few atomic layers of hexagonal boron nitride on melted copper.

PubMed

Khan, Majharul Haque; Huang, Zhenguo; Xiao, Feng; Casillas, Gilberto; Chen, Zhixin; Molino, Paul J; Liu, Hua Kun

2015-01-13

Hexagonal boron nitride nanosheets (h-BNNS) have been proposed as an ideal substrate for graphene-based electronic devices, but the synthesis of large and homogeneous h-BNNS is still challenging. In this contribution, we report a facile synthesis of few-layer h-BNNS on melted copper via an atmospheric pressure chemical vapor deposition process. Comparative studies confirm the advantage of using melted copper over solid copper as a catalyst substrate. The former leads to the formation of single crystalline h-BNNS that is several microns in size and mostly in mono- and bi-layer forms, in contrast to the polycrystalline and mixed multiple layers (1-10) yielded by the latter. This difference is likely to be due to the significantly reduced and uniformly distributed nucleation sites on the smooth melted surface, in contrast to the large amounts of unevenly distributed nucleation sites that are associated with grain boundaries and other defects on the solid surface. This synthesis is expected to contribute to the development of large-scale manufacturing of h-BNNS/graphene-based electronics.

Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

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

Klier, Kamil; Herman, Richard G

2005-11-30

This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. Themore » latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with blending octane No. of 105, and can replace aromatics in liquid fuels.« less

Direct synthesis of hydrogen peroxide and benzyl alcohol oxidation using Au-Pd catalysts prepared by sol immobilization.

PubMed

Pritchard, James; Kesavan, Lokesh; Piccinini, Marco; He, Qian; Tiruvalam, Ramchandra; Dimitratos, Nikolaos; Lopez-Sanchez, Jose A; Carley, Albert F; Edwards, Jennifer K; Kiely, Christopher J; Hutchings, Graham J

2010-11-02

We report the preparation of Au-Pd nanocrystalline catalysts supported on activated carbon prepared via a sol-immobilization technique and explore their use for the direct synthesis of hydrogen peroxide and the oxidation of benzyl alcohol. In particular, we examine the synthesis of a systematic set of Au-Pd colloidal nanoparticles having a range of Au/Pd ratios. The catalysts have been structurally characterized using a combination of UV-visible spectroscopy, transmission electron microscopy, STEM HAADF/XEDS, and X-ray photoelectron spectroscopy. The Au-Pd nanoparticles are found in the majority of cases to be homogeneous alloys, although some variation is observed in the AuPd composition at high Pd/Au ratios. The optimum performance for the synthesis of hydrogen peroxide is observed for a catalyst having a Au/Pd 1:2 molar ratio. However, the competing hydrogenation reaction of hydrogen peroxide increases with increasing Pd content, although Pd alone is less effective than when Au is also present. Investigation of the oxidation of benzyl alcohol using these materials also shows that the optimum selective oxidation to the aldehyde occurs for the Au/Pd 1:2 molar ratio catalyst. These measured activity trends are discussed in terms of the structure and composition of the supported Au-Pd nanoparticles.

One-pot facile synthesis of reusable tremella-like M1@M2@M1(OH)2 (M1 = Co, Ni, M2 = Pt/Pd, Pt, Pd and Au) three layers core-shell nanostructures as highly efficient catalysts

NASA Astrophysics Data System (ADS)

Liu, Yadong; Fang, Zhen; Kuai, Long; Geng, Baoyou

2014-07-01

In this work, a general, facile, successive and eco-friendly method for multilayer nanostructures has been established for the first time. We take full advantage of the structural and compositional character of M1@M2 (M1 = Co, Ni, M2 = Pt/Pd, Pt, Pd and Au) core-shell nanostructures to prepare a series of reusable tremella-like M1@M2@M1(OH)2 three layer core-shell or yolk-shell nanocomposites with a magnetic core, a porous noble metal shell, and an ultrathin cobalt or nickel hydroxide shell. We evaluated their catalytic performance using a model reaction based on the reduction of 4-nitrophenol. These novel M1@M2@M1(OH)2 nanomaterials with a unique internal micro environment promoted the efficiency of the catalytic reaction, prolonged the service life of the catalyst and enhanced the overall activity of the catalyst in the catalytic process. The novel three layer core-shell nanocomposites can be extended to other applications such as biomedical detection, energy conversion and storage systems.In this work, a general, facile, successive and eco-friendly method for multilayer nanostructures has been established for the first time. We take full advantage of the structural and compositional character of M1@M2 (M1 = Co, Ni, M2 = Pt/Pd, Pt, Pd and Au) core-shell nanostructures to prepare a series of reusable tremella-like M1@M2@M1(OH)2 three layer core-shell or yolk-shell nanocomposites with a magnetic core, a porous noble metal shell, and an ultrathin cobalt or nickel hydroxide shell. We evaluated their catalytic performance using a model reaction based on the reduction of 4-nitrophenol. These novel M1@M2@M1(OH)2 nanomaterials with a unique internal micro environment promoted the efficiency of the catalytic reaction, prolonged the service life of the catalyst and enhanced the overall activity of the catalyst in the catalytic process. The novel three layer core-shell nanocomposites can be extended to other applications such as biomedical detection, energy conversion and storage systems. Electronic supplementary information (ESI) available: Fig. S1-S6. See DOI: 10.1039/c4nr01470g

An Undergraduate Chemistry Laboratory: Synthesis of Well-Defined Polymers by Low-Catalyst-Concentration ATRP and Postpolymerization Modification to Fluorescent Materials

ERIC Educational Resources Information Center

Tsarevsky, Nicolay V.; Woodruf, Shannon R.; Wisian-Neilson, Patty J.

2016-01-01

A two-session experiment is designed to introduce undergraduate students to concepts in catalysis, transition metal complexes, polymer synthesis, and postpolymerization modifications. In the first session, students synthesize poly(glycidyl methacrylate) via low-catalyst-concentration atom transfer radical polymerization (ATRP). The…

Synthesis of an Epoxide Carbonylation Catalyst: Exploration of Contemporary Chemistry for Advanced Undergraduates

ERIC Educational Resources Information Center

Getzler, Yutan D. Y. L.; Schmidt, Joseph A. R.; Coates, Geoffrey W.

2005-01-01

A class of highly active, well-defined compounds for the catalytic carbonylation of epoxides and aziridines to beta-lactones and beta-lactams are introduced. The synthesis of one of the catalysts involves a simple imine condensation to form the ligand followed by air-sensitive metalation and salt metathesis steps.

CATALYST-FREE REACTIONS UNDER SOLVENT-FEE CONDITIONS: MICROWAVE-ASSISTED SYNTHESIS OF HETEROCYCLIC HYDRAZONES BELOW THE MELTING POINT OF NEAT REACTANTS: JOURNAL ARTICLE

EPA Science Inventory

NRMRL-CIN-1437 Jeselnik, M., Varma*, R.S., Polanc, S., and Kocevar, M. Catalyst-free Reactions under Solvent-fee Conditions: Microwave-assisted Synthesis of Heterocyclic Hydrazones below the Melting Point of Neat Reactants. Published in: Chemical Communications 18:1716-1717 (200...

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Swift tuning from spherical molybdenum microspheres to hierarchical molybdenum disulfide nanostructures by switching from solvothermal to hydrothermal synthesis route

NASA Astrophysics Data System (ADS)

Qureshi, Nilam; Arbuj, Sudhir; Shinde, Manish; Rane, Sunit; Kulkarni, Milind; Amalnerkar, Dinesh; Lee, Haiwon

2017-09-01

Herein, we report the synthesis of metallic molybdenum microspheres and hierarchical MoS2 nanostructures by facile template-free solvothermal and hydrothermal approach, respectively. The morphological transition of the Mo microspheres to hierarchical MoS2 nanoflower architectures is observed to be accomplished with change in solvent from ethylenediamine to water. The resultant marigold flower-like MoS2 nanostructures are few layers thick with poor crystallinity while spherical ball-like molybdenum microspheres exhibit better crystalline nature. This is the first report pertaining to the synthesis of Mo microspheres and MoS2 nanoflowers without using any surfactant, template or substrate in hydro/solvothermal regime. It is opined that such nanoarchitectures of MoS2 are useful candidates for energy related applications such as hydrogen evolution reaction, Li ion battery and pseudocapacitors. Inquisitively, metallic Mo can potentially act as catalyst as well as fairly economical Surface Enhanced Raman Spectroscopy (SERS) substrate in biosensor applications.

Methods for polymer synthesis

DOEpatents

Allen, Scott D.; Simoneau, Christopher A.; Keefe, William D.; Conuel, Jeff R.

2016-12-06

The present invention provides methods for reducing induction periods in epoxide-CO.sub.2 copolymerizations. In certain embodiments, the methods include the step of contacting an epoxide with CO.sub.2 in the presence of two catalysts: an epoxide hydrolysis catalyst and an epoxide CO.sub.2 copolymerization catalyst. In another aspect, the invention provides catalyst compositions comprising a mixture of an epoxide hydrolysis catalyst and an epoxide CO.sub.2 copolymerization catalyst.

Morphology controlled synthesis of 2-D Ni-Ni3S2 and Ni3S2 nanostructures on Ni foam towards oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Chaudhari, Nitin Kaduba; Oh, Aram; Sa, Young Jin; Jin, Haneul; Baik, Hionsuck; Kim, Sang Gu; Lee, Suk Joong; Joo, Sang Hoon; Lee, Kwangyeol

2017-03-01

Catalysts for oxygen evolution reactions (OER) are at the heart of key renewable energy technologies, and development of non-precious metal catalysts with high activity and stability remain a great challenge in this field. Among various material candidates, metal sulfides are receiving increasing attention. While morphology-dependent catalytic performances are well established in noble metal-based catalysts, relatively little is known for the morphology‒catalytic performance relationship in metal sulfide catalysts. In this study, uniform spider web-like Ni nanosheets-Ni3S2 and honeycomb-like Ni3S2 structures are deposited on nickel foam (Ni3S2/NF) by a facile one-step hydrothermal synthetic route. When used as an oxygen evolution electrode, the spider web-like Ni-Ni3S2/NF with the large exposed surface area shown excellent catalytic activity and stability with an overpotential of 310 mV to achieve at 10 mA/cm2 and a Tafel slope of 63 mV/dec in alkaline media, which is superior to the honeycomb-like structure without Ni nanosheet. The low Tafel slope of the spider web-like Ni-Ni3S2/NF represents one of the best OER kinetics among nickel sulfide-based OER catalysts. The results point to the fact that performance of the metal sulfide electrocatalysts might be fine-tuned and optimized with morphological controls.

Fe3O4 nanocubes assembled on RGO nanosheets: Ultrasound induced in-situ and eco-friendly synthesis, characterization and their excellent catalytic performance for the production of liquid fuel in Fischer-tropsch synthesis.

PubMed

Abbas, Mohamed; Zhang, Juan; Lin, Ke; Chen, Jiangang

2018-04-01

In this study, Fe 3 O 4 nanocubes (NCs) decorated on RGO nanosheets (NSs) structures were successfully synthesized through an innovative and environmentally-friendly rapid sonochemical method. More importantly, iron(II) sulfate heptahydrate and GO were employed as precursors and water as reaction medium, meanwhile, NaOH within the generated free radicals from the high intensity ultrasound were sufficient as reducing and base agent in our clean synthesis. Moreover, the hydrothermal method as a conventional approach was employed to synthesize the same catalysts for the comparison with the ultrasonocation technique. The as-synthesized Fe 3 O 4 and RGO/Fe 3 O 4 NSs catalysts were exposed to industrially relevant Fischer-tropsch synthesis (FTS) conditions at various reaction temperatures (250-290 °C), and they subjected to fully characterization before and after FTS reaction using XRD, TEM, HRTEM, EDS mapping, XPS, FTIR, BET, H 2 -TPR, H 2 -TPD and CO-TPD to understand the structure-performance relationships. Notably, the catalysts produced using the sonochemical method had a better CO conversion rate [Fe 3 O 4 (80%), RGO/Fe 3 O 4 (82%)] than the hydrothermally synthesized catalysts. However, compared to the naked-Fe 3 O 4 catalysts, the sonochemically and hydrothermally synthesized RGO-supported Fe 3 O 4 catalysts had higher long chain hydrocarbon (C5+) selectivity values (72% and 67%) and C 2 -C 4 olefin/paraffin selectivity ratio (3.2 and 2) and low CH4 selectivity values (6% and 8.5%), respectively. This can be attributed to their high surface area, the degree of reducibility, and content of Hägg iron carbide (χ-Fe 5 C 2 ) as the most active phase of the FTS reaction. Proposed reaction mechanisms for the sonochemical and hydrothermal reaction synthesis of Fe 3 O 4 and RGO/Fe 3 O 4 nanoparticles are discussed. In conclusion, our developed surfactantless-sonochemical method holds promise for the eco-friendly synthesis of highly efficient catalysts materials for FTS reaction. Copyright © 2017 Elsevier B.V. All rights reserved.

Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

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

Kardanpour, Reihaneh; Tangestaninejad, Shahram, E-mail: stanges@sci.ui.ac.ir; Mirkhani, Valiollah, E-mail: mirkhani@sci.ui.ac.ir

2016-03-15

Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl{sub 2}. The prepared catalyst was characterized by FT-IR, UV–vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N{sub 2} adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66–NH{sub 2}–TC–Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzenemore » or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency. - Graphical abstract: Efficient synthesis of benzimidazoles and benzothiazoles catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. - Highlights: • A copper Schiff base was immobilized on UiO-66 via postsynthetic modification. • The modified MOFs were fully characterized by a variety of methods. • The catalyst was used for the preparation of benzimidazoles and benzothiazoles. • In comparison of other catalysts, our catalyst was more efficient and forceful.« less

Combinatorial evolution of site- and enantioselective catalysts for polyene epoxidation

NASA Astrophysics Data System (ADS)

Lichtor, Phillip A.; Miller, Scott J.

2012-12-01

Selectivity in the catalytic functionalization of complex molecules is a major challenge in chemical synthesis. The problem is magnified when there are several possible stereochemical outcomes and when similar functional groups occur repeatedly within the same molecule. Selective polyene oxidation provides an archetypical example of this challenge. Historically, enzymatic catalysis has provided the only precedents. Although non-enzymatic catalysts that meet some of these challenges became known, a comprehensive solution has remained elusive. Here, we describe low molecular weight peptide-based catalysts, discovered through a combinatorial synthesis and screening protocol, that exhibit site- and enantioselective oxidation of certain positions of various isoprenols. This diversity-based approach, which exhibits features reminiscent of the directed evolution of enzymes, delivers catalysts that compare favourably to the state-of-the-art for the asymmetric oxidation of these compounds. Moreover, the approach culminated in catalysts that exhibit alternative-site selectivity in comparison to oxidation catalysts previously described.

Synthesis of Higher Alcohols via Syngas on Cu/Zn/Si Catalysts. Effect of Polyethylene Glycol Content

NASA Astrophysics Data System (ADS)

Cui, Rong-Ji; Yan, Xing; Fan, Jin-Chuan; Huang, Wei

2018-05-01

Cu/Zn/Si catalysts with different polyethylene glycol (PEG) content were prepared by a complete liquid-phase method, and characterized by XRD, H2-TPR, N2-adsorption, and XPS. The influence of PEG content on the higher alcohols synthesis from syngas was investigated. The results showed that addition of PEG can influence the texture and surface properties of the catalysts, and therefore affect their activity and product distribution. With an increase in PEG content, BET surface area, Cu crystallite size and surface active ingredient content of the catalysts first increased and then decreased, the CO conversion had similar variation tendency. However, the pore volume and pore diameter of the catalyst increased, and the binding energy of the active component and the content of Cu2O decreased, which resulted in higher catalyst selectivity towards higher alcohols. The highest C2+OH selectivity in total alcohols was 60.6 wt %.

Selective synthesis of vitamin K3 over mesoporous NbSBA-15 catalysts synthesized by an efficient hydrothermal method.

PubMed

Selvaraj, M; Park, D-W; Kim, I; Kawi, S; Ha, C S

2012-08-28

Well hexagonally ordered NbSBA-15 catalysts synthesized by an efficient hydrothermal method were used, for the first time, for the selective synthesis of vitamin K(3) by liquid-phase oxidation of 2-methyl-1-naphthol (2MN1-OH) under various reaction conditions. The recyclable NbSBA-15 catalysts were also reused to find their catalytic activities. To investigate the leaching of non-framework niobium species on the surface of silica networks, the results of original and recyclable NbSBA-15 catalysts were correlated and compared. To find an optimum condition for the selective synthesis of vitamin K(3), the washed NbSBA-15(2.2pH) was extensively used in this reaction with various reaction parameters such as temperature, time and ratios of reactant (2M1N-OH to H(2)O(2)), and the obtained results were also demonstrated. Additionally, the liquid-phase oxidation of 2M1N-OH was carried out with different solvents to find the best solvent with a good catalytic activity. Based on the all catalytic studies, the vitamin K(3) selectivity (97.3%) is higher in NbSBA-15(2.2pH) than that of other NbSBA-15 catalysts, and the NbSBA-15(2.2pH) is found to be a highly active and eco-friendly heterogeneous catalyst for the selective synthesis of vitamin K(3).

Structure and function of real catalysts

NASA Astrophysics Data System (ADS)

Klier, K.

1984-11-01

This paper addresses issues such as the relation between the physical and chemical nature of active centers, activation of reactant molecules, mechanisms of catalytic reactions and distribution of promoters in real catalysts which are invariably multicomponent multiphase systems. Interactions among the catalyst components and phases often result in the formation of compounds and defects that do not exist in the separate components. Although such interactions give rise to a great variety of morphologic, chemical, and electronic properties of the real catalysts, they can be controlled, mostly by careful preparation and doping procedures, to the degree that the catalyst displays reproducible activity and selectivity. Most of the examples given in this paper are based on the results from the author's laboratory concerning the activity and selectivity of copper-based catalysts for the hydrogenation of carbon monoxide and carbon dioxide, the water gas shift reaction, and some reactions of amines. Evidence is presented for the interactions between the copper and zinc oxide then analyzed in terms of defect equilibria using models and constants partially known from the literature and adapted for the present system. It is shown on the basis of boundary layer theory for small particles that charge transfer between copper metal particles, also present in the system, and the zinc oxide phase is insignificant. On the other hand, electron equilibria between the solute copper species and the zinc oxide matrix are dictated primarily by intrinsic ionization Cu 0 → Cu + + e - and oxygen vacancy formation. Optical absorption spectroscopy strongly corroborates the theoretical contention that a significant portion of the copper is in electron deficient state, and there is some evidence based on Auger spectroscopy for the presence of Cu + species on the catalyst surface. It is reiterated, as has been proposed before in our earlier work, that these copper species activate substrates such as carbon monoxide or unsaturated hydrocarbons through back-bonding of the copper d-orbitals into the π ∗ orbitals of the substrates. In a paper by D.L. Roberts and G.L. Griffin at this Symposium, additional evidence is presented that the same finely dispersed Cu species are the chemisorption and activation sites for hydrogen. Some significant mechanistic features of carbon monoxide hydrogenation are demonstrated by the enhancement of methanol synthesis rates and carbon-carbon bond formation in the presence of alkali promoters. The nature and concentration of the alkali ions on the catalyst surface determine the outcome of the carbon monoxide hydrogenations in the following way: (i) of all the alkali and alkaline earth promoters, cesium displays the most pronounced effects; (ii) at high temperatures and low hydrogen-to-carbon monoxide ratios, maximum amount of n-propanol and 2-methyl-propanol is observed in the product over the Cs/Cu/ZnO catalysts, consistent with the function of the alkali as base catalysts in aldol condensation of aldehydic or enolic surface intermediates; (iii) at low temperatures and high hydrogen-to-carbon monoxide ratios, cesium enhances methanol synthesis as well as water gas shift rates in water- and CO 2-free synthesis gas, retards the methanol synthesis rate in synthesis gas containing intermediate amounts of water, primarily due to loss of surface area upon cesium doping, and again accelerates the synthesis in water-rich synthesis gas. These latter effects point to a mechanism in which the rate of formation of surface formate is enhanced by cesium in water-free synthesis gas and a rapid removal of surface hydroxyls free sites that activate hydrogen in water-rich synthesis gas. The role of Group VIII metals as promoters of the Cu/ZnO catalysts for low alcohol and hydrocarbon synthesis is represented by the effects of small additions of iron. Product composition is intermediate between that in methanol and Fischer-Tropsch syntheses, with significant amount of low alcohols formed. Characterization of the 1%Fe/Cu/ZnO catalyst by analytical electron microscopy reveals two forms of iron, a fine dispersion in the Cu/ZnO catalyst and metallic particles, suggesting that the alcohol and hydrocarbon products are formed over two different parts of the catalyst. In the concluding remarks it is contended that in many systems the catalytic activity and selectivity is primarily controlled by chemical entities, defects with respect to the pure components, that are induced and stabilized by solid state reactions involving a significant part of the bulk of the catalyst particles. As the various spectroscopic techniques as well as the tools of high resolution and analytical electron microscopy are used in an increasingly refined way for the analysis of real catalysts, it seems inevitable that the traditional art of catalyst preparation will take advantage of the new understanding of catalyst structure and will become a branch of materials science firmly footed in solid state chemistry and physics.

Preparation and characterization of Ni based on natural zeolite catalyst for citronellol conversion to 3,7-Dimethyl-1-Octanol

NASA Astrophysics Data System (ADS)

Sudiyarmanto, Hidayati, Luthfiana N.; Kristiani, Anis; Ghaisani, Almira; Sukandar, Dede; Adilina, Indri B.; Tursiloadi, Silvester

2017-11-01

Citronella oil is a kind of essential oil that contains three main components, namely citronellal, citronellol, and geraniol. The high demand of citronellal and geraniol derivative prompted scientists to develop methods which are stereo-selective synthesis. A hydrogenation reaction using heterogeneous catalyst is one way of synthesis of citronella oil derivatives. In this research, synthesis of citronellol oil derivatives using Ni based on natural zeolite (Ni/ZAB) catalyst which is expected to produce the compound of 3,7-dimethyl-1-octanol. The catalyst was prepared by supporting Ni on natural zeolite by impregnation method. The physical and chemical properties of Ni/ZAB catalyst have been characterized by TGA, BET, XRD and FTIR instrumentations. Variation of pressure and temperature reactions were conducted to determine the optimum conditions for the hydrogenation of citronellol. The products from this reaction were analyzed using GC-MS instrumentation. The yield and selectivity of 3,7-dimethyl-1-octanol compound were achieved with optimum conditions at 200°C and 20 bar during 3 hours which produced around 51.97% and 47.81% respectively.

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.

Separation of catalyst from Fischer-Tropsch slurry

DOEpatents

White, C.M.; Quiring, M.S.; Jensen, K.L.; Hickey, R.F.; Gillham, L.D.

1998-10-27

In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst-free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc. The catalyst particles are returned to the Fischer-Tropsch Reactor by mixing them with a wax fraction of appropriate molecular weight, boiling point and viscosity to avoid reactor gelation. 2 figs.

Understanding the interplay of weak forces in [3,3]-sigmatropic rearrangement for stereospecific synthesis of diamines.

PubMed

So, Soon Mog; Mui, Leo; Kim, Hyunwoo; Chin, Jik

2012-08-21

Chiral diamines are important building blocks for constructing stereoselective catalysts, including transition metal based catalysts and organocatalysts that facilitate oxidation, reduction, hydrolysis, and C-C bond forming reactions. These molecules are also critical components in the synthesis of drugs, including antiviral agents such as Tamiflu and Relenza and anticancer agents such as oxaliplatin and nutlin-3. The diaza-Cope rearrangement reaction provides one of the most versatile methods for rapidly generating a wide variety of chiral diamines stereospecifically and under mild conditions. Weak forces such as hydrogen bonding, electronic, steric, oxyanionic, and conjugation effects can drive this equilibrium process to completion. In this Account, we examine the effect of these individual weak forces on the value of the equilibrium constant for the diaza-Cope rearrangement reaction using both computational and experimental methods. The availability of a wide variety of aldehydes and diamines allows for the facile synthesis of the diimines needed to study the weak forces. Furthermore, because the reaction generally takes place cleanly at ambient temperature, we can easily measure equilibrium constants for rearrangement of the diimines. We use the Hammett equation to further examine the electronic and oxyanionic effects. In addition, computations and experiments provide us with new insights into the origin and extent of stereospecificity for this rearrangement reaction. The diaza-Cope rearrangement, with its unusual interplay between weak forces and the equilibrium constant of the reaction, provides a rare opportunity to study the effects of the fundamental weak forces on a chemical reaction. Among these many weak forces that affect the diaza-Cope rearrangement, the anion effect is the strongest (10.9 kcal/mol) followed by the resonance-assisted hydrogen-bond effect (7.1 kcal/mol), the steric effect (5.7 kcal/mol), the conjugation effect (5.5 kcal/mol), and the electronic effect (3.2 kcal/mol). Based on both computation and experimental data, the effects of these weak forces are additive. Understanding the interplay of the weak forces in the [3,3]-sigmatropic reaction is interesting in its own right and also provides valuable insights for the synthesis of chiral diamine based drugs and catalysts in excellent yield and enantiopurity.

Design, Synthesis, and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

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

Enrique Iglesia; Akio Ishikawa; Manual Ojeda

2007-09-30

A detailed study of the catalyst composition, preparation and activation protocol of Fe-based catalysts for the Fischer-Tropsch Synthesis (FTS) have been carried out in this project. We have studied the effects of different promoters on the catalytic performance of Fe-based catalysts. Specifically, we have focused on how their sequence of addition dramatically influences the performance of these materials in the Fischer-Tropsch synthesis. The resulting procedures have been optimized to improve further upon the already unprecedented rates and C{sub 5+} selectivities of the Fe-based catalysts that we have developed as part of this project. Selectivity to C{sub 5+} hydrocarbon was closemore » to 90 % (CO{sub 2}-free basis) and CO conversion rate was about 6.7 mol h{sup -1} g-at Fe{sup -1} at 2.14 MPa, 508 K and with substoichiometric synthesis gas; these rates were larger than any reported previously for Fe-based FTS catalysts at these conditions. We also tested the stability of Fe-based catalysts during FTS reaction (10 days); as a result, the high hydrocarbon formation rates were maintained during 10 days, though the gradual deactivation was observed. Our investigation has also focused on the evaluation of Fe-based catalysts with hydrogen-poor synthesis gas streams (H{sub 2}/CO=1). We have observed that the Fe-based catalysts prepared in this project display also a high hydrocarbon synthesis rate with substoichiometric synthesis gas (H{sub 2}/CO=1) stream, which is a less desirable reactant mixture than stoichiometric synthesis gas (H{sub 2}/CO=2). We have improved the catalyst preparation protocols and achieved the highest FTS reaction rates and selectivities so far reported at the low temperatures required for selectivity and stability. Also, we have characterized the catalyst structural change and active phases formed, and their catalytic behavior during the activation process to evaluate their influences on FTS reaction. The efforts of this project led to (i) structural evolution of Fe-Zn oxide promoted with K and Cu, and (ii) evaluation of hydrocarbon and CH{sub 4} formation rates during activation procedures at various temperature and H{sub 2}/CO ratios. On the basis of the obtained results, we suggest that lower reactor temperature can be sufficient to activate catalysts and lead to the high FTS performance. In this project, we have also carried out a detailed kinetic and mechanistic study of the Fischer-Tropsch Synthesis with Fe-based catalysts. We have proposed a reaction mechanism with two CO activation pathways: unassisted and H-assisted. Both routes lead to the formation of the same surface monomers (CH{sub 2}). However, the oxygen removal mechanism is different. In the H-assisted route, oxygen is removed exclusively as water, while oxygen is rejected as carbon dioxide in the unassisted CO dissociation. The validity of the mechanism here proposed has been found to be in agreement with the experimental observation and with theoretical calculations over a Fe(110) surface. Also, we have studied the validity of the mechanism that we propose by analyzing the H{sub 2}/D{sub 2} kinetic isotope effect (r{sub H}/r{sub D}) over a conventional iron-based Fischer-Tropsch catalyst Fe-Zn-K-Cu. We have observed experimentally that the use of D{sub 2} instead of H{sub 2} leads to higher hydrocarbons formation rates (inverse kinetic isotopic effect). On the contrary, primary carbon dioxide formation is not influenced. These experimental observations can be explained by two CO activation pathways. We have also explored the catalytic performance of Co-based catalysts prepared by using inverse micelles techniques. We have studied several methods in order to terminate the silanol groups on SiO{sub 2} support including impregnation, urea homogeneous deposition-precipitation, or zirconium (IV) ethoxide titration. Although hydroxyl groups on the SiO{sub 2} surface are difficult to be stoichiometrically titrated by ZrO{sub 2}, a requirement to prevent the formation of strongly-interacting Co oxide species on SiO{sub 2}, modification of ZrO{sub 2} on SiO{sub 2} surface can improve the Co clusters dispersion leading to a marked increase in the number of accessible Co sites. Inverse micelle method allowed the synthesis of small Co clusters on SiO{sub 2}, but the required surfactant removal steps led to the re-oxidation of Co metal clusters and to the formation of difficult to reduce CoO{sub x} species.« less

Synthesis and Electrocatalytic Activity of Ammonium Nickel Phosphate, [NH4]NiPO4·6H2O, and β-Nickel Pyrophosphate, β-Ni2P2O7: Catalysts for Electrocatalytic Decomposition of Urea.

PubMed

Meguerdichian, Andrew G; Jafari, Tahereh; Shakil, Md R; Miao, Ran; Achola, Laura A; Macharia, John; Shirazi-Amin, Alireza; Suib, Steven L

2018-02-19

Electrocatalytic decomposition of urea for the production of hydrogen, H 2, for clean energy applications, such as in fuel cells, has several potential advantages such as reducing carbon emissions in the energy sector and environmental applications to remove urea from animal and human waste facilities. The study and development of new catalyst materials containing nickel metal, the active site for urea decomposition, is a critical aspect of research in inorganic and materials chemistry. We report the synthesis and application of [NH 4 ]NiPO 4 ·6H 2 O and β-Ni 2 P 2 O 7 using in situ prepared [NH 4 ] 2 HPO 4 . The [NH 4 ]NiPO 4 ·6H 2 O is calcined at varying temperatures and tested for electrocatalytic decomposition of urea. Our results indicate that [NH 4 ]NiPO 4 ·6H 2 O calcined at 300 °C with an amorphous crystal structure and, for the first time applied for urea electrocatalytic decomposition, had the greatest reported electroactive surface area (ESA) of 142 cm 2 /mg and an onset potential of 0.33 V (SCE) and was stable over a 24-h test period.

