CATALYTIC STEAM REFORMING OF CHLOROCARBONS: CATALYST COMPARISONS. (R822721C633)

EPA Science Inventory

Catalyst candidates for steam reforming chlorocarbons have been screened for activity using methyl chloride as a model reactant. At 500°C, a H₂O/C ratio of about 10 and a GHSV of 254 000 h^-1, catalysts comprising 0.5% loading of the metals o...

N/S/B-doped graphitized carbon encased Fe species as a highly active and durable catalyst towards oxygen reduction reaction.

PubMed

Li, Guang-Lan; Cheng, Guang-Chun; Chen, Wen-Wen; Liu, Cai-Di; Yuan, Li-Fang; Yang, Bei-Bei; Hao, Ce

2018-03-15

Exploring cost-effective, high-performance and durable non-precious metal catalysts is of great significance for the acceleration of sluggish oxygen reduction reaction (ORR). Here, we report an intriguing heteroatom-doped graphitized carbon encased Fe species composite by introducing N, S and B sequentially. The experimental approach was designed ingeniously for that the FeCl 3 ·6H 2 O could catalyze thiourea to synthesize N, S co-doped carbon materials which would further react with H 3 BO 3 and NH 3 (emerged at the heat-treatment process) to prepare N, S and B co-doped carbon materials (Fe-N/S/B-C). The Fe-N/S/B-C exhibits an impressive ORR activity for its half-wave potential of -0.1 V, which is 36 mV or 19 mV higher than that of the corresponding single or dual doped counterparts (Fe-N-C or Fe-N/S-C) and 31 mV positive than that of Pt/C catalyst, respectively. Further chronoamperometric measurement and accelerated aging test confirm the excellent electrochemical durability of Fe-N/S/B-C with the stable core-shell structure. The remarkable ORR performance and facile preparation method enable Fe-N/S/B-C as a potential candidate in electrochemical energy devices. Copyright © 2017 Elsevier Inc. All rights reserved.

Sol-Gel Synthesis, Electrochemical Characterization, and Stability Testing of Ti0.7W0.3O2 Nanoparticles for Catalyst Support Applications in Proton-Exchange Membrane Fuel Cells

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

Subban, Chinmayee V.; Zhou, Qin; Hu, Anthony

2010-11-19

The materials currently used in proton-exchange membrane fuel cells (PEMFCs) require complex control of operating conditions to make them sufficiently durable to permit commercial deployment. One of the major materials challenges to allow simplification of fuel cell operating strategies is the discovery of catalyst supports that are much more stable to oxidative decomposition than currently used carbon blacks. Here we report the synthesis and characterization of Ti 0.7W 0.3O 2 nanoparticles (approximately 50 nm diameter), a promising doped metal oxide that is a candidate for such a durable catalyst support. The synthesized nanoparticles were platinized, characterized by electrochemical testing, andmore » evaluated for stability under PEMFC and other oxidizing acidic conditions. Ti 0.7W 0.3O 2 nanoparticles show no evidence of decomposition when heated in a Nafion solution for 3 weeks at 80 °C. In contrast, when heated in sulfuric, nitric, perchloric, or hydrochloric acid, the oxide reacts to form salts such as titanylsulfatehydrate from sulfuric acid. Electrochemical tests show that rates of hydrogen oxidation and oxygen reduction by platinum nanoparticles supported on Ti 0.7W 0.3O 2 are comparable to those of commercial Pt on carbon black.« less

Process for coal liquefaction using electrodeposited catalyst

DOEpatents

Moore, Raymond H.

1978-01-01

A process for the liquefaction of solid hydrocarbonaceous materials is disclosed. Particles of such materials are electroplated with a metal catalyst and are then suspended in a hydrocarbon oil and subjected to hydrogenolysis to liquefy the solid hydrocarbonaceous material. A liquid product oil is separated from residue solid material containing char and the catalyst metal. The catalyst is recovered from the solid material by electrolysis for reuse. A portion of the product oil can be employed as the hydrocarbon oil for suspending additional particles of catalyst coated solid carbonaceous material for hydrogenolysis.

Palladium-Zeolite nanofiber as an effective recyclable catalyst membrane for water treatment.

PubMed

Choi, Jungsu; Chan, Sophia; Yip, Garriott; Joo, Hyunjong; Yang, Heejae; Ko, Frank K

2016-09-15

Zeolite is an exciting natural material due to its unique capability of ammonium nitrogen (NH3N) adsorption in water. In this study, multifunctional hybrid composites of zeolite/palladium (Ze/Pd) on polymer nanofiber membranes were fabricated and explored for sustainable contaminant removal. SEM and XRD demonstrated that zeolite and palladium nanoparticles were uniformly distributed and deposited on the nanofibers. NH3N recovery rate was increased from 23 to 92% when palladium coated zeolite was embedded on the nanofiber. Multifunctional nanofibers of Ze/Pd membranes were able to adsorb NH3N on the zeolites placed on the surface of fibers and palladium catalysts were capable of selective oxidation of NH3N to N2 gas. The cycling of NH3N adsorption-oxidation, high flux, hydrophilicity, and flexibility of the membrane makes it a strong candidate for water treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polyacrylonitrile Fibers Anchored Cobalt/Graphene Sheet Nanocomposite: A Low-Cost, High-Performance and Reusable Catalyst for Hydrogen Generation.

PubMed

Zhang, Fei; Huang, Guoji; Hou, Chengyi; Wang, Hongzhi; Zhang, Qinghong; Li, Yaogang

2016-06-01

Cobalt and its composites are known to be active and inexpensive catalysts in sodium borohydride (NaBH4) hydrolysis to generate clean and renewable hydrogen energy. A novel fiber catalyst, cobalt/graphene sheet nanocomposite anchored on polyacrylonitrile fibers (Co/GRs-PANFs), which can be easily recycled and used in any reactor with different shapes, were synthesized by anchoring cobalt/graphene (Co/GRs) on polyacrylonitrile fibers coated with graphene (GRs-PANFs) at low temperature. The unique structure design effectively prevents the inter-sheet restacking of Co/GRs and fully exploits the large surface area of novel hybrid material for generate hydrogen. And the extra electron transfer path supplied by GRs on the surface of GRs-PANFs can also enhance their catalysis performances. The catalytic activity of the catalyst was investigated by the hydrolysis of NaBH4 in aqueous solution with GRs-PANFs. GRs powders and Co powders were used as control groups. It was found that both GRs and fiber contributed to the hydrogen generation rate of Co/GRs-PANFs (3222 mL x min(-1) x g(-1)), which is much higher than that of cobalt powders (915 mL x min(-1) x g(-1)) and Co/GRs (995 mL x min(-1) x g(-1)). The improved hydrogen generation rate, low cost and uncomplicated recycling make the Co/GRs-PANFs promising candidate as catalysts for hydrogen generation.

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.

Silver doped catalysts for treatment of exhaust

DOEpatents

Park, Paul Worn; Hester, Virgil Raymond; Ragle, Christie Susan; Boyer, Carrie L.

2009-06-02

A method of making an exhaust treatment element includes washcoating a substrate with a slurry that includes a catalyst support material. At least some of the catalyst support material from the slurry may be transferred to the substrate, and silver metal (Ag) is dispersed within the catalyst support material.

Controlling the physical parameters of crystalline CIGS nanowires for use in superstrate configuration using vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Lee, Dongjin; Jeon, H. C.; Kang, T. W.; Kumar, Sunil

2018-03-01

Indium tin oxide (ITO) is a suitable candidate for smart windows and bifacial semi-transparent solar cell applications. In this study, highly crystalline CuInGaSe2 (CIGS) nanowires were successfully grown by horizontal-type vapor phase epitaxy on an ITO substrate. Length, diameter, and density of the nanowires were studied by varying the growth temperature (500, 520, and 560 °C), time (3.5, 6.5, and 9.5 h), and type of catalyst (In, Au, and Ga). Length, diameter, and density of the nanowires were found to be highly dependent on the growth conditions. At an optimized growth period and temperature of 3.5 h and 520 °C, respectively, the length and diameter of the nanowires were found to increase when grown in a catalyst-free environment. However, the density of the nanowires was found to be higher while using a catalyst during growth. Even in a catalyst-free environment, an Indium cluster formed at the bottom of the nanowires. The source of these nanowires is believed to be Indium from the ITO substrate which was observed in the EDS measurement. TEM-based EDS and line EDS indicated that the nanowires are made up of CIGS material with a very low Gallium content. XRD measurements also show the appearance of wurtzite CIS nanowires grown on ITO in addition to the chalcopyrite phase. PL spectroscopy was done to see the near-band-edge emission for finding band-to-band optical transition in this material. Optical response of the CIGS nanowire network was also studied to see the photovoltaic effect. This work creates opportunities for making real solar cell devices in superstrate configuration.

An Overview of Recent Development in Composite Catalysts from Porous Materials for Various Reactions and Processes

PubMed Central

Xie, Zaiku; Liu, Zhicheng; Wang, Yangdong; Yang, Qihua; Xu, Longya; Ding, Weiping

2010-01-01

Catalysts are important to the chemical industry and environmental remediation due to their effective conversion of one chemical into another. Among them, composite catalysts have attracted continuous attention during the past decades. Nowadays, composite catalysts are being used more and more to meet the practical catalytic performance requirements in the chemical industry of high activity, high selectivity and good stability. In this paper, we reviewed our recent work on development of composite catalysts, mainly focusing on the composite catalysts obtained from porous materials such as zeolites, mesoporous materials, carbon nanotubes (CNT), etc. Six types of porous composite catalysts are discussed, including amorphous oxide modified zeolite composite catalysts, zeolite composites prepared by co-crystallization or overgrowth, hierarchical porous catalysts, host-guest porous composites, inorganic and organic mesoporous composite catalysts, and polymer/CNT composite catalysts. PMID:20559508

Transitioning Rationally Designed Catalytic Materials to Real 'Working' Catalysts Produced at Commercial Scale: Nanoparticle Materials

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

Schaidle, Joshua A.; Habas, Susan E.; Baddour, Frederick G.

Catalyst design, from idea to commercialization, requires multi-disciplinary scientific and engineering research and development over 10-20 year time periods. Historically, the identification of new or improved catalyst materials has largely been an empirical trial-and-error process. However, advances in computational capabilities (new tools and increased processing power) coupled with new synthetic techniques have started to yield rationally-designed catalysts with controlled nano-structures and tailored properties. This technological advancement represents an opportunity to accelerate the catalyst development timeline and to deliver new materials that outperform existing industrial catalysts or enable new applications, once a number of unique challenges associated with the scale-up ofmore » nano-structured materials are overcome.« less

Isoelectronic Manganese and Iron Hydrogenation/Dehydrogenation Catalysts: Similarities and Divergences.

PubMed

Gorgas, Nikolaus; Kirchner, Karl

2018-06-19

Sustainable processes that utilize nontoxic, readily available, and inexpensive starting materials for organic synthesis constitute a major objective in modern chemical research. In this context, it is highly important to perform reactions under catalytic conditions and to replace precious metal catalysts by earth-abundant nonprecious metal catalysts. In particular, iron and manganese are promising candidates, as these are among the most abundant metals in the earth's crust, are inexpensive, and exhibit a low environmental impact. As far as chemical processes are concerned, hydrogenations and acceptorless alcohol dehydrogenation (AAD), sometimes in conjunction with hydrogen autotransfer reactions, are becoming important areas of research. While the first is a very important synthetic process representing a highly atom-efficient and clean methodology, AAD is an oxidant-free, environmentally benign reaction where carbonyl compounds together with dihydrogen as a valuable product and/or reactant (autotransfer) and water are formed. Carbonyl compounds, typically generated in situ, can be converted into other useful organic materials such as amines, imines, or heterocycles. In 2016 several groups, including ours, discovered for the first time the potential of hydride biscarbonyl Mn(I) complexes bearing strongly bound PNP pincer ligands or related tridentate ligands as highly effective and versatile catalysts for hydrogenation, transfer hydrogenation, and dehydrogenation reactions. These complexes are isoelectronic analogues of the respective hydride monocarbonyl Fe(II) PNP compounds and display similar reactivities but also quite divergent behavior depending on the coligands. Moreover, manganese compounds show improved long-term stability and high robustness toward harsh reaction conditions. In light of these recent achievements, this Account contrasts Mn(I) and Fe(II) PNP pincer catalysts, highlighting specific features that are connected to particular structural and electronic properties. It also addresses opportunities and restrictions in their catalytic applications. Apart from classical hydrogenations, it also covers the most recent developments of these catalysts for AAD resulting in the synthesis of complex organic molecules such as heterocycles via multicomponent reactions. The ambivalent hydrogen-based redox chemistry provides access to a variety of synthetically valuable reductive and oxidative coupling reactions. Hence, these catalysts cover a broad scope of catalytic applications and exhibit activities and productivities that are becoming competitive with those of well-established precious metal catalysts. The knowledge about the nature and characteristics of active Mn(I)- and Fe(II)-based systems paves the way for conceptually and mechanistically well-founded research, which might lead to further developments and the discovery of novel catalysts extending the current scope and limitations of reactivity. It underlines that base metal catalysts are beginning to challenge precious metal catalysts and contributes to the further advancement of waste-free sustainable base metal catalysis.

Extrusion-mixing compared with hand-mixing of polyether impression materials?