Structural and surface properties of CuO-ZnO-Cr{sub 2}O{sub 3} catalysts and their relationship with selectivity to higher alcohol synthesis

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

Campos-Martin, J.M.; Fierro, J.L.G.; Guerrero-Ruiz, A.

1995-10-01

A series of copper-zinc-chromium catalysts of different compositions and calcination temperatures has been prepared, characterized by several techniques (BET specific surface area, XRD, gravimetric TPR, TPD-CO, and XPS), and tested under high alcohol synthesis (HAS) conditions. CO hydrogenation was carried out at reaction temperatures of 523-598 K and 50 bar total pressure. The influence of catalyst composition, calcination temperature, and surface characteristics on the HAS selectivity was studied. The optimum HAS yields were found in the low Cr content region, but chromium was needed. Although chromium oxide does not seem to be involved in the catalytic site, its presence inmore » the catalyst composition is essential, owing to the larger specific surfaces and catalyst stability obtained at the highest reaction temperatures. For low Cr content composition, the temperature-programmed reduction (TPR) profiles were shifted to higher temperatures and simultaneously larger CO{sub 2} amounts were found in the temperature-programmed desorption profiles of adsorbed CO (TPD-CO). Photoelectron spectra (XPS) revealed that the oxidation state of copper is Cu{sup 2+} in the calcined catalysts and Cu{sup O} in the reduced ones; Cu{sup +} was only stabilized in a CuCr{sub 2}O{sub 4} spinel in the Cr-rich catalysts. These features derived from catalyst characterization are discussed in the framework of the catalytic behaviour for HAS synthesis. 53 refs., 7 figs., 4 tabs.« less

ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

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

JAMES G. GOODWIN, JR.; JAMES J. SPIVEY; K. JOTHIMURUGESAN

1998-09-17

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H{sub 2} ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a serious problem withmore » the use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C{sub 5}{sup +} selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation.« less

Strategies for the synthesis of supported gold palladium nanoparticles with controlled morphology and composition.

PubMed

Hutchings, Graham J; Kiely, Christopher J

2013-08-20

The discovery that supported gold nanoparticles are exceptionally effective catalysts for redox reactions has led to an explosion of interest in gold nanoparticles. In addition, incorporating a second metal as an alloy with gold can enhance the catalyst performance even more. The addition of small amounts of gold to palladium, in particular, and vice versa significantly enhances the activity of supported gold-palladium nanoparticles as redox catalysts through what researchers believe is an electronic effect. In this Account, we describe and discuss methodologies for the synthesis of supported gold-palladium nanoparticles and their use as heterogeneous catalysts. In general, three key challenges need to be addressed in the synthesis of bimetallic nanoparticles: (i) control of the particle morphology, (ii) control of the particle size distribution, and (iii) control of the nanoparticle composition. We describe three methodologies to address these challenges. First, we discuss the relatively simple method of coimpregnation. Impregnation allows control of particle morphology during alloy formation but does not control the particle compositions or the particle size distribution. Even so, we contend that this method is the best preparation method in the catalyst discovery phase of any project, since it permits the investigation of many different catalyst structures in one experiment, which may aid the identification of new catalysts. A second approach, sol-immobilization, allows enhanced control of the particle size distribution and the particle morphology, but control of the composition of individual nanoparticles is not possible. Finally, a modified impregnation method can allow the control of all three of these crucial parameters. We discuss the effect of the different methodologies on three redox reactions: benzyl alcohol oxidation, toluene oxidation, and the direct synthesis of hydrogen peroxide. We show that the coimpregnation method provides the best reaction selectivity for benzyl alcohol oxidation and the direct synthesis of hydrogen peroxide. However, because of the reaction mechanism, the sol-immobilzation method gives very active and selective catalysts for toluene oxidation. We discuss the possible nature of the preferred active structures of the supported nanoparticles for these reactions. This paper is based on the IACS Heinz Heinemann Award Lecture entitled "Catalysis using gold nanoparticles" which was given in Munich in July 2012.

Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

PubMed

Baran, Talat; Inanan, Tülden; Menteş, Ayfer

2016-07-10

The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.

Efficient FeCl3/SiO2 as heterogeneous nanocatalysis for the synthesis of benzimidazoles under mild conditions

NASA Astrophysics Data System (ADS)

Taher, Mohammad Ali; Karami, Changiz; Arabi, Mehdi Sheikh; Ahmadian, Hossein; Karami, Yasaman

2016-11-01

Iron(III) supported on nano silica as a new catalyst has been synthesized. Structural properties of this complex have been studied by TEM, SEM and EDX. The average crystalline size of Iron(III) supported on nano silica is 30-50 nm. Catalytic activity of this catalyst has been investigated by synthesis of benzimidazoles from 1, 2-diaminobenzene and aromatic aldehydes, and also the other variables investigated such as the amount of catalyst, reaction temperature and the effect of various solvents are also studied. The present procedure offers several advantages such as short reaction time, simple workup, recovery and reusability of the catalyst.

Peptide-templated noble metal catalysts: syntheses and applications

PubMed Central

Wang, Wei; Anderson, Caleb F.; Wang, Zongyuan; Wu, Wei

2017-01-01

Noble metal catalysts have been widely used in many applications because of their high activity and selectivity. However, a controllable preparation of noble metal catalysts still remains as a significant challenge. To overcome this challenge, peptide templates can play a critical role in the controllable syntheses of catalysts owing to their flexible binding with specific metallic surfaces and self-assembly characteristics. By employing peptide templates, the size, shape, facet, structure, and composition of obtained catalysts can all be specifically controlled under the mild synthesis conditions. In addition, catalysts with spherical, nanofiber, and nanofilm structures can all be produced by associating with the self-assembly characteristics of peptide templates. Furthermore, the peptide-templated noble metal catalysts also reveal significantly enhanced catalytic behaviours compared with conventional catalysts because the electron conductivity, metal dispersion, and reactive site exposure can all be improved. In this review, we summarize the research progresses in the syntheses of peptide-templated noble metal catalysts. The applications of the peptide-templated catalysts in organic reactions, photocatalysis, and electrocatalysis are discussed, and the relationship between structure and activity of these catalysts are addressed. Future opportunities, including new catalytic materials designed by using biological principles, are indicated to achieve selective, eco-friendly, and energy neutral synthesis approaches. PMID:28507701

SYNTHESIS AND CHARACTERIZATION OF A NOVEL SOLID ACID CATALYST FOR IMPROVED USE OF WASTE OIL FEEDSTOCK FOR BIODIESEL PRODUCTION

EPA Science Inventory

Carbon Catalyst Synthesis - Sucrose was treated directly with excess sulfuric acid sulfuric acid (9:1 mol/mol, 25°C). A carbon foam (nearly 20 fold increase in bulk volume) was immediately formed. The foam was then washed until no sulfate was dete...

Nano-particulate Aluminium Nitride/Al: An Efficient and Versatile Heterogeneous Catalyst for the Synthesis of Biginelli Scaffolds

NASA Astrophysics Data System (ADS)

Tekale, S. U.; Tekale, A. B.; Kanhe, N. S.; Bhoraskar, S. V.; Pawar, R. P.

2011-12-01

Nano-particulate aluminium nitride/Al (7:1) is reported as a new heterogeneous solid acid catalyst for the synthesis of 3, 4-dihydroxypyrimidi-2-(1H)-ones and their sulphur analogues using the Biginelli reaction. This method involves short reaction time, easy separation, high yields and purity of products.

Liquid phase low temperature method for production of methanol from synthesis gas and catalyst formulations therefor

DOEpatents

Mahajan, Devinder

2005-07-26

The invention provides a homogenous catalyst for the production of methanol from purified synthesis gas at low temperature and low pressure which includes a transition metal capable of forming transition metal complexes with coordinating ligands and an alkoxide, the catalyst dissolved in a methanol solvent system, provided the transition metal complex is not transition metal carbonyl. The coordinating ligands can be selected from the group consisting of N-donor ligands, P-donor ligands, O-donor ligands, C-donor ligands, halogens and mixtures thereof.

Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOH) Process

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

None

he Liquid Phase Methanol (LPMEOW) Demonstration Project at Kingsport Tennessee, is a $213.7 million cooperative agreement between the U.S. Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership) to produce methanol from coal-derived synthesis gas (syngas). Air Products and Chemicals, Inc. (Air Products) and Eastman Chemical Company (Eastman) formed the Partnership to execute the Demonstration Project. The LPMEOEP Process Demonstration Unit was built at a site located at the Eastman coal-to-chemicals complex in Kingsport. The LPMEOHW Demonstration Facility completed its first year of operation on 02 April 1998. The LPMEOW Demonstration Facility also completed themore » longest continuous operating run (65 days) on 21 April 1998. Catalyst activity, as defined by the ratio of the rate constant at any point in time to the rate constant for freshly reduced catalyst (as determined in the laboratory autoclave), was monitored throughout the reporting period. During a six-week test at a reactor temperature of 225oC and Balanced Gas flowrate of 700 KSCFH, the rate of decline in catalyst activity was steady at 0.29-0.36% per day. During a second one-month test at a reactor temperature of 220oC and a Balanced Gas flowrate of 550-600 KSCFH, the rate of decline in catalyst activity was 0.4% per day, which matched the pefiorrnance at 225"C, as well as the 4-month proof-of-concept run at the LaPorte AFDU in 1988/89. Beginning on 08 May 1998, the LPMEOW Reactor temperature was increased to 235oC, which was the operating temperature tier the December 1997 restart with the fresh charge of catalyst (50'Yo of design loading). The flowrate of the primary syngas feed stream (Balanced Gas) was also increased to 700-750 KSCFH. During two stable operating periods between 08 May and 09 June 1998, the average catalyst deactivation rate was 0.8% per day. Due to the scatter of the statistical analysis of the results, this test was extended to better quanti& the catalyst aging behavior. During the reporting perio~ two batches of fresh catalyst were activated and transferred to the reactor (on 02 April and 20 June 1998). The weight of catalyst in the LPMEOW Reactor has reached 80% of the design value. At the end of the reporting period, a step-change in the pressure-drop profile within the LPMEOW Reactor and an increase in the pressure of the steam system which provides cooling to the LPMEOW Reactor were observed. No change in the calculated activity of the catalyst was detected during either of these transients. These parameters will be monitored closely for any additional changes.« less

Tailored fischer-tropsch synthesis product distribution

DOEpatents

Wang, Yong [Richland, WA; Cao, Chunshe [Kennewick, WA; Li, Xiaohong Shari [Richland, WA; Elliott, Douglas C [Richland, WA

2012-06-19

Novel methods of Fischer-Tropsch synthesis are described. It has been discovered that conducting the Fischer-Tropsch synthesis over a catalyst with a catalytically active surface layer of 35 microns or less results in a liquid hydrocarbon product with a high ratio of C.sub.5-C.sub.20:C.sub.20+. Descriptions of novel Fischer-Tropsch catalysts and reactors are also provided. Novel hydrocarbon compositions with a high ratio of C.sub.5-C.sub.20:C.sub.20+ are also described.

Porous AgPt@Pt Nanooctahedra as an Efficient Catalyst toward Formic Acid Oxidation with Predominant Dehydrogenation Pathway.

PubMed

Jiang, Xian; Yan, Xiaoxiao; Ren, Wangyu; Jia, Yufeng; Chen, Jianian; Sun, Dongmei; Xu, Lin; Tang, Yawen

2016-11-16

For direct formic acid fuel cells (DFAFCs), the dehydrogenation pathway is a desired reaction pathway, to boost the overall cell efficiency. Elaborate composition tuning and nanostructure engineering provide two promising strategies to design efficient electrocatalysts for DFAFCs. Herein, we present a facile synthesis of porous AgPt bimetallic nanooctahedra with enriched Pt surface (denoted as AgPt@Pt nanooctahedra) by a selective etching strategy. The smart integration of geometric and electronic effect confers a substantial enhancement of desired dehydrogenation pathway as well as electro-oxidation activity for the formic acid oxidation reaction (FAOR). We anticipate that the obtained nanocatalyst may hold great promises in fuel cell devices, and furthermore, the facile synthetic strategy demonstrated here can be extendable for the fabrication of other multicomponent nanoalloys with desirable morphologies and enhanced electrocatalytic performances.

Green synthesis of layered 1T-MoS2/reduced graphene oxide nanocomposite with excellent catalytic performances for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Meng, Nannan; Cheng, Jian; Zhou, Yifeng; Nie, Wangyan; Chen, Pengpeng

2017-02-01

A green and facile process was developed to prepare layered octahedral phase MoS2/reduced graphene oxide (1T-MoS2/RGO) nanocomposite by a Vitamin C-assisted self-assemble method, in which graphene oxide (GO) and LiMoS2 were used as starting materials. Catalytic performances of 1T-MoS2/RGO were evaluated by hydrogenation of 4-nitrophenol (4-NP). It was demonstrated that the prepared 1T-MoS2/RGO nanocomposite presented excellent catalytic performance and cycling stability for 4-NP reduction, which made it a promising noble-metal-free catalyst. Additionally, broadening work suggested some other RGO-based metal nanocomposite with well-defined porous structure could be also generated via this facile self-assembly method.

A facile preparation of TiO2/ACF with Csbnd Ti bond and abundant hydroxyls and its enhanced photocatalytic activity for formaldehyde removal

NASA Astrophysics Data System (ADS)

Liu, R. F.; Li, W. B.; Peng, A. Y.

2018-01-01

The quantum yields and efficiency(ACF) was prepared via a modified deposition-precipitation method to facilitate its photon absorption and of photogenerated charge carriers have been the major issues for photocatalysis on titania catalyst. The TiO2/ACF catalyst with anatase TiO2 uniformly dispersed on activated carbon fibers electron transfer, thus improve the quantum yields and efficiency of the photogenerated electrons and holes. XPS analysis on the catalyst demonstrates the existence of Ti3+ and Ti2+ species, Csbnd Ti bond and abundant hydroxyls, which are also proved by UV-vis DRS and TG-DSC analysis. It is believed that the acid environment in preparation plays an essential role in the formation of Csbnd Ti bond and surface hydroxyls, which can be tuned by changing hydrothermal synthesis time. The Csbnd Ti bond can improve the electron transfer in the catalyst and the substantial surface hydroxyls lead to high absorption for UV lines and enhanced adsorption of water and formaldehyde, resulting in more active OH free radicals and the outstanding photocatalytic activity of TiO2/ACF, which is much higher than the titania powder for photocatalytic removal of low concentration formaldehyde. The essential role of surface hydroxyls for photocatalytic activity was confirmed surpassing that of chemical bond between carbon and titanium in TiO2-carbon composite for the first time.

Active Hydrogenation Catalyst with a Structured, Peptide-Based Outer-Coordination Sphere

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

Jain, Avijita; Buchko, Garry W.; Reback, Matthew L.

2012-10-05

The synthesis, catalytic activity, and structural features of a rhodium-based hydrogenation catalyst containing a phosphine ligand coupled to a 14-residue peptide are reported. Both CD and NMR spectroscopy show that the peptide adopts a helical structure in 1:1:1 TFE/MeCN/H2O that is maintained when the peptide is attached to the ligand and when the ligand is attached to the metal complex. The metal complex hydrogenates aqueous solutions of 3-butenol to 1-butanol at 360 ± 50 turnovers/Rh/h at 294 K. This peptide- based catalyst represents a starting point for developing and characterizing a peptide-based outer-coordination sphere that can be used to introducemore » enzyme-like features into molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (AJ, JCL and WJS), the Office of Science Early Career Research Program through the Office of Basic Energy Sciences (GWB, MLR and WJS). Part of the research was conducted at the W.R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. Department of Energy’s Office of Biolog-ical and Environmental Research (BER) program located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.« less

Oxygen reduction reaction of (C-PCTNB@CNTs): A nitrogen and phosphorus dual-doped carbon electro-catalyst derived from polyphosphazenes

NASA Astrophysics Data System (ADS)

Dar, Sami Ullah; Ud Din, Muhammad Aizaz; Hameed, Muhammad Usman; Ali, Shafqat; Akram, Raheel; Wu, Zhanpeng; Wu, Dezhen

2018-01-01

This research describes the synthesis of a novel type of poly [cyclotriphosphazene-co-1,3,5-triol nitrobenzene] (PCTNB) microspheres with uniform size and diameter of more than 2 μm having well characterization. These microspheres are further used to wrap the CNTs by a facile route using template based non-covalent method to form PCTNB@CNTs composite. This composite is further well analyzed before it is subjected to pyrolysis. The direct carbonization of the PCTNB@CNTs is performed at 600 °C at a rate of 5 °C/min under N2 atmosphere to render the N, P, O doped carbonized PCTNB@CNTs having enhanced electronic features to be applied as an ORR electrocatalysts in fuel cells accompanied by TEM, XPS, Raman, FT-IR, TGA and BET analyses. Here, we have designed a metal-free, N, P, O doped (C-PCTNB@CNTs) electro-catalyst which exhibit significantly high ORR performance in acidic PEM cells showing much higher onset potential of (0.94 V) and half-wave potential of (0.85 V) with electron transfer number (n) 3.9 at 0.4-0.7 V as compared to other non-metallic electro-catalysts. Thus, (C-PCTNB@CNTs) is a metal-free, methanol tolerant carbon-based ORR catalyst, and it opens up new avenues for clean energy generation for affordable and durable fuel cells.

Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts

DOEpatents

Gangwal, S.; Jothimurugesan, K.

1999-07-27

A heavy metal poisoned, spent FCC catalyst is treated by chemically impregnating the poisoned catalyst with a new catalytic metal or metal salt to provide an attrition resistant catalyst or sorbent for a different catalytic or absorption process, such as catalysts for Fischer-Tropsh Synthesis, and sorbents for removal of sulfur gases from fuel gases and flue-gases. The heavy metal contaminated FCC catalyst is directly used as a support for preparing catalysts having new catalytic properties and sorbents having new sorbent properties, without removing or passivating the heavy metals on the spent FCC catalyst as an intermediate step.

Attrition resistant catalysts and sorbents based on heavy metal poisoned FCC catalysts

DOEpatents

Gangwal, Santosh; Jothimurugesan, Kandaswamy

1999-01-01

A heavy metal poisoned, spent FCC catalyst is treated by chemically impregnating the poisoned catalyst with a new catalytic metal or metal salt to provide an attrition resistant catalyst or sorbent for a different catalytic or absorption processes, such as catalysts for Fischer-Tropsh Synthesis, and sorbents for removal of sulfur gasses from fuel gases and flue-gases. The heavy metal contaminated FCC catalyst is directly used as a support for preparing catalysts having new catalytic properties and sorbents having new sorbent properties, without removing or "passivating" the heavy metals on the spent FCC catalyst as an intermediate step.

System and method for controlling hydrogen elimination during carbon nanotube synthesis from hydrocarbons

DOEpatents

Reilly, Peter T. A.

2010-03-23

A system and method for producing carbon nanotubes by chemical vapor deposition includes a catalyst support having first and second surfaces. The catalyst support is capable of hydrogen transport from the first to the second surface. A catalyst is provided on the first surface of the catalyst support. The catalyst is selected to catalyze the chemical vapor deposition formation of carbon nanotubes. A fuel source is provided for supplying fuel to the catalyst.

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1985-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, P.K.; Rabo, J.A.

1985-12-03

Synthesis gas comprising carbon monoxide and hydrogen is converted to C[sub 5][sup +] hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising a SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

PubMed Central

2011-01-01

This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions. H2-TPR analysis of cobalt catalyst indicated three temperature regions at 506°C (low), 650°C (medium) and 731°C (high). The incorporation of iron up to 30% into cobalt catalysts increased the reduction, CO chemisorption and number of cobalt active sites of the catalyst while an opposite trend was observed for the iron-riched bimetallic catalysts. The CO conversion was 6.3% and 4.6%, over the monometallic cobalt and iron catalysts, respectively. Bimetallic catalysts enhanced the CO conversion. Amongst the catalysts studied, bimetallic catalyst with the composition of 70Co30Fe showed the highest CO conversion (8.1%) while exhibiting the same product selectivity as that of monometallic Co catalyst. Monometallic iron catalyst showed the lowest selectivity for C5+ hydrocarbons (1.6%). PMID:22047220

Facile synthesis of palladium nanoparticle doped polyaniline nanowires in soft templates for catalytic applications

NASA Astrophysics Data System (ADS)

Kshirasagar, Krushna J.; Markad, Uddhav S.; Saha, Abhijit; Sharma, Kiran Kumar K.; Sharma, Geeta K.

2017-02-01

Palladium nanoparticles doped polyaniline (Pd-PANI) nanocomposite (NCs) is synthesized in surfactant based liquid crystalline mesophase by chemical oxidation followed by radiolysis. The confinement of the liquid crystalline mesophase facilitates polymerization of aniline monomers and their 1D growth into polyaniline (PANI) nanowires by using ammonium persulfate. The PANI nanowires have an average diameter of 30-40 nm. The in situ radiolytic reduction of palladium ions ensures uniform size distribution of the palladium (Pd) nanoparticles on the surface of the PANI nanowires. The synthesized Pd-PANI nanocomposites show wire like structures of PANI (diameter ~30-40 nm) on which Pd nanoparticles of the size 10 nm are decorated. The identical average diameter of the PANI nanowires before and post gamma irradiation suggest high stability of the PANI nanowires in liquid crystalline mesophase. Surface characterization of the NCs were carried out using BET and XPS. The catalytic activity of Pd-PANI NCs are investigated in the reduction of methylene blue (MB) and 4-nitro phenol (4-NP) by sodium borohydride (NaBH4). The kinetics of the Pd-PANI NCs catalysed reactions are analysed using the Langmuir-Hinshelwood model. The apparent rate constant (k app) for the MB and 4-NP reduction reactions is 29  ×  10-3 s-1 and 20  ×  10-3 s-1 respectively with an actual Pd catalyst loading of 2.665  ×  10-4 ppm. Further, the recyclability of the Pd-PANI NCs catalyst in both the reduction reactions shows the stability of the catalyst up to four reaction cycles tested in this investigation and the multifunctional nature of the catalyst. The study provides a new approach for the directional synthesis of conducting polymer-metal nanocomposites and their possible application as a nanocatalyst in environmental remediation.

Attrition resistant bulk iron catalysts and processes for preparing and using same

DOEpatents

Jothimurugesan, Kandaswamy [Ponca City, OK; Goodwin, Jr., James G.; Gangwal, Santosh K [Cary, NC

2007-08-21

An attrition resistant precipitated bulk iron catalyst is prepared from iron oxide precursor and a binder by spray drying. The catalysts are preferably used in carbon monoxide hydrogenation processes such as Fischer-Tropsch synthesis. These catalysts are suitable for use in fluidized-bed reactors, transport reactors and, especially, slurry bubble column reactors.

Alcohol synthesis in a high-temperature slurry reactor

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

Roberts, G.W.; Marquez, M.A.; McCutchen, M.S.

1995-12-31

The overall objective of this contract is to develop improved process and catalyst technology for producing higher alcohols from synthesis gas or its derivatives. Recent research has been focused on developing a slurry reactor that can operate at temperatures up to about 400{degrees}C and on evaluating the so-called {open_quotes}high pressure{close_quotes} methanol synthesis catalyst using this reactor. A laboratory stirred autoclave reactor has been developed that is capable of operating at temperatures up to 400{degrees}C and pressures of at least 170 atm. The overhead system on the reactor is designed so that the temperature of the gas leaving the system canmore » be closely controlled. An external liquid-level detector is installed on the gas/liquid separator and a pump is used to return condensed slurry liquid from the separator to the reactor. In order to ensure that gas/liquid mass transfer does not influence the observed reaction rate, it was necessary to feed the synthesis gas below the level of the agitator. The performance of a commercial {open_quotes}high pressure {close_quotes} methanol synthesis catalyst, the so-called {open_quotes}zinc chromite{close_quotes} catalyst, has been characterized over a range of temperature from 275 to 400{degrees}C, a range of pressure from 70 to 170 atm., a range of H{sub 2}/CO ratios from 0.5 to 2.0 and a range of space velocities from 2500 to 10,000 sL/kg.(catalyst),hr. Towards the lower end of the temperature range, methanol was the only significant product.« less

ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

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

James G. Goodwin, Jr.; James J. Spivey; K. Jothimurugesan

1999-03-29

The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H{sub 2}) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. Iron-based (Fe) catalysts are preferred catalysts for F-T when using low CO/H2 ratio synthesis gases derived from modern coal gasifiers. This is because in addition to reasonable F-T activity, the F-T catalysts also possess high water gas shift (WGS) activity. However, a serious problem with themore » use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, making the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. The objectives of this research are to develop a better understanding of the parameters affecting attrition resistance of Fe F-T catalysts suitable for use in SBCRs and to incorporate this understanding into the design of novel Fe catalysts having superior attrition resistance. Catalyst preparations will be based on the use of spray drying and will be scalable using commercially available equipment. The research will employ among other measurements, attrition testing and F-T synthesis, including long duration slurry reactor runs in order to ascertain the degree of success of the various preparations. The goal is to develop an Fe catalyst which can be used in a SBCR having only an internal filter for separation of the catalyst from the liquid product, without sacrificing F-T activity and selectivity. The effect of silica addition via coprecipitation and as a binder to a doubly promoted Fischer-Tropsch synthesis iron catalyst (100 Fe/5 Cu/4.2 K) was studied. The catalysts were prepared by coprecipitation, followed by binder addition and drying in a 1 m diameter, 2 m tall spray dryer. The binder silica content was varied from 0 to 20 wt %. A catalyst with 12 wt % binder silica was found to have the highest attrition resistance. F-T reaction studies over 100 hours in a fixed-bed reactor showed that this catalyst maintained around 95 % CO conversion with a methane selectivity of less than 7 wt % and a C5 + selectivity of greater than 73 wt %. The effect of adding precipitated silica from 0 to 20 parts by weight to this catalyst (containing 12 wt % binder silica) was also studied. Addition of precipitated silica was found to be detrimental to attrition resistance and resulted in increased methane and reduced wax formation. An HPR series of proprietary catalysts was prepared to further improve the attrition resistance. Based on the experience gained, a proprietary HPR-43 catalyst has been successfully spray dried in 500 g quantity. This catalyst showed 95 % CO conversion over 125 h and had less than 4 % methane selectivity. Its attrition resistance was one of the highest among the catalyst tested.« less

Thin film hydrous metal oxide catalysts

DOEpatents

Dosch, Robert G.; Stephens, Howard P.

1995-01-01

Thin film (<100 nm) hydrous metal oxide catalysts are prepared by 1) synthesis of a hydrous metal oxide, 2) deposition of the hydrous metal oxide upon an inert support surface, 3) ion exchange with catalytically active metals, and 4) activating the hydrous metal oxide catalysts.

Fischer-Tropsch Catalysts

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Taylor, Jesse W. (Inventor)

2008-01-01

Catalyst compositions and methods for F-T synthesis which exhibit high CO conversion with minor levels (preferably less than 35% and more preferably less than 5%) or no measurable carbon dioxide generation. F-T active catalysts are prepared by reduction of certain oxygen deficient mixed metal oxides.

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, N.E.

1992-04-07

A catalyst is described which is useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols. The catalyst consists essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

The Dependence of CNT Aerogel Synthesis on Sulfur-driven Catalyst Nucleation Processes and a Critical Catalyst Particle Mass Concentration.

PubMed

Hoecker, Christian; Smail, Fiona; Pick, Martin; Weller, Lee; Boies, Adam M

2017-11-06

The floating catalyst chemical vapor deposition (FC-CVD) process permits macro-scale assembly of nanoscale materials, enabling continuous production of carbon nanotube (CNT) aerogels. Despite the intensive research in the field, fundamental uncertainties remain regarding how catalyst particle dynamics within the system influence the CNT aerogel formation, thus limiting effective scale-up. While aerogel formation in FC-CVD reactors requires a catalyst (typically iron, Fe) and a promotor (typically sulfur, S), their synergistic roles are not fully understood. This paper presents a paradigm shift in the understanding of the role of S in the process with new experimental studies identifying that S lowers the nucleation barrier of the catalyst nanoparticles. Furthermore, CNT aerogel formation requires a critical threshold of Fe x C y  > 160 mg/m 3 , but is surprisingly independent of the initial catalyst diameter or number concentration. The robustness of the critical catalyst mass concentration principle is proved further by producing CNTs using alternative catalyst systems; Fe nanoparticles from a plasma spark generator and cobaltocene and nickelocene precursors. This finding provides evidence that low-cost and high throughput CNT aerogel routes may be achieved by decoupled and enhanced catalyst production and control, opening up new possibilities for large-scale CNT synthesis.

SBA-15/hydrotalcite nanocomposite as an efficient support for the immobilization of heteropolyacid: A triply-hybrid catalyst for the synthesis of 2-amino-4H-pyrans in water

NASA Astrophysics Data System (ADS)

Sadjadi, Samahe; Heravi, Majid M.; Zadsirjan, Vahideh; Farzaneh, Vahid

2017-12-01

To circumvent the high solubility and low surface area of heteropolyacid and in attempt to develop a bi-functional heterogeneous catalyst for promoting organic transformations, heteropolyacid was embedded in functionalized SBA-15 and subsequently hybridized with layered double hydroxide. The catalyst could be considered as a bi-functional catalyst with both acidic and basic properties. The acidic properties emerged from the SBA-15 and heteropolyacid component while layered double hydroxide render the catalyst basic. The catalyst was characterized by using SEM/EDX, FT-IR, XRD, ICP-AES, BET and elemental mapping analysis. The catalytic activity of the catalyst was studied for promoting one-pot three-component condensation of aromatic aldehydes, malononitrile or ethyl cyanoacetate and C-H activated acidic molecules in aqueous media for the synthesis of 2-amino-4H-pyran derivatives. The catalyst exhibited high catalytic activity, which was superior to the previously reported ones. Moreover, the reusability of the catalyst was excellent and the leaching of heteropolyacid was dramatically suppressed. High yields, short reaction times, eco-friendly conditions, simplicity of the procedure, reusability of the catalyst and broad substrate scope are the merits of this protocol.

Syntheses, Characterization and Kinetics of Nickel-Tungsten Nitride Catalysts for Hydrotreating of Gas Oil

NASA Astrophysics Data System (ADS)

Botchwey, Christian

This thesis summarizes the methods and major findings of Ni-W(P)/gamma-Al 2O3 nitride catalyst synthesis, characterization, hydrotreating activity, kinetic analysis and correlation of the catalysts' activities to their synthesis parameters and properties. The range of parameters for catalyst synthesis were W (15-40 wt%), Ni (0-8 wt%), P (0-5 wt%) and nitriding temperature (TN) (500-900 °C). Characterization techniques used included: N2 sorption studies, chemisorption, elemental analysis, temperature programmed studies, x-ray diffraction, scanning electron microscopy, energy dispersive x-ray, infrared spectroscopy, transmission electron microscopy and x-ray absorption near edge structure. Hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) were performed at: temperature (340-380 °C), pressure (6.2-9.0 MPa), liquid hourly space velocity (1-3 h-1) and hydrogen to oil ratio (600 ml/ml, STP). The predominant species on the catalyst surface were Ni3N, W2N and bimetallic Ni2W3N. The bimetallic Ni-W nitride species was more active than the individual activities of the Ni3N and W2N. P increased weak acid sites while nitriding temperature decreased amount of strong acid sites. Low nitriding temperature enhanced dispersion of metal particles. P interacted with Al 2O3 which increased the dispersion of metal nitrides on the catalyst surface. HDN activity increased with Ni and P loading but decreased with increase in nitriding temperature (optimum conversion; 60 wt%). HDS and HDA activities went through a maximum with increase in the synthesis parameters (optimum conversions; 88. wt% for HDS and 47 wt% for HDA). Increase in W loading led to increase in catalyst activity. The catalysts were stable to deactivation and had the nitride structure conserved during hydrotreating in the presence of hydrogen sulfide. The results showed good correlation between hydrotreating activities (HDS and HDN) and the catalyst nitrogen content, number of exposed active sites, catalyst particle size and BET surface area. HDS and HDN kinetic analyses, using Langmuir-Hinshelwood models, gave activation energies of 66 and 32 kJ/mol, respectively. There were no diffusion limitations in the reaction process. Two active sites were involved in HDS reaction while one site was used for HDN. HDS and HDN activities of the Ni-W(P)/gamma-Al 2O3 nitride catalysts were comparable to the corresponding sulfides.

Design, Synthesis and Mechanistic Evaluation of Iron-Based Catalysis for Synthesis Gas Conversion to Fuels and Chemicals

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

Akio Ishikawa; Manuel Ojeda; Nan Yao

2007-03-31

This project extends previously discovered Fe-based catalysts to hydrogen-poor synthesis gas streams derived from coal and biomass sources. These catalysts have shown unprecedented Fischer-Tropsch synthesis rates and selectivities for synthesis gas derived from methane. During the first reporting period, we certified a microreactor, installed required analytical equipment, and reproduced synthetic protocols and catalytic results previously reported. During the second reporting period, we prepared several Fe-based compositions for Fischer-Tropsch Synthesis and tested the effects of product recycle under both subcritical and supercritical conditions. During the third and fourth reporting periods, we improved the catalysts preparation method, which led to Fe-based materialsmore » with the highest FTS reaction rates and selectivities so far reported, a finding that allowed their operation at lower temperatures and pressures with high selectivity to desired products (C{sub 5+}, olefins). During the fifth and sixth reporting period, we studied the effects of different promoters on catalytic performance, specifically how their sequence of addition dramatically influenced the performance of these materials in the Fischer-Tropsch synthesis. We also continued our studies of the kinetic behavior of these materials during the sixth reporting period. Specifically, the effects of H{sub 2}, CO, and CO{sub 2} on the rates and selectivities of Fischer-Tropsch Synthesis reactions led us to propose a new sequence of elementary steps on Fe and Co Fischer-Tropsch catalysts. Finally, we also started a study of the use of colloidal precipitation methods for the synthesis small Co clusters using recently developed methods to explore possible further improvements in FTS rates and selectivities. We found that colloidal synthesis makes possible the preparation of small cobalt particles, although large amount of cobalt silicate species, which are difficult to reduce, were formed. During this seventh reporting period, we have explored several methods to modify the silanol groups on SiO{sub 2} by using either a homogeneous deposition-precipitation method or surface titration of Si-OH on SiO{sub 2} with zirconium (IV) ethoxide to prevent the formation of unreducible and unreactive CoO{sub x} species during synthesis and FTS catalysis. We have synthesized monometallic Co/ZrO{sub 2}/SiO{sub 2} catalysts with different Co loadings (11-20 wt%) by incipient wetness impregnation methods and characterized the prepared Co supported catalysts by H{sub 2} temperature-programmed reduction (H{sub 2}-TPR) and H{sub 2}-chemisorption. We have measured the catalytic performance in FTS reactions and shown that although the hydroxyl groups on the SiO{sub 2} surface are difficult to be fully titrated by ZrO{sub 2}, modification of ZrO{sub 2} on SiO{sub 2} surface can improve the Co clusters dispersion and lead to a larger number of exposed Co surface atoms after reduction and during FTS reactions. During this seventh reporting period, we have also advanced our development of the reaction mechanism proposed in the previous reporting period. Specifically, we have shown that our novel proposal for the pathways involved in CO activation on Fe and Co catalysts is consistent with state-of-the-art theoretical calculations carried out in collaboration with Prof. Manos Mavrikakis (University of Wisconsin-Madison). Finally, we have also worked on the preparation of several manuscripts describing our findings about the preparation, activation and mechanism of the FTS with Fe-based catalysts and we have started redacting the final report for this project.« less

Titanium compounds as catalysts of higher alpha-olefin-based super-high-molecular polymers synthesis

NASA Astrophysics Data System (ADS)

Konovalov, K. B.; Kazaryan, M. A.; Manzhay, V. N.; Vetrova, O. V.

2016-01-01

The synthesis of polymers of 10 million or more molecular weight is a difficult task even in a chemical lab. Higher α-olefin-based polymer agents of such kind have found a narrow but quite important niche, the reduction of drag in the turbulent flow of hydrocarbon fluids such as oil and oil-products. In its turn, searching for a catalytic system capable to produce molecules of such a high length and to synthesize polymers of a low molecular-mass distribution is part of a global task of obtaining a high-quality product. In this paper we had observed a number of industrial catalysts with respect to their suitability for higher poly-α- olefins synthesis. A number samples representing copolymers of 1-hexene with 1-decene obtained on a previous generation catalyst, a microsphere titanium chloride catalytic agent had been compared to samples synthesized using a titanium-magnesium catalyst both in solution and in a polymer medium.

Organic Analysis of Catalytic Fischer-Tropsch Type Synthesis Products: Are they Similar to Organics in Chondritic Meteorites?

NASA Technical Reports Server (NTRS)

Yazzie, Cyriah A.; Locke, Darren R.; Johnson, Natasha M.

2014-01-01

Fischer-Tropsch Type (FTT) synthesis of organic compounds has been hypothesized to occur in the early solar nebula that formed our Solar System. FTT is a collection of abiotic chemical reactions that convert a mixture of carbon monoxide and hydrogen over nano-catalysts into hydrocarbons and other more complex aromatic compounds. We hypothesized that FTT can generate similar organic compounds as those seen in chondritic meteorites; fragments of asteroids that are characteristic of the early solar system. Specific goals for this project included: 1) determining the effects of different FTT catalyst, reaction temperature, and cycles on organic compounds produced, 2) imaging of organic coatings found on the catalyst, and 3) comparison of organic compounds produced experimentally by FTT synthesis and those found in the ordinary chondrite LL5 Chelyabinsk meteorite. We used Pyrolysis Gas Chromatography Mass Spectrometry (PY-GCMS) to release organic compounds present in experimental FTT and meteorite samples, and Scanning Electron Microscopy (SEM) to take images of organic films on catalyst grains.

USSR Report, Chemistry.

DTIC Science & Technology

1985-01-17

potas- sium oxides. Only then does the mixture react to form ammonia . A method for synthesizing ammonium from nitrogen and hydrogen, along with a...manufactured by this method , most of which is used in the synthesis of nitrogen fertilizers. A modern ammonia factory is a complex, highly automated...V. Karyakin; ZHURNAL ANALITICHESKOY KHIMII, No 8, Aug 84) 5 CATALYSTS Ammonia Synthesis and Homogenous Catalysts (0. Yefimov; LENINSKOYE ZNAMYA

Microemulsion impregnated catalyst composite and use thereof in a synthesis gas conversion process

DOEpatents

Abrevaya, Hayim; Targos, William M.

1987-01-01

A catalyst composition for synthesis gas conversion comprising a ruthenium metal component deposited on a support carrier wherein the average metal particle size is less than about 100 A. The method of manufacture of the composition via a reverse micelle impregnation technique and the use of the composition in a Fischer-Tropsch conversion process is also disclosed.

Nicholas Cleveland | NREL

Science.gov Websites

tools for complex sample analysis Affiliated Research Programs Biochemical Catalysis Working Group The synthesis Catalyst characterization Catalyst testing and reaction screening Analysis of complex organics

Facile fabrication of palladium-ionic liquids-nitrogen-doped graphene nanocomposites as enhanced electro-catalyst for ethanol oxidation

NASA Astrophysics Data System (ADS)

Li, Shuwen; Yang, Honglei; Ren, Ren; Ma, Jianxin; Jin, Jun; Ma, Jiantai

2015-10-01

The palladium-ionic liquids-nitrogen-doped graphene nanocomposites are facile fabricated as enhanced electro-catalyst for ethanol oxidation. First, the ionic liquids functionalized nitrogen-doping graphene nanosheets (PDIL-NGS) with few layers is synthesized through a facile and effective one-pot hydrothermal method with graphene oxide as raw material, urea as reducing-doping agents and ionic liquids (ILs) derived from 3,4,9,10-perylene tetracarboxylic acid as functional molecules. The results of systematic characterization reveal that the PDIL molecules not only can functionalize NGS by π-π stacking with no affecting the nitrogen doping but also prevent the agglomeration of NGS. More importantly, the processing performance and the property of electron transfer are remarkably enhanced duo to introducing a large number of ILs groups. Then, the enhanced electrocatalytic Pd nanoparticles are successfully anchored on PDIL-NGS by a facile and surfactant-free synthetic technique. As an anode catalyst, the novel catalyst exhibits better kinetics, more superior electrocatalytic performance, higher tolerance and electrochemical stability than the other catalysts toward ethanol electrooxidation, owing to the role of PDIL molecules. Therefore, the new catalyst is believed to have the potential use for direct alcohol fuel cells in the future and the functionalized NGS is promising useful materials applied in other fields.

Macrokinetics of carbon nanotubes synthesis by the chemical vapor deposition method

NASA Astrophysics Data System (ADS)

Rukhov, Artem; Dyachkova, Tatyana; Tugolukov, Evgeny; Besperstova, Galina

2017-11-01

A new approach to studying and developing basic processes which take place on the surface of a metal catalyst during the thermal decomposition of carbonaceous substances in the carbon nanotubes synthesis by the chemical vapor deposition method was proposed. In addition, an analysis was made of the interrelationships between these thermal, diffusion, hydrodynamic and other synthesis processes. A strong effect of the catalyst regeneration stage on the stage of nanotube formation has been shown. Based on the developed approach, a mathematical model was elaborated. Comparison of the calculation and the experiment carried out with the NiO-MgO catalyst at propane flow rate of 50 mL/min (standard conditions) and ethanol flow rate 0.3 mL/min (liq.) has revealed a discrepancy of less than 10%.

Efficient catalytic ozonation of bisphenol-A over reduced graphene oxide modified sea urchin-like α-MnO(2) architectures.

PubMed

Li, Gang; Lu, Yongtao; Lu, Cheng; Zhu, Mingshan; Zhai, Chunyang; Du, Yukou; Yang, Ping

2015-08-30

Considering the biological deleterious effect of bisphenol-A (BPA) in water to the human beings, great efforts have been made for the elimination of this contaminant from water sources. Herein, we report a novel nanocomposite composed of three-dimensional (3D) sea urchin-like α-MnO2 nanoarchitectures and reduced graphene oxide (RGO) for the elimination of BPA in water in the presence of ozone. The synthesis of the as-prepared nanocomposite is facile, and the nanocomposites were well characterized by SEM, TEM, XRD, and Raman spectra. The as-synthesized α-MnO2/RGO nanocomposite was found to be a highly efficient catalyst to eliminate BPA from water in the presence of ozone. The intermediates of ozonzation were also detected by gas chromatography-mass spectrometry (GC-MS). Our investigation initiates a new opportunity to explore the high-performance catalysts for the removal of the organic pollutions in water. Copyright © 2015 Elsevier B.V. All rights reserved.

Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts

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

Zhu, Chengzhou; Fu, Shaofang; Song, Junhua

Finely controlled synthesis of high active and robust non-precious metal catalysts with excellent electrocatalytic efficiency towards oxygen reduction reaction is extremely vital for successful implementation of fuel cells and metal batteries. Unprecedented oxygen reduction reaction electrocatalytic performances and the diversified synthetic procedure in term of favorable structure/morphology characteristics make transition metals-derived M–N–C (M=Fe, Co) structures the most promising nanocatalysts. Herein, using the nitrogen-containing small molecular and inorganic salt as precursors and ultrathin tellurium nanowires as templates, we successfully synthesized a series of well-defined M-N-doped hollow carbon nanowire aerogels through one step hydrothermal route and subsequent facile annealing treatment. Taking advantagemore » of the porous nanostructures, one-dimensional building block as well as homogeneity of active sites, the resultant Fe-N-doped carbon hollow nanowire aerogels exhibited excellent ORR electrocatalytic performance even better than commercial Pt/C in alkaline solution, holding great potential in fuel cell applications.« less

Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

DOE PAGES

Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna; ...

2016-05-11

Here, we describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations.more » The unprecedented attack of water at a neutral six-coordinate [Ru IV] center to yield an anionic seven-coordinate [Ru IV–OH] – intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.« less

Facile synthesis of hollow Co3O4 microspheres and its use as a rapid responsive CL sensor of combustible gases.

PubMed

Teng, Fei; Yao, Wenqing; Zheng, Youfei; Ma, Yutao; Xu, Tongguang; Gao, Guizhi; Liang, Shuhui; Teng, Yang; Zhu, Yongfa

2008-09-15

The hollow Co(3)O(4) microspheres (HCMs) were prepared by the carbonaceous templates, which did not need the surface pretreatment. The chemiluminescence (CL) and catalytic properties for CO oxidation over these hollow samples were evaluated. The samples were characterized by scanning electron microscopy (SEM), energy disperse spectra (EDS), transmission electron microscopy (TEM), selected area electron diffraction (ED), X-ray diffraction (XRD), temperature-programmed desorption (TPD) and N(2) adsorption. The influences of filter' band length, flow rate of gas, test temperature, and particle structure on CL intensities were mainly investigated. It was found that compared with the solid Co(3)O(4) particles (SCPs), HCMs had a stronger CL intensity, which was ascribed to its hollow structure; and that CL properties of the catalysts were well correlated with their reaction activities. Moreover, HCMs were used to fabricate a highly sensitive gas detector, which is a rapid and effective method for the selection of catalysts or the detection of environmental deleterious gases.

l-Glutamic acid assisted eco-friendly one-pot synthesis of sheet-assembled platinum-palladium alloy networks for methanol oxidation and oxygen reduction reactions.

PubMed

Shi, Ya-Cheng; Mei, Li-Ping; Wang, Ai-Jun; Yuan, Tao; Chen, Sai-Sai; Feng, Jiu-Ju

2017-10-15

In this work, bimetallic platinum-palladium sheet-assembled alloy networks (PtPd SAANs) were facilely synthesized by an eco-friendly one-pot aqueous approach under the guidance of l-glutamic acid at room temperature, without any additive, seed, toxic or organic solvent involved. l-Glutamic acid was served as the green shape-director and weak-stabilizing agent. A series of characterization techniques were employed to examine the morphology, structure and formation mechanism of the product. The architectures exhibited improved electrocatalytic activity and durable ability toward methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in contrast with commercial Pt black and Pd black catalysts. This is ascribed to the unique structures of the obtained PtPd SAANs and the synergistic effects of the bimetals. These results demonstrate the potential application of the prepared catalyst in fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Facile Synthesis of BiOI Nanoparticles at Room Temperature and Evaluation of their Photoactivity Under Sunlight Irradiation.

PubMed

Mahmoodi, Vahid; Ahmadpour, Ali; Rohani Bastami, Tahereh; Hamed Mousavian, Mohammad Taghi

2018-01-01

In this study, highly photoactive BiOI nanoparticles (NPs) under sunlight irradiation were synthesized by a facile precipitation method using polyvinylpyrrolidone (PVP) at room temperature. The as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transition electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), Fourier transform infrared (FTIR) and UV-vis diffuse reflectance spectra (UV-vis DRS). The results of XRD showed that PVP did not have any significant effect on tetragonal crystalline structure of BiOI. Also, using different amounts of PVP in the synthesis led to different morphologies and sizes of BiOI particles. It was found that using 0.2 g of PVP in the synthesis method changed morphology from 1-μm platelets to NPs with size under 10 nm. In addition, the photocatalytic performance of prepared photocatalysts was evaluated in the photodegradation of reactive blue 19 (RB19) dye under sunlight irradiation. The BiOI synthesized using 0.2 g PVP (BiOI0.2) showed higher degradation efficiency compared to BiOI prepared without any additive. Excellent visible light photocatalytic properties of nano-scaled BiOI0.2 samples compared to BiOI platelets could be attributed to higher surface-to-volume ratio and narrow band-gap energy of as-prepared BiOI0.2 NPs. © 2017 The American Society of Photobiology.

Design of a Photoredox Catalyst that Enables the Direct Synthesis of Carbamate-Protected Primary Amines via Photoinduced, Copper-Catalyzed N-Alkylation Reactions of Unactivated Secondary Halides.

PubMed

Ahn, Jun Myun; Peters, Jonas C; Fu, Gregory C

2017-12-13

Despite the long history of S N 2 reactions between nitrogen nucleophiles and alkyl electrophiles, many such substitution reactions remain out of reach. In recent years, efforts to develop transition-metal catalysts to address this deficiency have begun to emerge. In this report, we address the challenge of coupling a carbamate nucleophile with an unactivated secondary alkyl electrophile to generate a substituted carbamate, a process that has not been achieved effectively in the absence of a catalyst; the product carbamates can serve as useful intermediates in organic synthesis as well as bioactive compounds in their own right. Through the design and synthesis of a new copper-based photoredox catalyst, bearing a tridentate carbazolide/bisphosphine ligand, that can be activated upon irradiation by blue-LED lamps, we can achieve the coupling of a range of primary carbamates with unactivated secondary alkyl bromides at room temperature. Our mechanistic observations are consistent with the new copper complex serving its intended role as a photoredox catalyst, working in conjunction with a second copper complex that mediates C-N bond formation in an out-of-cage process.

Process for the production of liquid hydrocarbons

DOEpatents

Bhatt, Bharat Lajjaram; Engel, Dirk Coenraad; Heydorn, Edward Clyde; Senden, Matthijis Maria Gerardus

2006-06-27

The present invention concerns a process for the preparation of liquid hydrocarbons which process comprises contacting synthesis gas with a slurry of solid catalyst particles and a liquid in a reactor vessel by introducing the synthesis gas at a low level into the slurry at conditions suitable for conversion of the synthesis gas into liquid hydrocarbons, the solid catalyst particles comprising a catalytic active metal selected from cobalt or iron on a porous refractory oxide carrier, preferably selected from silica, alumina, titania, zirconia or mixtures thereof, the catalyst being present in an amount between 10 and 40 vol. percent based on total slurry volume liquids and solids, and separating liquid material from the solid catalyst particles by using a filtration system comprising an asymmetric filtration medium (the selective side at the slurry side), in which filtration system the average pressure differential over the filtration medium is at least 0.1 bar, in which process the particle size distribution is such that at least a certain amount of the catalyst particles is smaller than the average pore size of the selective layer of the filtration medium. The invention also comprises an apparatus to carry out the process described above.

Nanocrystalline Iron-Ore-Based Catalysts for Fischer-Tropsch Synthesis.

PubMed

Yong, Seok; Park, Ji Chan; Lee, Ho-Tae; Yang, Jung-Il; Hong, SungJun; Jung, Heon; Chun, Dong Hyun

2016-02-01

Nanocrystalline iron ore particles were fabricated by a wet-milling process using an Ultra Apex Mill, after which they were used as raw materials of iron-based catalysts for low-temperature Fischer-Tropsch synthesis (FTS) below 280 degrees C, which usually requires catalysts with a high surface area, a large pore volume, and a small crystallite size. The wet-milling process using the Ultra Apex Mill effectively destroyed the initial crystallite structure of the natural iron ores of several tens to hundreds of nanometers in size, resulting in the generation of nanocrystalline iron ore particles with a high surface area and a large pore volume. The iron-ore-based catalysts prepared from the nanocrystalline iron ore particles effectively catalyzed the low-temperature FTS, displaying a high CO conversion (about 90%) and good C5+ hydrocarbon productivity (about 0.22 g/g(cat)(-h)). This demonstrates the feasibility of using the iron-ore-based catalysts as inexpensive and disposable catalysts for the low-temperature FTS.

Synthesis of Dicyclopentadiene Oligomer Over Nanoporous Al-MCM-41 Catalysts.

PubMed

Park, Eunseo; Kim, Jinhan; Yim, Jin-Heong; Han, Jeongsik; Kwon, Tae Soo; Park, Y K; Jeon, Jong-Ki

2016-05-01

One step reaction composed of DCPD oligomerization and DCPD oligomer isomerization was investigated over nanoporous Al-MCM-41 catalysts. The effects of aluminum grafting over MCM-41 on the catalyst characteristics were studied with respect to the synthesis of TCPD isomer. Physical and chemical properties of the catalysts were analyzed by N2 adsorption, temperature-programmed desorption of ammonia, and infrared spectroscopy of adsorbed pyridine. The overall number of acid sites as well as the number of Lewis acid sites increased with increasing of aluminum content over MCM-41. When utilizing MCM-41 and Al-MCM-41 as the catalyst, DCPD oligomerization reaction activity greatly increased compared to the thermal reaction. The highest TCPD isomer selectivity over the Al-MCM-41 catalyst with the highest aluminum content could be ascribed to the largest amount of acid sites. This study showed an increased level of TCPD isomer selectivity by an increasing level of Lewis acid sites through aluminum addition over MCM-41.

Synthesis of methyl esters from waste cooking oil using construction waste material as solid base catalyst.

PubMed

Balakrishnan, K; Olutoye, M A; Hameed, B H

2013-01-01

The current research investigates synthesis of methyl esters by transesterification of waste cooking oil in a heterogeneous system, using barium meliorated construction site waste marble as solid base catalyst. The pretreated catalyst was calcined at 830 °C for 4h prior to its activity test to obtained solid oxide characterized by scanning electron microscopy/energy dispersive spectroscopy, BET surface area and pore size measurement. It was found that the as prepared catalyst has large pores which contributed to its high activity in transesterification reaction. The methyl ester yield of 88% was obtained when the methanol/oil molar ratio was 9:1, reaction temperature at 65 °C, reaction time 3h and catalyst/oil mass ratio of 3.0 wt.%. The catalyst can be reused over three cycles, offer low operating conditions, reduce energy consumption and waste generation in the production of biodiesel. Copyright © 2012 Elsevier Ltd. All rights reserved.

Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

NASA Astrophysics Data System (ADS)

Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

2018-05-01

Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

Synthesis of metal free ultrathin graphitic carbon nitride sheet for photocatalytic dye degradation of Rhodamine B under visible light irradiation

NASA Astrophysics Data System (ADS)

Rahman, Shakeelur; Momin, Bilal; Higgins M., W.; Annapure, Uday S.; Jha, Neetu

2018-04-01

In recent times, low cost and metal free photocatalyts driven under visible light have attracted a lot of interest. One such photo catalyst researched extensively is bulk graphitic carbon nitride sheets. But the low surface area and weak mobility of photo generated electrons limits its photocatalytic performance in the visible light spectrum. Here we present the facile synthesis of ultrathin graphitic carbon nitride using a cost effective melamine precursor and its application in highly efficient photocatalytic dye degradation of Rhodamine B molecules. Compared to bulk graphitic carbon nitride, the synthesized ultrathin graphitic carbon nitride shows an increase in surface area, a a decrease in optical band gap and effective photogenerated charge separation which facilitates the harvest of visible light irradiation. Due to these optimal properties of ultrathin graphitic carbon nitride, it shows excellent photocatalytic activity with photocatalytic degradation of about 95% rhodamine B molecules in 1 hour.

Synthesis of hollow silica spheres with hierarchical shell structure by the dual action of liquid indium microbeads in vapor-liquid-solid growth.

PubMed

Wang, Jian-Tao; Wang, Hui; Ou, Xue-Mei; Lee, Chun-Sing; Zhang, Xiao-Hong

2011-07-05

Geometry-based adhesion arising from hierarchical surface structure enables microspheres to adhere to cells strongly, which is essential for inorganic microcapsules that function as drug delivery or diagnostic imaging agents. However, constructing a hierarchical structure on the outer shell of the products via the current microcapsule synthesis method is difficult. This work presents a novel approach to fabricating hollow microspheres with a hierarchical shell structure through the vapor-liquid-solid (VLS) process in which liquid indium droplets act as both templates for the formation of silica capsules and catalysts for the growth of hierarchical shell structure. This hierarchical shell structure offers the hollow microsphere an enhanced geometry-based adhesion. The results provide a facile method for fabricating hollow spheres and enriching their function through tailoring the geometry of their outer shells. © 2011 American Chemical Society

Highly Efficient Catalysis of Azo Dyes Using Recyclable Silver Nanoparticles Immobilized on Tannic Acid-Grafted Eggshell Membrane

NASA Astrophysics Data System (ADS)

Liu, Xiaojing; Liang, Miao; Liu, Mingyue; Su, Rongxin; Wang, Mengfan; Qi, Wei; He, Zhimin

2016-10-01

In this study, a facile one-step synthesis of a novel nanocomposite catalytic film was developed based on silver nanoparticles (AgNPs) immobilized in tannic acid-modified eggshell membrane (Tan-ESM). Tannic acid, as a typical plant polyphenol from oak wood, was first grafted onto ESM fibers to serve as both the reductant and the stabilizer during the synthesis of AgNPs. The morphology, constitution, and thermal stability of the resulting AgNPs@Tan-ESM composites were fully characterized to explain the excellent catalytic efficiency of AgNPs@Tan-ESM composites. These composite catalysts were applied to the degradation of azo dyes which exhibited the high catalytic activity toward Congo red and methyl orange according to the kinetic curves. More importantly, they can be easily recovered and reused for many times because of their good stability.

Lantana camara Linn leaf extract mediated green synthesis of gold nanoparticles and study of its catalytic activity

NASA Astrophysics Data System (ADS)

Dash, Shib Shankar; Bag, Braja Gopal; Hota, Poulami

2015-03-01

A facile one-step green synthesis of stable gold nanoparticles (AuNPs) has been described using chloroauric acid (HAuCl4) and the leaf extract of Lantana camara Linn (Verbenaceae family) at room temperature. The leaf extract enriched in various types of plant secondary metabolites is highly efficient for the reduction of chloroaurate ions into metallic gold and stabilizes the synthesized AuNPs without any additional stabilizing or capping agents. Detailed characterizations of the synthesized gold nanoparticles were carried out by surface plasmon resonance spectroscopy, transmission electron microscopy, dynamic light scattering, Zeta potential, X-ray diffraction and Fourier transform-infrared spectroscopy studies. The synthesized AuNPs have been utilized as a catalyst for the sodium borohydride reduction of 4-nitrophenol to 4-aminophenol in water at room temperature under mild reaction condition. The kinetics of the reduction reaction has been studied spectrophotometrically.

Ferrocene-Based Hyperbranched Polytriazoles: Synthesis by Click Polymerization and Application as Precursors to Nanostructured Magnetoceramics.

PubMed

Li, Hongkun; Chi, Weiwen; Liu, Yajing; Yuan, Wei; Li, Yaowen; Li, Yongfang; Tang, Ben Zhong

2017-09-01

Ferrocene-based polymers have drawn much attention in the past decades due to their unique properties and promising applications. However, the synthesis of hyperbranched polymers is still a great challenge. Here, two ferrocene-based hyperbranched polytriazoles with high molecular weights are facilely prepared by the click polymerization reactions of ferrocene-containing diazides (1) and tris(4-ethynylphenyl)amine (2) using Cu(PPh 3 ) 3 Br as catalyst in dimethylformamide at 60 °C for 5 and 9 h in satisfactory yields of 54.0% and 52.3%. The resulting polytriazoles are soluble in common organic solvents and thermally stable, with 5% weight loss temperatures up to 307 °C. They can be used as precursors to produce nanostructured ceramics with good magnetizability by pyrolysis at elevated temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fischer-Tropsch Cobalt Catalyst Activation and Handling Through Wax Enclosure Methods

NASA Technical Reports Server (NTRS)

Klettlinger, Jennifer L. S.; Yen, Chia H.; Nakley, Leah M.; Surgenor, Angela D.

2016-01-01

Fischer-Tropsch (F-T) synthesis is considered a gas to liquid process which converts syn-gas, a gaseous mixture of hydrogen and carbon monoxide, into liquids of various hydrocarbon chain length and product distributions. Cobalt based catalysts are used in F-T synthesis and are the focus of this paper. One key concern with handling cobalt based catalysts is that the active form of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air. In laboratory experiments, the precursor cobalt oxide catalyst is activated in a fixed bed at 350 ?C then transferred into a continuous stirred tank reactor (CSTR) with inert gas. NASA has developed a process which involves the enclosure of active cobalt catalyst in a wax mold to prevent oxidation during storage and handling. This improved method allows for precise catalyst loading and delivery into a CSTR. Preliminary results indicate similar activity levels in the F-T reaction in comparison to the direct injection method. The work in this paper was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.

Synthesis of High-Quality Biodiesel Using Feedstock and Catalyst Derived from Fish Wastes.

PubMed

Madhu, Devarapaga; Arora, Rajan; Sahani, Shalini; Singh, Veena; Sharma, Yogesh Chandra

2017-03-15

A low-cost and high-purity calcium oxide (CaO) was prepared from waste crab shells, which were extracted from the dead crabs, was used as an efficient solid base catalyst in the synthesis of biodiesel. Raw fish oil was extracted from waste parts of fish through mechanical expeller followed by solvent extraction. Physical as well as chemical properties of raw fish oil were studied, and its free fatty acid composition was analyzed with GC-MS. Stable and high-purity CaO was obtained when the material was calcined at 800 °C for 4 h. Prepared catalyst was characterized by XRD, FT-IR, and TGA/DTA. The surface structure of the catalyst was analyzed with SEM, and elemental composition was determined by EDX spectra. Esterification followed by transesterification reactions were conducted for the synthesis of biodiesel. The effect of cosolvent on biodiesel yield was studied in each experiment using different solvents such as toluene, diethyl ether, hexane, tetrahydrofuran, and acetone. High-quality and pure biodiesel was synthesized and characterized by 1 H NMR and FT-IR. Biodiesel yield was affected by parameters such as reaction temperature, reaction time, molar ratio (methanol:oil), and catalyst loading. Properties of synthesized biodiesel such as density, kinematic viscosity, and cloud point were determined according to ASTM standards. Reusability of prepared CaO catalyst was checked, and the catalyst was found to be stable up to five runs without significant loss of catalytic activity.