PubMed

McMahon, Caroline; Kinsella, Daniel; Fleming, Garry J P

2010-12-01

The hypotheses tested were two-fold (a) whether altering the base:catalyst ratio influences working time, elastic recovery and strain in compression properties of a hand-mixed polyether impression material and (b) whether an extrusion-mixed polyether impression material would have a significant advantage over a hand-mixed polyether impression material mixed to the optimum base:catalyst ratio. The polyether was hand-mixed at the optimum (manufacturers recommended) base:catalyst ratios (7:1) and further groups were made by increasing or decreasing the catalyst length by 25%. Additionally specimens were also made from an extrusion-mixed polyether impression material and compared with the optimum hand-mixed base:catalyst ratio. A penetrometer assembly was used to measure the working time (n=5). Five cylindrical specimens for each hand-mixed and extrusion mixed group investigated were employed for elastic recovery and strain in compression testing. Hand-mixing polyether impression materials with 25% more catalyst than that recommended significantly decreased the working time while hand-mixing with 25% less catalyst than that recommended significantly increased the strain in compression. The extrusion-mixed polyether impression material provided similar working time, elastic recovery and strain in compression to the hand-mixed polyether mixed at the optimum base:catalyst ratio.

Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution

NASA Astrophysics Data System (ADS)

Liu, Yuanyue; Wu, Jingjie; Hackenberg, Ken P.; Zhang, Jing; Wang, Y. Morris; Yang, Yingchao; Keyshar, Kunttal; Gu, Jing; Ogitsu, Tadashi; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M.; Wood, Brandon C.; Yakobson, Boris I.

2017-09-01

Low-cost, layered transition-metal dichalcogenides (MX2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. The catalysts reach 10 mA cm-2 current density at an overpotential of ˜50-60 mV with a loading of 10-55 μg cm-2, surpassing other reported MX2 candidates without any performance-enhancing additives.

Principles and Methods for the Rational Design of Core-Shell Nanoparticle Catalysts with Ultralow Noble Metal Loadings.

PubMed

Hunt, Sean T; Román-Leshkov, Yuriy

2018-05-15

Conspecuts Commercial and emerging renewable energy technologies are underpinned by precious metal catalysts, which enable the transformation of reactants into useful products. However, the noble metals (NMs) comprise the least abundant elements in the lithosphere, making them prohibitively scarce and expensive for future global-scale technologies. As such, intense research efforts have been devoted to eliminating or substantially reducing the loadings of NMs in various catalytic applications. These efforts have resulted in a plethora of heterogeneous NM catalyst morphologies beyond the traditional supported spherical nanoparticle. In many of these new architectures, such as shaped, high index, and bimetallic particles, less than 20% of the loaded NMs are available to perform catalytic turnovers. The majority of NM atoms are subsurface, providing only a secondary catalytic role through geometric and ligand effects with the active surface NM atoms. A handful of architectures can approach 100% NM utilization, but severe drawbacks limit general applicability. For example, in addition to problems with stability and leaching, single atom and ultrasmall cluster catalysts have extreme metal-support interactions, discretized d-bands, and a lack of adjacent NM surface sites. While monolayer thin films do not possess these features, they exhibit such low surface areas that they are not commercially relevant, serving predominantly as model catalysts. This Account champions core-shell nanoparticles (CS NPs) as a vehicle to design highly active, stable, and low-cost materials with high NM utilization for both thermo- and electrocatalysis. The unique benefits of the many emerging NM architectures could be preserved while their fundamental limitations could be overcome through reformulation via a core-shell morphology. However, the commercial realization of CS NPs remains challenging, requiring concerted advances in theory and manufacturing. We begin by formulating seven constraints governing proper core material design, which naturally point to early transition metal ceramics as suitable core candidates. Two constraints prove extremely challenging. The first relates to the core modifying the shell work function and d-band. To properly investigate materials that could satisfy this constraint, we discuss our development of a new heat, quench, and exfoliation (HQE) density functional theory (DFT) technique to model heterometallic interfaces. This technique is used to predict how transition metal carbides can favorably tune the catalytic properties of various NM monolayer shell configurations. The second challenging constraint relates to the scalable manufacturing of CS NP architectures with independent synthetic control of the thickness and composition of the shell and the size and composition of the core. We discuss our development of a synthetic method that enables high temperature self-assembly of tunable CS NP configurations. Finally, we discuss how these principles and methods were used to design catalysts for a variety of applications. These include the design of a thermally stable sub-monolayer CS catalyst, a highly active methanol electrooxidation catalyst, CO-tolerant Pt catalysts, and a hydrogen evolution catalyst that is less expensive than state-of-the-art NM-free catalysts. Such core-shell architectures offer the promise of ultralow precious metal loadings while ceramic cores hold the promise of thermodynamic stability and access to unique catalytic activity/tunability.

Layered double hydroxide supported gold nanoclusters by glutathione-capped Au nanoclusters precursor method for highly efficient aerobic oxidation of alcohols.

PubMed

Li, Lun; Dou, Liguang; Zhang, Hui

2014-04-07

M3Al-layered double hydroxide (LDH, M = Mg, Ni, Co) supported Au nanoclusters (AuNCs) catalysts have been prepared for the first time by using water-soluble glutathione-capped Au nanoclusters as precursor. Detailed characterizations show that the ultrafine Au nanoclusters (ca. 1.5 ± 0.6 nm) were well dispersed on the surface of LDH with a loading of Au below ∼0.23 wt% upon synergetic interaction between AuNCs and M3Al-LDH. AuNCs/Mg3Al-LDH-0.23 exhibits much higher catalytic performance for the oxidation of 1-phenylethanol in toluene than Au/Mg3Al-LDH(DP) by the conventional deposition precipitation method and can be applied for a wide range of alcohols without basic additives. This catalyst can also be reused without loss of activity or selectivity. The AuNCs/M(= Ni, Co)3Al-LDH catalysts present even higher alcohol oxidation activity than AuNCs/Mg3Al-LDH. Particularly, AuNCs/Ni3Al-LDH-0.22 exhibits the highest activity (46 500 h(-1)) for the aerobic oxidation of 1-phenylethanol under solvent-free conditions attributed to its strongest Au-support synergy. The excellent activity and stability of AuNCs/M3Al-LDH catalysts render these materials promising candidates for green base-free selective oxidation of alcohols by molecular oxygen.

Development of advanced fuel cell system

NASA Technical Reports Server (NTRS)

Grevstad, P. E.

1972-01-01

Weight, life and performance characteristics optimization of hydrogen-oxygen fuel cell power systems were considered. A promising gold alloy cathode catalyst was identified and tested in a cell for 5,000 hours. The compatibility characteristics of candidate polymer structural materials were measured after exposure to electrolyte and water vapor for 8,000 hours. Lightweight cell designs were prepared and fabrication techniques to produce them were developed. Testing demonstrated that predicted performance was achieved. Lightweight components for passive product water removal and evaporative cooling of cells were demonstrated. Systems studies identified fuel cell powerplant concepts for meeting the requirements of advanced spacecraft.

Integrated current collector and catalyst support

DOEpatents

Bregoli, Lawrence J.

1985-10-22

An integrated current collecting electrode for a molten carbonate fuel cell includes a corrugated metal conductive strip positioned in contact with a catalyst layer. The corrugations of the metal strip form a plurality of gas channels immediately adjacent the surface of the catalyst through which a reactant gas flows. Each channel is filled with a particulate material to maintain separation between the metal strip and the catalyst in ensuring gas channel integrity. The catalyst may be in the form of a compacted, particulate material provided the particle size of the material within the gas channels is larger than that of the catalyst particles to prevent catalyst migration to the metal conductor and provide reactant gas access to the catalyst layer. The gas channels formed by the corrugations of the metal strip are arranged in an offset pattern along the direction of gas flow for improved reactant gas distribution to the catalyst layer. The particulate material positioned within the gas flow channels may be a ceramic conductor such as a perovskite or a spinel for enhanced current collection.

Integrated current collector and catalyst support

DOEpatents

Bregoli, L.J.

1984-10-17

An integrated current collecting electrode for a molten carbonate fuel cell includes a corrugated metal conductive strip positioned in contact with a catalyst layer. The corrugations of the metal strip form a plurality of gas channels immediately adjacent the surface of the catalyst through which a reactant gas flows. Each channel is filled with a particulate material to maintain separation between the metal strip and the catalyst in ensuring gas channel integrity. The catalyst may be in the form of a compacted, particulate material provided the particle size of the material within the gas channels is larger than that of the catalyst particles to prevent catalyst migration to the metal conductor and provide reactant gas access to the catalyst layer. The gas channels formed by the corrugations of the metal strip are arranged in an offset pattern along the direction of gas flow for improved reactant gas distribution to the catalyst layer. The particulate material positioned within the gas flow channels may be a ceramic conductor such as a perovskite or a spinel for enhanced current collection.

Hollow Pd/MOF Nanosphere with Double Shells as Multifunctional Catalyst for Hydrogenation Reaction.

PubMed

Wan, Mingming; Zhang, Xinlu; Li, Meiyan; Chen, Bo; Yin, Jie; Jin, Haichao; Lin, Lin; Chen, Chao; Zhang, Ning

2017-10-01

A new type of hollow nanostructure featured double metal-organic frameworks shells with metal nanoparticles (MNPs) is designed and fabricated by the methods of ship in a bottle and bottle around the ship. The nanostructure material, hereinafter denoted as Void@HKUST-1/Pd@ZIF-8, is confirmed by the analyses of photograph, transmission electron microscopy, scanning electron microscopy, powder X-ray diffraction, inductively coupled plasma, and N 2 sorption. It possesses various multifunctionally structural characteristics such as hollow cavity which can improve mass transfer, the adjacent of the inner HKUST-1 shell to the void which enables the matrix of the shell to host and well disperse MNPs, and an outer ZIF-8 shell which acts as protective layer against the leaching of MNPs and a sieve to guarantee molecular-size selectivity. This makes the material eligible candidates for the heterogeneous catalyst. As a proof of concept, the liquid-phase hydrogenation of olefins with different molecular sizes as a model reaction is employed. It demonstrates the efficient catalytic activity and size-selectivity of Void@HKUST-1/Pd@ZIF-8. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activation of molecular catalysts using semiconductor quantum dots

DOEpatents

Meyer, Thomas J [Chapel Hill, NC; Sykora, Milan [Los Alamos, NM; Klimov, Victor I [Los Alamos, NM

2011-10-04

Photocatalytic materials based on coupling of semiconductor nanocrystalline quantum dots (NQD) and molecular catalysts. These materials have capability to drive or catalyze non-spontaneous chemical reactions in the presence of visible radiation, ultraviolet radiation, or both. The NQD functions in these materials as a light absorber and charge generator. Following light absorption, the NQD activates a molecular catalyst adsorbed on the surface of the NQD via transfer of one or more charges (either electrons or electron-holes) from the NQD to the molecular catalyst. The activated molecular catalyst can then drive a chemical reaction. A photoelectrolytic device that includes such photocatalytic materials is also described.

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

Conductive polymer layers to limit transfer of fuel reactants to catalysts of fuel cells to reduce reactant crossover

DOEpatents

Stanis, Ronald J.; Lambert, Timothy N.

2016-12-06

An apparatus of an aspect includes a fuel cell catalyst layer. The fuel cell catalyst layer is operable to catalyze a reaction involving a fuel reactant. A fuel cell gas diffusion layer is coupled with the fuel cell catalyst layer. The fuel cell gas diffusion layer includes a porous electrically conductive material. The porous electrically conductive material is operable to allow the fuel reactant to transfer through the fuel cell gas diffusion layer to reach the fuel cell catalyst layer. The porous electrically conductive material is also operable to conduct electrons associated with the reaction through the fuel cell gas diffusion layer. An electrically conductive polymer material is coupled with the fuel cell gas diffusion layer. The electrically conductive polymer material is operable to limit transfer of the fuel reactant to the fuel cell catalyst layer.

SiP monolayers: New 2D structures of group IV-V compounds for visible-light photohydrolytic catalysts

NASA Astrophysics Data System (ADS)

Ma, Zhinan; Zhuang, Jibin; Zhang, Xu; Zhou, Zhen

2018-06-01

Because of graphene and phosphorene, two-dimensional (2D) layered materials of group IV and group V elements arouse great interest. However, group IV-V monolayers have not received due attention. In this work, three types of SiP monolayers were computationally designed to explore their electronic structure and optical properties. Computations confirm the stability of these monolayers, which are all indirect-bandgap semiconductors with bandgaps in the range 1.38-2.21 eV. The bandgaps straddle the redox potentials of water at pH = 0, indicating the potential of the monolayers for use as watersplitting photocatalysts. The computed optical properties demonstrate that certain monolayers of SiP 2D materials are absorbers of visible light and would serve as good candidates for optoelectronic devices.

High liquid yield process for retorting various organic materials including oil shale

DOEpatents

Coburn, Thomas T.

1990-01-01

This invention is a continuous retorting process for various high molecular weight organic materials, including oil shale, that yields an enhanced output of liquid product. The organic material, mineral matter, and an acidic catalyst, that appreciably adsorbs alkenes on surface sites at prescribed temperatures, are mixed and introduced into a pyrolyzer. A circulating stream of olefin enriched pyrolysis gas is continuously swept through the organic material and catalyst, whereupon, as the result of pyrolysis, the enhanced liquid product output is provided. Mixed spent organic material, mineral matter, and cool catalyst are continuously withdrawn from the pyrolyzer. Combustion of the spent organic material and mineral matter serves to reheat the catalyst. Olefin depleted pyrolysis gas, from the pyrolyzer, is enriched in olefins and recycled into the pyrolyzer. The reheated acidic catalyst is separated from the mineral matter and again mixed with fresh organic material, to maintain the continuously cyclic process.

A high liquid yield process for retorting various organic materials including oil shale

DOEpatents

Coburn, T.T.