Rare-Earth-compound nanowires, nanotubes, and fullerene-like nanoparticles: synthesis, characterization, and properties.

PubMed

Wang, Xun; Li, Yadong

2003-11-21

Various low-dimensional nanostructures, such as nanowires, nanotubes, nanosheets, and fullerene-like nanoparticles have been selectively synthesized from rare-earth compounds (hydroxides, fluorides) based on a facile hydrothermal method. The subsequent dehydration, sulfidation, and fluoridation processes lead to the formation of rare-earth oxide, oxysulfide, and oxyhalide nanostructures, which can be functionalized further by doping with other rare-earth ions or by coating with metal nanoparticles. Owing to the interesting combination of novel nanostructures and functional compounds, these nanostructures can be expected to bring new opportunities in the vast research areas of and application in biology, catalysts, and optoelectronic devices.

Derek R. Vardon | NREL

Science.gov Websites

reaction engineering. Derek's research interests include: Catalytic conversion of biomass to fuels and synthesis Catalyst characterization Catalyst testing and reaction engineering Analysis of complex organics

Hemostatic kaolin-polyurethane foam composites for multifunctional wound dressing applications.

PubMed

Lundin, Jeffrey G; McGann, Christopher L; Daniels, Grant C; Streifel, Benjamin C; Wynne, James H

2017-10-01

There are numerous challenges associated with the acute care of traumatic limb injuries in forward military settings. A lack of immediate medical facilities necessitates that the wound dressing perform multiple tasks including exudate control, infection prevention, and physical protection of the wound for extended periods of time. Here, kaolin was incorporated into recently developed robust polyurethane (PU) hydrogel foams at 1-10wt% in an effort to impart hemostatic character. ATR-IR and gel fraction analysis demonstrated that the facile, one-pot synthesis of the PU hydrogel was unaffected by kaolin loading, as well as the use of a non-toxic catalyst, which significantly improved cytocompatibility of the materials. Kaolin was generally well dispersed throughout the PU matrix, though higher loadings exhibited minor evidence of aggregation. Kaolin-PU composites exhibited burst release of ciprofloxacin over 2h, the initial release rates of which increased with kaolin loading. Kaolin loading imparted excellent hemostatic character to the PU foams at relatively low loading levels (5wt%). This work demonstrates the simple and inexpensive synthesis of robust, hemostatic, and absorptive kaolin-PU foams that have promising potential as multifunctional wound dressing materials. Published by Elsevier B.V.

Synthesis of 5'-O-DMT-2'-O-TBS Mononucleosides Using an Organic Catalyst.

PubMed

Lee, Sunggi; Blaisdell, Thomas P; Kasaplar, Pinar; Sun, Xixi; Tan, Kian L

2014-06-24

This unit describes a highly effective method to produce 5'-O-DMT-2'-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2'- and 3'-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps, starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2'-O-TBS protected mono-nucleosides, U, A(Bz), G(Ib), and C(Ac), were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol in the preparation of monomers useful for automated synthesis of RNA. Copyright © 2014 John Wiley & Sons, Inc.

Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon Nanotubes-``Super-Growth''

NASA Astrophysics Data System (ADS)

Hata, Kenji

2005-03-01

We demonstrate an extremely efficient chemical vapour deposition synthesis of single-walled carbon nanotubes where the activity and lifetime of the catalysts are enhanced by water [1]. Water-stimulated enhanced catalytic activity results in massive growth of super-dense and vertically-aligned nanotube forests with heights up to 2.5 millimeters that can be easily separated from the catalysts, providing nanotube material with carbon purity above 99.98%. Moreover, patterned highly organized intrinsic nanotube structures were successfully fabricated. The water-assisted synthesis method addresses many critical problems that currently plague carbon nanotube synthesis. [1] K. Hata, et al., Science, 306, 1362 (2004).

Catalytic chemical amide synthesis at room temperature: one more step toward peptide synthesis.

PubMed

Mohy El Dine, Tharwat; Erb, William; Berhault, Yohann; Rouden, Jacques; Blanchet, Jérôme

2015-05-01

An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, α-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported.

Simulation of the Dynamics of Isothermal Growth of Single-Layer Graphene on a Copper Catalyst in the Process of Chemical Vapor Deposition of Hydrocarbons

NASA Astrophysics Data System (ADS)

Futko, S. I.; Shulitskii, B. G.; Labunov, V. A.; Ermolaeva, E. M.

2018-01-01

A new kinetic model of isothermal growth of single-layer graphene on a copper catalyst as a result of the chemical vapor deposition of hydrocarbons on it at a low pressure has been developed on the basis of in situ measurements of the growth of graphene in the process of its synthesis. This model defines the synthesis of graphene with regard for the chemisorption and catalytic decomposition of ethylene on the surface of a copper catalyst, the diffusion of carbon atoms in the radial direction to the nucleation centers within the thin melted near-surface copper layer, and the nucleation and autocatalytic growth of graphene domains. It is shown that the time dependence of the rate of growth of a graphene domain has a characteristic asymmetrical bell-like shape. The dependences of the surface area and size of a graphene domain and the rate of its growth on the time at different synthesis temperatures and ethylene concentrations have been obtained. Time characteristics of the growth of graphene domains depending on the parameters of their synthesis were calculated. The results obtained can be used for determining optimum regimes of synthesis of graphene in the process of chemical vapor deposition of hydrocarbons on different catalysts with a low solubility of carbon.

Enhanced conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1986-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst system capable of enhancing the selectivity of said conversion to motor fuel range hydrocarbons and the quality of the resulting motor fuel product. The catalyst composition employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component comprising SAPO silicoaluminophosphate, non-zeolitic molecular sieve catalyst.

A Facile Synthesis of MPd (M=Co, Cu) Nanoparticles and Their Catalysis for Formic Acid Oxidation

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

Mazumder, Vismadeb; Chi, Miaofang; Mankin, Max

2012-01-01

Monodisperse CoPd nanoparticles (NPs) were synthesized and studied for catalytic formic acid (HCOOH) oxidation (FAO). The NPs were prepared by coreduction of Co(acac)2 (acac = acetylacetonate) and PdBr2 at 260 C in oleylamine and trioctylphosphine, and their sizes (5-12 nm) and compositions (Co10Pd90 to Co60Pd40) were controlled by heating ramp rate, metal salt concentration, or metal molar ratios. The 8 nm CoPd NPs were activated for HCOOH oxidation by a simple ethanol wash. In 0.1 M HClO4 and 2 M HCOOH solution, their catalytic activities followed the trend of Co50Pd50 > Co60Pd40 > Co10Pd90 > Pd. The Co50Pd50 NPs hadmore » an oxidation peak at 0.4 V with a peak current density of 774 A/gPd. As a comparison, commercial Pd catalysts showed an oxidation peak at 0.75 V with peak current density of only 254 A/gPd. The synthesis procedure could also be extended to prepare CuPd NPs when Co(acac)2 was replaced by Cu(ac)2 (ac = acetate) in an otherwise identical condition. The CuPd NPs were less active catalysts than CoPd or even Pd for FAO in HClO4 solution. The synthesis provides a general approach to Pd-based bimetallic NPs and will enable further investigation of Pd-based alloy NPs for electro-oxidation and other catalytic reactions.« less

Final Technical Report for GO15052 Intematix: Combinatorial Synthesis and High Throughput Screening of Effective Catalysts for Chemical Hydrides

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

Melman, Jonathan

The objectives of this project are: to discover cost-effective catalysts for release of hydrogen from chemical hydrogen storage systems; and to discover cost-effective catalysts for the regeneration of spent chemical hydrogen storage materials.

Catalyst and method for production of methylamines

DOEpatents

Klier, Kamil; Herman, Richard G.; Vedage, Gamini A.

1987-01-01

This invention relates to an improved catalyst and method for the selective production of methylamines. More particularly, it is concerned with the preparation of stable highly active catalysts for producing methylamines by a catalytic reaction of ammonia or substituted amines and binary synthesis gas (CO+H.sub.2).

Silicon nanowire synthesis by a vapor-liquid-solid approach.

PubMed

Mao, Aaron; Ng, H T; Nguyen, Pho; McNeil, Melanie; Meyyappan, M

2005-05-01

Synthesis of silicon nanowires is studied by using a vapor-liquid-solid growth technique. Silicon tetrachloride reduction with hydrogen in the gas phase is used with gold serving as catalyst to facilitate growth. Only a narrow set of conditions of SiCl4 concentration and temperature yield straight nanowires. High concentrations and temperatures generally result in particulates, catalyst coverage and deactivation, and coatinglike materials.

Silicon nanowire synthesis by a vapor-liquid-solid approach

NASA Technical Reports Server (NTRS)

Mao, Aaron; Ng, H. T.; Nguyen, Pho; McNeil, Melanie; Meyyappan, M.

2005-01-01

Synthesis of silicon nanowires is studied by using a vapor-liquid-solid growth technique. Silicon tetrachloride reduction with hydrogen in the gas phase is used with gold serving as catalyst to facilitate growth. Only a narrow set of conditions of SiCl4 concentration and temperature yield straight nanowires. High concentrations and temperatures generally result in particulates, catalyst coverage and deactivation, and coatinglike materials.

Synthesis of 4-(5-iodo-3-methylpyrazolyl) phenylsulfonamide and its elaboration to a COX II inhibitor library by solution-phase suzuki coupling using Pd/C as a solid-supported catalyst.

PubMed

Organ, Michael G; Mayer, Stanislas

2003-01-01

An effective synthesis of 4-(5-iodo-3-methylpyrazolyl) phenylsulfonamide has been developed. This aromatic iodide template served as an efficient oxidative addition partner for the preparation of a solution-phase library of Celecoxib analogues via Suzuki coupling using Pd/C, a readily filterable catalyst.

Effect of steam during Fischer–Tropsch Synthesis using biomass-derived syngas

Treesearch

Zi Wang; Khiet Mai; Nitin Kumar; Thomas Elder; Leslie H. Groom; James J. Spivey

2017-01-01

Fischer–Tropsch synthesis (FTS) with biomass- derived syngas was performed using both iron-based 100Fe/6Cu/4K/25Al catalyst and ruthenium-based 5 % Ru/SiO2 catalyst. During FTS, different concentrations of steam were co-fed with the biomass-derived syngas to promote the water gas shift reaction and increase the H2/ CO ratio...

Biaryl Phosphine Ligands in Palladium-Catalyzed Amination

PubMed Central

Surry, David S.

2012-01-01

Palladium-catalyzed amination of aryl halides has undergone rapid development in the last 12 years. This has been largely driven by implementation of new classes of ligands. Biaryl phosphines have proven to provide especially active catalysts in this context. This review discusses the applications that these catalysts have found in C-N cross-coupling in heterocycle synthesis, pharmaceuticals, materials science and natural product synthesis. PMID:18663711

Microemulsion impregnated catalyst composite and use thereof in a synthesis gas conversion process

DOEpatents

Abrevaya, H.; Targos, W.M.

1987-12-22

A catalyst composition is described for synthesis gas conversion comprising a ruthenium metal component deposited on a support carrier wherein the average metal particle size is less than about 100 A. The method of manufacture of the composition via a reverse micelle impregnation technique and the use of the composition in a Fischer-Tropsch conversion process is also disclosed.

Enantioselective synthesis of cis-decalins using organocatalysis and sulfonyl Nazarov reagents.

PubMed

Peña, Javier; Silveira-Dorta, Gastón; Moro, Rosalina F; Garrido, Narciso M; Marcos, Isidro S; Sanz, Francisca; Díez, David

2015-04-10

The first organocatalytic synthesis of cis-decalins using sulfonyl Nazarov reagents is reported. The Jørgensen's catalyst directs this highly enantioselective synthesis using different cyclohexenal derivatives.

Chirality specific and spatially uniform synthesis of single-walled carbon nanotubes from a sputtered Co-W bimetallic catalyst

NASA Astrophysics Data System (ADS)

An, Hua; Kumamoto, Akihito; Takezaki, Hiroki; Ohyama, Shinnosuke; Qian, Yang; Inoue, Taiki; Ikuhara, Yuichi; Chiashi, Shohei; Xiang, Rong; Maruyama, Shigeo

2016-07-01

Synthesis of single-walled carbon nanotubes (SWNTs) with well-defined atomic arrangements has been widely recognized in the past few decades as the biggest challenge in the SWNT community, and has become a bottleneck for the application of SWNTs in nano-electronics. Here, we report a selective synthesis of (12, 6) SWNTs with an enrichment of 50%-70% by chemical vapor deposition (CVD) using sputtered Co-W as a catalyst. This is achieved under much milder reduction and growth conditions than those in the previous report using transition-metal molecule clusters as catalyst precursors (Nature, 2014, 510, 522). Meanwhile, in-plane transmission electron microscopy unambiguously identified an intermediate structure of Co6W6C, which is strongly associated with selective growth. However, most of the W atoms disappear after a 5 min CVD growth, which implies that anchoring W may be important in this puzzling Co-W system.Synthesis of single-walled carbon nanotubes (SWNTs) with well-defined atomic arrangements has been widely recognized in the past few decades as the biggest challenge in the SWNT community, and has become a bottleneck for the application of SWNTs in nano-electronics. Here, we report a selective synthesis of (12, 6) SWNTs with an enrichment of 50%-70% by chemical vapor deposition (CVD) using sputtered Co-W as a catalyst. This is achieved under much milder reduction and growth conditions than those in the previous report using transition-metal molecule clusters as catalyst precursors (Nature, 2014, 510, 522). Meanwhile, in-plane transmission electron microscopy unambiguously identified an intermediate structure of Co6W6C, which is strongly associated with selective growth. However, most of the W atoms disappear after a 5 min CVD growth, which implies that anchoring W may be important in this puzzling Co-W system. Electronic supplementary information (ESI) available: Raman spectroscopy (G-band) of SWNTs grown from Co and Co-W catalyst; Kataura plot for chirality assignment; Raman spectra (RBM region) of SWNTs grown from low temperature reduced monometallic Co; relative intensities of the 197 cm-1 peak with respect to the total sum intensity; TEM image of Co-W catalyst reduced at six different temperatures (600, 650, 700, 750, 800, and 850 °C) TEM images of SWNTs grown from Co monometallic catalyst. See DOI: 10.1039/c6nr02749k

Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

2017-09-01

Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol.

PubMed

Das, Vijay Kumar; Mazhar, Sumaira; Gregor, Lennon; Stein, Barry D; Morgan, David Gene; Maciulis, Nicholas A; Pink, Maren; Losovyj, Yaroslav; Bronstein, Lyudmila M

2018-06-14

Here, we report transfer hydrogenation of nitroarenes to aminoarenes using 2-propanol as a hydrogen source and Ag-containing magnetically recoverable catalysts based on partially reduced graphene oxide (pRGO) sheets. X-ray diffraction and X-ray photoelectron spectroscopy data demonstrated that, during the one-pot catalyst synthesis, formation of magnetite nanoparticles (NPs) is accompanied by the reduction of graphene oxide (GO) to pRGO. The formation of Ag 0 NPs on top of magnetite nanoparticles does not change the pRGO structure. At the same time, the catalyst structure is further modified during the transfer hydrogenation, leading to a noticeable increase of sp 2 carbons. These carbons are responsible for the adsorption of substrate and intermediates, facilitating a hydrogen transfer from Ag NPs and creating synergy between the components of the catalyst. The nitroarenes with electron withdrawing and electron donating substituents allow for excellent yields of aniline derivatives with high regio and chemoselectivity, indicating that the reaction is not disfavored by these functionalities. The versatility of the catalyst synthetic protocol was demonstrated by a synthesis of an Ru-containing graphene derivative based catalyst, also allowing for efficient transfer hydrogenation. Easy magnetic separation and stable catalyst performance in the transfer hydrogenation make this catalyst promising for future applications.

Reverse Micelle Synthesis and Characterization of Supported Pt/Ni Bimetallic Catalysts on gamma-Al2O3

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

B Cheney; J Lauterbach; J Chen

2011-12-31

Reverse micelle synthesis was used to improve the nanoparticle size uniformity of bimetallic Pt/Ni nanoparticles supported on {gamma}-Al{sub 2}O{sub 3}. Two impregnation methods were investigated to optimize the use of the micelle method: (1) step-impregnation, where Ni nanoparticles were chemically reduced in microemulsion and then supported, followed by Pt deposition using incipient wetness impregnation, and (2) co-impregnation, where Ni and Pt were chemically reduced simultaneously in microemulsion and then supported. Transmission electron microscopy (TEM) was used to characterize the particle size distribution. Atomic absorption spectroscopy (AAS) was used to perform elemental analysis of bimetallic catalysts. Extended X-ray absorption fine structuremore » (EXAFS) measurements were utilized to confirm the formation of the Pt-Ni bimetallic bond in the step-impregnated catalyst. CO pulse chemisorption and Fourier transform infrared spectroscopy (FTIR) studies of 1,3-butadiene hydrogenation in a batch reactor were performed to determine the catalytic activity. Step-impregnated Pt/Ni catalyst demonstrated enhanced hydrogenation activity over the parent monometallic Pt and Ni catalysts due to bimetallic bond formation. The catalyst synthesized using co-impregnation showed no enhanced activity, behaving similarly to monometallic Ni. Overall, our results indicate that reverse micelle synthesis combined with incipient wetness impregnation produced small, uniform nanoparticles with bimetallic bonds that enhanced hydrogenation activity.« less

Highly efficient and recyclable basic mesoporous zeolite catalyzed condensation, hydroxylation, and cycloaddition reactions.

PubMed

Sarmah, Bhaskar; Satpati, Biswarup; Srivastava, Rajendra

2017-05-01

Crystalline mesoporous ZSM-5 zeolite was prepared in the presence of 1,4-diazabicyclo[2.2.2]octane derived multi-cationic structure directing agent. The calcined form of the mesoprous zeolite was treated with NH 4 OH to obtain basic mesoporous ZSM-5. Catalyst was characterized by the complementary combination of X-ray diffraction, N 2 -adsorption, electron microscopes, and temperature programme desorption techniques. Catalytic activity of the basic mesoporous ZSM-5 was systematically assessed using Knoevenagel condensation reaction for the synthesis a wide range of substituted styrene. Applications of the catalyst were investigated in the benzamide hydroxylation for the synthesis of carbinolamides and one-pot, multi-component condensation reaction for the synthesis of naphthopyrans. Finally, the catalyst was evaluated in the cycloaddition of CO 2 to epoxide for the synthesis of cyclic carbonates. Recycling study shows that no significant decrease in the catalytic activity was observed after five recycles. Copyright © 2017. Published by Elsevier Inc.

Synthesis of palladium nanoparticles with leaf extract of Chrysophyllum cainito (Star apple) and their applications as efficient catalyst for C-C coupling and reduction reactions

NASA Astrophysics Data System (ADS)

Majumdar, Rakhi; Tantayanon, Supawan; Bag, Braja Gopal

2017-10-01

A simple green chemical method for the one-step synthesis of palladium nanoparticles (PdNPs) has been described by reducing palladium (II) chloride with the leaf extract of Chrysophyllum cainito in aqueous medium. The synthesis of the palladium nanoparticles completed within 2-3 h at room temperature, whereas on heat treatment (70-80 °C), the synthesis of colloidal PdNPs completed almost instantly. The stabilized PdNPs have been characterized in detail by spectroscopic, electron microscopic and light scattering measurements. The synthesized PdNPs have been utilized as a green catalyst for C-C coupling reactions under aerobic and phosphine-free conditions in aqueous medium. In addition, the synthesized PdNPs have also been utilized as a catalyst for a very efficient sodium borohydride reduction of 3- and 4-nitrophenols. The synthesized PdNPs can retain their catalytic activity for several months.

Synthesis and Characterization of Cobalt Containing Nanoparticles on Alumina A Potential Catalyst for Gas to Liquid Fuels Production

NASA Technical Reports Server (NTRS)

Cowen, Jonathan; Hepp, Aloysius F.

2016-01-01

Fisher-Tröpsch synthesis (FTS) is a century-old gas-to-liquid (GTL) technology that commonly employs cobalt (Co, on an oxide support) or iron (supported or not) species catalysts. It has been well established that the activity of the Co catalyst depends directly upon the number of surface Co atoms. The addition of promoter (mainly noble) metals has been widely utilized to increase the fraction of Co that is available for surface catalysis. Direct synthesis of Co nanoparticles is a possible alternative approach; our preliminary synthesis and characterization efforts are described. Materials were characterized by various transmission microscopies and energy dispersive spectroscopy. Tri-n-octylphosphine oxide (TOPO) and dicobalt octacarbonyl were heated under argon to a temperature of 180 deg with constant stirring for 1 hr. Quenching the reaction in toluene produced Co-containing nanoparticles with a diameter of 5 to 10 nm. Alternatively, an alumina support (SBA-200 Al2O3) was added; the reaction was further stirred and the temperature was decreased to 140 deg to reduce the rate of further growth/ripening of the nucleated Co nanoparticles. A typical size of Co-containing NPs was also found to be in the range of 5 to 10 nm. This can be contrasted with a range of 50 to 200 nm for conventionally-produced Co-Al2O3 Fischer-Tröpsch catalysts. This method shows great potential for production of highly dispersed catalysts that are either supported or unsupported.

Production of carbon nanotubes: Chemical vapor deposition synthesis from liquefied petroleum gas over Fe-Co-Mo tri-metallic catalyst supported on MgO

NASA Astrophysics Data System (ADS)

Setyopratomo, P.; Wulan, Praswasti P. D. K.; Sudibandriyo, M.

2016-06-01

Carbon nanotubes were produced by chemical vapor deposition method to meet the specifications for hydrogen storage. So far, the various catalyst had been studied outlining their activities, performances, and efficiencies. In this work, tri-metallic catalyst consist of Fe-Co-Mo supported on MgO was used. The catalyst was prepared by wet-impregnation method. Liquefied Petroleum Gas (LPG) was used as carbon source. The synthesis was conducted in atmospheric fixed bed reactor at reaction temperature range 750 - 850 °C for 30 minutes. The impregnation method applied in this study successfully deposed metal component on the MgO support surface. It found that the deposited metal components might partially replace Mg(OH)2 or MgO molecules in their crystal lattice. Compare to the original MgO powder; it was significant increases in pore volume and surface area has occurred during catalyst preparation stages. The size of obtained carbon nanotubes is ranging from about 10.83 nm OD/4.09 nm ID up to 21.84 nm OD/6.51 nm ID, which means that multiwall carbon nanotubes were formed during the synthesis. Yield as much as 2.35 g.CNT/g.catalyst was obtained during 30 minutes synthesis and correspond to carbon nanotubes growth rate of 0.2 μm/min. The BET surface area of the obtained carbon nanotubes is 181.13 m2/g and around 50 % of which is contributed by mesopores. Micropore with half pore width less than 1 nm contribute about 10% volume of total micro and mesopores volume of the carbon nanotubes. The existence of these micropores is very important to increase the hydrogen storage capacity of the carbon nanotubes.

Tandem Reactions for Streamlining Synthesis

PubMed Central

HUSSAIN, MAHMUD M.; WALSH, PATRICK J.

2009-01-01

CONSPECTUS In 1980 Sharpless and Katsuki introduced the asymmetric epoxidation of prochiral allylic alcohols (the Sharpless-Katsuki Asymmetric Epoxidation), which enabled the rapid synthesis of highly enantioenriched epoxy alcohols. This reaction was a milestone in the development of asymmetric catalysis because it was the first highly enantioselective oxidation reaction. Furthermore, it provided access to enantioenriched allylic alcohols that are now standard starting materials in natural product synthesis. In 1981 Sharpless and coworkers made another seminal contribution by describing the kinetic resolution (KR) of racemic allylic alcohols. This work demonstrated that small-molecule catalysts could compete with enzymatic catalysts in KRs. For these pioneering works, Sharpless was awarded the 2001 Nobel Prize with Knowles and Noyori. Despite these achievements, the Sharpless KR is not an efficient method to prepare epoxy alcohols with high enantiomeric excess (ee). First, the racemic allylic alcohol must be prepared and purified. KR of the racemic allylic alcohol must be stopped at low conversion, because the ee of the product epoxy alcohol decreases as the KR progresses. Thus, better methods to prepare epoxy alcohols containing stereogenic carbinol carbons are needed. This Account summarizes our efforts to develop one-pot methods for the synthesis of various epoxy alcohols and allylic epoxy alcohols with high enantio-, diastereo-, and chemoselectivity. Our laboratory developed titanium-based catalysts for use in the synthesis of epoxy alcohols with tertiary carbinols. The catalysts are involved in the first step, which is an asymmetric alkyl or allyl addition to enones. The resulting intermediates are then subjected to a titanium-directed diastereoselective epoxidation to provide tertiary epoxy alcohols. Similarly, the synthesis of acyclic epoxy alcohols begins with asymmetric additions to enals and subsequent epoxidation. The methods described here enable the synthesis of skeletally diverse epoxy alcohols. PMID:18710197

Facile Synthesis of Highly Aligned Multiwalled Carbon Nanotubes from Polymer Precursors

DOE PAGES

Han, Catherine Y.; Xiao, Zhi-Li; Wang, H. Hau; ...

2009-01-01

We report a facile one-step approach which involves no flammable gas, no catalyst, and no in situ polymerization for the preparation of well-aligned carbon nanotube array. A polymer precursor is placed on top of an anodized aluminum oxide (AAO) membrane containing regular nanopore arrays, and slow heating under Ar flow allows the molten polymer to wet the template through adhesive force. The polymer spread into the nanopores of the template to form polymer nanotubes. Upon carbonization the resulting multi-walled carbon nanotubes duplicate the nanopores morphology precisely. The process is demonstrated for 230, 50, and 20 nm pore membranes. The synthesized carbonmore » nanotubes are characterized with scanning/transmission electron microscopies, Raman spectroscopy, and resistive measurements. Convenient functionalization of the nanotubes with this method is demonstrated through premixing CoPt nanoparticles in the polymer precursors.« less

In Situ Nanoreactors: Controllable Photoluminescent Carbon-Rich Polymer Nanodots Derived from Fatty Acid under Photoirradiation.

PubMed

Dai, Qin; Zhao, He; Fan, Zhuangjun; Zhao, Wentao; Wang, Guangwei; Zhang, Jimei; Hou, Rong; Du, Penghui; Cao, Hongbin

2018-05-17

Amphiphilic nanoreactors have been recently used to fabricate photoluminescent carbon-rich polymer nanodots (PCPNs). However, the applications of PCPNs have been limited by their requirements for high temperature and toxic organic solvents or catalysts and the difficult control of their luminescent properties. Herein, a novel and facile strategy is reported for the synthesis of controllable PCPNs. This strategy involves the use of in situ vesicular nanoreactors under mild photoirradiation with fatty acid as the precursor. The conjugation degree of the uniformly sized PCPNs can be increased by extending photoreaction time, thus enabling the tuning of the optical properties of PCPNs. The PCPNs, which feature controllable and outstanding luminescent properties, low cytotoxicity, and biocompatibility, are successfully applied in bioimaging and as fluorescent ink. The present strategy is an attractive and facile platform for the preparation of carbon-rich nanomaterials with controllable photoluminescence. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile electrosynthesis of silicon carbide nanowires from silica/carbon precursors in molten salt.

PubMed

Zou, Xingli; Ji, Li; Lu, Xionggang; Zhou, Zhongfu

2017-08-30

Silicon carbide nanowires (SiC NWs) have attracted intensive attention in recent years due to their outstanding performances in many applications. A large-scale and facile production of SiC NWs is critical to its successful application. Here, we report a simple method for the production of SiC NWs from inexpensive and abundantly available silica/carbon (SiO 2 /C) precursors in molten calcium chloride. The solid-to-solid electroreduction and dissolution-electrodeposition mechanisms can easily lead to the formation of homogenous SiC NWs. This template/catalyst-free approach greatly simplifies the synthesis procedure compared to conventional methods. This general strategy opens a direct electrochemical route for the conversion of SiO 2 /C into SiC NWs, and may also have implications for the electrosynthesis of other micro/nanostructured metal carbides/composites from metal oxides/carbon precursors.

Stable metal-organic frameworks as a host platform for catalysis and biomimetics.

PubMed

Qin, Jun-Sheng; Yuan, Shuai; Lollar, Christina; Pang, Jiandong; Alsalme, Ali; Zhou, Hong-Cai

2018-04-24

Recent years have witnessed the exploration and synthesis of an increasing number of metal-organic frameworks (MOFs). The utilization of stable MOFs as a platform for catalysis and biomimetics is discussed. This Feature Article will provide insights into the rational design and synthesis of three types of stable MOF catalysts on the basis of structural features of MOFs, that is, (i) MOF catalysts with catalytic sites on metal nodes, (ii) MOF catalysts with catalytic sites immobilized in organic struts, and (iii) MOF catalysts with catalytic centres encapsulated in the pores. Then, MOFs used in biomimetics including biomimetic mineralization, biosensors and biomimetic replication are introduced. Finally, a discussion on the challenges that must be addressed for successful implementation of MOFs in catalysis and biomimetics is presented.

Laser Synthesis of Supported Catalysts for Carbon Nanotubes

NASA Technical Reports Server (NTRS)

VanderWal, Randall L.; Ticich, Thomas M.; Sherry, Leif J.; Hall, Lee J.; Schubert, Kathy (Technical Monitor)

2003-01-01

Four methods of laser assisted catalyst generation for carbon nanotube (CNT) synthesis have been tested. These include pulsed laser transfer (PLT), photolytic deposition (PLD), photothermal deposition (PTD) and laser ablation deposition (LABD). Results from each method are compared based on CNT yield, morphology and structure. Under the conditions tested, the PLT was the easiest method to implement, required the least time and also yielded the best pattemation. The photolytic and photothermal methods required organometallics, extended processing time and partial vacuums. The latter two requirements also held for the ablation deposition approach. In addition to control of the substrate position, controlled deposition duration was necessary to achieve an active catalyst layer. Although all methods were tested on both metal and quartz substrates, only the quartz substrates proved to be inactive towards the deposited catalyst particles.

Large-scale synthesis of arrays of high-aspect-ratio rigid vertically aligned carbon nanofibres

NASA Astrophysics Data System (ADS)

Melechko, A. V.; McKnight, T. E.; Hensley, D. K.; Guillorn, M. A.; Borisevich, A. Y.; Merkulov, V. I.; Lowndes, D. H.; Simpson, M. L.

2003-09-01

We report on techniques for catalytic synthesis of rigid, high-aspect-ratio, vertically aligned carbon nanofibres by dc plasma enhanced chemical vapour deposition that are tailored for applications that require arrays of individual fibres that feature long fibre lengths (up to 20 µm) such as scanning probe microscopy, penetrant cell and tissue probing arrays and mechanical insertion approaches for gene delivery to cell cultures. We demonstrate that the definition of catalyst nanoparticles is the critical step that enables growth of individual, long-length fibres and discuss methods for catalyst particle preparation that allow the growth of individual isolated nanofibres from catalyst dots with diameters as large as 500 nm. This development enables photolithographic definition of catalyst and therefore the inexpensive, large-scale production of such arrays.

Recent progress in solution plasma-synthesized-carbon-supported catalysts for energy conversion systems

NASA Astrophysics Data System (ADS)

Lun Li, Oi; Lee, Hoonseung; Ishizaki, Takahiro

2018-01-01

Carbon-based materials have been widely utilized as the electrode materials in energy conversion and storage technologies, such as fuel cells and metal-air batteries. In these systems, the oxygen reduction reaction is an important step that determines the overall performance. A novel synthesis route, named the solution plasma process, has been recently utilized to synthesize various types of metal-based and heteroatom-doped carbon catalysts. In this review, we summarize cutting-edge technologies involving the synthesis and modeling of carbon-supported catalysts synthesized via solution plasma process, followed by current progress on the electrocatalytic performance of these catalysts. This review provides the fundamental and state-of-the-art performance of solution-plasma-synthesized electrode materials, as well as the remaining scientific and technological challenges for this process.

Metal-organic cooperative catalysis in C-H and C-C bond activation and its concurrent recovery.

PubMed

Park, Young Jun; Park, Jung-Woo; Jun, Chul-Ho

2008-02-01

The development of an efficient catalytic activation (cleavage) system for C-H and C-C bonds is an important challenge in organic synthesis, because these bonds comprise a variety of organic molecules such as natural products, petroleum oils, and polymers on the earth. Among many elegant approaches utilizing transition metals to activate C-H and C-C bonds facilely, chelation-assisted protocols based on the coordinating ability of an organic moiety have attracted great attention, though they have often suffered from the need for an intact coordinating group in a substrate. In this Account, we describe our entire efforts to activate C-H or C-C bonds adjacent to carbonyl groups by employing a new concept of metal-organic cooperative catalysis (MOCC), which enables the temporal installation of a 2-aminopyridyl group into common aldehydes or ketones in a catalytic way. Consequently, a series of new catalytic reactions such as alcohol hydroacylation, oxo-ester synthesis, C-C triple bond cleavage, hydrative dimerization of alkynes, and skeletal rearrangements of cyclic ketones was realized through MOCC. In particular, in the quest for an optimized MOCC system composed of a Wilkinson's catalyst (Ph 3P) 3RhCl and an organic catalyst (2-amino-3-picoline), surprising efficiency enhancements could be achieved when benzoic acid and aniline were introduced as promoters for the aldimine formation process. Furthermore, a notable accomplishment of C-C bond activation has been made using 2-amino-3-picoline as a temporary chelating auxiliary in the reactions of unstrained ketones with various terminal olefins and Wilkinson's catalyst. In the case of seven-membered cyclic ketones, an interesting ring contraction to five- or six-membered ones takes place through skeletal rearrangements initiated by the C-C bond activation of MOCC. On the other hand, the fundamental advances of these catalytic systems into recyclable processes could be achieved by immobilizing both metal and organic components using a hydrogen-bonded self-assembled system as a catalyst support. This catalyst-recovery system provides a homogeneous phase at high temperature during the reaction and a heterogeneous phase at room temperature after the reaction. The product could be separated conveniently from the self-assembly support system by decanting the upper layer. The immobilized catalysts of both 2-aminopyridine and rhodium metal species sustained high catalytic activity for up to the eight catalytic reactions. In conclusion, the successful incorporation of an organocatalytic cycle into a transition metal catalyzed reaction led us to find MOCC for C-H and C-C bond activation. In addition, the hydrogen-bonded self-assembled support has been developed for an efficient and effective recovery system of homogeneous catalysts and could be successful in immobilizing both metal and organic catalysts.

Method for making methanol

DOEpatents

Mednick, R. Lawrence; Blum, David B.

1987-01-01

Methanol is made in a liquid-phase methanol reactor by entraining a methanol-forming catalyst in an inert liquid and contacting said entrained catalyst with a synthesis gas comprising hydrogen and carbon monoxide.

Catalysts for conversion of syngas to liquid motor fuels

DOEpatents

Rabo, Jule A.; Coughlin, Peter K.

1987-01-01

Synthesis gas comprising carbon monoxide and hydrogen is converted to C.sub.5.sup.+ hydrocarbons suitable for use as liquid motor fuels by contact with a dual catalyst composition capable of ensuring the production of only relatively minor amounts of heavy products boiling beyond the diesel oil range. The catalyst composition, having desirable stability during continuous production operation, employs a Fischer-Tropsch catalyst, together with a co-catalyst/support component. The latter component is a steam-stabilized zeolite Y catalyst of hydrophobic character, desirably in acid-extracted form.

Biopolymer Processing Using Ionic Liquids

DTIC Science & Technology

2014-08-07

solvents and catalysts for the dissolution and degradation of chitin and chitosan. This project will:1) synthesis various IL catalysts to study their...effects on depolymerization of chitin and chitosan, 2) synthesis a variety of IL’s to invesitgate the effects of dissolution solvents on the rate of...chitin. The current state of technology has focused on the short-chained imidazolium cations with the chloride and acetate anion. This project will

Towards the Rational Design of Nanoparticle Catalysts

NASA Astrophysics Data System (ADS)

Dash, Priyabrat

This research is focused on development of routes towards the rational design of nanoparticle catalysts. Primarily, it is focused on two main projects; (1) the use of imidazolium-based ionic liquids (ILs) as greener media for the design of quasi-homogeneous nanoparticle catalysts and (2) the rational design of heterogeneous-supported nanoparticle catalysts from structured nanoparticle precursors. Each project has different studies associated with the main objective of the design of nanoparticle catalysts. In the first project, imidazolium-based ionic liquids have been used for the synthesis of nanoparticle catalysts. In particular, studies on recyclability, reuse, mode-of-stability, and long-term stability of these ionic-liquid supported nanoparticle catalysts have been done; all of which are important factors in determining the overall "greenness" of such synthetic routes. Three papers have been published/submitted for this project. In the first publication, highly stable polymer-stabilized Au, Pd and bimetallic Au-Pd nanoparticle catalysts have been synthesized in imidazolium-based 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid (Journal of Molecular Catalysis A: Chemical, 2008, 286, 114). The resulting nanoparticles were found to be effective and selective quasi-homogeneous catalysts towards a wide-range of hydrogenation reactions and the catalyst solution was reused for further catalytic reactions with minimal loss in activity. The synthesis of very pure and clean ILs has allowed a platform to study the effects of impurities in the imidazolium ILs on nanoparticle stability. In a later study, a new mode of stabilization was postulated where the presence of low amounts of 1-methylimidazole has substantial effects on the resulting stability of Au and Pd-Au nanoparticles in these ILs (Chemical Communications, 2009, 812). In further continuation of this study, a comparative study involving four stabilization protocols for nanoparticle stabilization in BMIMPF6 IL is described, and have shown that nanoparticle stability and catalytic activity of nanoparticles is dependent on the overall stability of the nanoparticles towards aggregation (manuscript submitted). The second major project is focused on synthesizing structurally well-defined supported catalysts by incorporating the nanoparticle precursors (both alloy and core shell) into oxide frameworks (TiO2 and Al2O 3), and examining their structure-property relationships and catalytic activity. a full article has been published on this project (Journal of Physical Chemistry C, 2009, 113, 12719) in which a route to rationally design supported catalysts from structured nanoparticle precursors with precise control over size, composition, and internal structure of the nanoparticles has been shown. In a continuation of this methodology for the synthesis of heterogeneous catalysts, efforts were carried out to apply the same methodology in imidazolium-based ILs as a one-pot media for the synthesis of supported-nanoparticle heterogeneous catalysts via the trapping of pre-synthesized nanoparticles into porous inorganic oxide materials. Nanoparticle catalysts in highly porous titania supports were synthesized using this methodology (manuscript to be submitted).

Ultra-high-performance core–shell structured Ru@Pt/C catalyst prepared by a facile pulse electrochemical deposition method

DOE PAGES

Chen, Dan; Li, Yuexia; Liao, Shijun; ...

2015-08-03

Core–shell structured catalysts, made by placing either a monolayer or a thin layer of a noble metal on relatively cheap core-metal nanoparticles, are fascinating and promising fuel cell catalysts due to their high utilization of noble metals. Here, we report our development of a core–shell structured catalyst, Ru@Pt/C, generated by a novel and facile pulse electrochemical deposition (PED) approach. We demonstrate that compared with a commercial Pt/C catalyst, this novel catalyst achieves over four times higher mass activity towards the anodic oxidation of methanol, and 3.6 times higher mass activity towards the cathodic reduction of oxygen. Importantly, we find thatmore » the intrinsic activity of Pt in this Ru@Pt/C catalyst is doubled due to the formation of the core–shell structure. The catalyst also shows superior stability: even after 2000 scans, it still retains up to 90% of the peak current. As a result, our findings demonstrate that this novel PED approach is a promising method for preparing high-performance core–shell catalysts for fuel cell applications.« less

Two Catalysts for Selective Oxidation of Contaminant Gases

NASA Technical Reports Server (NTRS)

Wright, John D.

2011-01-01

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.

An efficient protocol for the synthesis of quinoxaline derivatives at room temperature using recyclable alumina-supported heteropolyoxometalates.

PubMed

Ruiz, Diego M; Autino, Juan C; Quaranta, Nancy; Vázquez, Patricia G; Romanelli, Gustavo P

2012-01-01

We report a suitable quinoxaline synthesis using molybdophosphovanadates supported on commercial alumina cylinders as catalysts. These catalysts were prepared by incipient wetness impregnation. The catalytic test was performed under different reaction conditions in order to know the performance of the synthesized catalysts. The method shows high yields of quinoxaline derivatives under heterogeneous conditions. Quinoxaline formation was obtained using benzyl, o-phenylenediamine, and toluene as reaction solvent at room temperature. The CuH(2)PMo(11)VO(40) supported on alumina showed higher activity in the tested reaction. Finally, various quinoxalines were prepared under mild conditions and with excellent yields.

General synthesis and definitive structural identification of MN 4C 4 single-atom catalysts with tunable electrocatalytic activities

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

Fei, Huilong; Dong, Juncai; Feng, Yexin

Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MNsub>4C 4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical predictionmore » of MNsub>4C 4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.« less

General synthesis and definitive structural identification of MN 4C 4 single-atom catalysts with tunable electrocatalytic activities

DOE PAGES

Fei, Huilong; Dong, Juncai; Feng, Yexin; ...

2018-01-08

Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MNsub>4C 4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical predictionmore » of MNsub>4C 4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.« less

Facile synthesis of light harvesting semiconductor bismuth oxychloride nano photo-catalysts for efficient removal of hazardous organic pollutants

PubMed Central

Seddigi, Zaki S.; Baig, Umair; Ahmed, Saleh A.; Abdulaziz, M. A.; Danish, Ekram Y.; Khaled, Mazen M.; Lais, Abul

2017-01-01

In the present work, bismuth oxychloride nanoparticles–a light harvesting semiconductor photocatalyst–were synthesized by a facile hydrolysis route, with sodium bismuthate and hydroxylammonium chloride as the precursor materials. The as-synthesized semiconductor photocatalysts were characterized using X-ray diffraction analysis, Fourier transform infra-red spectroscopy, Raman spectroscopy, Field emission scanning electron microscopy, X-ray photoelectron spectroscopy and Photoluminescence spectroscopy techniques. The crystal structure, morphology, composition, and optical properties of these facile synthesized bismuth oxychloride nanoparticles (BiOCl NPs) were compared to those of traditional bismuth oxychloride. In addition, the photocatalytic performance of facile-synthesized BiOCl NPs and traditional BiOCl, as applied to the removal of hazardous organic dyes under visible light illumination, is thoroughly investigated. Our results reveal that facile-synthesized BiOCl NPs display strong UV-Vis light adsorption, improved charge carrier mobility and an inhibited rate of charge carrier recombination, when compared to traditional BiOCl. These enhancements result in an improved photocatalytic degradation rate of hazardous organic dyes under UV-Vis irradiance. For instance, the facile-synthesized BiOCl NPs attained 100% degradation of methylene blue and methyl orange dyes in approximately 30 mins under UV-Vis irradiation, against 55% degradation for traditional BiOCl under similar experimental conditions. PMID:28245225

Facile synthesis of light harvesting semiconductor bismuth oxychloride nano photo-catalysts for efficient removal of hazardous organic pollutants.

PubMed

Seddigi, Zaki S; Gondal, Mohammed A; Baig, Umair; Ahmed, Saleh A; Abdulaziz, M A; Danish, Ekram Y; Khaled, Mazen M; Lais, Abul

2017-01-01

In the present work, bismuth oxychloride nanoparticles-a light harvesting semiconductor photocatalyst-were synthesized by a facile hydrolysis route, with sodium bismuthate and hydroxylammonium chloride as the precursor materials. The as-synthesized semiconductor photocatalysts were characterized using X-ray diffraction analysis, Fourier transform infra-red spectroscopy, Raman spectroscopy, Field emission scanning electron microscopy, X-ray photoelectron spectroscopy and Photoluminescence spectroscopy techniques. The crystal structure, morphology, composition, and optical properties of these facile synthesized bismuth oxychloride nanoparticles (BiOCl NPs) were compared to those of traditional bismuth oxychloride. In addition, the photocatalytic performance of facile-synthesized BiOCl NPs and traditional BiOCl, as applied to the removal of hazardous organic dyes under visible light illumination, is thoroughly investigated. Our results reveal that facile-synthesized BiOCl NPs display strong UV-Vis light adsorption, improved charge carrier mobility and an inhibited rate of charge carrier recombination, when compared to traditional BiOCl. These enhancements result in an improved photocatalytic degradation rate of hazardous organic dyes under UV-Vis irradiance. For instance, the facile-synthesized BiOCl NPs attained 100% degradation of methylene blue and methyl orange dyes in approximately 30 mins under UV-Vis irradiation, against 55% degradation for traditional BiOCl under similar experimental conditions.

Pt-Pd Bimetal Popcorn Nanocrystals: Enhancing the Catalytic Performance by Combination Effect of Stable Multipetals Nanostructure and Highly Accessible Active Sites.

PubMed

Ma, Yanxia; Yin, Lisi; Cao, Guojian; Huang, Qingli; He, Maoshuai; Wei, Wenxian; Zhao, Hong; Zhang, Dongen; Wang, Mingyan; Yang, Tao

2018-04-01

Exploration of highly efficient electrocatalysts is significantly urgent for the extensive adoption of the fuel cells. Because of their high activity and super stability, Pt-Pd bimetal nanocrystals have been widely recognized as one class of promising electrocatalysts for oxygen reduction. This article presents the synthesis of popcorn-shaped Pt-Pd bimetal nanoparticles with a wide composition range through a facile hydrothermal strategy. The hollow-centered nanoparticles are surrounded by several petals and concave surfaces. By exploring the oxygen reduction reaction on the carbon supported Pt-Pd popcorns in perchloric acid solution, it is found that compared with the commercial Pt/C catalyst the present catalysts display superior catalytic performances in aspects of catalytic activity and stability. More importantly, the Pt-Pd popcorns display minor performance degradations through prolonged potential cycling. The enhanced performances can be mainly attributed to the unique popcorn structure of the Pt-Pd components, which allows the appearance and long existence of the high active sites with more accessibility. The present work highlights the key roles of accessible high active sites in the oxygen reduction reaction, which will ultimately guide the design of highly durable Pt-Pd catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-Pot Green Synthesis of Ag-Decorated SnO2 Microsphere: an Efficient and Reusable Catalyst for Reduction of 4-Nitrophenol.

PubMed

Hu, Min; Zhang, Zhenwei; Luo, Chenkun; Qiao, Xiuqing

2017-12-01

In this paper, hierarchical Ag-decorated SnO 2 microspheres were synthesized by a facile one-pot hydrothermal method. The resulting composites were characterized by XRD, SEM, TEM, XPS, BET, and FTIR analysis. The catalytic performances of the samples were evaluated with the reduction of 4-nitrophenol to 4-aminophenol by potassium borohydride (KBH 4 ) as a model reaction. Time-dependent experiments indicated that the hierarchical microspheres assembled from SnO 2 and Ag nanoparticles can be formed when the react time is less than 10 h. With the increase of hydrothermal time, SnO 2 nanoparticles will self-assemble into SnO 2 nanosheets and Ag nanoparticles decorated SnO 2 nanosheets were obtained. When evaluated as catalyst, the obtained Ag-decorated SnO 2 microsphere prepared for 36 h exhibited excellent catalytic performance with normalized rate constant (κ nor ) of 6.20 min -1 g -1 L, which is much better than that of some previous reported catalysts. Moreover, this Ag-decorated SnO 2 microsphere demonstrates good reusability after the first five cycles. In addition, we speculate the formation mechanism of the hierarchical Ag-decorated SnO 2 microsphere and discussed the possible origin of the excellent catalytic activity.

Fluxing template-assisted synthesis of sponge-like Fe2O3 microspheres toward efficient catalysis for CO oxidation

NASA Astrophysics Data System (ADS)

Li, Wenge; Hu, Yanjie; Jiang, Hao; Jiang, Yi; Wang, Yang; Huang, Su; Biswas, Pratim; Li, Chunzhong

2018-06-01

Constructing a porous architecture is a considerable strategy to enhance the catalytic activity of metal oxides catalysts for CO oxidation. In this work, we have developed porous sponge-like Fe2O3 microspheres by employing a facile aerosol spray pyrolysis. The NaNO3 salt in the spray solution plays a crucial role as a fluxing sacrifice template in the formation of the sponge-like structure, in which a high surface area of 216.2 m2 g-1 and an average pore size of 4 nm are obtained. This novel Fe2O3 catalyst exhibits an improved catalytic activity compared to usual iron oxides catalysts. Nearly 50% CO conversion at a relatively low temperature of 200 °C and 100% CO conversion at 300 °C at a space velocity of 60 000 ml h-1 g-1 are achieved. Furthermore, it displays an outstanding catalytic stability without distinct decay for 1000 min in a continuous stream at 300 °C. In addition to the effect of plentiful adsorption sites for the gas reactant, the promoted catalytic performance is also attributed to the function of abundant OH groups rooted in the large surface of the sponge-like structure, which induces faster reaction rate of CO oxidation via a bicarbonate route.

An investigation into the effects of different existing states of aluminum isopropoxide on copper-based catalysts for direct synthesis of dimethyl ether from syngas

NASA Astrophysics Data System (ADS)

Sun, Kai; Wang, Peng; Bian, Zhongkai; Huang, Wei

2018-01-01

Aluminum isopropoxide (AIP) is a vital raw material to produce high surface area alumina catalyst, which is used for catalytic applications, such as hydrocracking, Fischer-Tropsch and STD (syngas to dimethyl ether) reactions. However, the different existing states have an effect on hydrolysis and condensation in the process of precursor preparation. The Cu/Zn/Al slurry catalysts were prepared by aluminum isopropoxide, which were liquid state, crystalline state and solid state, utilizing a complete liquid phase preparation technology. In the dimethyl ether (DME) synthesis reaction, the aluminum resource of crystalline state was prepared for slurry catalyst, which presented high CO conversion and DME selectivity of 54.32% and 69.74%, respectively. Characterization results indicated that different forms of AIP have the variant coordination numbers of Al-O and polymerization degrees, and the catalyst prepared by crystalline state consists amount of tetra-coordinated Al and few hexa-coordinated Al, which can exert different hydrolysis and condensation process compared with other aluminum sources, and finally it contributes to the strong interaction between active site copper species and Zn/Al species, confirming more Cu+ is responsible for the synthesis of DME in the slurry reactor.

Carbon and Mo transformations during the synthesis of mesoporous Mo2C/carbon catalysts by carbothermal hydrogen reduction

NASA Astrophysics Data System (ADS)

Wang, Haiyan; Liu, Shida; Liu, Bing; Montes, Vicente; Hill, Josephine M.; Smith, Kevin J.

2018-02-01

The synthesis of mesoporous Mo2C/carbon catalysts by carbothermal hydrogen reduction is reported. Petroleum coke (petcoke) was activated with KOH at 800 °C to obtain high surface area microporous activated petcoke (APC; 2000 m2/g). The APC was wet impregnated with ammonium heptamolybdate (AHM: 10 wt% Mo), dried and reduced in H2 at temperatures from 400 to 800 °C, to yield Mo2C/APC catalysts. Increased reduction temperature increased the Mo2C yield and the mesoporous volume of the Mo2C/APC. At a reduction temperature of 750 °C the mesopore volume of the catalyst doubled compared to the APC support and accounted for 37% of the total pore volume. Maintaining the final CHR temperature for 90 min further increased the Mo2C yield and mesoporosity of the catalyst. The role of Mo2C in the catalytic hydrogenation of the APC and mesopore generation is demonstrated. The activity of the Mo2C/carbon catalysts in the hydrodeoxygenation of 4-methyl phenol increased with increased CHR temperature and catalyst mesoporosity.

Synthesis of high-quality diesel with furfural and 2-methylfuran from hemicellulose.

PubMed

Li, Guangyi; Li, Ning; Wang, Zhiqiang; Li, Changzhi; Wang, Aiqin; Wang, Xiaodong; Cong, Yu; Zhang, Tao

2012-10-01

Hydroxyalkylation-alkylation (HAA) coupled with hydrodeoxygenation is a promising route for the synthesis of renewable high-quality diesel or jet fuel. In this work, a series of solid-acid catalysts were firstly used for HAA between lignocellulose-derived furan and carbonyl compounds. Among the investigated catalysts, Nafion-212 resin demonstrated the highest activity and stability. Owing to the high activity of the reactants and the advantage in industrial integration, the HAA of 2-methylfuran (2-MF) and furfural can be considered as a prospective route in future applications. Catalyst loading, reaction temperature, and time had evident effects on the HAA of 2-MF and furfural over Nafion-212 resin. Finally, the HAA product of 2-MF and furfural was hydrogenated over a Pd/C catalyst and hydrodeoxygenated over Pt-loaded solid-acid catalysts. Pt/zirconium phosphate (Pt/ZrP) was found to be the best catalyst for hydrodeoxygenation. Over the 4 % Pt/ZrP catalyst, a 94 % carbon yield of diesel and 75 % carbon yield of C15 hydrocarbons (with 6-butylundecane as the major component) was achieved. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by co-precipitation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04130b Click here for additional data file.

PubMed Central

Smith, Paul J.; Kondrat, Simon A.; Chater, Philip A.; Yeo, Benjamin R.; Shaw, Greg M.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.

2017-01-01

Zincian georgeite, an amorphous copper–zinc hydroxycarbonate, has been prepared by co-precipitation using acetate salts and ammonium carbonate. Incorporation of zinc into the georgeite phase and mild ageing conditions inhibits crystallisation into zincian malachite or aurichalcite. This zincian georgeite precursor was used to prepare a Cu/ZnO catalyst, which exhibits a superior performance to a zincian malachite derived catalyst for methanol synthesis and the low temperature water–gas shift (LTS) reaction. Furthermore, the enhanced LTS activity and stability in comparison to that of a commercial Cu/ZnO/Al2O3 catalyst, indicates that the addition of alumina as a stabiliser may not be required for the zincian georgeite derived Cu/ZnO catalyst. The enhanced performance is partly attributed to the exclusion of alkali metals from the synthesis procedure, which are known to act as catalyst poisons. The effect of residual sodium on the microstructural properties of the catalyst precursor was investigated further from preparations using sodium carbonate. PMID:28451351

Fischer–Tropsch Synthesis: XANES Spectra of Potassium in Promoted Precipitated Iron Catalysts as a Function of Time On-stream

DOE PAGES

Jacobs, Gary; Pendyala, Venkat Ramana Rao; Martinelli, Michela; ...

2017-06-06

XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer–Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course ofmore » the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. This method serves as a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.« less

Alcohol synthesis from CO or CO.sub.2

DOEpatents

Hu, Jianli [Kennewick, WA; Dagle, Robert A [Richland, WA; Holladay, Jamelyn D [Kennewick, WA; Cao, Chunshe [Houston, TX; Wang, Yong [Richland, WA; White, James F [Richland, WA; Elliott, Douglas C [Richland, WA; Stevens, Don J [Richland, WA

2010-12-28

Methods for producing alcohols from CO or CO.sub.2 and H.sub.2 utilizing a palladium-zinc on alumina catalyst are described. Methods of synthesizing alcohols over various catalysts in microchannels are also described. Ethanol, higher alcohols, and other C.sub.2+ oxygenates can produced utilizing Rh--Mn or a Fisher-Tropsch catalyst.

Nobel Chemistry in the Laboratory: Synthesis of a Ruthenium Catalyst for Ring-Closing Olefin Metathesis--An Experiment for the Advanced Inorganic or Organic Laboratory

ERIC Educational Resources Information Center

Greco, George E.

2007-01-01

An experiment for the upper-level undergraduate laboratory is described in which students synthesize a ruthenium olefin metathesis catalyst, then use the catalyst to carry out the ring-closing metathesis of diethyl diallylmalonate. The olefin metathesis reaction was the subject of the 2005 Nobel Prize in chemistry. The catalyst chosen for this…

Development of GREET Catalyst Module

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

Wang, Zhichao; Benavides, Pahola T.; Dunn, Jennifer B.

2015-09-01

In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al 2O3, and Pt/ γ-Al 2O 3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

Studies on KIT-6 Supported Cobalt Catalyst for Fischer–Tropsch Synthesis

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

Gnanamani, M.; Jacobs, G; Graham, U

2010-01-01

KIT-6 molecular sieve was used as a support to prepare cobalt catalyst for Fischer-Tropsch synthesis (FTS) using an incipient wetness impregnation method to produce cobalt loadings of 15 and 25 wt%. The catalysts were characterized by BET surface area, X-ray diffraction, scanning transmission election microscopy (STEM), extended X-ray absorption fine spectroscopy and X-ray absorption near edge spectroscopy. The catalytic properties for FTS were evaluated using a 1L CSTR reactor. XRD, pore size distribution, and STEM analysis indicate that the KIT-6 mesostructure remains stable during and after cobalt impregnation and tends to form smaller cobalt particles, probably located inside the mesopores.more » The mesoporous KIT-6 exhibited a slightly higher cobalt dispersion compared to amorphous SiO{sub 2} supported catalyst. With the higher Co loading (25 wt%) on KIT-6, partial structural collapse was observed after the FTS reaction. Compared to an amorphous SiO{sub 2} supported cobalt catalyst, KIT-6 supported cobalt catalyst displayed higher methane selectivity at a similar Co loading, likely due to diffusion effects.« less

Hybrid Pd/Fe{sub 3}O{sub 4} nanowires: Fabrication, characterization, optical properties and application as magnetically reusable catalyst for the synthesis of N-monosubstituted ureas under ligand-free conditions

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

Nasrollahzadeh, Mahmoud, E-mail: mahmoudnasr81@gmail.com; Azarian, Abbas; Ehsani, Ali

2014-07-01

Highlights: • Preparation of Pd/Fe{sub 3}O{sub 4} nanowires as magnetically reusable catalysts. • The optical properties of the catalyst were studied using Gans theory. • N-arylation of benzylurea and in situ hydrogenolysis of 1-benzyl-3-arylureas. - Abstract: This paper reports the synthesis and use of Pd/Fe{sub 3}O{sub 4} nanowires, as magnetically separable catalysts for ligand-free amidation coupling reactions of aryl halides with benzylurea under microwave irradiation. Then, the in situ hydrogenolysis of the products was performed to afford the N-monosubstituted ureas from good to excellent yields. This method has the advantages of high yields, simple methodology and easy work up. Themore » catalyst can be recovered by using a magnet and reused several times without significant loss of its catalytic activity. The catalyst was characterized using the powder XRD, SEM, EDS and UV–vis spectroscopy. Experimental absorbance spectra was compared with results from the Gans theory.« less

A comparative synthesis and physicochemical characterizations of Ni/Al2O3-MgO nanocatalyst via sequential impregnation and sol-gel methods used for CO2 reforming of methane.

PubMed

Aghamohammadi, Sogand; Haghighi, Mohammad; Karimipour, Samira

2013-07-01

Carbon dioxide reforming of methane is an interesting route for synthesis gas production especially over nano-sized catalysts. The present research deals with catalyst development for dry reforming of methane with the aim of reaching the most stable catalyst. Effect of preparation method, one of the most significant variables, on the properties of the catalysts was taken in to account. The Ni/Al2O3-MgO catalysts were prepared via sol-gel and sequential impregnation methods and characterized with XRD, FESEM, EDAX, BET and FTIR techniques. The reforming reactions were carried out using different feed ratios, gas hourly space velocities (GHSV) and reaction temperatures to identify the influence of operational variables. FESEM images indicate uniform particle size distribution for the sample synthesized with sol-gel method. It has been found that the sol-gel method has the potential to improve catalyst desired properties especially metal surface enrichment resulting in catalytic performance enhancement. The highest yield of products was obtained at 850 degrees C for both of the catalysts. During the 10 h stability test, CH4 and CO2 conversions gained higher values in the case of sol-gel made catalyst compared to impregnated one.

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.

Biodiesel synthesis via transesterification of lipid Chlorophyta cultivated in walne rich carbon medium using KOH/Zeolite catalyst

NASA Astrophysics Data System (ADS)

Dianursanti, Hayati, Siti Zahrotul; Putri, Dwini Normayulisa

2017-11-01

Microalgae from the Chlorophyta division such as Nannochloropsis oculata and Chlorella vulgaris are highly potential to be developed as biodiesel feedstocks because they have a high oil content up to 58%. Biodiesel is produced by transesterification of triglycerides and alcohols with the aid of homogeneous catalysts such as KOH. However, the use of KOH catalysts produces soaps in the biodiesel synthesis. Heterogeneous catalysts are known to solve this problem. One of them is natural zeolite. Zeolite can be used as a catalyst and as a support catalyst. Loading KOH on the zeolite surface is expected to increase alkalinity in KOH/Zeolite catalysts so as to increase the activity of KOH/Zeolite catalyst in transesterification of triglyceride with methanol. In this experimental lipid of microalgae will be used for produced biodiesel via transesterification reaction with methanol and KOH/Zeolite as a catalyst heterogeneous at 60 °C for 3h and utilized catalyst modificated KOH/Zeolite with variation 0.5 M, 1 M and 1.5 M KOH. The modified zeolite was then analyzed by XRF, XRD and BET. The result showed that the yield of biodiesel from lipid N.oculata was 81,09% by 0.5KOH/Zeolite catalyst, 86,53% by 1KOH/Zeolite catalyst, 1,5KOH/Zeolite and 88,13% by 1.5KOH/Zeolit, while the biodiesel produced from lipid C.vulgaris was 59.29% by 0.5KOH/Zeolite, 82.27% by 1KOH/Zeolite and 83.72% by 1.5KOH/Zeolite.