1988-07-26

This invention is a continuous retorting process for various high molecular weight organic materials, including oil shale, that yields an enhanced output of liquid product. The organic material, mineral matter, and an acidic catalyst, that appreciably adsorbs alkenes on surface sites at prescribed temperatures, are mixed and introduced into a pyrolyzer. A circulating stream of olefin enriched pyrolysis gas is continuously swept through the organic material and catalyst, whereupon, as the result of pyrolysis, the enhanced liquid product output is provided. Mixed spent organic material, mineral matter, and cool catalyst are continuously withdrawn from the pyrolyzer. Combustion of the spent organic material and mineral matter serves to reheat the catalyst. Olefin depleted pyrolysis gas, from the pyrolyzer, is enriched in olefins and recycled into the pyrolyzer. The reheated acidic catalyst is separated from the mineral matter and again mixed with fresh organic material, to maintain the continuously cyclic process. 2 figs.

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline W. (Inventor); Geiger, Cherie L. (Inventor); Aitken, Brian S. (Inventor); Clausen, Christian A. (Inventor)

2012-01-01

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline W. (Inventor); Aitken, Brian S. (Inventor); Clausen, Christian A. (Inventor); Geiger, Cherie L. (Inventor)

2010-01-01

A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. Preferably, the hydrogenation catalyst is a bimetallic particle including zero-valent metal particles coated with a catalytic material. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts.

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, Prabhakar; Shockling, Larry A.; George, Raymond A.; Basel, Richard A.

1996-01-01

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall.

Hydrocarbon reforming catalyst material and configuration of the same

DOEpatents

Singh, P.; Shockling, L.A.; George, R.A.; Basel, R.A.

1996-06-18

A hydrocarbon reforming catalyst material comprising a catalyst support impregnated with catalyst is provided for reforming hydrocarbon fuel gases in an electrochemical generator. Elongated electrochemical cells convert the fuel to electrical power in the presence of an oxidant, after which the spent fuel is recirculated and combined with a fresh hydrocarbon feed fuel forming the reformable gas mixture which is fed to a reforming chamber containing a reforming catalyst material, where the reforming catalyst material includes discrete passageways integrally formed along the length of the catalyst support in the direction of reformable gas flow. The spent fuel and/or combusted exhaust gases discharged from the generator chamber transfer heat to the catalyst support, which in turn transfers heat to the reformable gas and to the catalyst, preferably via a number of discrete passageways disposed adjacent one another in the reforming catalyst support. The passageways can be slots extending inwardly from an outer surface of the support body, which slots are partly defined by an exterior confining wall. According to a preferred embodiment, the catalyst support is non-rigid, porous, fibrous alumina, wherein the fibers are substantially unsintered and compressible, and the reforming catalyst support is impregnated, at least in the discrete passageways with Ni and MgO, and has a number of internal slot passageways for reformable gas, the slot passageways being partly closed by a containing outer wall. 5 figs.

New Ni-based quaternary disk-shaped catalysts for low-temperature CO2 methanation: Fabrication, characterization, and performance.

PubMed

Moon, Dea Hyun; Lee, Sang Moon; Ahn, Jeong Yoon; Nguyen, Dinh Duc; Kim, Sung Su; Chang, Soon Woong

2018-07-15

Ni-based quaternary disk catalysts were manufactured for low-temperature CO 2 methanation reactions, and the reaction activity was examined with respect to the thermal treatment conditions. By applying varying reduction and combustion treatments, the same catalysts were compared, and the Ni oxidation conditions and physical features were confirmed through X-Ray diffraction, scanning electron microscopy, and energy dispersive X-ray analyses. In addition, oxygen adsorption/desorption changes were measured by temperature-programmed reduction after pre-treating with oxygen and hydrogen. The reduction treatment catalyst showed a conversion of 20% at 280 °C, and the 70% calcined catalyst did not form a NiO crystalloid. The activation of the catalyst increased because of NiO movement on the catalyst surface, which enabled easy transformation to metallic Ni. The prepared catalyst is a highly reactive, yet stable, candidate for practical catalytic CO 2 methanation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study.

PubMed

Sheng, Tian; Lin, Xiao; Chen, Zhao-Yang; Hu, P; Sun, Shi-Gang; Chu, You-Qun; Ma, Chun-An; Lin, Wen-Feng

2015-10-14

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

High performance, high durability non-precious metal fuel cell catalysts

DOEpatents

Wood, Thomas E.; Atanasoski, Radoslav; Schmoeckel, Alison K.

2016-03-15

This invention relates to non-precious metal fuel cell cathode catalysts, fuel cells that contain these catalysts, and methods of making the same. The fuel cell cathode catalysts are highly nitrogenated carbon materials that can contain a transition metal. The highly nitrogenated carbon materials can be supported on a nanoparticle substrate.

Homogeneously Dispersed Co9S8 Anchored on Nitrogen and Sulfur Co-Doped Carbon Derived from Soybean as Bifunctional Oxygen Electrocatalysts and Supercapacitors.

PubMed

Xiao, Zhen; Xiao, Guozheng; Shi, Minhao; Zhu, Ying

2018-05-16

Developing low-cost and highly active multifunctional electrocatalysts to replace noble metal catalysts is crucial for the commercialization of future clean energy technology. Herein, homogeneous Co 9 S 8 nanoparticles anchored on nitrogen and sulfur co-doped porous carbon nanomaterials (CoS@NSCs) are fabricated by pyrolysis of natural soybean treated with cobalt nitrate. The unique porous structures of the soybean are utilized to provide space for the oxidation and complexation reactions for cobalt compounds, thus leading to in situ generation of homogenously dispersed cobalt sulfide nanoparticles that anchored on the N,S co-doped carbon framework. Because of the coupling effect of cobalt sulfide and doping heteroatoms, CoS@NSC-800 not only displays excellent electrocatalytic performances with low overpotential and high current density toward both oxygen reduction reaction and oxygen evolution reaction comparable to the commercial Pt/C catalyst and IrO 2 catalyst, but also might be a promising candidate for high-performance supercapacitors. The method for the preparation of the multifunctional hybrids is simple but effective for the formation of uniformly distributed metal sulfide nanoparticles anchored on carbon materials, therefore providing a new perspective for the design and synthesis of multifunctional electrocatalysts for electrochemical energy conversion and storage at a large scale.

Development of materials for mini DMFC working at room temperature for portable applications

NASA Astrophysics Data System (ADS)

Coutanceau, C.; Koffi, R. K.; Léger, J.-M.; Marestin, K.; Mercier, R.; Nayoze, C.; Capron, P.

Methanol permeability measurements and direct methanol fuel cell tests were performed at room temperature with different commercially available or recast Nafion ® membranes and sulfonated polyimide (SPI) membranes. Power densities as high as 20 mW cm -2 could be obtained with Nafion ® 115. However, in order to meet the technological requirements for portable applications, thinner membranes have to be considered. As the MeOH crossover increases greatly (from (7 to 20) × 10 -8 mol s -1 cm -2) while Nafion ® membranes thickness decreases, non-perfluorinated polymers having high IEC are promising candidates for DMFC working at room temperature. The development catalysts tolerant to methanol is also relevant for this application. In spite of the low permeability to MeOH of SPI membranes, the obtained electrical performance with E-TEK electrodes based MEAs was lower than that obtained with Nafion ® membranes. No significant increase of performances was neither evidenced by using homemade PtCr(7:3)/C and PtRu(4:1)/C catalysts instead of E-TEK electrodes with recast Nafion ® based MEAs. However, MEAs composed with thin SPI membranes (50 μm) and homemade PtCr/C catalysts gave very promising results (18 mW cm -2). Based on experimental observations, a speculative explanation of this result is given.

Study of Catalyst Variation Effect in Glycerol Conversion Process to Hydrogen Gas by Steam Reforming

NASA Astrophysics Data System (ADS)

Widayat; Hartono, R.; Elizabeth, E.; Annisa, A. N.

2018-04-01

Along with the economic development, needs of energy being increase too. Hydrogen as alternative energy has many usages. Besides that, hydrogen is one source of energy that is a clean fuel, but process production of hydrogen from natural gas as a raw material has been used for a long time. Therefore, there is need new invention to produce hydrogen from the others raw material. Glycerol, a byproduct of biodiesel production, is a compound which can be used as a raw material for hydrogen production. By using glycerol as a raw material of hydrogen production, we can get added value of glycerol as well as an energy source solution. The process production of hydrogen by steam reforming is a thermochemical process with efficiency 70%. This process needs contribution of catalyst to improve its efficiency and selectivity of the process. In this study will be examined the effect variation of catalyst for glycerol conversion process to hydrogen by steam reforming. The method for catalyst preparation was variation of catalyst impregnation composition, catalyst calcined with difference concentration of hydrochloric acid and calcined with difference hydrochloric acid ratio. After that, all of catalyst which have been prepared, used for steam reforming process for hydrogen production from glycerol as a raw material. From the study, the highest yield of hydrogen gas showed in the process production by natural zeolite catalyst with 1:15 Hydrochloric acid ratio was 42.28%. Hydrogen yield for 2M calcined natural zeolite catalyst was 38.37%, for ZSM-5 catalyst was 15.83%, for 0.5M calcined natural zeolite was 13.09% and for ultrasonic natural zeolite was 11.43%. The lowest yield of hydrogen gas showed in catalyst 2Zn/ZSM-5 with 11.22%. This result showed that hydrogen yield product was affected by catalyst variation because of the catalyst has difference characteristic and difference catalytic activity after the catalyst preparation process.

First-Principles Design of Novel Catalytic and Chemoresponsive Materials

NASA Astrophysics Data System (ADS)

Roling, Luke T.

An emerging trend in materials design is the use of computational chemistry tools to accelerate materials discovery and implementation. In particular, the parallel nature of computational models enables high-throughput screening approaches that would be laborious and time-consuming with experiments alone, and can be useful for identifying promising candidate materials for experimental synthesis and evaluation. Additionally, atomic-scale modeling allows researchers to obtain a detailed understanding of phenomena invisible to many current experimental techniques. In this thesis, we highlight mechanistic studies and successes in catalyst design for heterogeneous electrochemical reactions, discussing both anode and cathode chemistries. In particular, we evaluate the properties of a new class of Pd-Pt core-shell and hollow nanocatalysts toward the oxygen reduction reaction. We do not limit our study to electrochemical reactivity, but also consider these catalysts in a broader context by performing in-depth studies of their stability at elevated temperatures as well as investigating the mechanisms by which they are able to form. We also present fundamental surface science studies, investigating graphene formation and H2 dissociation, which are processes of both fundamental and practical interest in many catalytic applications. Finally, we extend our materials design paradigm outside the field of catalysis to develop and apply a model for the detection of small chemical analytes by chemoresponsive liquid crystals, and offer several predictions for improving the detection of small chemicals. A close connection between computation, synthesis, and experimental evaluation is essential to the work described herein, as computations are used to gain fundamental insight into experimental observations, and experiments and synthesis are in turn used to validate predictions of material activities from computational models.

Catalyzed borohydrides for hydrogen storage

DOEpatents

Au, Ming [Augusta, GA

2012-02-28

A hydrogen storage material and process is provided in which alkali borohydride materials are created which contain effective amounts of catalyst(s) which include transition metal oxides, halides, and chlorides of titanium, zirconium, tin, and combinations of the various catalysts. When the catalysts are added to an alkali borodydride such as a lithium borohydride, the initial hydrogen release point of the resulting mixture is substantially lowered. Additionally, the hydrogen storage material may be rehydrided with weight percent values of hydrogen at least about 9 percent.

High Performance Fe- and N- Doped Carbon Catalyst with Graphene Structure for Oxygen Reduction

NASA Astrophysics Data System (ADS)

Peng, Hongliang; Mo, Zaiyong; Liao, Shijun; Liang, Huagen; Yang, Lijun; Luo, Fan; Song, Huiyu; Zhong, Yiliang; Zhang, Bingqing

2013-05-01

Proton exchange membrane fuel cells are promising candidates for a clean and efficient energy conversion in the future, the development of carbon based inexpensive non-precious metal ORR catalyst has becoming one of the most attractive topics in fuel cell field. Herein we report a Fe- and N- doped carbon catalyst Fe-PANI/C-Mela with graphene structure and the surface area up to 702 m2 g-1. In 0.1 M HClO4 electrolyte, the ORR onset potential for the catalyst is high up to 0.98 V, and the half-wave potential is only 60 mV less than that of the Pt/C catalyst (Loadings: 51 μg Pt cm-2). The catalyst shows high stability after 10,000 cyclic voltammetry cycles. A membrane electrode assembly made with the catalyst as a cathode is tested in a H2-air single cell, the maximum power density reached ~0.33 W cm2 at 0.47 V.

Engineering New Catalysts for In-Process Elimination of Tars

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

Felix, Larry G.