Optimization of Synthesis Conditions of Carbon Nanotubes via Ultrasonic-Assisted Floating Catalyst Deposition Using Response Surface Methodology

PubMed Central

Mohammadian, Narges; Ghoreishi, Seyyed M.; Hafeziyeh, Samira; Saeidi, Samrand; Dionysiou, Dionysios D.

2018-01-01

The growing use of carbon nanotubes (CNTs) in a plethora of applications has provided to us a motivation to investigate CNT synthesis by new methods. In this study, ultrasonic-assisted chemical vapor deposition (CVD) method was employed to synthesize CNTs. The difficulty of controlling the size of clusters and achieving uniform distribution—the major problem in previous methods—was solved by using ultrasonic bath and dissolving ferrocene in xylene outside the reactor. The operating conditions were optimized using a rotatable central composite design (CCD), which helped optimize the operating conditions of the method. Response surface methodology (RSM) was used to analyze these experiments. Using statistical software was very effective, considering that it decreased the number of experiments needed to achieve the optimum conditions. Synthesis of CNTs was studied as a function of three independent parameters viz. hydrogen flow rate (120–280 cm3/min), catalyst concentration (2–6 wt %), and synthesis temperature (800–1200 °C). Optimum conditions for the synthesis of CNTs were found to be 3.78 wt %, 184 cm3/min, and 976 °C for catalyst concentration, hydrogen flow rate, and synthesis temperature, respectively. Under these conditions, Raman spectrum indicates high values of (IG/ID), which means high-quality CNTs. PMID:29747451

Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials

NASA Astrophysics Data System (ADS)

Ghampson, Isaac Tyrone

The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silica-supported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, analyzed as a three-phase system containing Cofcc, Cohcp and CoO particles. Catalyst properties were determined at three stages in catalyst history: (1) after the initial calcination step to thermally decompose the catalyst precursor into Co3O4, (2) after the hydrogen reduction step to activate the catalyst to Co and (3) after the FT reaction. From the study, it was observed that larger pore diameters supported higher turnover frequency; smaller pore diameters yielded larger mole fraction of CoO; XRD on post-reduction and post-FTS catalyst samples indicated significant changes in dispersivity after reduction. In the next section, the catalytic behaviors of unsupported, activated carbon-, alumina-, and SBA-15 mesoporous silica-supported molybdenum nitride catalysts were evaluated for the hydrodeoxygenation of guaiacol (2-methoxy phenol) at 300°C and 5 MPa. The nitride catalysts were prepared by thermal decomposition of bulk and supported ammonium heptamolybdate to form MoO 3 followed by nitridation in either flowing ammonia or a nitrogen/hydrogen mixture. The catalytic properties were strongly affected by the nitriding and purging treatment as well as the physical and chemical properties of support. The overall reaction was influenced by the crystalline phase present in the catalyst, dispersion of molybdenum nitride/oxynitride, and the porosity of the support. The hydrodeoxygenation of guaiacol followed two proposed reaction pathways: demethylation (DME) of guaiacol to form catechol, followed by dehydroxylation to form phenol; or a direct demethoxylation (DMO) to form phenol. The selectivity of the reaction was expressed in terms of the phenol/catechol ratio. Phenol was the predominant product for all the catalysts studied, except for the alumina-supported catalysts (an effect of the alumina support). The results from this thesis are encouraging for the application of Mo nitride based catalysts for hydrodeoxygenation of whole pyrolysis oil.

Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems

DOEpatents

Singleton, Alan H.; Oukaci, Rachid; Goodwin, James G.

2001-01-01

A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a .gamma.-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support wherein the cobalt has been applied to the .gamma.-alumina support by totally aqueous, incipient wetness-type impregnation. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support with an amount of a lanthana promoter effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support produced from boehmite having a crystallite size, in the 021 plane, in the range of from about 30 to about 55 .ANG.ngstrons. In another aspect, the inventive method of producing an attrition-resistant catalyst comprises the step of treating a .gamma.-alumina support, after calcination of and before adding catalytic material to the support, with an acidic solution effective for increasing the attrition resistance of the catalyst. In another aspect, the inventive method of producing an attrition-resistant catalyst support comprises the step of treating calcined .gamma.-alumina with an acidic, aqueous solution effective for increasing the attrition resistance of the .gamma.-alumina.

Supported cluster catalysts synthesized to be small, simple, selective, and stable

DOE PAGES

Guan, Erjia; Fang, Chia-Yu; Yang, Dong; ...

2018-01-01

Molecular metal complexes on supports have drawn wide attention as catalysts offering new properties and opportunities for precise synthesis to make uniform catalytic species that can be understood in depth.

Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalysts to Poisons from High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

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

Burton Davis; Gary Jacobs; Wenping Ma

2011-09-30

There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased.more » Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations. In the second and third years, researchers from the University of Kentucky Center for Applied Energy Research (UK-CAER) continued the project by evaluating the sensitivity of a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to a number of different compounds, including KHCO{sub 3}, NaHCO{sub 3}, HCl, HBr, HF, H{sub 2}S, NH{sub 3}, and a combination of H{sub 2}S and NH{sub 3}. Cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts were also subjected to a number of the same compounds in order to evaluate their sensitivities at different concentration levels of added contaminant.« less

Efficient and Convenient Synthesis of 1,8-Dioxodecahydroacridine Derivatives Using Cu-Doped ZnO Nanocrystalline Powder as a Catalyst under Solvent-Free Conditions

PubMed Central

Alinezhad, Heshmatollah; Mohseni Tavakkoli, Sahar

2013-01-01

A simple and convenient one-step method for synthesis of acridines and their derivatives from condensation of aromatic aldehydes, cyclic diketones, and aryl amines using Cu-doped ZnO nanocrystalline powder as a catalyst is reported. The present protocol provides several advantages such as good yields, short reaction time, easy workup, and simplicity in operation. PMID:24294130

Lanthanide alkyl and silyl compounds: Synthesis, reactivity and catalysts for green

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

Pindwal, Aradhana

2016-01-01

The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl compounds containing tris(dimethylsilyl)methyl ligand and explored their reactivity. This thesis focusses on extending the study of lanthanide alkyl and silyl compounds to develop strategies for their synthesis and explore their reactivity and role as catalysts in processes such as hydrosilylation and cross-dehydrocoupling.

ZnO nanoparticles as an efficient, heterogeneous, reusable, and ecofriendly catalyst for four-component one-pot green synthesis of pyranopyrazole derivatives in water.

PubMed

Sachdeva, Harshita; Saroj, Rekha

2013-01-01

An extremely efficient catalytic protocol for the synthesis of a series of pyranopyrazole derivatives developed in a one-pot four-component approach in the presence of ZnO nanoparticles as heterogeneous catalyst using water as a green solvent is reported. Greenness of the process is well instituted as water is exploited both as reaction media and medium for synthesis of catalyst. The ZnO nanoparticles exhibited excellent catalytic activity, and the proposed methodology is capable of providing the desired products in good yield (85-90%) and short reaction time. After reaction course, ZnO nanoparticles can be recycled and reused without any apparent loss of activity which makes this process cost effective and hence ecofriendly. All the synthesized compounds have been characterized on the basis of elemental analysis, IR, ¹H NMR, and ¹³C NMR spectral studies.

Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

PubMed

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

Combinatorial electrochemical synthesis and screening of Pt-WO3 catalysts for electro-oxidation of methanol

NASA Astrophysics Data System (ADS)

Jayaraman, Shrisudersan; Baeck, Sung-Hyeon; Jaramillo, Thomas F.; Kleiman-Shwarsctein, Alan; McFarland, Eric W.

2005-06-01

An automated system for high-throughput electrochemical synthesis and screening of fuel cell electro-oxidation catalysts is described. This system consists of an electrode probe that contains counter and reference electrodes that can be positioned inside an array of electrochemical cells created within a polypropylene block. The electrode probe is attached to an automated of X-Y-Z motion system. An externally controlled potentiostat is used to apply the electrochemical potential to the catalyst substrate. The motion and electrochemical control are integrated using a user-friendly software interface. During automated synthesis the deposition potential and/or current may be controlled by a pulse program triggered by the software using a data acquisition board. The screening includes automated experiments to obtain cyclic voltammograms. As an example, a platinum-tungsten oxide (Pt-WO3) library was synthesized and characterized for reactivity towards methanol electro-oxidation.

Catalytic Enantioselective Olefin Metathesis in Natural Product Synthesis. Chiral Metal-Based Complexes that Deliver High Enantioselectivity and More

PubMed Central

Malcolmson, Steven J.; Meek, Simon J.; Zhugralin, Adil R.

2012-01-01

Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations. PMID:19967680

Kinetics of NiO and NiCl2 Hydrogen Reduction as Precursors and Properties of Produced Ni/Al2O3 and Ni-Pd/Al2O3 Catalysts

PubMed Central

Sokić, Miroslav; Kamberović, Željko; Nikolić, Vesna; Marković, Branislav; Korać, Marija; Anđić, Zoran; Gavrilovski, Milorad

2015-01-01

The objects of this investigation were the comparative kinetic analysis of the NiO and NiCl2 reduction by hydrogen during an induction period and elimination of the calcination during the synthesis of Ni/Al2O3 catalysts. The effect of temperature and time on NiO and NiCl2 reduction degrees was studied. Avrami I equation was selected as the most favorable kinetic model and used to determine activation energy of the NiO and NiCl2 reduction for the investigated temperature range (623–923 K) and time intervals (1–5 minutes). The investigation enabled reaching conclusions about the reaction ability and rate of the reduction processes. Afterward, Ni/Al2O3 catalysts were obtained by using oxide and chloride precursor for Ni. The catalysts were supported on alumina-based foam and prepared via aerosol route. Properties of the samples before and after low-temperature hydrogen reduction (633 K) were compared. Obtained results indicated that the synthesis of Ni/Al2O3 catalysts can be more efficient if chloride precursor for Ni is directly reduced by hydrogen during the synthesis process, without the calcination step. In addition, Ni-Pd/Al2O3 catalysts with different metal content were prepared by using chloride precursors. Lower reduction temperature was utilized and the chlorides were almost completely reduced at 533 K. PMID:25789335

Fast Optimization of LiMgMnOx/La2O3 Catalysts for the Oxidative Coupling of Methane.

PubMed

Li, Zhinian; He, Lei; Wang, Shenliang; Yi, Wuzhong; Zou, Shihui; Xiao, Liping; Fan, Jie

2017-01-09

The development of efficient catalyst for oxidative coupling of methane (OCM) reaction represents a grand challenge in direct conversion of methane into other useful products. Here, we reported that a newly developed combinatorial approach can be used for ultrafast optimization of La 2 O 3 -based multicomponent metal oxide catalysts in OCM reaction. This new approach integrated inkjet printing assisted synthesis (IJP-A) with multidimensional group testing strategy (m-GT) tactfully takes the place of conventionally high-throughput synthesis-and-screen experiment. Just within a week, 2048 formulated LiMgMnO x -La 2 O 3 catalysts in a 64·8·8·8·8 = 262 144 compositional space were fabricated by IJP-A in a four-round synthesis-and-screen process, and an optimized formulation has been successfully identified through only 4·8 = 32 times of tests via m-GT screening strategy. The screening process identifies the most promising ternary composition region is Li 0-0.48 Mg 0-6.54 Mn 0-0.62 -La 100 O x with an external C 2 yield of 10.87% at 700 °C. The yield of C 2 is two times as high as the pure nano-La 2 O 3 . The good performance of the optimized catalyst formulation has been validated by the manual preparation, which further prove the effectiveness of the new combinatorial methodology in fast discovery of heterogeneous catalyst.

Synthesis of new 2-amino-4H-pyran-3,5-dicarboxylate derivatives using nanocrystalline MIIZr4(PO4)6 ceramics as reusable and robust catalysts under microwave irradiation

NASA Astrophysics Data System (ADS)

Safaei-Ghomi, Javad; Javidan, Abdollah; Ziarati, Abolfazl; Shahbazi-Alavi, Hossein

2015-08-01

In the present paper, we report the successful synthesis of nanocrystalline MIIZr4(PO4)6 ceramics (M: Mn, Ni, Fe, Co). These nano-structures were characterized by X-ray diffraction, scanning electron microscopy, and vibrating sample magnetometer (VSM). Size of nano-structures was in the range of 20-150 nm. Nano-MIIZr4(PO4)6 as an efficient and green catalyst has been used for the preparation of 2-amino-4H-pyran-3,5-dicarboxylate derivatives by the three-component condensation reaction of ethyl cyanoacetate, ethyl acetoacetate, and various aromatic aldehydes under microwave irradiation. Extraordinarily, the best results were obtained using MnZr4(PO4)6 nanocrystallines as an efficient catalyst. This method provides several advantages including easy work-up, excellent yields, short reaction times, using of microwave as green method, recoverability of the catalyst, and little catalyst loading.

An economically viable synthesis of biodiesel from a crude Millettia pinnata oil of Jharkhand, India as feedstock and crab shell derived catalyst.

PubMed

Madhu, Devarapaga; Chavan, Supriya B; Singh, Veena; Singh, Bhaskar; Sharma, Yogesh C

2016-08-01

Biodiesel has emerged as a prominent source to replace petroleum diesel. The cost incurred in the production of biodiesel is higher than that for refining of crude oil to obtain mineral diesel. The heterogeneous catalyst was prepared from crab shells by calcining the crushed mass at 800°C. The solid waste catalyst was characterized with XRD, XPS, BET, SEM-EDS, and FT-IR. Millettia pinnata (karanja) oil extracted from its seeds was used as a feedstock for the synthesis of biodiesel. Biodiesel was synthesized through esterification followed by transesterification in a two-step process. Characterization of biodiesel was done using proton NMR spectroscopy. Reaction parameters such as reaction time, reaction temperature, concentration of catalyst and stirrer speed were optimized. Reusability of catalyst was checked and found that there was no loss of catalytic activity up to five times. Copyright © 2016. Published by Elsevier Ltd.

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

PubMed Central

Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

2016-01-01

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

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

Manna, Kuntal; Ji, Pengfei; Lin, Zekai

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less

Synthesis of novel perfluoroalkylglucosides on zeolite and non-zeolite catalysts.

PubMed

Nowicki, Janusz; Mokrzycki, Łukasz; Sulikowski, Bogdan

2015-04-08

Perfluoroalkylglucosides comprise a very important class of fluorine-containing surfactants. These compounds can be synthesized by using the Fisher reaction, starting directly from glucose and the required perfluoroalcohols. We wish to report on the use of zeolite catalysts of different structure and composition for the synthesis of perfluoroalkylglucosides when using glucose and 1-octafluoropentanol as substrates. Zeolites of different pore architecture have been chosen (ZSM-5, ZSM-12, MCM-22 and Beta). Zeolites were characterized by XRD, nitrogen sorption, scanning electron microscopy (SEM) and solid-state 27Al MAS NMR spectroscopy. The activity of the zeolite catalysts in the glycosidation reaction was studied in a batch reactor at 100 °C below atmospheric pressure. The performance of zeolites was compared to other catalysts, an ion-exchange resin (Purolite) and a montmorillonite-type layered aluminosilicate. The catalytic performance of zeolite Beta was the highest among the zeolites studied and the results were comparable to those obtained over Purolite and montmorillonite type catalysts.

Synthesis of biodiesel from a model waste oil feedstock using a carbon-based solid acid catalyst: reaction and separation.

PubMed

Shu, Qing; Nawaz, Zeeshan; Gao, Jixian; Liao, Yuhui; Zhang, Qiang; Wang, Dezheng; Wang, Jinfu

2010-07-01

A solid acid catalyst that can keep high activity and stability is necessary when low cost feedstocks are utilized for biodiesel synthesis because the reaction medium contains a large amount of water. Three solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt. The structure of these catalysts was characterized by a variety of techniques. A new process that used the coupling of the reaction and separation was employed, which greatly improved the conversion of cottonseed oil (triglyceride) and free fatty acids (FFA) when a model waste oil feedstock was used. The vegetable oil asphalt-based catalyst showed the highest catalytic activity. This was due to the high density and stability of its acid sites, its loose irregular network, its hydrophobicity that prevented the hydration of -OH species, and large pores that provided more acid sites for the reactants. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Silver iodide microstructures of a uniform towerlike shape: morphology purification via a chemical dissolution, simultaneously boosted catalytic durability, and enhanced catalytic performances.

PubMed

Lei, Bin; Zhu, Mingshan; Chen, Penglei; Chen, Chuncheng; Ma, Wanhong; Li, Tiesheng; Liu, Minghua

2014-03-26

The fabrication of microstructures/nanostructures of a uniform yet well-defined morphology has attracted broad interest from a variety of fields of advanced functional materials, especially catalysts. Most of the conventional methods generally suffer from harsh synthesis conditions, requirement of bulky apparatus, or incapability of scalable production, etc. To meet these formidable challenges, it is strongly desired to develop a facile, cost-effective, scalable method to fulfill a morphology purification. By a precipitation reaction between AgNO3 and KI, we report that irregular AgI structures, or their mixture with towerlike AgI architectures could be fabricated. Compared to the former, the mixed structures exhibit enhanced catalytic reactivity toward the photodegradation of Methyl Orange pollutant. However, its catalytic durability, which is one of the most crucial criteria that are required by superior catalysts, is poor. We further show that the irregular structures could be facilely removed from the mixture via a KI-assisted chemical dissolution, producing AgI of a uniform towerlike morphology. Excitingly, after such simple morphology purification, our towerlike AgI displays not only a boosted catalytic durability but also an enhanced catalytic reactivity. Our chemical dissolution-based morphology purification protocol might be extended to other systems, wherein high-quality advanced functional materials of desired properties might be developed.

Ce-Doped NiFe-Layered Double Hydroxide Ultrathin Nanosheets/Nanocarbon Hierarchical Nanocomposite as an Efficient Oxygen Evolution Catalyst.

PubMed

Xu, Huajie; Wang, Bingkai; Shan, Changfu; Xi, Pinxian; Liu, Weisheng; Tang, Yu

2018-02-21

Developing convenient doping to build highly active oxygen evolution reaction (OER) electrocatalysts is a practical process for solving the energy crisis. Herein, a facile and low-cost in situ self-assembly strategy for preparing a Ce-doped NiFe-LDH nanosheets/nanocarbon (denoted as NiFeCe-LDH/CNT, LDH = layered double hydroxide and CNT = carbon nanotube) hierarchical nanocomposite is established for enhanced OER, in which the novel material provides its overall advantageous structural features, including high intrinsic catalytic activity, rich redox properties, high, flexible coordination number of Ce 3+ , and strongly coupled interface. Further experimental results indicate that doped Ce into NiFe-LDH/CNT nanoarrays brings about the reinforced specific surface area, electrochemical surface area, lattice defects, and the electron transport between the LDH nanolayered structure and the framework of CNTs. The effective synergy prompts the NiFeCe-LDH/CNT nanocomposite to possess superior OER electrocatalytic activity with a low onset potential (227 mV) and Tafel slope (33 mV dec -1 ), better than the most non-noble metal-based OER electrocatalysts reported. Therefore, the combination of the remarkable catalytic ability and the facile normal temperature synthesis conditions endows the Ce-doped LDH nanocomposite as a promising catalyst to expand the field of lanthanide-doped layered materials for efficient water-splitting electrocatalysis with scale-up potential.

Synthesis and Hydrodeoxygenation Properties of Ruthenium Phosphide Catalysts

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

Bowker, Richard H.; Smith, Mica C.; Pease, Melissa

2011-07-01

Ru2P/SiO2 and RuP/SiO2 catalysts were prepared by the temperature-programmed reduction (TPR) of uncalcined precursors containing hypophosphite ion (H2PO2-) as the phosphorus source. The Ru2P/SiO2 and RuP/SiO2 catalysts had small average particle sizes (~4 nm) and high CO chemisorption capacities (90-110 umol/g). The Ru phosphide catalysts exhibited similar or higher furan (C4H4O) hydrodeoxygenation (HDO) activities than did a Ru/SiO2 catalyst, and the phosphide catalysts favored C4 hydrocarbon products while the Ru metal catalyst produced primarily C3 hydrocarbons.

Direct synthesis of Fe3 C-functionalized graphene by high temperature autoclave pyrolysis for oxygen reduction.

PubMed

Hu, Yang; Jensen, Jens Oluf; Zhang, Wei; Huang, Yunjie; Cleemann, Lars N; Xing, Wei; Bjerrum, Niels J; Li, Qingfeng

2014-08-01

We present a novel approach to direct fabrication of few-layer graphene sheets with encapsulated Fe3 C nanoparticles from pyrolysis of volatile non-graphitic precursors without any substrate. This one-step autoclave approach is facile and potentially scalable for production. Tested as an electrocatalyst, the graphene-based composite exhibited excellent catalytic activity towards the oxygen reduction reaction in alkaline solution with an onset potential of ca. 1.05 V (vs. the reversible hydrogen electrode) and a half-wave potential of 0.83 V, which is comparable to the commercial Pt/C catalyst. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phosphine-free Stille-Migita chemistry for the mild and orthogonal modification of DNA and RNA.

PubMed

Krause, André; Hertl, Alexander; Muttach, Fabian; Jäschke, Andres

2014-12-08

An optimized catalyst system of [Pd2 (dba)3 ] and AsPh3 efficiently catalyzes the Stille reaction between a diverse set of functionalized stannanes and halogenated mono-, di- and oligonucleotides. The methodology allows for the facile conjugation of short and long nucleic acid molecules with moieties that are not compatible with conventional chemical or enzymatic synthesis, among them acid-, base-, or fluoride-labile protecting groups, fluorogenic and synthetically challenging moieties with good to near-quantitative yields. Notably, even azides can be directly introduced into oligonucleotides and (deoxy)nucleoside triphosphates, thereby giving direct access to "clickable" nucleic acids. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective Oxidation of n-Hexane by Cu (II) Nanoclusters Supported on Nanocrystalline Zirconia Catalyst.

PubMed

Acharyya, Shankha Shubhra; Ghosh, Shilpi; Adak, Shubhadeep; Singh, Raghuvir; Saran, Sandeep; Bal, Rajaram

2015-08-01

Cu (II) nanoclusters supported on nanocrystalline zirconia catalyst (with size ~15 nm), was prepared by using cationic surfactant cetyltrimethylammonium in a hydrothermal synthesis method. The catalyst was characterized by XRD, XPS, TGA, SEM, TEM, FTIR and ICP-AES. The catalyst was found to be efficient in selective oxidation of n-hexane to 2-hexanol. An n-hexane conversion of 55%, with a 2-hexanol selectivity of 70% was achieved over this catalyst in liquid phase, without the use of any solvent. The catalyst can be reused several times without any significant activity loss.

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

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

Alptekin, Gokhan

2013-02-15

Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investingmore » in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H 2S, NH 3, HCN, AsH 3, PH 3, HCl, NaCl, KCl, AS 3, NH 4NO 3, NH 4OH, KNO 3, HBr, HF, and HNO 3) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.« less

A Mixed-Ligand Chiral Rhodium(II) Catalyst Enables the Enantioselective Total Synthesis of Piperarborenine B.

PubMed

Panish, Robert A; Chintala, Srinivasa R; Fox, Joseph M

2016-04-11

A novel, mixed-ligand chiral rhodium(II) catalyst, Rh2(S-NTTL)3(dCPA), has enabled the first enantioselective total synthesis of the natural product piperarborenine B. A crystal structure of Rh2(S-NTTL)3(dCPA) reveals a "chiral crown" conformation with a bulky dicyclohexylphenyl acetate ligand and three N-naphthalimido groups oriented on the same face of the catalyst. The natural product was prepared on large scale using rhodium-catalyzed bicyclobutanation/ copper-catalyzed homoconjugate addition chemistry in the key step. The route proceeds in ten steps with an 8% overall yield and 92% ee. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Synthesis of three-dimensionally ordered macro-/mesoporous Pt with high electrocatalytic activity by a dual-templating approach

NASA Astrophysics Data System (ADS)

Zhang, Chengwei; Yang, Hui; Sun, Tingting; Shan, Nannan; Chen, Jianfeng; Xu, Lianbin; Yan, Yushan

2014-01-01

Three dimensionally ordered macro-/mesoporous (3DOM/m) Pt catalysts are fabricated by chemical reduction employing a dual-templating synthesis approach combining both colloidal crystal (opal) templating (hard-templating) and lyotropic liquid crystal templating (soft-templating) techniques. The macropore walls of the prepared 3DOM/m Pt exhibit a uniform mesoporous structure composed of polycrystalline Pt nanoparticles. Both the size of the mesopores and Pt nanocrystallites are in the range of 3-5 nm. The 3DOM/m Pt catalyst shows a larger electrochemically active surface area (ECSA), and higher catalytic activity as well as better poisoning tolerance for methanol oxidation reaction (MOR) than the commercial Pt black catalyst.

Fischer-Tropsch synthesis from a low H/sub 2/:CO gas in a dry fluidized-bed system. Volume 2. Development of microreactor systems for unsteady-state Fischer-Tropsch synthesis. Final technical report. [408 references

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

Whiting, G.K.; Liu, Y.A.; Squires, A.M.

1986-10-01

Vibrofluidized microreactor systems have been developed for studies of unsteady-state Fischer-Tropsch synthesis. This development is aimed at preventing carbon deposition on a fused-iron catalyst in a novel reactor called the ''heat tray.'' This reactor involves a supernatant gas flowing over a shallow fluidized bed of catalyst particles. Three systems were built: (1) a vibrofluidized-bed microreactor system for obtaining baseline carbon deposition information under industrially important reaction conditions; (2) a sliding-plug vibrofluidized-bed microreactor system for rapid switching of feed gases in the F-T synthesis; and (3) a cold-flow microreactor model for studying the gas mixing characteristics of the sliding-plug vibrofluidized-bed microreactor.more » The results show that catalyst defluidization occurred under steady-state synthesis conditions below 395 C using a feed gas of H/sub 2//CO ratio of 2:1 or less. Above 395 C, the probability of hydrocarbon chain growth (..cap alpha.. < 0.50 to prevent accumulation of high-molecular-weight species that cause defluidization. Carbon deposition was rapid above 395 C when a feed gas of H/sub 2//CO ratio of 2:1 or less was used. Cold-flow microreactor model studies show that rapid (on the order of seconds), quantitative switching of feed gases over a vibrofluidized bed of catalyst could be achieved. Vibrofluidization of the catalyst bed induced little backmixing of feed gas over the investigated flow-rate range of 417 to 1650 actual mm/sup 3//s. Further, cold-flow microreactor model studies showed intense solid mixing when a bed of fused-iron catalyst (150 to 300 microns) was vibrofluidized at 24 cycles per second with a peak-to-peak amplitude of 4 mm. The development of the microreactor systems provided an easy way of accurately determining integral fluid-bed kinetics in a laboratory reactor. 408 refs., 156 figs., 27 tabs.« less

Sensitivity of Fischer-Tropsch Synthesis and Water-Gas Shift Catalystes to Poisons form High-Temperature High-Pressure Entrained-Flow (EF) Oxygen-Blown Gasifier Gasification of Coal/Biomass Mixtures

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

Burton Davis; Gary Jacobs; Wenping Ma

2009-09-30

There has been a recent shift in interest in converting not only natural gas and coal derived syngas to Fischer-Tropsch synthesis products, but also converting biomass-derived syngas, as well as syngas derived from coal and biomass mixtures. As such, conventional catalysts based on iron and cobalt may not be suitable without proper development. This is because, while ash, sulfur compounds, traces of metals, halide compounds, and nitrogen-containing chemicals will likely be lower in concentration in syngas derived from mixtures of coal and biomass (i.e., using entrained-flow oxygen-blown gasifier gasification gasification) than solely from coal, other compounds may actually be increased.more » Of particular concern are compounds containing alkali chemicals like the chlorides of sodium and potassium. In the first year, University of Kentucky Center for Applied Energy Research (UK-CAER) researchers completed a number of tasks aimed at evaluating the sensitivity of cobalt and iron-based Fischer-Tropsch synthesis (FT) catalysts and a commercial iron-chromia high temperature water-gas shift catalyst (WGS) to alkali halides. This included the preparation of large batches of 0.5%Pt-25%Co/Al{sub 2}O{sub 3} and 100Fe: 5.1Si: 3.0K: 2.0Cu (high alpha) catalysts that were split up among the four different entities participating in the overall project; the testing of the catalysts under clean FT and WGS conditions; the testing of the Fe-Cr WGS catalyst under conditions of co-feeding NaCl and KCl; and the construction and start-up of the continuously stirred tank reactors (CSTRs) for poisoning investigations.« less

Alkali promoted molybdenum (IV) sulfide based catalysts, development and characterization for alcohol synthesis from carbon monoxide and hydrogen

NASA Astrophysics Data System (ADS)

Molina, Belinda Delilah

For more than a century transition metal sulfides (TMS) have been the anchor of hydro-processing fuels and upgrading bitumen and coal in refineries worldwide. As oil supplies dwindle and environmental laws become more stringent, there is a greater need for cleaner alternative fuels and/or synthetic fuels. The depletion of oil reserves and a rapidly increasing energy demand worldwide, together with the interest to reduce dependence on foreign oil makes alcohol production for fuels and chemicals via the Fischer Tropsch synthesis (FTS) very attractive. The original Fischer-Tropsch (FT) reaction is the heart of all gas-to-liquid technologies; it creates higher alcohols and hydrocarbons from CO/H2 using a metal catalyst. This research focuses on the development of alkali promoted MoS2-based catalysts to investigate an optimal synthesis for their assistance in the production of long chain alcohols (via FTS) for their use as synthetic transportation liquid fuels. Properties of catalytic material are strongly affected by every step of the preparation together with the quality of the raw materials. The choice of a laboratory method for preparing a given catalyst depends on the physical and chemical characteristics desired in the final composition. Characterization methods of K0.3/Cs0.3-MoS2 and K0.3 /Cs0.3-Co0.5MoS2 catalysts have been carried out through Scanning Electron Microscopy (SEM), BET porosity and surface analysis, Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD). Various characterization methods have been deployed to correlate FTS products versus crystal and morphological properties of these heterogeneous catalysts. A lab scale gas to liquid system has been developed to evaluate its efficiency in testing FT catalysts for their production of alcohols.

An Eco-Friendly Improved Protocol for the Synthesis of Bis(3-indolyl)methanes Using Poly(4-vinylpyridinium)hydrogen Sulfate as Efficient, Heterogeneous, and Recyclable Solid Acid Catalyst

PubMed Central

Banothu, Janardhan; Gali, Rajitha; Velpula, Ravibabu; Bavantula, Rajitha; Crooks, Peter A.