2012-09-30

The key objective of this project was to develop a new and more efficient methodology for engineering and economically producing optimized robust catalysts for the reduction or elimination of tars in biomass gasification. Whereas current catalyst technology typically disposes thin layers of catalytically-active material onto rigid supports via wet chemistry-based methods, this project investigated novel thermal methods for directly incorporating catalytically active materials onto robust supports as well as novel approaches for incorporating catalytically active materials on and/or within an otherwise inert refractory support material which is then subsequently formed and processed to create a catalytically-active material on all exposedmore » surfaces. Specifically, the focus of this engineered catalyst development was on materials which were derived from, or otherwise related to, olivine-like minerals, due to the inherent attrition resistance and moderate catalytic properties exhibited by natural olivine when used in a fluidized bed biomass gasifier. Task 1 of this project successfully demonstrated the direct thermal impregnation of catalytically-active materials onto an olivine substrate, with the production of a Ni-olivine catalyst. Nickel and nickel oxide were thermally impregnated onto an olivine substrate and when reduced were shown to demonstrate improved catalytic activity over the baseline olivine material and equal the tar-decomposing performance of Ni-olivine catalysts prepared by conventional wet impregnation. Task 2 involved coordination with our subcontracted project partners to further develop and characterize catalyst formulations and to optimize activity and production methods. Within this task, several significant new materials were developed. NexTech Materials developed a sintered ceramic nickel-magnesium-silicate catalyst that demonstrated superb catalytic activity and high resistance to deactivation by H2S. Alfred University developed both supported and integrated (bulk) catalysts via a glass-ceramic processing route which were shown to exhibit excellent catalytic activity and superior resistance to attrition deactivation. With the discovery of these active, robust, glass-based catalysts, and with the permission of the project officer, the investigation of waste-based materials as originally proposed for Task 3 and pilot-scale testing proposed in Task 5 were deferred indefinitely in favor of further investigation of the glass-ceramic based catalyst materials. This choice was justified in part because during FY 2006 and through FY 2007, funding restrictions imposed by congressional budget choices significantly reduced funding for DOE biomass-related projects. Funding for this project was limited to what had been authorized which slowed the pace of project work at GTI so that our project partners could continue in their work. Thereafter, project work was allowed to resume and with restored funding, the project continued and concentrated on the development and testing of glass-ceramic catalysts in bulk or supported formats. Work concluded with a final development devoted to increasing the surface area of glass-ceramic catalysts in the form of microspheres. Following that development, project reporting was completed and the project was concluded.« less

SISGR-Fundamental Experimental and Theoretical Studies on a Novel Family of Oxide Catalyst Supports for Water Electrolysis

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

Kumta, Prashant

2014-10-03

Identification and development of non-noble metal based electro-catalysts or electro-catalysts with significant reduction of expensive noble metal contents (E.g. IrO2, Pt) with comparable electrochemical performance as the standard noble metal/metal oxide for proton exchange membrane (PEM) based water electrolysis would constitute a major breakthrough in the generation of hydrogen by water electrolysis. Accomplishing such a system would not only result reduction of the overall capital costs of PEM based water electrolyzers, but also help attain the targeted hydrogen production cost [< $ 3.0 / gallon gasoline equivalent (gge)] comparable to conventional liquid fuels. In line with these goals, it wasmore » demonstrated that fluorine doped IrO2 thin films and nanostructured high surface area powders display remarkably higher electrochemical activity, and comparable durability as pure IrO2 electro-catalyst for the oxygen evolution reaction (OER) in PEM based water electrolysis. Furthermore, corrosion resistant SnO2 and NbO2 support has been doped with F and coupled with IrO2 or RuO2 for use as an OER electro-catalyst. A solid solution of SnO2:F or NbO2:F with only 20 - 30 mol.% IrO2 or RuO2 yielding a rutile structure in the form of thin films and bulk nanoparticles displays similar electrochemical activity and stability as pure IrO2/RuO2. This would lead to more than 70 mol.% reduction in the noble metal oxide content. Novel nanostructured ternary (Ir,Sn,Nb)O2 thin films of different compositions FUNDAMENTAL STUDY OF NANOSTRUCTURED ELECTRO-CATALYSTS WITH REDUCED NOBLE METAL CONTENT FOR PEM BASED WATER ELECTROLYSIS 4 have also been studied. It has been shown that (Ir0.40Sn0.30Nb0.30)O2 shows similar electrochemical activity and enhanced chemical robustness as compared to pure IrO2. F doping of the ternary (Ir,Sn,Nb)O2 catalyst helps in further decreasing the noble metal oxide content of the catalyst. As a result, these reduced noble metal oxide catalyst systems would potentially be preferred as OER electro-catalysts for PEM electrolysis. The excellent performance of the catalysts coupled with its robustness would make them great candidates for contributing to significant reduction in the overall capital costs of PEM based water electrolyzers. This s.thesis provides a detailed fundamental study of the synthesis, materials, characterization, theoretical studies and detailed electrochemical response and potential mechanisms of these novel electro-catalysts for OER processes.« less

Method of fabrication of anchored nanostructure materials

DOEpatents

Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

2013-11-26

Methods for fabricating anchored nanostructure materials are described. The methods include heating a nano-catalyst under a protective atmosphere to a temperature ranging from about 450.degree. C. to about 1500.degree. C. and contacting the heated nano-catalysts with an organic vapor to affix carbon nanostructures to the nano-catalysts and form the anchored nanostructure material.

Preparation of PEMFC Electrodes from Milligram-Amounts of Catalyst Powder

DOE PAGES

Yarlagadda, Venkata; McKinney, Samuel E.; Keary, Cristin L.; ...

2017-06-03

Development of electrocatalysts with higher activity and stability is one of the highest priorities in enabling cost-competitive hydrogen-air fuel cells. Although the rotating disk electrode (RDE) technique is widely used to study new catalyst materials, it has been often shown to be an unreliable predictor of catalyst performance in actual fuel cell operation. Fabrication of membrane electrode assemblies (MEA) for evaluation which are more representative of actual fuel cells generally requires relatively large amounts (>1 g) of catalyst material which are often not readily available in early stages of development. In this study, we present two MEA preparation techniques usingmore » as little as 30 mg of catalyst material, providing methods to conduct more meaningful MEA-based tests using research-level catalysts amounts.« less

Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction

PubMed Central

Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P.; Zhang, Jiujun

2016-01-01

A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst. PMID:26860889

Metal-Organic Framework-Derived Reduced Graphene Oxide-Supported ZnO/ZnCo2O4/C Hollow Nanocages as Cathode Catalysts for Aluminum-O2 Batteries.

PubMed

Liu, Yisi; Jiang, Hao; Hao, Jiayu; Liu, Yulong; Shen, Haibo; Li, Wenzhang; Li, Jie

2017-09-20

Aluminum-air battery is a promising candidate for large-scale energy applications because of its low cost and high energy density. Remarkably, tremendous efforts have been concentrated on developing efficient and stable cathode electrocatalysts toward the oxygen reduction reaction. In this work, a hydrothermal-calcination approach was utilized to prepare novel reduced graphene oxide (rGO)-supported hollow ZnO/ZnCo 2 O 4 nanoparticle-embedded carbon nanocages (ZnO/ZnCo 2 O 4 /C@rGO) using a zeolitic imidazolate framework (ZIF-67)/graphene oxide/zinc nitrate composite as the precursor. The ZnO/ZnCo 2 O 4 /C@rGO hybrid exhibits remarkable electrocatalytic performance for oxygen reduction reaction under alkaline conditions and superior stability and methanol tolerance to those of the commercial Pt/C catalyst. Furthermore, novel and simple Al-air coin cells were first fabricated using the hybrid materials as cathode catalysts under ambient air conditions to further investigate their catalytic performance. The coin cell with the ZnO/ZnCo 2 O 4 /C@rGO cathode catalyst displays a higher open circuit voltage and discharge voltage and more sluggish potential drop than those of the cell with the ZnO/ZnCo 2 O 4 /C cathode catalyst, which confirms that rGO can enhance the electrocatalytic activity and stability of the catalyst system. The excellent electrocatalytic performance of the ZnO/ZnCo 2 O 4 /C@rGO hybrid is attributed to the prominent conductivity and high specific surface area resulting from rGO, the more accessible catalytic active sites induced by the unique porous hollow nanocage structure, and synergic covalent coupling between rGO sheets and ZnO/ZnCo 2 O 4 /C nanocages.

Anchored nanostructure materials and method of fabrication

DOEpatents

Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

2012-11-27

Anchored nanostructure materials and methods for their fabrication are described. The anchored nanostructure materials may utilize nano-catalysts that include powder-based or solid-based support materials. The support material may comprise metal, such as NiAl, ceramic, a cermet, or silicon or other metalloid. Typically, nanoparticles are disposed adjacent a surface of the support material. Nanostructures may be formed as anchored to nanoparticles that are adjacent the surface of the support material by heating the nano-catalysts and then exposing the nano-catalysts to an organic vapor. The nanostructures are typically single wall or multi-wall carbon nanotubes.

Novel Attrition-Resistant Fischer Tropsch Catalyst

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

Weast, Logan, E.; Staats, William, R.

2009-05-01

There is a strong national interest in the Fischer-Tropsch synthesis process because it offers the possibility of making liquid hydrocarbon fuels from reformed natural gas or coal and biomass gasification products. This project explored a new approach that had been developed to produce active, attrition-resistant Fischer-Tropsch catalysts that are based on glass-ceramic materials and technology. This novel approach represented a promising solution to the problem of reducing or eliminating catalyst attrition and maximizing catalytic activity, thus reducing costs. The technical objective of the Phase I work was to demonstrate that glass-ceramic based catalytic materials for Fischer-Tropsch synthesis have resistance tomore » catalytic deactivation and reduction of particle size superior to traditional supported Fischer-Tropsch catalyst materials. Additionally, these novel glass-ceramic-based materials were expected to exhibit catalytic activity similar to the traditional materials. If successfully developed, the attrition-resistant Fischer-Tropsch catalyst materials would be expected to result in significant technical, economic, and social benefits for both producers and public consumers of Fischer-Tropsch products such as liquid fuels from coal or biomass gasification. This program demonstrated the anticipated high attrition resistance of the glass-ceramic materials. However, the observed catalytic activity of the materials was not sufficient to justify further development at this time. Additional testing documented that a lack of pore volume in the glass-ceramic materials limited the amount of surface area available for catalysis and consequently limited catalytic activity. However, previous work on glass-ceramic catalysts to promote other reactions demonstrated that commercial levels of activity can be achieved, at least for those reactions. Therefore, we recommend that glass-ceramic materials be considered again as potential Fischer-Tropsch catalysts if it can be demonstrated that materials with adequate pore volume can be produced. During the attrition resistance tests, it was learned that the glass-ceramic materials are very abrasive. Attention should be paid in any further developmental efforts to the potential for these hard, abrasive materials to damage reactors.« less

Corrosion testing of candidates for the alkaline fuel cell cathode

NASA Technical Reports Server (NTRS)

Singer, Joseph; Fielder, William L.

1989-01-01

Current/voltage data was obtained for specially made corrosion electrodes of some oxides and of gold materials for the purpose of developing a screening test of catalysts and supports for use at the cathode of the alkaline fuel cell. The data consists of measurements of current at fixed potentials and cyclic voltammograms. These data will have to be correlated with longtime performance data in order to fully evaluate this approach to corrosion screening. Corrosion test screening of candidates for the oxygen reduction electrode of the alkaline fuel cell was applied to two substances, the pyrochlore Pb2Ru2O6.5 and the spinel NiCo2O4. The substrate gold screen and a sample of the IFC Orbiter Pt-Au performance electrode were included as blanks. The pyrochlore data indicate relative stability, although nothing yet can be said about long term stability. The spinel was plainly unstable. For this type of testing to be validated, comparisons will have to be made with long term performance tests.

Modeling of hydrogen evolution reaction on the surface of GaInP2

NASA Astrophysics Data System (ADS)

Choi, Woon Ih; Wood, Brandon; Schwegler, Eric; Ogitsu, Tadashi

2012-02-01

GaInP2 is promising candidate material for hydrogen production using sunlight. It reduces solvated proton into hydrogen molecule using light-induced excited electrons in the photoelectrochemical cell. However, it is challenging to model hydrogen evolution reaction (HER) using first-principles molecular dynamics. Instead, we use Anderson-Newns model and generalized solvent coordinate in Marcus-Hush theory to describe adiabatic free energy surface of HER. Model parameters are fitted from the DFT calculations. We model Volmer-Heyrovsky reaction path on the surfaces of CuPt phase of GaInP2. We also discuss effects of surface oxide and catalyst atoms that exist on top of bare surfaces in experimental circumstances.

Opportunities for the chemical industry in space, part 1

NASA Technical Reports Server (NTRS)

1984-01-01

The chemical/petrochemical industry devotes a large percentage of its gross income to research and development, with much of its R and D of a long-term nature. As the chemical industry is examined as a candidate for space investigations, it is readily apparent that research and development in the space environment may lead to attractive commercial opportunities. The advantages of low gravity manufacturing, with a particular emphasis on chemical catalysts, are presented herein specifically for the chemical industry. Research from the Skylab program and Apollo Soyuz test project is reviewed, including acoustic levitation, crystal growth, and container less melts. Space processing of composite materials, alloys, and coatings is also discussed.

Water electrolysis on La 1-xSr xCoO 3-δ perovskite electrocatalysts

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

Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.

2016-03-23

Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr 2+ substitution into La 1-xSr xCoO 3-δ. We attempt tomore » rationalize the high activities of La 1-xSr xCoO 3-δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

Water electrolysis on La 1-xSr xCoO 3-δ perovskite electrocatalysts

DOE PAGES

Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; ...

2016-03-23

Here, perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr 2+ substitution into La 1–xSr xCoO 3–δ. We attemptmore » to rationalize the high activities of La 1–xSr xCoO 3–δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts

PubMed Central

Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; Hardin, William G.; Dai, Sheng; Kolpak, Alexie M.; Johnston, Keith P.; Stevenson, Keith J.

2016-01-01

Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1−xSrxCoO3−δ. We attempt to rationalize the high activities of La1−xSrxCoO3−δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis. PMID:27006166

Method of producing catalytic material for fabricating nanostructures

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

Seals, Roland D.; Menchhofer, Paul A.; Howe, Jane Y.