2013-01-01

Highly efficient and eco-friendly protocol for the synthesis of bis(3-indolyl)methanes by the electrophilic substitution reaction of indole with aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate was described. Excellent yields, shorter reaction times, simple work-up procedure, avoiding hazardous organic solvents, and reusability of the catalyst are the most obvious advantages of this method. PMID:24052864

Toward Small-Diameter Carbon Nanotubes Synthesized from Captured Carbon Dioxide: Critical Role of Catalyst Coarsening.

PubMed

Douglas, Anna; Carter, Rachel; Li, Mengya; Pint, Cary L

2018-06-06

Small-diameter carbon nanotubes (CNTs) often require increased sophistication and control in synthesis processes, but exhibit improved physical properties and greater economic value over their larger-diameter counterparts. Here, we study mechanisms controlling the electrochemical synthesis of CNTs from the capture and conversion of ambient CO 2 in molten salts and leverage this understanding to achieve the smallest-diameter CNTs ever reported in the literature from sustainable electrochemical synthesis routes, including some few-walled CNTs. Here, Fe catalyst layers are deposited at different thicknesses onto stainless steel to produce cathodes, and atomic layer deposition of Al 2 O 3 is performed on Ni to produce a corrosion-resistant anode. Our findings indicate a correlation between the CNT diameter and Fe metal layer thickness following electrochemical catalyst reduction at the cathode-molten salt interface. Further, catalyst coarsening during long duration synthesis experiments leads to a 2× increase in average diameters from 3 to 60 min durations, with CNTs produced after 3 min exhibiting a tight diameter distribution centered near ∼10 nm. Energy consumption analysis for the conversion of CO 2 into CNTs demonstrates energy input costs much lower than the value of CNTs-a concept that strictly requires and motivates small-diameter CNTs-and is more favorable compared to other costly CO 2 conversion techniques that produce lower-value materials and products.

Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G; Liu, Shetian

2014-12-09

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.

Exploring green catalysts for production of biofuels and value added chemicals for renewable and sustainable energy future

NASA Astrophysics Data System (ADS)

Budhi, Sridhar

Porous silica have attracted significant attention in the past few decades due to their unique textural properties. They were extensively investigated for applications in catalysis, separation, environmental remediation and drug delivery. We have investigated the porous metal incorporated silica in the synthetic as well as catalytic perspectives. The synthesis of metal incorporated mesoporous silica via co-condensation such as SBA-15, KIT-5 are still challenging as it involves acidic synthetic route. Synthesis in high acidity conditions affects the incorporation of metal in silica due to high dissolution of metal precursors and breaking of metal oxygen and silica bond. The research presented here demonstrates an efficient way to incorporate metals by addition of diammonium hydrogen phosphate along with metal precursor during the synthesis. The incorporation efficiency has increased 2-3 times with this approach. Catalytic studies were performed to support our hypothesis. Such synthesized molybdenum incorporated mesoporous silica were investigated as catalyst for fast pyrolysis. When molydenum incorporated in silica was used as catalyst for fast pyrolysis of pine, it selectively produced furans (furan, methylfuran and dimethylfuran). Furans are considered value-added chemicals and can be used as a blendstock for diesel/jet grade fuel. The catalyst was very stable to harsh pyrolysis conditions and had a longer life before deactivation when compared with traditional zeolites. Further, this catalyst did not produce aromatic hydrocarbons in significant yields unlike zeolites. The origin of the furans was determined to be biopolymer cellulose and the selectivity for furans are attributed to low catalyst acidity. The effect of silica to alumina ratio (SAR) of beta-zeolite was investigated ranging to elucidate the relationship between the of number of acid sites on product speciation and catalyst deactivation on catalysts supplied by Johnson Matthey. The catalyst with low SAR (more acid sites) produced predominantly aromatic hydrocarbons and olefins with no detectable oxygen containing species. In contrary, the catalyst with high SAR (fewer acid sites) produced a suite of oxygenated products such as furans, phenols and cresols. The coke deposited on each catalyst and the yield of aromatic hydrocarbons were in direct proportion to the number of acid sites. When catalysts were active, the biomass selectivity towards hydrocarbons and amount of coke were constant regardless of SAR.

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, Nancy E.

1991-01-01

A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, Nancy E.

1992-01-01

A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Synthesis of Enantioenriched Indolines by a Conjugate Addition/Asymmetric Protonation/Aza-Prins Cascade Reaction

PubMed Central

Daniels, Blake E.; Ni, Jane; Reisman, Sarah E.

2016-01-01

A conjugate addition/asymmetric protonation/aza-Prins cascade reaction has been developed for the enantioselective synthesis of fused polycyclic indolines. A catalyst system generated from ZrCl4 and 3,3’-dibromo-BINOL enables the synthesis of a range of polycyclic indolines in good yields and high enantioselectivity. A key finding is the use of TMSCl and 2,6-dibromophenol as a stoichiometric source of HCl to facilitate catalyst turnover. This transformation is the first in which a ZrCl4•BINOL complex serves as a chiral Lewis acid-assisted Brønsted acid. PMID:26844668

POROUS ALUMINOPHOSPHATES :From Molecular Sieves to Designed Acid Catalysts

NASA Astrophysics Data System (ADS)

Pastore, H. O.; Coluccia, S.; Marchese, L.

2005-08-01

This review covers the synthesis, characterization, and physico-chemical properties of microporous and mesoporous aluminophosphates and silicoaluminophosphates molecular sieves. Particular emphasis is given to the materials that have found applications as acid catalysts. We consider the evolution of the synthesis procedures from the first discoveries to the current methodologies and give perspectives for new possible synthesis strategies. Emphasis is given to the use of specially prepared precursors/reactants designed for the use as molecular sieves. Experimental (especially MAS-NMR and FTIR spectroscopy) and theoretical approaches to the description of the Si insertion into the ALPO framework and to the acidic properties of SAPOs and MeAPSOs materials are discussed.

Effect of zeolite catalyst on sugar dehydration for 5-Hydroxymethylfurfural synthesis

NASA Astrophysics Data System (ADS)

Mostapha, Marhaini; Jahar, Noorhasmiera Abu; Chin, Siew Xian; Jaafar, Sharifah Nabihah Syed; Zakaria, Sarani; Aizat, Wan M.; Azizan, Kamalrul Azlan

2016-11-01

The effectiveness in the dehydration of sugars into 5-Hydroxymethylfurfural is related to the catalyst existence. A comprehensive synthesis of 5-Hydroxymethylfurfural from fructose, glucose and sucrose (3.73 mmol) with and without addition zeolite catalyst was performed in this study. The reactions were carried out in water-methanol solvent system for 3 hours reaction time at 180°C temperature. The catalytic results from HPLC showed that the reaction with zeolite increases the yield of 5-Hydroxymethylfurfural with 51.72 %, 34.01% and 50.10% for fructose, glucose and sucrose respectively. The study suggests that zeolites promote the isomerization of glucose into fructose to occur and simultaneously catalyze the dehydration of fructose into 5-Hydroxymethylfurfural. Only slight changes on FT-IR spectra of use zeolite after the reaction was observed. Thus suggest that zeolite was a potential catalyst for catalytic reaction for the conversion of sugar into 5-Hydroxymethylfurfural.

Bio‐palladium: from metal recovery to catalytic applications

PubMed Central

De Corte, Simon; Hennebel, Tom; De Gusseme, Bart; Verstraete, Willy; Boon, Nico

2012-01-01

Summary While precious metals are available to a very limited extent, there is an increasing demand to use them as catalyst. This is also true for palladium (Pd) catalysts and their sustainable recycling and production are required. Since Pd catalysts exist nowadays mostly under the form of nanoparticles, these particles need to be produced in an environment‐friendly way. Biological synthesis of Pd nanoparticles (‘bio‐Pd’) is an innovative method for both metal recovery and nanocatalyst synthesis. This review will discuss the different bio‐Pd precipitating microorganisms, the applications of the catalyst (both for environmental purposes and in organic chemistry) and the state of the art of the reactors based on the bio‐Pd concept. In addition, some main challenges are discussed, which need to be overcome in order to create a sustainable nanocatalyst. Finally, some outlooks for bio‐Pd in environmental technology are presented. PMID:21554561

Palladium-tin catalysts for the direct synthesis of H 2O 2 with high selectivity

DOE PAGES

Freakley, Simon J.; He, Qian; Harrhy, Jonathan H.; ...

2016-02-25

The direct synthesis of hydrogen peroxide (H 2O 2 ) from H 2 and O 2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H 2O 2 . This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. In conclusion, we show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriatemore » second metal oxide component, and we set out the design principles for producing high-selectivity Pd-based catalysts for direct H 2O 2 production that do not contain gold.« less

A heterogeneous Pd-Bi/C catalyst in the synthesis of L-lyxose and L-ribose from naturally occurring D-sugars.

PubMed

Fan, Ao; Jaenicke, Stephan; Chuah, Gaik-Khuan

2011-10-26

A critical step in the synthesis of the rare sugars, L-lyxose and L-ribose, from the corresponding D-sugars is the oxidation to the lactone. Instead of conventional oxidizing agents like bromine or pyridinium dichromate, it was found that a heterogeneous catalyst, Pd-Bi/C, could be used for the direct oxidation with molecular oxygen. The composition of the catalyst was optimized and the best results were obtained with 5 : 1 atomic ratio of Pd : Bi. The overall yields of the five-step procedure to L-ribose and L-lyxose were 47% and 50%, respectively. The synthetic procedure is advantageous from the viewpoint of overall yield, reduced number of steps, and mild reaction conditions. Furthermore, the heterogeneous oxidation catalyst can be easily separated from the reaction mixture and reused with no loss of activity.

Synthesis of glycerol mono-laurate from lauric acid and glycerol for food antibacterial additive

NASA Astrophysics Data System (ADS)

Setianto, W. B.; Wibowo, T. Y.; Yohanes, H.; Illaningtyas, F.; Anggoro, D. D.

2017-05-01

Synthesis of glycerol mono-laurate (GML) has been performed using esterification reaction of glycerol and lauric acid. The reaction was performed at the condition of temperature of 120-140 °C within 7 hour, variation of molar ratio of glycerol - lauric acid, and was using heterogeneous catalyst of zeolist Y. Without catalyst dealumination the maximum acid conversion was 78%, with GML contained in the sample was 38.6%, and it was obtained at the reaction condition of 140 oC, 15wt% catalyst, and 8:1 molar ratio of glycerol - lauric acid. At the same condition, using dealuminated catalyst, the maximum acid conversion was increased up to 98%, with GML contained in the sample was 50.4%. The GML antibacterial activity was examined. It was observed that the GML has antibacterial activity against gram positive bacterial such as B. cereus and S. aureus.

Carbon nanotubes shynthesis in fluidized bed reactor equipped with a cyclone

NASA Astrophysics Data System (ADS)

Setyopratomo, P.; Sudibandriyo, M.; Wulan, P. P. D. K.

2018-03-01

This work aimed to observe the performance of a fluidized bed reactor which was equipped with a cyclone in the synthesis of carbon nanotubes (CNT) by chemical vapor deposition. Liquefied petroleum gas with a constant volumetric flow rate of 1940 cm3/minutes was fed to the reactor as a carbon source, while a combination of metal components of Fe-Co-Mo supported on MgO was used as catalyst. The CNT synthesis was carried out at a reaction temperature which was maintained at around 800 – 850 °C for 1 hour. The CNT yield was decreased sharply when the catalyst feed was increased. The carbon efficiency is directly proportional to the mass of catalyst fed. It was found from the experiment that the mass of as-grown CNT increased in proportion to the increase of the catalyst mass fed. A sharp increase of the mass percentage of carbon nanotubes entrainment happened when the catalyst feed was raised from 3 to 7 grams. Agglomerates of carbon nanotubes have been formed. The agglomerates composed of mutually entangled carbon nanotubes which have an outer diameter range 8 – 14 nm and an inner diameter range 4 – 10 nm, which confirmed that the multi-walled carbon nanotubes were formed in this synthesis. It was found that the mesopores dominate the pore structure of the CNT product and contribute more than 90 % of the total pore volume.

Heterogeneous Pd catalysts as emulsifiers in Pickering emulsions for integrated multistep synthesis in flow chemistry.

PubMed

Hiebler, Katharina; Lichtenegger, Georg J; Maier, Manuel C; Park, Eun Sung; Gonzales-Groom, Renie; Binks, Bernard P; Gruber-Woelfler, Heidrun

2018-01-01

Within the "compartmentalised smart factory" approach of the ONE-FLOW project the implementation of different catalysts in "compartments" provided by Pickering emulsions and their application in continuous flow is targeted. We present here the development of heterogeneous Pd catalysts that are ready to be used in combination with biocatalysts for catalytic cascade synthesis of active pharmaceutical ingredients (APIs). In particular, we focus on the application of the catalytic systems for Suzuki-Miyaura cross-coupling reactions, which is the key step in the synthesis of the targeted APIs valsartan and sacubitril. An immobilised enzyme will accomplish the final product formation via hydrolysis. In order to create a large interfacial area for the catalytic reactions and to keep the reagents separated until required, the catalyst particles are used to stabilise Pickering emulsions of oil and water. A set of Ce-Sn-Pd oxides with the molecular formula Ce 0.99- x Sn x Pd 0.01 O 2-δ ( x = 0-0.99) has been prepared utilising a simple single-step solution combustion method. The high applicability of the catalysts for different functional groups and their minimal leaching behaviour is demonstrated with various Suzuki-Miyaura cross-coupling reactions in batch as well as in continuous flow employing the so-called "plug & play reactor". Finally, we demonstrate the use of these particles as the sole emulsifier of oil-water emulsions for a range of oils.

Catalysis and Sonocatalysis for the Synthesis of Biofuels

NASA Astrophysics Data System (ADS)

Deshmane, Vishwanath Ganpat

The goal of this study was to investigate the synthesis of biofuels from edible and non-edible sources using commercially available and laboratory synthesized heterogeneous catalysts with and without the aid of ultrasound. The transesterification of soybean oil using calcium methoxide as solid base catalyst and the process parameters affecting the yield of biodiesel such as the catalyst concentration, methanol/oil molar ratio and the reaction temperature were investigated in detail. The kinetics of this process with and without ultrasound was also evaluated using a previously reported kinetic and mass transfer model for heterogeneous systems. Nanocrystalline mesoporous ZrO 2 with high surface area and thermal stability was synthesized using ethylene diamine as precipitating agent. Sulfonation of obtained Zr(OH) 2 at different digestion times was carried out using sulfuric acid and chlorosulfonic acid as the sulfonating agents and the effects of process parameters including digestion time, pH, precursor concentration and calcination temperature on structural, textural and catalytic properties were studied. Parametric and optimization (Taguchi statistical methodology) studies were carried out to evaluate the effects of cellulase, cellobiase, cellulose concentration and ultrasonic power on the intensification of cellulose hydrolysis to glucose. The catalysts and cellulose were characterized by using BET, NH3-TPD, XRD, SEM, TGA-DSC, EDX and FTIR. The results of these studies suggest that synthesis of biofuels can be improved by heterogeneous catalysts and ultrasound with potential reduction in production costs compared with conventional methods.

Facile Synthesis of Core/Shell-like NiCo2O4-Decorated MWCNTs and its Excellent Electrocatalytic Activity for Methanol Oxidation

PubMed Central

Ko, Tae-Hoon; Devarayan, Kesavan; Seo, Min-Kang; Kim, Hak-Yong; Kim, Byoung-Suhk

2016-01-01

The design and development of an economic and highly active non-precious electrocatalyst for methanol electrooxidation is challenging due to expensiveness of the precursors as well as processes and non-ecofriendliness. In this study, a facile preparation of core-shell-like NiCo2O4 decorated MWCNTs based on a dry synthesis technique was proposed. The synthesized NiCo2O4/MWCNTs were characterized by infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and selected area energy dispersive spectrum. The bimetal oxide nanoparticles with an average size of 6 ± 2 nm were homogeneously distributed onto the surface of the MWCNTs to form a core-shell-like nanostructure. The NiCo2O4/MWCNTs exhibited excellent electrocatalytic activity for the oxidation of methanol in an alkaline solution. The NiCo2O4/MWCNTs exhibited remarkably higher current density of 327 mA/cm2 and a lower onset potential of 0.128 V in 1.0 M KOH with as high as 5.0 M methanol. The impressive electrocatalytic activity of the NiCo2O4/MWCNTs is promising for development of direct methanol fuel cell based on non-Pt catalysts. PMID:26828633

Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G.; Ranaweera, Samantha A.; Henry, William P.

2016-08-02

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality distillates, gasoline components, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel supported bimetallic ion complex catalyst for conversion, and provides methods of preparing such novel catalysts and use of the novel catalysts in the process and system of the invention.

Synthesis and characterization of Sn/zeolite and catalytic activity test in the esterification reaction of sludge oil

NASA Astrophysics Data System (ADS)

Alimuddin, Andi Hairil; Usman, Thamrin; Wahyuni, Nelly; Rudiyansyah, Prawatya, Yopa Eka; Astar, Ismail; Yustira, Yudi

2017-03-01

Synthesis of Sn-Zeolite has been made to use for esterification reaction of free fatty acids in sludge oil. Catalyst characterization was accomplished using X-Ray Diffraction (XRD), X-Ray Flourecence (XRF), and Fourier Transform Infra Red (FTIR). Catalyst Sn/zeolite was synthesized by impregnated Sn of SnCl2 into the zeolite. The amount of Sn impregnated base on the value of cation exchange capacity (CEC) of zeolites. Esterification reaction of fatty acids from sludge oil using Sn/Zeolite catalyst was did by variated the reaction time. XRD analysis results showed that the catalyst Sn/zeolite was dominated by modernit and quartz. XRF analysis results was increasing amount of Sn metal and the Si/Al ratio on Sn/zeolite catalyst along with addition of Sn metal. FTIR analysis results showed that the catalyst synthesized had Bronsted acid side (the spectrum 1639.4; 1656.7; 1654.8 cm-1) and the Lewis acid (spectrum 1400.2 and 1402.2 cm-1). The results showed that the optimum conditions of esterification reaction in 4 hours reaction time, 5% concentration of the catalyst, and molar ratio was about 1:10 with a conversion percentage of products reached 96.00%, which can be achieved with a ratio was about 4:1 between Sn and zeolite on Sn/zeolite catalyst.

Gary Grim | NREL

Science.gov Websites

@nrel.gov | 303-384-7781 Research Interests Synthesis and characterization of heterogeneous catalysts for Chemie (2014) "Synthesis and Characterization of sI Clathrate Hydrates Containing Hydrogen," J

Mathematical Model of Heat Transfer in the Catalyst Granule with Point Reaction Centers

NASA Astrophysics Data System (ADS)

Derevich, I. V.; Fokina, A. Yu.

2018-01-01

This paper considers a catalyst granule with a porous ceramic chemically inert base and active point centers, at which an exothermic reaction of synthesis takes place. The rate of a chemical reaction depends on temperature by the Arrhenius law. The heat is removed from the catalyst granule surface to the synthesis products by heat transfer. Based on the idea of self-consistent field, a closed system of equations is constructed for calculating the temperatures of the active centers. As an example, a catalyst granule of the Fischer-Tropsch synthesis with active metallic cobalt particles is considered. The stationary temperatures of the active centers are calculated by the timedependent technique by solving a system of ordinary differential equations. The temperature distribution inside the granule has been found for the local centers located on one diameter of the granule and distributed randomly in the granule's volume. The existence of the critical temperature inside the reactor has been established, the excess of which leads to substantial superheating of local centers. The temperature distribution with local reaction centers differs qualitatively from the granule temperature calculated in the homogeneous approximation. The results of calculations are given.

Chiral-catalyst-based convergent synthesis of HIV protease inhibitor GRL-06579A.

PubMed

Mihara, Hisashi; Sohtome, Yoshihiro; Matsunaga, Shigeki; Shibasaki, Masakatsu

2008-02-01

Catalytic asymmetric synthesis of GRL-06579A (1), an HIV-1 protease inhibitor effective against multi-protease-inhibitor-resistant viruses, is described. A convergent strategy that utilizes heterobimetallic multifunctional catalysts developed in our group is a key feature of the synthesis. The chirality of the bicyclic tetrahydrofuran unit of 1 was introduced through Al-Li-bis(binaphthoxide) (ALB) catalyst-controlled Michael addition of dimethyl malonate to racemic 4-O-protected cyclopentenone. ALB afforded not only the trans adduct with up to 96% ee from a matched substrate through kinetic resolution, but also the cis adduct with 99% ee through a catalyst-controlled Michael addition to a mismatched substrate. The Michael addition to produce the unusual cis adduct is described in detail. The framework of the bicyclic tetrahydrofuran was constructed by an intramolecular oxy-Michael reaction. The amino alcohol unit was constructed by an La-Li3-tris(binaphthoxide) (LLB)-catalyzed diastereoselective nitroaldol reaction of N-Boc aldehyde (Boc = tert-butoxycarbonyl) derived from L-phenylalanine. LLB promoted the nitroaldol reaction without racemization of the chiral aldehyde to give the nitroaldol adduct in 85% yield and with 93:7 diastereoselectivity and over 99% ee.

Sol-gel (template) synthesis of macroporous Mo-based catalysts for hydrothermal oxidation of radionuclide-organic complexes

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Palamarchuk, M. S.; Mayorov, V. Yu; Modin, E. B.; Portnyagin, A. S.; Sokol'nitskaya, T. A.; Belov, A. A.; Tananaev, I. G.; Avramenko, V. A.

2017-07-01

Molybdenum compounds are industrially demanding as heterogeneous catalysts for oxidation of various organic substances. Highly porous structure of molybdenum-containing catalysts avoids surface's colmatation and prevents blocking catalytic sites that makes these materials play a key role in processes of hydrothermal oxidation of radionuclide organic complexes. The study presents an original way of sol-gel synthesis of new macroporous molybdenum compounds using ;core-shell; colloid template (polymer latex) as poreforming agent. We have described three individual routs of template removal via thermal decomposition to obtain porous materials based on molybdenum compounds. Thermal treatment conditions (temperature, gaseous atmosphere) have been studied with respect to their influence on composition, structure and catalytic properties of synthesized molybdenum systems. The optimal way to synthesis of crystal molybdenum (VI) oxide with ordered porous structure (mean pore size 100-160 nm) has been suggested. Catalytic properties of macroporous molybdenum materials have been investigated in the process of liquid phase and hydrothermal oxidation of such organic substances thiazine and stable Co-EDTA complex. It was shown that macroporous molybdenum oxides could be applied as prospective catalysts for hydrothermal oxidation of organic radionuclide complexes during the processing of radioactive waste.

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

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

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

DOE PAGES

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.; ...

2017-08-24

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Synthesis Under 'Greener' Conditions: Role of Sustainable Nano-Catalysts

EPA Science Inventory

The presentation summarizes our recent activity in chemical synthesis involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a varie...

Greener Synthesis and Chemical transformations Using Sustainable Alternative Methods and Applications of Nano-Catalysts

EPA Science Inventory

The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, namely greener reaction medium in aqueous or solventfree conditions and using alternative activation via microwave or photocatalytic activation. Eco-friendly synthesis of nanoma...

Fabrication of hierarchical CoP nanosheet@microwire arrays via space-confined phosphidation toward high-efficiency water oxidation electrocatalysis under alkaline conditions.

PubMed

Ji, Xuqiang; Zhang, Rong; Shi, Xifeng; Asiri, Abdullah M; Zheng, Baozhan; Sun, Xuping

2018-05-03

In spite of recent advances in the synthesis of transition metal phosphide nanostructures, the simple fabrication of hierarchical arrays with more accessible active sites still remains a great challenge. In this Communication, we report a space-confined phosphidation strategy toward developing hierarchical CoP nanosheet@microwire arrays on nickel foam (CoP NS@MW/NF) using a Co(H2PO4)2·2H3PO4 microwire array as the precursor. The thermally stable nature of the anion in the precursor is key to hierarchical nanostructure formation. When used as a 3D electrode for water oxidation electrocatalysis, such CoP NS@MW/NF needs an overpotential as low as 296 mV to drive a geometrical catalytic current density of 100 mA cm-2 in 1.0 M KOH, outperforming all reported Co phosphide catalysts in alkaline media. This catalyst also shows superior long-term electrochemical durability, maintaining its activity for at least 65 h. This study offers us a general method for facile preparation of hierarchical arrays for applications.

Constructing hierarchical interfaces: TiO 2-supported PtFe-FeO x nanowires for room temperature CO oxidation

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

Zhu, Huiyuan; Wu, Zili; Dong, Su

2015-08-05

This is a report of a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO 2-supported PtFe–FeO x nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeO x within each NW and the interactions between NWs and support (TiO 2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeO x and TiO 2 participate in the initial CO oxidation, facilitating the reactionmore » through a redox pathway. Moreover, the intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe–FeO x/TiO2 catalyst exhibits no activity decay. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.« less

Slat templated formation of efficient oxygen reduction electrocatalyst with a fluidic precursor

NASA Astrophysics Data System (ADS)

Tan, Yao

2018-05-01

Development of cost-effective and efficient oxygen reduction catalyst is critical for the commercialization of proton exchange membrane fuel cell. Metal and nitrogen co-doped carbon is recognized as a promising alternative to traditional platinum-based oxygen reduction catalyst. Herein, we report a novel metal and nitrogen co-doped carbon catalyst with an ionic liquid precursor. Salt template, which can be easily removed with mild treatment after the synthesis, is used to generate abundant mesopores in the resulting catalyst. We show that the novel catalyst shows a superior activity comparable to commercial Pt/C catalyst. Furthermore, the important role of the mesopore for the activity of the catalyst is demonstrated.

Scaleable catalytic asymmetric Strecker syntheses of unnatural α-amino acids

PubMed Central

Zuend, Stephan J.; Coughlin, Matthew P.; Lalonde, Mathieu P.; Jacobsen, Eric N.

2009-01-01

α-Amino acids are essential building blocks for protein synthesis, and are also widely useful as components of medicinally active molecules and chiral catalysts.1,2,3,4,5 Efficient chemo-enzymatic methods for the synthesis of enantioenriched α-amino acids have been devised, but the scope of these methods for the synthesis of unnatural amino acids is limited.6,7 Alkene hydrogenation is broadly useful for enantioselective catalytic synthesis of many classes of amino acids,8,9 but this approach is not applicable to the synthesis of α-amino acids bearing aryl or quaternary alkyl α-substituents. The Strecker synthesis—the reaction of an imine or imine equivalent with hydrogen cyanide, followed by nitrile hydrolysis—is an especially versatile chemical method for the synthesis of racemic α-amino acids (Fig. 1).10,11 Asymmetric Strecker syntheses using stoichiometric chiral reagents have been applied successfully on gram-to-multi-kilogram scales to the preparation of enantiomerically enriched α-amino acids.12,13,14 In principle, Strecker syntheses employing sub-stoichiometric quantities of a chiral reagent provide a practical alternative to these approaches, but the reported catalytic asymmetric methods have seen only limited use on preparative scales (e.g., > 1 gram).15,16 The limited use of existing catalytic methodologies may be ascribed to several important practical drawbacks, including the relatively complex and precious nature of the catalysts, and the requisite use of hazardous cyanide sources. Herein we report a new catalytic asymmetric method for the syntheses of highly enantiomerically enriched non-proteinogenic amino acids using a simple chiral amido-thiourea catalyst to control the key hydrocyanation step. Because this catalyst is robust and lacks sensitive functional groups, it is compatible with safely handled aqueous cyanide salts, and is thus adaptable to large-scale synthesis. This new methodology can be applied to the efficient syntheses of amino acids that are not readily prepared by enzymatic methods or by chemical hydrogenation. PMID:19829379

Application of Heterogeneous Copper Catalyst in a Continuous Flow Process: Dehydrogenation of Cyclohexanol

ERIC Educational Resources Information Center

Glin´ski, Marek; Ulkowska, Urszula; Iwanek, Ewa

2016-01-01

In this laboratory experiment, the synthesis of a supported solid catalyst (Cu/SiO2) and its application in the dehydrogenation of cyclohexanol performed under flow conditions was studied. The experiment was planned for a group of two or three students for two 6 h long sessions. The copper catalyst was synthesized using incipient wetness…

A trifunctional mesoporous silica-based, highly active catalyst for one-pot, three-step cascade reactions.

PubMed

Biradar, Ankush V; Patil, Vijayshinha S; Chandra, Prakash; Doke, Dhananjay S; Asefa, Tewodros

2015-05-18

We report the synthesis of a trifunctional catalyst containing amine, sulphonic acid and Pd nanoparticle catalytic groups anchored on the pore walls of SBA-15. The catalyst efficiently catalyzes one-pot three-step cascade reactions comprising deacetylation, Henry reaction and hydrogenation, giving up to ∼100% conversion and 92% selectivity to the final product.

Effects of the Acrylic Polyol Structure and the Selectivity of the Employed Catalyst on the Performance of Two-Component Aqueous Polyurethane Coatings

PubMed Central

Cakic, Suzana; Lacnjevac, Caslav; Stamenkovic, Jakov; Ristic, Nikola; Takic, Ljiljana; Barac, Miroljub; Gligoric, Miladin

2007-01-01

Two kinds of aqueous acrylic polyols (single step and multi step synthesis type) have been investigated for their performance in the two-component aqueous polyurethane application, by using more selective catalysts. The aliphatic polyfunctional isocyanates based on hexamethylen diisocyanates have been employed as suitable hardeners. The complex of zirconium, commercially known as K-KAT®XC-6212, and manganese (III) complexes with mixed ligands based on the derivative of maleic acid have been used as catalysts in this study. Both of the aqueous polyols give good results, in terms of application and hardness, when elevated temperatures and more selective catalysts are applied. A more selective catalyst promotes the reaction between the isocyanate and polyol component. This increases the percentage of urethane bonds and the degree of hardness in the films formed from the two components of aqueous polyurethane lacquers. The polyol based on the single step synthesis route is favourable concerning potlife and hardness. The obtained results show that the performance of the two-component aqueous polyurethane coatings depends on the polymer structure of the polyols as well as on the selectivity of the employed catalyst.

Graphene-supported platinum catalyst prepared with ionomer as surfactant for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zeng, L.; Zhao, T. S.; An, L.; Zhao, G.; Yan, X. H.; Jung, C. Y.

2015-02-01

In this work, we have synthesized an ionomer-coated graphene-supported platinum catalyst for anion exchange membrane fuel cells. Unlike the common surfactant stabilized colloidal method, we employ a home-made anion exchange ionomer (AEI), namely quaternary ammonia poly (2, 6-dimethyl-1, 4-phenylene oxide) (QAPPO), as the surfactant. The AEI coated on reduced graphene oxide (rGO) surfaces serves as a stabilizer to anchor the platinum precursor on rGO surfaces due to electrostatic interactions. As a result, platinum nanoparticles (Pt NPs) can be easily deposited onto rGO surfaces with a uniform distribution. The remarkable feature of the present synthesis method is that the surfactant, the coated AEI, does not need to be removed from the catalyst, but serves as hydroxide-conductive paths in the catalyst layer, leading to enhanced triple phase boundaries. It is demonstrated that the use of the catalyst obtained with the present method enables a H2/O2 AEMFC to yield a peak power density of 264.8 mW cm-2 at 60 °C, which is 30% higher than that produced from the same fuel cell but with the use of the catalyst synthesized by the conventional synthesis method.

Biodiesel Derive Bio-oil of Hermetia illucens Pre-pupae Catalysed by Sulphonated Biochar

NASA Astrophysics Data System (ADS)

Yoong Leong, Siew; Chong, Soo Shin; Chin, Kah Seng

2018-03-01

This study investigates the development of biochar catalyst from bamboo applied for biodiesel synthesis. A non-conventional biodiesel feedstock was used in the in-situ transesterification reaction. This non-conventional feedstock is obtained from an insect's fly, the Hermetia illucens fly. Biochar derived from bamboo has been investigated as a promising catalyst for biodiesel synthesis. The biochar acid catalysts were prepared by sulphonation via impregnation with concentrated sulphuric acid. The prepared catalysts were investigated for their performance to catalyse in-situ transesterification via ultra-sonication of Hermetia illucens bio-oil. The effects of carbonisation time (1 hour and 2 hour) and temperature (400°C, 500°C and 600°C) as well as catalyst loading (5-20 wt% on oil basis) on the transesterification yield were studied. Result showed that the highest yield of FAME obtained was 95.6% with catalyst loading of 15 wt% carbonized at 500°C for 2 hours. Sharp band of methyl ester functional groups were observed in the FTIR spectra at 1735-1750cm-1. The composition of this methyl ester was further deduced using gas chromatography and the fatty acid was predominantly lauric acid.

The synthesis and characterization of iron nanoparticles

NASA Astrophysics Data System (ADS)

Bennett, Tyler

Nanoparticle synthesis has garnered attention for technological applications for catalysts, industrial processing, and medical applications. The size ranges for these is in the particles nanostructural domain. Pure iron nanoparticles have been of particular interest for their reactivity and relative biological inertness. Applications include cancer treatment and carrying medicine to a relevant site. Unfortunately, because of their reactivity, pure iron nanoparticles have been difficult to study. This is because of their accelerated tendency to form oxides in air, due to the increased surface area to volume ratio. Using synthesis processes with polyphenols or long chain amines, air stable iron nanoparticles have been produced with a diameter size range of ~ 2 to about ~10 nm, but apparently have transformed due to internal pressure and crystallographic defects to the FCC phase. The FCC crystals have been seen to form icosahedral and decahedral shapes. This size is within the range for use as a catalyst for the growth of both carbon nanotubes and boron nitride nanotubes as well for biomedical applications. The advantages of these kinds of catalysts are that nanotube growth can be for the first time separated from the catalyst formation. Additionally, the catalyst size can be preselected for a certain size nanotube to grow. In summary: (1) we found the size distributions of nanoparticles for various synthesis processes, (2) we discovered the right size range for growth of nanotubes from the iron nanoparticles, (3) the nanoparticles are under a very high internal pressure, (4) the nanoparticles are in the FCC phase, (5) they appear to be in icosahedral and decahedral structures, (6) they undergo room temperature twinning, (7) the FCC crystals are distorted due to carbon in octahedral sites, (8) the iron nanoparticles are stable in air, (9) adding small amounts of copper make the iron nanoparticles smaller.

Biotechnology Opens New Routes to High-Performance Materials for Improved Photovoltaics, Batteries, Uncooled IR Detectors, Ferroelectrics and Optical Applications

DTIC Science & Technology

2006-11-01

for High Power-Density, Safe Batteries and Solar Energy applications Cloning reveals: Protein template is an enzyme catalyst: γ- Ga2O3 Enzyme that...catalyzes & templates synthesis of silica at low temperature also makes semiconductors from molecular precursors: TiO2 , Ga2O3 , ZnO...CoO, RuOx (311) γ- Ga2O3 Low-temperature catalysis & templating of semiconductor synthesis The catalyst IS the template! Catalytic & Structure

Rapid and facile CuCl assistant synthesis of PtCu3 nanoframes as efficient catalysts for electroxidation of methanol

NASA Astrophysics Data System (ADS)

Bai, Lei; Bai, Yuwei

2018-02-01

Hollow-structured nanomaterials generally showed enhanced catalytic abilities due to their high utilization. In this work, a general method for the synthesis of PtCu3 nanoframes was reported with the employment of hexadecyltrimethylammonium chloride (CTAC), copper(I) chloride, and various kinds of platinum precursors such as K2PtCl6, H2PtCl6, and Pt(acac)2. It was revealed that the presence of CTAC was crucial for the formation of frame structures. On the one hand, CTAC could act as a structure director, and on the other hand, the galvanic replacement and etching effect of the chloride ions together with oxygen was also responsible for the formation of the frame structure. A similar effect was also evidenced in the case of hexadecyltrimethylammonium bromide. Finally, the as-obtained PtCu3 nanoframes demonstrated high catalytic abilities in the oxidation of methanol as a model reaction. [Figure not available: see fulltext.

Encapsulation of ultrafine metal-oxide nanoparticles within mesopores for biomass-derived catalytic applications† †Electronic supplementary information (ESI) available: Experimental section, additional characterization and reaction results. See DOI: 10.1039/c7sc04724j

PubMed Central

Fang, Ruiqi; Tian, Panliang; Yang, Xianfeng

2018-01-01

The development of efficient encapsulation strategies has attracted intense interest for preparing highly active and stable heterogeneous metal catalysts. However, issues related to low loadings, costly precursors and complex synthesis processes restrict their potential applications. Herein, we report a novel and general strategy to encapsulate various ultrafine metal-oxides nanoparticles (NPs) into the mesoporous KIT-6. The synthesis is facile, which only involves self-assembly of a metal–organic framework (MOF) precursor in the silica mesopores and a subsequent calcination process to transform the MOF into metal-oxide NPs. After the controlled calcination, the metal-oxide NPs produced from MOF decomposition are exclusively confined and uniformly distributed in the mesopores of KIT-6 with high metal loadings. Benefitting from the encapsulation effects, as-synthesized Co@KIT-6 materials exhibit superior catalytic activity and recycling stability in biomass-derived HMF oxidation under mild reaction conditions. PMID:29675231

Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis.

PubMed

Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

2015-06-04

Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, Co(x)Mn(3-x)O4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation-precipitation and insertion-crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn-air and Li-air batteries.

A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

NASA Astrophysics Data System (ADS)

Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid-phase chemical reaction by varying the development time of the catalyst. Investigation results of the catalyst such as surface area, pore radius, lattice size, and photographs of scanning electron microscope (SEM) were also given. In the simulation of energy transport efficiency of this system, by simulating the energy transfer system using two-step liquid phase methanol decomposition and synthetic reactions, and comparing with the technology so far, it can be expected that an innovative energy transfer system is possible to realize.

Synthesis H-Zeolite catalyst by impregnation KI/KIO3 and performance test catalyst for biodiesel production

NASA Astrophysics Data System (ADS)

Widayat, W.; Rizky Wicaksono, Adit; Hakim Firdaus, Lukman; Okvitarini, Ndaru

2016-02-01

The objective of this research is to produce H-catalyst catalyst that was impregnated with KI/KIO3. The catalyst was analyzed about surface area, X-Ray Diffraction (XRD) and performance test of catalyst for biodiesel production. An H-Zeolite catalyst was synthesized from natural zeolite with chemical treatment processing, impregnation KI/KIO3 and physical treatment. The results shows that the surface area of the catalyst by 27.236 m2/g at a concentration of 5% KI. XRD analysis shows peak 2-θ at 23.627o indicating that KI was impregnated on H-zeolite catalyst. The catalyst was tested in production of biodiesel using palm oil with conventional methods for 3 hour at temperature of 70-80 oC. The result for conversion Fatty Acid Methyl Ester (FAME) reached maximum value on 87.91% under production process using catalyst 5% KIO3-H zeolite.

Greener Synthesis of Organics and Nanomaterials: Sustainable Applications of Nano-Catalysts

EPA Science Inventory

The presentation summarizes our recent activity in chemical synthesis involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a varie...

Synthesis and Characterization of Polyethylene/Starch Nanocomposites: A Spherical Starch-Supported Catalyst and In Situ Ethylene Polymerization.

PubMed

Zhanga, Hao; Xi, Shixia; Wang, Shuwei; Liu, Jingsheng; Yoon, Keun-Byoung; Lee, Dong-Ho; Zhang, Hexin; Zhang, Xuequan

2017-01-01

In the present article, a novel spherical starch-supported vanadium (V)-based Ziegler-Natta catalyst was synthesized. The active centers of the obtained catalyst well dispersed in the starch through the SEM-EDX analysis. The effects of reaction conditions on ethylene polymerization were studied. The synthesized catalyst exhibited high activity toward ethylene polymerization in the presence of ethylaluminium sesquichloride (EASC) cocatalyst. Interestingly, the fiber shape PE was obtained directly during the polymerization process.

Biomass-derived Syngas Utilization for Fuels and Chemicals - Final Report

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

Dayton, David C

2010-03-24

Executive Summary The growing gap between petroleum production and demand, mounting environmental concerns, and increasing fuel prices have stimulated intense interest in research and development (R&D) of alternative fuels, both synthetic and bio-derived. Currently, the most technically defined thermochemical route for producing alternative fuels from lignocellulosic biomass involves gasification/reforming of biomass to produce syngas (carbon monoxide [CO] + hydrogen [H2]), followed by syngas cleaning, Fischer-Tropsch synthesis (FTS) or mixed alcohol synthesis, and some product upgrading via hydroprocessing or separation. A detailed techno-economic analysis of this type of process has recently been published [1] and it highlights the need for technicalmore » breakthroughs and technology demonstration for gas cleanup and fuel synthesis. The latter two technical barrier areas contribute 40% of the total thermochemical ethanol cost and 70% of the production cost, if feedstock costs are factored out. Developing and validating technologies that reduce the capital and operating costs of these unit operations will greatly reduce the risk for commercializing integrated biomass gasification/fuel synthesis processes for biofuel production. The objective of this project is to develop and demonstrate new catalysts and catalytic processes that can efficiently convert biomass-derived syngas into diesel fuel and C2-C4 alcohols. The goal is to improve the economics of the processes by improving the catalytic activity and product selectivity, which could lead to commercialization. The project was divided into 4 tasks: Task 1: Reactor Systems: Construction of three reactor systems was a project milestone. Construction of a fixed-bed microreactor (FBR), a continuous stirred tank reactor (CSTR), and a slurry bubble column reactor (SBCR) were completed to meet this milestone. Task 2: Iron Fischer-Tropsch (FT) Catalyst: An attrition resistant iron FT catalyst will be developed and tested. Task 3: Chemical Synthesis: Promising process routes will be identified for synthesis of selected chemicals from biomass-derived syngas. A project milestone was to select promising mixed alcohol catalysts and screen productivity and performance in a fixed bed micro-reactor using bottled syngas. This milestone was successfully completed in collaboration withour catalyst development partner. Task 4: Modeling, Engineering Evaluation, and Commercial Assessment: Mass and energy balances of conceptual commercial embodiment for FT and chemical synthesis were completed.« less

Cobalt–iron nano catalysts supported on TiO{sub 2}–SiO{sub 2}: Characterization and catalytic performance in Fischer–Tropsch synthesis

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

Feyzi, Mostafa, E-mail: Dalahoo2011@yahoo.com; Yaghobi, Nakisa; Eslamimanesh, Vahid

2015-12-15

Graphical abstract: The Co–Fe/TiO{sub 2}–SiO{sub 2} catalysts were prepared. The prepared catalysts were tested for light olefins and C{sub 5}–C{sub 12} production. The best operational conditions are 250 °C, H{sub 2}/CO = 1/1 under 5 bar pressure. - Highlights: • The TiO{sub 2}–SiO{sub 2} supported cobalt–iron catalysts were prepared via sol–gel method. • The best operational conditions were 250 °C, GHSV = 2000 h{sup −1}, H{sub 2}/CO = 1/1 and 5 bar. • The (Co/Fe)/TiO{sub 2}–SiO{sub 2} is efficient catalyst for light olefins and C{sub 5}–C{sub 12} production. - Abstract: A series of Co–Fe catalysts supported on TiO{sub 2}–SiO{sub 2}more » were prepared by the sol–gel method. This research investigated the effects of (Co/Fe) wt.%, the solution pH, different Co/Fe molar ratio, calcination conditions and different promoters on the catalytic performance of cobalt–iron catalysts for the Fisher–Tropsch synthesis (FTS). It was found that the catalyst containing 35 wt.% (Co–Fe)/TiO{sub 2}–SiO{sub 2} (Co/Fe molar ratio is 80/20) promoted with 1.5 wt.% Cu and calcined in air atmosphere at 600 °C for 7 h with a heating rate of 3 °C min{sup −1} is an optimal nano catalyst for converting synthesis gas to light olefins and C{sub 5}–C{sub 12} hydrocarbons. The effects of operational conditions such as the H{sub 2}/CO ratio, gas hourly space velocity (GHSV), different reaction temperature, and reaction pressure were investigated. The results showed that the best operational conditions for optimal nano catalyst are 250 °C, GHSV = 2000 h{sup −1}, H{sub 2}/CO molar ratio 1/1 under 5 bar total pressure. Catalysts and precursors were characterized by, X-ray diffraction (XRD), scanning electron microcopy (SEM), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), temperature program reduction (TPR) and N{sub 2} adsorption–desorption measurements.« less

Cl-Assisted Large Scale Synthesis of Cm-Scale Buckypapers of Fe₃C-Filled Carbon Nanotubes with Pseudo-Capacitor Properties: The Key Role of SBA-16 Catalyst Support as Synthesis Promoter.

PubMed

Boi, Filippo S; He, Yi; Wen, Jiqiu; Wang, Shanling; Yan, Kai; Zhang, Jingdong; Medranda, Daniel; Borowiec, Joanna; Corrias, Anna

2017-10-23

We show a novel chemical vapour deposition (CVD) approach, in which the large-scale fabrication of ferromagnetically-filled cm-scale buckypapers is achieved through the deposition of a mesoporous supported catalyst (SBA-16) on a silicon substrate. We demonstrate that SBA-16 has the crucial role of promoting the growth of carbon nanotubes (CNTs) on a horizontal plane with random orientation rather than in a vertical direction, therefore allowing a facile fabrication of cm-scale CNTs buckypapers free from the onion-crust by-product observed on the buckypaper-surface in previous reports. The morphology and composition of the obtained CNTs-buckypapers are analyzed in detail by scanning electron microscopy (SEM), Energy Dispersive X-ray (EDX), transmission electron microscopy (TEM), high resolution TEM (HRTEM), and thermogravimetric analysis (TGA), while structural analysis is performed by Rietveld Refinement of XRD data. The room temperature magnetic properties of the produced buckypapers are also investigated and reveal the presence of a high coercivity of 650 Oe. Additionally, the electrochemical performances of these buckypapers are demonstrated and reveal a behavior that is compatible with that of a pseudo-capacitor (resistive-capacitor) with better performances than those presented in other previously studied layered-buckypapers of Fe-filled CNTs, obtained by pyrolysis of dichlorobenzene-ferrocene mixtures. These measurements indicate that these materials show promise for applications in energy storage systems as flexible electrodes.

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

Rioux, Robert M.

In this work, we have primarily utilized isothermal titration calorimetry (ITC) and complimentary catalyst characterization techniques to study and assess the impact of solution conditions (i.e., solid-liquid) interface on the synthesis of heterogeneous and electro-catalysts. Isothermal titration calorimetry is well-known technique from biochemistry/physics, but has been applied to a far lesser extent to characterize buried solid-liquid interfaces in materials science. We demonstrate the utility and unique information provided by ITC for two distinct catalytic systems. We explored the thermodynamics associated catalyst synthesis for two systems: (i) ion-exchange or strong electrostatic adsorption for Pt and Pd salts on silica and aluminamore » materials (ii) adsorption to provide covalent attachment of metal and metal-oxo clusters to Dion-Jacobsen perovskite materials.« less

Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions.

PubMed

Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Bagherzadeh, Mojtaba

2015-06-15

We report the green synthesis of palladium/CuO nanoparticles (Pd/CuO NPs) using Theobroma cacao L. seeds extract and their catalytic activity for the reduction of 4-nitrophenol and Heck coupling reaction under aerobic conditions. The catalyst was characterized using the powder XRD, TEM, EDS, UV-vis and FT-IR. This method has the advantages of high yields, elimination of surfactant, ligand and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

High-indexed Pt 3Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching

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

Wang, Chenyu; Zhang, Lihua; Yang, Hongzhou

2017-03-07

Here, chemically controlling crystal structures in nanoscale is challenging, yet provides an effective way to improve catalytic performances. Pt-based nanoframes are a new class of nanomaterials that have great potential as high-performance catalysts. To date, these nanoframes are formed through acid etching in aqueous solutions, which demands long reaction time and often yields ill-defined surface structures. Herein we demonstrate a robust and unprecedented protocol for facile development of high-performance nanoframe catalysts using size and crystallographic facet-controlled PtNi 4 tetrahexahedral nanocrystals prepared through a colloidal synthesis approach as precursors. This new protocol employs the Mond process to preferentially dealloy nickel componentmore » in the <100> direction through carbon monoxide etching of carbon-supported PtNi 4 tetrahexahedral nanocrystals at an elevated temperature. The resultant Pt 3Ni alloy tetrahexahedral nanoframes possess an open, stable, and high-indexed microstructure, containing a segregated Pt thin layer strained to the Pt–Ni alloy surfaces and featuring a down-shift d-band center as revealed by the density functional theory calculations. These nanoframes exhibit much improved catalytic performance, such as high stability under prolonged electrochemical potential cycles, promoting direct electro-oxidation of formic acid to carbon dioxide and enhancing oxygen reduction reaction activities. Because carbon monoxide can be generated from the carbon support through thermal annealing in air, a common process for pretreating supported catalysts, the developed approach can be easily adopted for preparing industrial scale catalysts that are made of Pt–Ni and other alloy nanoframes.« less

Sugar Blowing-Induced Porous Cobalt Phosphide/Nitrogen-Doped Carbon Nanostructures with Enhanced Electrochemical Oxidation Performance toward Water and Other Small Molecules

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

Zhu, Chengzhou; Fu, Shaofang; Xu, Bo Z.

Finely controlled synthesis of high active and robust nonprecious metal catalysts with excellent catalytic efficiency in oxygen evolution reaction (OER) is extremely vital for making the water splitting process more energy-efficient and economical. Among these noble metal-free catalysts, transition-metal-based nanomaterials are considered as one of the most promising OER catalysts due to their relatively low-cost intrinsic activities, high abundance and diversity in terms of structure and morphology. In this work, we reported a facile sugar-blowing technique and low-temperature phosphorization to generate 3D self-supported metal involved carbon nanostructures, which termed as Co2P@Co/nitrogen-doped carbon (Co2P@Co/N-C). By capitalizing on the 3D porous nanostructuresmore » with high surface area, generously dispersed active sites, the intimate interaction between active sites and 3D N-doped carbon, the resultant Co2P@Co/N-C exhibited satisfying OER performance superior to CoO@Co/N-C, delivering 10 mA cm-2 at overpotential of 0.32 V. It is noting that in contrast to the substantial current density loss of RuO2, Co2P@Co/N-C showed much enhanced catalytic activity during the stability test and the 1.8-fold increase in current density was observed after stability test. Furthermore, the obtained Co2P@Co/N-C can also be served as an excellent nonprecious metal catalyst for methanol and glucose electrooxidation in alkaline media, further extending their potential applications.« less

Effect of TiO2, ZrO2, and TiO2-ZrO2 on the performance of CuO-ZnO catalyst for CO2 hydrogenation to methanol

NASA Astrophysics Data System (ADS)

Xiao, Jie; Mao, Dongsen; Guo, Xiaoming; Yu, Jun

2015-05-01

The influence of TiO2, ZrO2, and TiO2-ZrO2 mixed oxide on the catalytic performance of CuO-ZnO catalyst in the methanol synthesis from CO2 hydrogenation was studied. The catalysts were prepared by oxalate co-precipitation method and characterized by TGA, N2 adsorption, XRD, reactive N2O adsorption, XPS, H2-TPR, H2-TPD, and CO2-TPD techniques. Characterization results reveal that all the additives improve the CuO dispersion in the catalyst body and increase the Cu surface area and adsorption capacities of CO2 and H2. The results of catalytic test reveal that the additives increase both the CO2 conversion and methanol selectivity, and TiO2-ZrO2 mixed oxide is more effective than single components of TiO2 or ZrO2. Moreover, the activity of methanol synthesis is correlated directly with CO2 adsorption capacity over the catalysts.

Adsorptive removal of catalyst poisons from coal gas for methanol synthesis

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

Bhatt, B.L.; Golden, T.C.; Hsiung, T.H.

1991-12-01

As an integral part of the liquid-phase methanol (LPMEOH) process development program, the present study evaluated adsorptive schemes to remove traces of catalyst poisons such as iron carbonyl, carbonyl sulfide, and hydrogen sulfide from coal gas on a pilot scale. Tests were conducted with coal gas from the Cool Water gasification plant at Daggett, California. Iron carbonyl, carbonyl sulfide, and hydrogen sulfide were effectively removed from the coal gas. The adsorption capacities of Linde H-Y zeolite and Calgon BPL carbon for Fe(CO){sub 5} compared well with previous bench-scale results at similar CO{sub 2} partial pressure. Adsorption of COS by Calgonmore » FCA carbon appeared to be chemical and nonregenerable by thermal treatment in nitrogen. A Cu/Zn catalyst removed H{sub 2}S very effectively. With the adsorption system on-line, a methanol catalyst showed stable activity during 120 h operation, demonstrating the feasibility of adsorptive removal of trace catalyst poisons from the synthesis gas. Mass transfer coefficients were estimated for Fe(CO){sub 5} and COS removal which can be directly used for design and scale up.« less

Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production.

PubMed

Volli, Vikranth; Purkait, M K

2015-10-30

This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity. Copyright © 2015 Elsevier B.V. All rights reserved.

In-line localized monitoring of catalyst activity in selective catalytic NO.sub.x reduction systems

DOEpatents

Muzio, Lawrence J [Laguna Niguel, CA; Smith, Randall A [Huntington Beach, CA

2009-12-22

Localized catalyst activity in an SCR unit for controlling emissions from a boiler, power plant, or any facility that generates NO.sub.x-containing flue gases is monitored by one or more modules that operate on-line without disrupting the normal operation of the facility. Each module is positioned over a designated lateral area of one of the catalyst beds in the SCR unit, and supplies ammonia, urea, or other suitable reductant to the catalyst in the designated area at a rate that produces an excess of the reductant over NO.sub.x on a molar basis through the designated area. Sampling probes upstream and downstream of the designated area draw samples of the gas stream for NO.sub.x analysis, and the catalyst activity is determined from the difference in NO.sub.x levels between the two probes.

Economy of Catalyst Synthesis-Convenient Access to Libraries of Di- and Tetranaphtho Azepinium Compounds.

PubMed

Tharamak, Sorachat; Knittl-Frank, Christian; Manaprasertsak, Auraya; Pengsook, Anchulee; Suchy, Lydia; Schuller, Philipp; Happl, Barbara; Roller, Alexander; Widhalm, Michael

2018-03-24

Efficient optimization procedures in chiral catalysis are usually linked to a straightforward strategy to access groups of structurally similar catalysts required for fine-tuning. The ease of building up such ligand libraries can be increased when the structure-modifying step (introduction of a substituent) is done at a later stage of the synthesis. This is demonstrated for the extended family of di- and tetranaphtho azepinium compounds, widely used as chiral phase transfer catalysts (PTC). Using 2,6-diiodo-4,5-dihydro-3 H -dinaphtho[2,1-c:1',2'-e]azepine and 4,8-diiodo-6,7-dihydro-5 H -dibenzo[c,e]azepine, respectively, as key intermediates, 18 spiro -azepinium compounds were synthesized in a total yield of 25-42% over 6-7 steps from 1,1'-binaphthyl-2,2'-dicarboxylic acid or diphenic acid, respectively. The replacement of iodo groups with aryl substituents was performed as the last or the penultimate step of the synthesis.

A novel protocol for solvent-free synthesis of 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-ones catalyzed by metal oxide-MWCNTs nanocomposites

NASA Astrophysics Data System (ADS)

Safari, Javad; Gandomi-Ravandi, Soheila

2014-09-01

A Biginelli-like condensation is described using acetophenone as active methylene compound with aldehydes and urea to furnish pyrimidinone analogues under solvent-free conditions. In this paper, besides the preparation of nanocomposites based on MWCNTs, our investigations have been focused on the catalytic efficiency of metal oxide-MWCNTs composites. The requisites of a good catalyst are high activity, selectivity, reusability, reasonable cost and long lifetime. The application of solvent-free conditions and transition metal oxides decorated-MWCNTs (MOx-MWCNTs) nanocomposites as attractive, effective and reusable catalysts leads to the efficient synthesis of 4,6-diaryl-3,4-dihydropyrimidin-2-(1H)-ones. This recyclable heterogeneous catalytic system provides a simple strategy to generate a variety of pyrimidinones under solvent-free conditions. Utilization of easy reaction condition, recyclable green catalyst, reduced environmental impacts and simple work-up make this methodology as an interesting option for the eco-friendly synthesis of Biginelli-like compounds.

The Effects of Secondary Oxides on Copper-Based Catalysts for Green Methanol Synthesis.

PubMed

Hayward, James S; Smith, Paul J; Kondrat, Simon A; Bowker, Michael; Hutchings, Graham J

2017-05-10

Catalysts for methanol synthesis from CO 2 and H 2 have been produced by two main methods: co-precipitation and supercritical anti-solvent (SAS) precipitation. These two methods are compared, along with the behaviour of copper supported on Zn, Mg, Mn, and Ce oxides. Although the SAS method produces initially active material with high Cu specific surface area, they appear to be unstable during reaction losing significant amounts of surface area and hence activity. The CuZn catalysts prepared by co-precipitation, however, showed much greater thermal and reactive stability than the other materials. There appeared to be the usual near-linear dependence of activity upon Cu specific area, though the initial performance relationship was different from that post-reaction, after some loss of surface area. The formation of the malachite precursor, as reported before, is important for good activity and stability, whereas if copper oxides are formed during the synthesis and ageing process, then a detrimental effect on these properties is seen.

The Effects of Secondary Oxides on Copper‐Based Catalysts for Green Methanol Synthesis

PubMed Central

Hayward, James S.; Smith, Paul J.; Kondrat, Simon A.; Bowker, Michael

2017-01-01

Abstract Catalysts for methanol synthesis from CO2 and H2 have been produced by two main methods: co‐precipitation and supercritical anti‐solvent (SAS) precipitation. These two methods are compared, along with the behaviour of copper supported on Zn, Mg, Mn, and Ce oxides. Although the SAS method produces initially active material with high Cu specific surface area, they appear to be unstable during reaction losing significant amounts of surface area and hence activity. The CuZn catalysts prepared by co‐precipitation, however, showed much greater thermal and reactive stability than the other materials. There appeared to be the usual near‐linear dependence of activity upon Cu specific area, though the initial performance relationship was different from that post‐reaction, after some loss of surface area. The formation of the malachite precursor, as reported before, is important for good activity and stability, whereas if copper oxides are formed during the synthesis and ageing process, then a detrimental effect on these properties is seen. PMID:28706570

Exploiting nanospace for asymmetric catalysis: confinement of immobilized, single-site chiral catalysts enhances enantioselectivity.

PubMed

Thomas, John Meurig; Raja, Robert

2008-06-01

In the mid-1990s, it became possible to prepare high-area silicas having pore diameters controllably adjustable in the range ca. 20-200 Å. Moreover, the inner walls of these nanoporous solids could be functionalized to yield single-site, chiral, catalytically active organometallic centers, the precise structures of which could be determined using in situ X-ray absorption and FTIR and multinuclear magic angle spinning (MAS) NMR spectroscopy. This approach opened up the prospect of performing heterogeneous enantioselective conversions in a novel manner, under the spatial restrictions imposed by the nanocavities within which the reactions occur. In particular, it suggested an alternative method for preparing pharmaceutically and agrochemically useful asymmetric products by capitalizing on the notion, initially tentatively perceived, that spatial confinement of prochiral reactants (and transition states formed at the chiral active center) would provide an altogether new method of boosting the enantioselectivity of the anchored chiral catalyst. Initially, we anchored chiral single-site heterogeneous catalysts to nanopores covalently via a ligand attached to Pd(II) or Rh(I) centers. Later, we employed a more convenient and cheaper electrostatic method, relying in part on strong hydrogen bonding. This Account provides many examples of these processes, encompassing hydrogenations, oxidations, and aminations. Of particular note is the facile synthesis from methyl benzoylformate of methyl mandelate, which is a precursor in the synthesis of pemoline, a stimulant of the central nervous system; our procedure offers several viable methods for reducing ketocarboxylic acids. In addition to relying on earlier (synchrotron-based) in situ techniques for characterizing catalysts, we have constructed experimental procedures involving robotically controlled catalytic reactors that allow the kinetics of conversion and enantioselectivity to be monitored continually, and we have access to sophisticated, high-sensitivity chiral chromatographic facilities and automated high-throughput combinatorial test rigs so as to optimize the reaction conditions (e.g., H(2) pressure, temperature, time on-stream, pH, and choice of ligand and central metal ion) for high enantioselectivity. This Account reports our discoveries of selective hydrogenations and aminations of synthetic, pharmaceutical, and biological significance, and the findings of other researchers who have achieved similar success in oxidations, dehydrations, cyclopropanations, and hydroformylations. Although the practical advantages and broad general principles governing the enhancement of enantioselectivity through spatial confinement are clear, we require a deeper theoretical understanding of the details pertaining to the phenomenology involved, particularly through molecular dynamics simulations. Ample scope exists for the general exploitation of nanospace in asymmetric hydrogenations with transition metal complexes and for its deployment for the formation of C-N, C-C, C-O, C-S, and other bonds.

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2011 CFR

2011-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device...) and (d) of this section. (c) Any fluid catalytic cracking unit catalyst regenerator under paragraph (b...

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2012 CFR

2012-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device...) and (d) of this section. (c) Any fluid catalytic cracking unit catalyst regenerator under paragraph (b...