Methods of fabricating nano-catalysts are described. In some embodiments the nano-catalyst is formed from a powder-based substrate material and is some embodiments the nano-catalyst is formed from a solid-based substrate material. In some embodiments the substrate material may include metal, ceramic, or silicon or another metalloid. The nano-catalysts typically have metal nanoparticles disposed adjacent the surface of the substrate material. The methods typically include functionalizing the surface of the substrate material with a chelating agent, such as a chemical having dissociated carboxyl functional groups (--COO), that provides an enhanced affinity for metal ions. The functionalized substrate surface may then bemore » exposed to a chemical solution that contains metal ions. The metal ions are then bound to the substrate material and may then be reduced, such as by a stream of gas that includes hydrogen, to form metal nanoparticles adjacent the surface of the substrate.« less

Method of producing catalytic materials for fabricating nanostructures

DOEpatents

Seals, Roland D; Menchhofer, Paul A; Howe, Jane Y; Wang, Wei

2013-02-19

Methods of fabricating nano-catalysts are described. In some embodiments the nano-catalyst is formed from a powder-based substrate material and is some embodiments the nano-catalyst is formed from a solid-based substrate material. In some embodiments the substrate material may include metal, ceramic, or silicon or another metalloid. The nano-catalysts typically have metal nanoparticles disposed adjacent the surface of the substrate material. The methods typically include functionalizing the surface of the substrate material with a chelating agent, such as a chemical having dissociated carboxyl functional groups (--COO), that provides an enhanced affinity for metal ions. The functionalized substrate surface may then be exposed to a chemical solution that contains metal ions. The metal ions are then bound to the substrate material and may then be reduced, such as by a stream of gas that includes hydrogen, to form metal nanoparticles adjacent the surface of the substrate.

Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

PubMed

Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

2017-12-01

In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Monolithic catalyst beds for hydrazine reactors

NASA Technical Reports Server (NTRS)

1973-01-01

A monolithic catalyst bed for monopropellant hydrazine decomposition was evaluated. The program involved the evaluation of a new hydrazine catalyst concept wherein open-celled foamed materials are used as supports for the active catalysts. A high-surface-area material is deposited upon the open-celled foamed material and is then coated with an active metal to provide a spontaneous catalyst. Only a fraction of the amount of expensive active metal in currently available catalysts is needed to promote monolithic catalyst. Numerous parameters were evaluated during the program, and the importance of additional parameters became obvious only while the program was in progress. A demonstration firing (using a 2.2-Newton (N)(0.5-lbf) reactor) successfully accumulated 7,700 seconds of firing time and 16 ambient temperature starts without degradation. Based on the excellent results obtained throughout the program and the demonstrated life capability of the monolithic foam, it is recommended that additional studies be conducted to further exploit the advantages of this concept.

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

Highly efficient hydrogen release from formic acid using a graphitic carbon nitride-supported AgPd nanoparticle catalyst

NASA Astrophysics Data System (ADS)

Yao, Fang; Li, Xiao; Wan, Chao; Xu, Lixin; An, Yue; Ye, Mingfu; Lei, Zhao

2017-12-01

Bimetallic AgPd nanoparticles with various molar ratios immobilized on graphitic carbon nitride (g-C3N4) were successfully synthesized via a facile co-reduction approach. The powder XRD, XPS, TEM, EDX, ICP-AES and BET were employed to characterize the structure, size, composition and loading metal electronic states of the AgPd/g-C3N4 catalysts. The catalytic property of as-prepared catalysts for the dehydrogenation of formic acid (FA) with sodium formate (SF) as the additive was investigated. The performance of these catalysts, as indicated by the turnover frequency (TOF), depended on the composition of the prepared catalysts. Among all the AgPd/g-C3N4 catalysts tested, Ag9Pd91/g-C3N4 was found to be an exceedingly high activity for decomposing FA into H2 with TOF up to 480 h-1 at 323 K. The prepared catalyst is thus a potential candidate for triggering the widespread use of FA for H2 storage.

Carbon nanocages: a new support material for Pt catalyst with remarkably high durability.

PubMed

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-03-24

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for "real world" application.

Oxygen-reducing catalyst layer

DOEpatents

O'Brien, Dennis P [Maplewood, MN; Schmoeckel, Alison K [Stillwater, MN; Vernstrom, George D [Cottage Grove, MN; Atanasoski, Radoslav [Edina, MN; Wood, Thomas E [Stillwater, MN; Yang, Ruizhi [Halifax, CA; Easton, E Bradley [Halifax, CA; Dahn, Jeffrey R [Hubley, CA; O'Neill, David G [Lake Elmo, MN

2011-03-22

An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

Options and processes for spent catalyst handling and utilization.

PubMed

Marafi, M; Stanislaus, A

2003-07-18

The quantity of spent hydroprocessing catalysts discarded as solid wastes in the petroleum refining industries has increased remarkably in recent years due to a rapid growth in the hydroprocessing capacity to meet the rising demand for low-sulfur fuels. Due to their toxic nature, spent hydroprocessing catalysts have been branded as hazardous wastes, and the refiners are experiencing pressure from environmental authorities to handle them safely. Several alternative methods such as reclamation of metals, rejuvenation and reuse, disposal in landfills and preparation of useful materials using spent catalysts as raw materials are available to deal with the spent catalyst problem. The technical feasibility as well as the environmental and economic aspects of these options are reviewed. In addition, details of two bench-scale processes, one for rejuvenation of spent hydroprocessing catalysts, and the other for producing non-leachable synthetic aggregate materials that were developed in this laboratory, are presented in this paper.

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

PubMed

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

2015-08-26

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

Recent Advances in Bismuth-Based Nanomaterials for Photoelectrochemical Water Splitting.

PubMed

Bhat, Swetha S M; Jang, Ho Won

2017-08-10

In recent years, bismuth-based nanomaterials have drawn considerable interest as potential candidates for photoelectrochemical (PEC) water splitting owing to their narrow band gaps, nontoxicity, and low costs. The unique electronic structure of bismuth-based materials with a well-dispersed valence band comprising Bi 6s and O 2p orbitals offers a suitable band gap to harvest visible light. This Review presents significant advancements in exploiting bismuth-based nanomaterials for solar water splitting. An overview of the different strategies employed and the new ideas adopted to improve the PEC performance of bismuth-based nanomaterials are discussed. Morphology control, the construction of heterojunctions, doping, and co-catalyst loading are several approaches that are implemented to improve the efficiency of solar water splitting. Key issues are identified and guidelines are suggested to rationalize the design of efficient bismuth-based materials for sunlight-driven water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel self-healing materials chemistries for targeted applications

NASA Astrophysics Data System (ADS)

Wilson, Gerald O.

Self-healing materials of the type developed by White and co-workers [1] were designed to autonomically heal themselves when damaged, thereby extending the lifetime of various applications in which such material systems are employed. The system was based on urea-formaldehyde microcapsules containing dicyclopentadiene (DCPD) and Grubbs' catalyst particles embedded together in an epoxy matrix. When a crack propagates through the material, it ruptures the microcapsules, releasing DCPD into the crack plane, where it comes in contact and reacts with the catalyst to initiate a ring opening metathesis polymerization (ROMP), bonding the crack and restoring structural continuity. The present work builds on this concept in several ways. Firstly, it expands the scope and versatility of the ROMP self-healing chemistry by incorporation into epoxy vinyl ester matrices. Major technical challenges in this application include protection of the catalyst from deactivation by aggressive curing agents, and optimization of the concentration of healing agents in the matrix. Secondly, new ruthenium catalysts are evaluated for application in ROMP-based self-healing materials. The use of alternative derivatives of Grubbs' catalyst gave rise to self-healing systems with improved healing efficiencies and thermal properties. Evaluation of the stability of these new catalysts to primary amine curing agents used in the curing of common epoxy matrices also led to the discovery and characterization of new ruthenium catalysts which exhibited ROMP initiation kinetics superior to those of first and second generation Grubbs' catalysts. Finally, free radical polymerization was evaluated for application in the development of bio-compatible self-healing materials. [1] White, S. R.; Sottos, N. R.; Geubelle, P. R.; Moore, J. S.; Kessler, M. R.; Sriram, S. R.; Brown, E. N.; Viswanathan, S. Nature 2001, 409, 794.

Porous Ni-Mn oxide nanosheets in situ formed on nickel foam as 3D hierarchical monolith de-NOx catalysts

NASA Astrophysics Data System (ADS)

Cai, Sixiang; Zhang, Dengsong; Shi, Liyi; Xu, Jing; Zhang, Lei; Huang, Lei; Li, Hongrui; Zhang, Jianping

2014-06-01

In this work, we successfully in situ decorated nickel foam with porous Ni-Mn oxide nanosheets (3DH-NM/NF) as 3D hierarchical monolith de-NOx catalysts via a simple hydrothermal reaction and calcination process. The catalysts were carefully examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, elemental mapping, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction and NH3 temperature-programmed desorption measurements. The results indicated that the nanosheets are composed of a Ni6Mn1O8 spinel and the metal species are uniformly dispersed in bi-metal oxides. As a result, the strong synergistic effects between the Mn and Ni species have been observed. The active oxygen species, reducible species and acidity are enhanced by the in situ formation of the nanosheets on the surface of nickel foam. These desirable features of 3DH-NM/NF catalysts bring about the excellent de-NOx performance. Moreover, the 3DH-NM/NF catalysts also present good stability and H2O resistance. Based on these favorable properties, 3DH-NM/NF could be considered as a promising candidate for the monolith de-NOx catalysts.In this work, we successfully in situ decorated nickel foam with porous Ni-Mn oxide nanosheets (3DH-NM/NF) as 3D hierarchical monolith de-NOx catalysts via a simple hydrothermal reaction and calcination process. The catalysts were carefully examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, elemental mapping, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction and NH3 temperature-programmed desorption measurements. The results indicated that the nanosheets are composed of a Ni6Mn1O8 spinel and the metal species are uniformly dispersed in bi-metal oxides. As a result, the strong synergistic effects between the Mn and Ni species have been observed. The active oxygen species, reducible species and acidity are enhanced by the in situ formation of the nanosheets on the surface of nickel foam. These desirable features of 3DH-NM/NF catalysts bring about the excellent de-NOx performance. Moreover, the 3DH-NM/NF catalysts also present good stability and H2O resistance. Based on these favorable properties, 3DH-NM/NF could be considered as a promising candidate for the monolith de-NOx catalysts. Electronic supplementary information (ESI) available: Experimental details and catalytic performance of the NM/cordierite catalysts, SEM image and EDX analysis of the NF and 3DH-N/NF catalysts, N2 selectivity and catalytic performance under different gas hourly space velocities of the 3DH-NM/NF catalysts. See DOI: 10.1039/c4nr00475b

Activation of Hydrogen Peroxide by Iron-Containing Minerals and Catalysts in Circumneutral pH Solutions: Implications for ex situ and in situ Treatment of Contaminated Water and Soil

NASA Astrophysics Data System (ADS)

Pham, Anh Le Tuan

The decomposition of hydrogen peroxide (H2O2) on iron minerals can generate hydroxyl radical (•OH), a strong oxidant capable of transforming a wide range of contaminants. This reaction is critical to ex situ advanced oxidation processes employed in waste treatment systems, as well as in situ chemical oxidation processes used for soil and groundwater remediation. Unfortunately, the process in the ex situ treatment systems is relatively inefficient at circumneutral pH values. In this research, the development of iron-containing catalysts with improved efficiency was investigated. In addition, little is known about the factors that control the performance of in situ treatment systems. Another aim of this dissertation was to elucidate those factors to provide a basis for improving the efficiency of the remediation method. Two types of silica- and alumina-containing iron (hydr)oxide catalysts were synthesized by sol-gel processing techniques (Chapter 2). Relative to iron oxides, such as hematite and goethite, these catalysts were 10 to 80 times more effective in catalyzing the production of •OH from H2O2 under circumneutral conditions. The higher efficiency makes these catalysts promising candidates for ex situ advanced oxidation processes. Moreover, because alumina and silica alter the reactivity of the iron oxides with H2O2, understanding the activity of iron associated with natural aluminosilicates and silica-containing minerals in the subsurface is crucial to explaining the variability of •OH production observed in in situ treatment systems. In addition to the sol-gel technique used in Chapter 2, silica-containing iron (hydr)oxide catalysts were synthesized by immobilizing iron oxide onto mesoporous silica supports, such as SBA-15 (Chapter 5). The iron-containing SBA-15 was 10 times more effective than iron oxides in catalyzing the production of •OH from H2O2. Moreover, this catalyst could be employed for selective oxidation of small organic contaminants based on size exclusion. However, a major drawback of the mesoporous silica-based catalysts is their instability under circumneutral conditions (Chapter 6). The dissolution of mesoporous silica materials raises questions about their use for water treatment, because silica dissolution might compromise the behavior of the material. To gain insight into factors that control H2O2 persistence and •OH yield in in situ processes, the decomposition of H2O2 and transformation of contaminants were investigated in the presence of iron-containing minerals and aquifer materials (Chapter 3). Consistent with the observation described in Chapter 2, iron-containing aluminosilicates were more effective than iron oxides in converting H2O2 into •OH. In both iron-containing mineral and aquifer material systems, the yield of •OH was inversely correlated with the rate of H 2O2 decomposition. In the aquifer material systems, the yield also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce •OH. The inverse correlation between Mn content and H2O2 loss rate and •OH yield suggests that the amount of Mn in aquifer materials could serve as a proxy for predicting H2O2 decomposition rates and contaminant oxidation efficiency. In addition to the surface and structure properties of iron solids, the presence of solutes, such as dissolved silica, also affected the decomposition of H2O2 (Chapter 4). The adsorption of dissolved silica onto mineral surfaces altered the catalytic sites, thereby decreasing the reactivity of iron- and manganese-containing minerals with H2O 2. Therefore, the presence of dissolved SiO2 could lead to greater persistence of H2O2 in groundwater, which should be considered in the design of in situ H2O 2-based treatment systems. In addition to in situ treatment, dissolved silica also can affect the reactivity of iron-containing catalysts used in ex situ processes. Therefore, its presence in contaminated industrial wastewater should be considered when ex situ treatment systems are designed.

Method for dispersing catalyst onto particulate material and product thereof

DOEpatents

Utz, Bruce R.; Cugini, Anthony V.

1992-01-01

A method for dispersing finely divided catalyst precursors onto the surface of coal or other particulate material includes the steps of forming a wet paste mixture of the particulate material and a liquid solution containing a dissolved transition metal salt, for instance a solution of ferric nitrate. The wet paste mixture is in a state of incipient wetness with all of this solution adsorbed onto the surfaces of the particulate material without the presence of free moisture. On adding a precipitating agent such as ammonia, a catalyst precursor such as hydrated iron oxide is deposited on the surfaces of the coal. The catalyst is activated by converting it to the sulfide form for the hydrogenation or direct liquefaction of the coal.

Method for dispersing catalyst onto particulate material

DOEpatents

Utz, Bruce R.; Cugini, Anthony V.

1992-01-01

A method for dispersing finely divided catalyst precursors onto the surface of coal or other particulate material includes the steps of forming a wet paste mixture of the particulate material and a liquid solution containing a dissolved transition metal salt, for instance a solution of ferric nitrate. The wet paste mixture is in a state of incipient wetness with all of this solution adsorbed onto the surfaces of the particulate material without the presence of free moisture. On adding a precipitating agent such as ammonia, a catalyst precursor such as hydrated iron oxide is deposited on the surfaces of the coal. The catalyst is activated by converting it to the sulfide form for the hydrogenation or direct liquefaction of the coal.

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

Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

DOEpatents

Zelenay, Piotr; Wu, Gang

2014-04-29

A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

Method of making chalcogen catalysts for polymer electrolyte fuel cells

DOEpatents

Choi, Jong-Ho; Zelenay, Piotr; Wieckowski, Andrzej; Cao, Dianxue

2010-12-14

A method of making an electrode catalyst material using aqueous solutions. The electrode catalyst material includes a support comprising at least one transition metal and at least one chalcogen disposed on a surface of the transition metal. The method includes reducing a metal powder, mixing the metal powder with an aqueous solution containing at least one inorganic compound of the chalcogen to form a mixture, and providing a reducing agent to the mixture to form nanoparticles of the electrode catalyst. The electrode catalyst may be used in a membrane electrode assembly for a fuel cell.

Controlled growth of vertically aligned carbon nanotubes on metal substrates

NASA Astrophysics Data System (ADS)

Gao, Zhaoli

Carbon nanotube (CNT) is a fascinating material with extraordinary electrical thermal and mechanical properties. Growing vertically aligned CNT (VACNT) arrays on metal substrates is an important step in bringing CNT into practical applications such as thermal interface materials (TIMs) and microelectrodes. However, the growth process is challenging due to the difficulties in preventing catalyst diffusion and controlling catalyst dewetting on metal substrates with physical surface heterogeneity. In this work, the catalyst diffusion mechanism and catalyst dewetting theory were studied for the controlled growth of VACNTs on metal substrates. The diffusion time of the catalyst, the diffusion coefficients for the catalyst in the substrate materials and the number density of catalyst nanoparticles after dewetting are identified as the key parameters, based on which three strategies are developed. Firstly, a fast-heating catalyst pretreatment strategy was used, aiming at preserving the amount of catalyst prior to CNT growth by reducing the catalyst diffusion time. The catalyst lifetime is extended from half an hour to one hour on a patterned Al thin film and a VACNT height of 106 mum, about twenty fold of that reported in the literature, was attained. Secondly, a diffusion barrier layer strategy is employed for a reduction of catalyst diffusion into the substrate materials. Enhancement of VACNT growth on Cu substrates was achieved by adopting a conformal Al2O 3 diffusion barrier layer fabricated by a specially designed atomic layer deposition (ALD) system. Lastly, a novel catalyst glancing angle deposition (GLAD) strategy is performed to manipulate the morphology of a relatively thick catalyst on metal substrates with physical surface heterogeneity, aiming to obtain uniform and dense catalyst nanoparticles after dewetting in the pretreatment process for enhanced VACNT growth. We are able to control the VACNT growth conditions on metal substrates in terms of their distribution, heights and alignments. Catalyst loss is controlled by the catalyst diffusion time and catalyst diffusion coefficients. A shorter catalyst diffusion time and smaller diffusion coefficient enhance VACNT growth on metals due to reduced catalyst loss during the pretreatment process. The dewetting behaviors of the thin film catalysts are influenced by the physical surface heterogeneity of the substrates which leads to non-uniform growth of VACNTs. The GLAD process facilitates the deposition of a relatively thick catalyst layer for the creation of dense and uniform catalyst nanoparticles. Applications of VACNT-metal structures in TIMs and microelectrodes are demonstrated. The VACNT-TIMs fabricated on Al alloy substrates have a typical thermal contact resistivity of 17.1 mm2˙K/W and their effective application in high-brightness LED thermal management was demonstrated. Electrochemical characterization was carried out on VACNT microelectrodes for the development of high resolution retinal prostheses and a satisfactory electrochemical property was again demonstrated.

A review on photocatalytic CO2 reduction using perovskite oxide nanomaterials

NASA Astrophysics Data System (ADS)

Zeng, Sheng; Kar, Piyush; Thakur, Ujwal Kumar; Shankar, Karthik

2018-02-01

As the search for efficient catalysts for CO2 photoreduction continues, nanostructured perovskite oxides have emerged as a class of high-performance photocatalytic materials. The perovskite oxide candidates for CO2 photoreduction are primarily nanostructured forms of titanates, niobates, tantalates and cobaltates. These materials form the focus of this review article because they are much sought-after due to their nontoxic nature, adequate chemical stability, and tunable crystal structures, bandgaps and surface energies. As compared to conventional semiconductors and nanomaterial catalysts, nanostructured perovskite oxides also exhibit an extended optical-absorption edge, longer charge carrier lifetimes, and favorable band-alignment with respect to reduction potential of activated CO2 and reduction products of the same. While CO2 reduction product yields of several hundred μmol-1 h-1 are observed with many types of perovskite oxide nanomaterials in stand-alone forms, yield of such quantities are not common with semiconductor nanomaterials of other types. In this review, we present current state-of-the-art synthesis methods to form perovskite oxide nanomaterials, and procedures to engineer their bandgaps. This review also presents a comprehensive summary and discussion on crystal structures, defect distribution, morphologies and electronic properties of the perovskite oxides, and correlation of these properties to CO2 photoreduction performance. This review offers researchers key insights for developing advanced perovskite oxides in order to further improve the yields of CO2 reduction products.

Transition-metal-free catalysts for the sustainable epoxidation of alkenes: from discovery to optimisation by means of high throughput experimentation.

PubMed

Lueangchaichaweng, Warunee; Geukens, Inge; Peeters, Annelies; Jarry, Benjamin; Launay, Franck; Bonardet, Jean-Luc; Jacobs, Pierre A; Pescarmona, Paolo P

2012-02-01

Transition-metal-free oxides were studied as heterogeneous catalysts for the sustainable epoxidation of alkenes with aqueous H₂O₂ by means of high throughput experimentation (HTE) techniques. A full-factorial HTE approach was applied in the various stages of the development of the catalysts: the synthesis of the materials, their screening as heterogeneous catalysts in liquid-phase epoxidation and the optimisation of the reaction conditions. Initially, the chemical composition of transition-metal-free oxides was screened, leading to the discovery of gallium oxide as a novel, active and selective epoxidation catalyst. On the basis of these results, the research line was continued with the study of structured porous aluminosilicates, gallosilicates and silica-gallia composites. In general, the gallium-based materials showed the best catalytic performances. This family of materials represents a promising class of heterogeneous catalysts for the sustainable epoxidation of alkenes and offers a valid alternative to the transition-metal heterogeneous catalysts commonly used in epoxidation. High throughput experimentation played an important role in promoting the development of these catalytic systems.

Carbon nanotube synthesis with different support materials and catalysts

NASA Astrophysics Data System (ADS)

Gümüş, Fatih; Yuca, Neslihan; Karatepe, Nilgün

2013-09-01

Having remarkable characteristics, carbon nanotubes (CNTs) have attracted a lot of interest. Their mechanical, electrical, thermal and chemical properties make CNTs suitable for several applications such as electronic devices, hydrogen storage, textile, drug delivery etc. CNTs have been synthesized by various methods, such as arc discharge, laser ablation and catalytic chemical vapor deposition (CCVD). In comparison with the other techniques, CCVD is widely used as it offers a promising route for mass production. High capability of decomposing hydrocarbon formation is desired for the selected catalysts. Therefore, transition metals which are in the nanometer scale are the most effective catalysts. The common transition metals that are being used are Fe, Co, Ni and their binary alloys. The impregnation of the catalysts over the support material has a crucial importance for the CNT production. In this study, the influence of the support materials on the catalytic activity of metals was investigated. CNTs have been synthesized over alumina (Al2O3), silica (SiO2) and magnesium oxide (MgO) supported Fe, Co, Fe-Co catalysts. Catalyst - support material combinations have been investigated and optimum values for each were compared. Single walled carbon nanotubes (SWCNTs) were produced at 800°C. The duration of synthesis was 30 minutes for all support materials. The synthesized materials were characterized by thermal gravimetric analysis (TGA), Raman spectroscopy and transmission electron microscopy.

Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

NASA Astrophysics Data System (ADS)

Albayati, Talib M.; Doyle, Aidan M.

2015-02-01

Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

PubMed Central

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

Catalyst for microelectromechanical systems microreactors

DOEpatents

Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

2010-06-29

A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

Catalyst for microelectromechanical systems microreactors

DOEpatents

Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

2011-11-15

A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

Optimization on electrochemical synthesis of HKUST-1 as candidate catalytic material for Green diesel production

NASA Astrophysics Data System (ADS)

Lestari, W. W.; Nugraha, R. E.; Winarni, I. D.; Adreane, M.; Rahmawati, F.

2016-04-01

In the effort to support the discovery of new renewable energy sources in Indonesia, biofuel is one of promising options. The conversion of vegetable oil into ready-biofuel, especially green diesel, needs several steps, one of which is a hydrogenation or hydro-deoxygenation reaction. In this case, the catalyst plays a very important role regarding to its activity and selectivity, and Metal-Organic Frameworks (MOFs) becoming a new generation of heterogeneous catalyst in this area. In this research, a preliminary study to optimize electrochemical synthesis of the catalytic material based on MOFs, namely HKUST-1 [Cu3(BTC)2], has been conducted. Some electrochemical reaction parameters were tested, for example by modifying the electrochemical synthetic conditions, i.e. by performing variation of voltages (12, 13, 14, and 15 Volt), temperatures (RT, 40, 60, and 80 °C) and solvents (ethanol, water, methanol and dimethyl-formamide (DMF)). Material characterization was carried out by XRD, SEM, FTIR, DTA/TG and SAA. The results showed that the optimum synthetic conditions of HKUST-1 are performed at room temperature in a solvent combination of water: ethanol (1: 1) and a voltage of 15 Volt for 2 hours. The XRD-analysis revealed that the resulted peaks are identical to the simulated powder pattern generated from single crystal data and comparable to the peaks of solvothermal method. However, the porosity of the resulting material through electrochemical method is still in the range of micro-pore according to IUPAC and 50% smaller than the porosity resulted from solvothermal synthesis. The corresponding compounds are thermally stable until 300 °C according to TG/DTA.

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.

Carbon nanocages: A new support material for Pt catalyst with remarkably high durability

PubMed Central

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-01-01

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for “real world” application. PMID:24658614

Method for producing catalysts from coal

DOEpatents

Farcasiu, M.; Derbyshire, F.; Kaufman, P.B.; Jagtoyen, M.

1998-02-24

A method for producing catalysts from coal is provided comprising mixing an aqueous alkali solution with the coal, heating the aqueous mixture to treat the coal, drying the now-heated aqueous mixture, reheating the mixture to form carbonized material, cooling the mixture, removing excess alkali from the carbonized material, and recovering the carbonized material, wherein the entire process is carried out in controlled atmospheres, and the carbonized material is a hydrocracking or hydrodehalogenation catalyst for liquid phase reactions. The invention also provides for a one-step method for producing catalysts from coal comprising mixing an aqueous alkali solution with the coal to create a mixture, heating the aqueous mixture from an ambient temperature to a predetermined temperature at a predetermined rate, cooling the mixture, and washing the mixture to remove excess alkali from the treated and carbonized material, wherein the entire process is carried out in a controlled atmosphere. 1 fig.

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

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

DOE PAGES

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

2015-03-20

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

Down-flow moving-bed gasifier with catalyst recycle

DOEpatents

Halow, John S.

1999-01-01

The gasification of coal and other carbonaceous materials by an endothermic gasification reaction is achieved in the presence of a catalyst in a down-flow, moving-bed gasifier. Catalyst is removed along with ash from the gasifier and is then sufficiently heated in a riser/burner by the combustion of residual carbon in the ash to volatilize the catalyst. This volatilized catalyst is returned to the gasifier where it uniformly contacts and condenses on the carbonaceous material. Also, the hot gaseous combustion products resulting from the combustion of the carbon in the ash along with excess air are introduced into the gasifier for providing heat energy used in the endothermic reaction.

Bifunctional catalysts for upgrading of biomass-derived oxygenates: A review

DOE PAGES

Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

2016-06-21

Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the differentmore » types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. Finally, these studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.« less

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.

Synthesis of Ordered Mesoporous CuO/CeO2 Composite Frameworks as Anode Catalysts for Water Oxidation

PubMed Central

Markoulaki, Vassiliki Ι.; Papadas, Ioannis T.; Kornarakis, Ioannis; Armatas, Gerasimos S.

2015-01-01

Cerium-rich metal oxide materials have recently emerged as promising candidates for the photocatalytic oxygen evolution reaction (OER). In this article, we report the synthesis of ordered mesoporous CuO/CeO2 composite frameworks with different contents of copper(II) oxide and demonstrate their activity for photocatalytic O2 production via UV-Vis light-driven oxidation of water. Mesoporous CuO/CeO2 materials have been successfully prepared by a nanocasting route, using mesoporous silica as a rigid template. X-ray diffraction, electron transmission microscopy and N2 porosimetry characterization of the as-prepared products reveal a mesoporous structure composed of parallel arranged nanorods, with a large surface area and a narrow pore size distribution. The molecular structure and optical properties of the composite materials were investigated with Raman and UV-Vis/NIR diffuse reflectance spectroscopy. Catalytic results indicated that incorporation of CuO clusters in the CeO2 lattice improved the photochemical properties. As a result, the CuO/CeO2 composite catalyst containing ~38 wt % CuO reaches a high O2 evolution rate of ~19.6 µmol·h−1 (or 392 µmol·h−1·g−1) with an apparent quantum efficiency of 17.6% at λ = 365 ± 10 nm. This OER activity compares favorably with that obtained from the non-porous CuO/CeO2 counterpart (~1.3 µmol·h−1) and pure mesoporous CeO2 (~1 µmol·h−1). PMID:28347106

HSPES membrane electrode assembly

NASA Technical Reports Server (NTRS)

Kindler, Andrew (Inventor); Yen, Shiao-Ping (Inventor)

2000-01-01

An improved fuel cell electrode, as well as fuel cells and membrane electrode assemblies that include such an electrode, in which the electrode includes a backing layer having a sintered layer thereon, and a non-sintered free-catalyst layer. The invention also features a method of forming the electrode by sintering a backing material with a catalyst material and then applying a free-catalyst layer.

Recent developments of nano-structured materials as the catalysts for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Kang, SungYeon; Kim, HuiJung; Chung, Yong-Ho

2018-04-01

Developments of high efficient materials for electrocatalyst are significant topics of numerous researches since a few decades. Recent global interests related with energy conversion and storage lead to the expansion of efforts to find cost-effective catalysts that can substitute conventional catalytic materials. Especially, in the field of fuel cell, novel materials for oxygen reduction reaction (ORR) have been noticed to overcome disadvantages of conventional platinum-based catalysts. Various approaching methods have been attempted to achieve low cost and high electrochemical activity comparable with Pt-based catalysts, including reducing Pt consumption by the formation of hybrid materials, Pt-based alloys, and not-Pt metal or carbon based materials. To enhance catalytic performance and stability, numerous methods such as structural modifications and complex formations with other functional materials are proposed, and they are basically based on well-defined and well-ordered catalytic active sites by exquisite control at nanoscale. In this review, we highlight the development of nano-structured catalytic materials for ORR based on recent findings, and discuss about an outlook for the direction of future researches.

Catalyst support structure, catalyst including the structure, reactor including a catalyst, and methods of forming same

DOEpatents

Van Norman, Staci A.; Aston, Victoria J.; Weimer, Alan W.

2017-05-09

Structures, catalysts, and reactors suitable for use for a variety of applications, including gas-to-liquid and coal-to-liquid processes and methods of forming the structures, catalysts, and reactors are disclosed. The catalyst material can be deposited onto an inner wall of a microtubular reactor and/or onto porous tungsten support structures using atomic layer deposition techniques.

Design and application of sporopollenin microcapsule supported palladium catalyst: Remarkably high turnover frequency and reusability in catalysis of biaryls.

PubMed

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

2017-01-15

Bio-based catalyst support materials with high thermal and structural stability are desired for catalysts systems requiring harsh conditions. In this study, a thermally stable palladium catalyst (up to 440°C) was designed from sporopollenin, which occurs naturally in the outer exine layer of pollens and is widely acknowledged as chemically very stable and inert biological material. Catalyst design procedure included (1) extraction of sporopollenin microcapsules from Betula pendula pollens (∼25μm), (2) amino-functionalisation of the microcapsules, (3) Schiff base modification and (4) preparation of Pd(II) catalyst. The catalytic activity of the sporopollenin microcapsule supported palladium catalyst was tested in catalysis of biaryls by following a fast, simple and green microwave-assisted method. We recorded outstanding turnover number (TON: 40,000) and frequency (TOF: 400,000) for the catalyst in Suzuki coupling reactions. The catalyst proved to be reusable at least in eight cycles. The catalyst can be suggested for different catalyst systems due to its thermal and structural durability, reusability, inertness to air and its eco-friendly nature. Copyright © 2016 Elsevier Inc. All rights reserved.

Fluorescence imaging technology (FI) for high-throughput screening of selenide-modified nano-TiO2 catalysts.

PubMed

Wang, Liping; Lee, Jianchao; Zhang, Meijuan; Duan, Qiannan; Zhang, Jiarui; Qi, Hailang

2016-02-18

A high-throughput screening (HTS) method based on fluorescence imaging (FI) was implemented to evaluate the catalytic performance of selenide-modified nano-TiO2. Chemical ink-jet printing (IJP) technology was reformed to fabricate a catalyst library comprising 1405 (Ni(a)Cu(b)Cd(c)Ce(d)In(e)Y(f))Se(x)/TiO2 (M6Se/Ti) composite photocatalysts. Nineteen M6Se/Tis were screened out from the 1405 candidates efficiently.

Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

2016-02-01

High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

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

PubMed

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

2011-01-01

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

Catalyst material and method of making

DOEpatents

Matson, Dean W.; Fulton, John L.; Linehan, John C.; Bean, Roger M.; Brewer, Thomas D.; Werpy, Todd A.; Darab, John G.

1997-01-01

The material of the present invention is a mixture of catalytically active material and carrier materials, which may be catalytically active themselves. Hence, the material of the present invention provides a catalyst particle that has catalytically active material throughout its bulk volume as well as on its surface. The presence of the catalytically active material throughout the bulk volume is achieved by chemical combination of catalytically active materials with carrier materials prior to or simultaneously with crystallite formation.

Catalyst material and method of making

DOEpatents

Matson, D.W.; Fulton, J.L.; Linehan, J.C.; Bean, R.M.; Brewer, T.D.; Werpy, T.A.; Darab, J.G.

1997-07-29

The material of the present invention is a mixture of catalytically active material and carrier materials, which may be catalytically active themselves. Hence, the material of the present invention provides a catalyst particle that has catalytically active material throughout its bulk volume as well as on its surface. The presence of the catalytically active material throughout the bulk volume is achieved by chemical combination of catalytically active materials with carrier materials prior to or simultaneously with crystallite formation. 7 figs.

Advanced materials for automobiles

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

Narula, C.K.; Allison, J.E.; Bauer, D.R.

Quite early on, manufacturers realized that lighter automobiles (with gas and diesel engines) would be more fuel efficient and produce fewer tailpipe emissions. They also realized that burning diesel fuel at elevated temperatures (1,315 C) would result in similar improvements. However, materials limitations prevent the operation of diesel vehicles at high temperatures. The fuel efficiency of gasoline-powered vehicles is currently improved by reducing the weight of the automobile and treated the emissions with a three-way catalyst. Additional improvements can be achieved with the use of advanced materials that reduce the weight of vehicles without compromising safety. The use of ceramics,more » fiber-reinforced plastics, and metal-matrix composites are discussed. The paper also discusses automotive catalysts and their components, electrically heated catalyst devices, a lean-burn NOx catalyst, and the future for materials chemistry.« less

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

PubMed

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

2009-07-08

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

Apparatus and Process for Controlled Nanomanufacturing Using Catalyst Retaining Structures

NASA Technical Reports Server (NTRS)

Nguyen, Cattien (Inventor)

2013-01-01

An apparatus and method for the controlled fabrication of nanostructures using catalyst retaining structures is disclosed. The apparatus includes one or more modified force microscopes having a nanotube attached to the tip portion of the microscopes. An electric current is passed from the nanotube to a catalyst layer of a substrate, thereby causing a localized chemical reaction to occur in a resist layer adjacent the catalyst layer. The region of the resist layer where the chemical reaction occurred is etched, thereby exposing a catalyst particle or particles in the catalyst layer surrounded by a wall of unetched resist material. Subsequent chemical vapor deposition causes growth of a nanostructure to occur upward through the wall of unetched resist material having controlled characteristics of height and diameter and, for parallel systems, number density.

Down-flow moving-bed gasifier with catalyst recycle

DOEpatents

Halow, J.S.

1999-04-20

The gasification of coal and other carbonaceous materials by an endothermic gasification reaction is achieved in the presence of a catalyst in a down-flow, moving-bed gasifier. Catalyst is removed along with ash from the gasifier and is then sufficiently heated in a riser/burner by the combustion of residual carbon in the ash to volatilize the catalyst. This volatilized catalyst is returned to the gasifier where it uniformly contacts and condenses on the carbonaceous material. Also, the hot gaseous combustion products resulting from the combustion of the carbon in the ash along with excess air are introduced into the gasifier for providing heat energy used in the endothermic reaction. 1 fig.

Fabrication of fuel cell electrodes and other catalytic structures

DOEpatents

Smith, J.L.

1987-02-11

A porous layer of catalyst material suitable for use as an electrode in a molten carbonate fuel cell includes elongated pores substantially extending across the layer thickness. The catalyst layer is prepared by depositing particulate catalyst material into polymeric flocking on a substrate surface by a procedure such as tape casting. The loaded substrate is heated in a series of steps with rising temperatures to set the tape, thermally decompose the substrate with flocking and sinter bond the catalyst particles into a porous catalytic layer with elongated pores across its thickness. Employed as an electrode, the elongated pores provide distribution of reactant gas into contact with catalyst particles wetted by molten electrolyte. 1 fig.

Fabrication of catalytic electrodes for molten carbonate fuel cells

DOEpatents

Smith, James L.

1988-01-01

A porous layer of catalyst material suitable for use as an electrode in a molten carbonate fuel cell includes elongated pores substantially extending across the layer thickness. The catalyst layer is prepared by depositing particulate catalyst material into polymeric flocking on a substrate surface by a procedure such as tape casting. The loaded substrate is heated in a series of steps with rising temperatures to set the tape, thermally decompose the substrate with flocking and sinter bond the catalyst particles into a porous catalytic layer with elongated pores across its thickness. Employed as an electrode, the elongated pores provide distribution of reactant gas into contact with catalyst particles wetted by molten electrolyte.

High-Performance Carbon Dioxide Electrocatalytic Reduction by Easily Fabricated Large-Scale Silver Nanowire Arrays.

PubMed

Luan, Chuhao; Shao, Yang; Lu, Qi; Gao, Shenghan; Huang, Kai; Wu, Hui; Yao, Kefu

2018-05-30

An efficient and selective catalyst is in urgent need for carbon dioxide electroreduction and silver is one of the promising candidates with affordable costs. Here we fabricated large-scale vertically standing Ag nanowire arrays with high crystallinity and electrical conductivity as carbon dioxide electroreduction catalysts by a simple nanomolding method that was usually considered not feasible for metallic crystalline materials. A great enhancement of current densities and selectivity for CO at moderate potentials was achieved. The current density for CO ( j co ) of Ag nanowire array with 200 nm in diameter was more than 2500 times larger than that of Ag foil at an overpotential of 0.49 V with an efficiency over 90%. The origin of enhanced performances are attributed to greatly increased electrochemically active surface area (ECSA) and higher intrinsic activity compared to those of polycrystalline Ag foil. More low-coordinated sites on the nanowires which can stabilize the CO 2 intermediate better are responsible for the high intrinsic activity. In addition, the impact of surface morphology that induces limited mass transportation on reaction selectivity and efficiency of nanowire arrays with different diameters was also discussed.

Tuning of CO2 Reduction Selectivity on Metal Electrocatalysts.

PubMed

Wang, Yuhang; Liu, Junlang; Wang, Yifei; Al-Enizi, Abdullah M; Zheng, Gengfeng

2017-11-01

Climate change, caused by heavy CO 2 emissions, is driving new demands to alleviate the rising concentration of atmospheric CO 2 levels. Enlightened by the photosynthesis of green plants, photo(electro)chemical catalysis of CO 2 reduction, also known as artificial photosynthesis, is emerged as a promising candidate to address these demands and is widely investigated during the past decade. Among various artificial photosynthetic systems, solar-driven electrochemical CO 2 reduction is widely recognized to possess high efficiencies and potentials for practical application. The efficient and selective electroreduction of CO 2 is the key to the overall solar-to-chemical efficiency of artificial photosynthesis. Recent studies show that various metallic materials possess the capability to play as electrocatalysts for CO 2 reduction. In order to achieve high selectivity for CO 2 reduction products, various efforts are made including studies on electrolytes, crystal facets, oxide-derived catalysts, electronic and geometric structures, nanostructures, and mesoscale phenomena. In this Review, these methods for tuning the selectivity of CO 2 electrochemical reduction of metallic catalysts are summarized. The challenges and perspectives in this field are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advanced screening of electrode couples

NASA Technical Reports Server (NTRS)

Giner, J. D.; Cahill, K.

1980-01-01

The chromium (Cr(3+)/Cr(2+)) redox couple (electrolyte and electrode) was investigated to determine its suitability as negative electrode for the iron (Fe(3+)/Fe(2+))-chromium (Cr(3+)/Cr(2+)) redox flow battery. Literature search and laboratory investigation established that the solubility and stability of aqueous acidic solutions of chromium(3) chloride and chromium(2) chloride are sufficient for redox battery application. Four categories of electrode materials were tested; namely, metals and metalloid materials (elements and compounds), alloys, plated materials, and Teflon-bonded materials. In all, the relative performance of 26 candidate electrode materials was evaluated on the basis of slow scan rate linear sweep voltammetry in stirred solution. No single material tested gave both acceptable anodic an acceptable cathodic performance. However, the identification of lead as a good cathodic electrocatalyst and gold as a good anodic electrocatalyst led to the invention of the lead/gold combination electrocatalyst. This type of catalyst can be fabricated in several ways and appears to offer the advantages of each metal without the disadvantages associated with their use as single materials. This lead/gold electrocatalyst was tested by NASA-Lewis Research Center in complete, flowing, redox batteries comprising a stack of several cells. A large improvement in the battery's coulombic and energy efficiency was observed.

Catalysts for converting syngas into liquid hydrocarbons and methods thereof

DOEpatents

Yu, Fei; Yan, Qiangu; Batchelor, William

2016-03-15

The presently-disclosed subject matter includes methods for producing liquid hydrocarbons from syngas. In some embodiments the syngas is obtained from biomass and/or comprises a relatively high amount of nitrogen and/or carbon dioxide. In some embodiments the present methods can convert syngas into liquid hydrocarbons through a one-stage process. Also provided are catalysts for producing liquid hydrocarbons from syngas, wherein the catalysts include a base material, a transition metal, and a promoter. In some embodiments the base material includes a zeolite-iron material or a cobalt-molybdenum carbide material. In still further embodiments the promoter can include an alkali metal.

Applications of polymeric smart materials to environmental problems.

PubMed Central

Gray, H N; Bergbreiter, D E

1997-01-01

New methods for the reduction and remediation of hazardous wastes like carcinogenic organic solvents, toxic materials, and nuclear contamination are vital to environmental health. Procedures for effective waste reduction, detection, and removal are important components of any such methods. Toward this end, polymeric smart materials are finding useful applications. Polymer-bound smart catalysts are useful in waste minimization, catalyst recovery, and catalyst reuse. Polymeric smart coatings have been developed that are capable of both detecting and removing hazardous nuclear contaminants. Such applications of smart materials involving catalysis chemistry, sensor chemistry, and chemistry relevant to decontamination methodology are especially applicable to environmental problems. PMID:9114277

Highly active nitrogen-doped nanocarbon electrocatalysts for alkaline direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Kruusenberg, Ivar; Ratso, Sander; Vikkisk, Merilin; Kanninen, Petri; Kallio, Tanja; Kannan, Arunachala M.; Tammeveski, Kaido

2015-05-01

Direct methanol fuel cells are assembled and evaluated using Fumatech FAA3 alkaline anion exchange membrane. Two novel metal-free cathode catalysts are synthesised, investigated and compared with the commercial Pt-based catalyst. In this work nitrogen-doped few-layer graphene/multi-walled carbon nanotube (N-FLG/MWCNT) composite and nitrogen-doped MWCNT (N-MWCNT) catalyst are prepared by pyrolysing the mixture of dicyandiamide (DCDA) and carbon nanomaterials at 800 °C. The resulting cathode catalyst material shows a remarkable electrocatalytic activity for oxygen reduction reaction (ORR) in 0.1 M KOH solution employing the rotating disk electrode (RDE) method. Fuel cell tests are performed by using 1 M methanol as anode and pure oxygen gas cathode feed. The maximum power density obtained with the N-FLG/MWCNT material (0.72 mW cm-2) is similar to that of the Pt/C catalyst (0.72 mW cm-2), whereas the N-MWCNT material shows higher peak power density (0.92 mW cm-2) than the commercial Pt/C catalyst.

A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide

PubMed Central

Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush

2018-01-01

Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil–5 (ZSM-5), TiO2, and Al2O3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir–Hinshelwood or Eley–Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH3 catalyst are suggested. PMID:29600136

A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide.

PubMed

Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush; Mohamed, Abdul Rahman Bin

2018-01-01

Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil-5 (ZSM-5), TiO 2 , and Al 2 O 3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir-Hinshelwood or Eley-Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH 3 catalyst are suggested.

Study on the pyrolysis of cellulose for bio-oil with mesoporous molecular sieve catalysts.

PubMed

Yu, Feng-wen; Ji, Deng-xiang; Nie, Yong; Luo, Yao; Huang, Cheng-jie; Ji, Jian-bing

2012-09-01

Mesoporous materials possess a hexagonal array of uniform mesopores, high surface areas, and moderate acidity. They are one of the important catalysts in the field of catalytic pyrolysis. In this paper, mesoporous materials of Al-MCM-41, La-Al-MCM-41, and Ce-Al-MCM-41 were synthesized, characterized, and tested as catalysts in the cellulose catalytic pyrolysis process using a fixed bed pyrolysis reactor. The results showed that mesoporous materials exhibited a strong influence on the pyrolytic behavior of cellulose. The presence of these mesoporous molecular sieve catalysts could vary the yield of products, which was that they could decrease the yield of liquid and char and increase the yield of gas product, and could promote high-carbon chain compounds to break into low-carbon chain compounds. Mesoporous molecular sieve catalysts were benefit to the reaction of dehydrogenation and deoxidation and the breakdown of carbon chain. Further, La-Al-MCM-41 and Ce-Al-MCM-41 catalysts can produce more toluene and 2-methoxy-phenol, as compared to the non-catalytic runs.

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

Catalysts and methods of using the same

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

Slowing, Igor Ivan; Kandel, Kapil

2017-02-14

The present invention provides a catalyst including a mesoporous silica nanoparticle and a catalytic material comprising iron. In various embodiments, the present invention provides methods of using and making the catalyst. In some examples, the catalyst can be used to hydrotreat fatty acids or to selectively remove fatty acids from feedstocks.

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

PubMed Central

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

2017-01-01

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

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

Catalyst containing oxygen transport membrane

DOEpatents

Lane, Jonathan A.; Wilson, Jamie R.; Christie, Gervase Maxwell; Petigny, Nathalie; Sarantopoulos, Christos

2017-02-07

A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a microstructure exhibiting substantially uniform pore size distribution as a result of using PMMA pore forming materials or a bi-modal particle size distribution of the porous support layer materials. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

Corrosion-resistant catalyst supports for phosphoric acid fuel cells

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

Kosek, J.A.; Cropley, C.C.; LaConti, A.B.

High-surface-area carbon blacks such as Vulcan XC-72 (Cabot Corp.) and graphitized carbon blacks such as 2700{degree}C heat-treated Black Pearls 2000 (HTBP) (Cabot Corp.) have found widespread applications as catalyst supports in phosphoric acid fuel cells (PAFCs). However, due to the operating temperatures and pressures being utilized in PAFCs currently under development, the carbon-based cathode catalyst supports suffer from corrosion, which decreases the performance and life span of a PAFC stack. The feasibility of using alternative, low-cost, corrosion-resistant catalyst support (CRCS) materials as replacements for the cathode carbon support materials was investigated. The objectives of the program were to prepare high-surface-areamore » alternative supports and to evaluate the physical characteristics and the electrochemical stability of these materials. The O{sub 2} reduction activity of the platinized CRCS materials was also evaluated. 2 refs., 3 figs.« less

Method for reducing NOx during combustion of coal in a burner

DOEpatents

Zhou, Bing [Cranbury, NJ; Parasher, Sukesh [Lawrenceville, NJ; Hare, Jeffrey J [Provo, UT; Harding, N Stanley [North Salt Lake, UT; Black, Stephanie E [Sandy, UT; Johnson, Kenneth R [Highland, UT

2008-04-15

An organically complexed nanocatalyst composition is applied to or mixed with coal prior to or upon introducing the coal into a coal burner in order to catalyze the removal of coal nitrogen from the coal and its conversion into nitrogen gas prior to combustion of the coal. This process leads to reduced NOx production during coal combustion. The nanocatalyst compositions include a nanoparticle catalyst that is made using a dispersing agent that can bond with the catalyst atoms. The dispersing agent forms stable, dispersed, nano-sized catalyst particles. The catalyst composition can be formed as a stable suspension to facilitate storage, transportation and application of the catalyst nanoparticles to a coal material. The catalyst composition can be applied before or after pulverizing the coal material or it may be injected directly into the coal burner together with pulverized coal.

Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

DOEpatents

Gorin, Everett

1979-01-01

In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

Robust Catalysis on 2D Materials Encapsulating Metals: Concept, Application, and Perspective.

PubMed

Deng, Jiao; Deng, Dehui; Bao, Xinhe

2017-11-01

Great endeavors are undertaken to search for low-cost, rich-reserve, and highly efficient alternatives to replace precious-metal catalysts, in order to cut costs and improve the efficiency of catalysts in industry. However, one major problem in metal catalysts, especially nonprecious-metal catalysts, is their poor stability in real catalytic processes. Recently, a novel and promising strategy to construct 2D materials encapsulating nonprecious-metal catalysts has exhibited inimitable advantages toward catalysis, especially under harsh conditions (e.g., strong acidity or alkalinity, high temperature, and high overpotential). The concept, which originates from unique electron penetration through the 2D crystal layer from the encapsulated metals to promote a catalytic reaction on the outermost surface of the 2D crystal, has been widely applied in a variety of reactions under harsh conditions. It has been vividly described as "chainmail for catalyst." Herein, recent progress concerning this chainmail catalyst is reviewed, particularly focusing on the structural design and control with the associated electronic properties of such heterostructure catalysts, and also on their extensive applications in fuel cells, water splitting, CO 2 conversion, solar cells, metal-air batteries, and heterogeneous catalysis. In addition, the current challenges that are faced in fundamental research and industrial application, and future opportunities for these fantastic catalytic materials are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules

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

Al-Hamdani, Yasmine S.; Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ; Alfè, Dario

2016-04-21

Novel uses for 2-dimensional materials like graphene and hexagonal boron nitride (h-BN) are being frequently discovered especially for membrane and catalysis applications. Still however, a great deal remains to be understood about the interaction of environmentally and industrially relevant molecules such as water with these materials. Taking inspiration from advances in hybridising graphene and h-BN, we explore using density functional theory, the dissociation of water, hydrogen, methane, and methanol on graphene, h-BN, and their isoelectronic doped counterparts: BN doped graphene and C doped h-BN. We find that doped surfaces are considerably more reactive than their pristine counterparts and by comparingmore » the reactivity of several small molecules, we develop a general framework for dissociative adsorption. From this a particularly attractive consequence of isoelectronic doping emerges: substrates can be doped to enhance their reactivity specifically towards either polar or non-polar adsorbates. As such, these substrates are potentially viable candidates for selective catalysts and membranes, with the implication that a range of tuneable materials can be designed.« less

Tuning dissociation using isoelectronically doped graphene and hexagonal boron nitride: Water and other small molecules

NASA Astrophysics Data System (ADS)

Al-Hamdani, Yasmine S.; Alfè, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos

2016-04-01

Novel uses for 2-dimensional materials like graphene and hexagonal boron nitride (h-BN) are being frequently discovered especially for membrane and catalysis applications. Still however, a great deal remains to be understood about the interaction of environmentally and industrially relevant molecules such as water with these materials. Taking inspiration from advances in hybridising graphene and h-BN, we explore using density functional theory, the dissociation of water, hydrogen, methane, and methanol on graphene, h-BN, and their isoelectronic doped counterparts: BN doped graphene and C doped h-BN. We find that doped surfaces are considerably more reactive than their pristine counterparts and by comparing the reactivity of several small molecules, we develop a general framework for dissociative adsorption. From this a particularly attractive consequence of isoelectronic doping emerges: substrates can be doped to enhance their reactivity specifically towards either polar or non-polar adsorbates. As such, these substrates are potentially viable candidates for selective catalysts and membranes, with the implication that a range of tuneable materials can be designed.

Egg derived nitrogen-self-doped carbon/carbon nanotube hybrids as noble-metal-free catalysts for oxygen reduction

NASA Astrophysics Data System (ADS)

Zhang, Jian; Wu, Siyu; Chen, Xu; Pan, Mu; Mu, Shichun

2014-12-01

Currently, the development of nitrogen (N) doped carbon based non-precious metal ORR catalysts has become one of the most attractive topics in low temperature fuel cells. Here, we demonstrate a green synthesis route of N-self-doped carbon materials by using eggs as N sources combining with iron sources and multi-walled carbon nanotubes (CE-Fe-MWNT). After carbonized, such hybrid materials possess an outstanding electrocatalytic activity towards ORR comparable to the commercial Pt/C catalyst in alkaline media, and both superior stability and fuel (methanol and CO) tolerance than the commercial Pt/C catalyst, which provide a promising alternative to noble metal catalysts by using abundant natural biological resources.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor

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

Song, Ping; Barkholtz, Heather M.; Wang, Ying

We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives ofmore » Pt-based catalysts with best performance/price.« less

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.

Oxygen electrocatalysts in metal-air batteries: from aqueous to nonaqueous electrolytes.

PubMed

Wang, Zhong-Li; Xu, Dan; Xu, Ji-Jing; Zhang, Xin-Bo

2014-11-21

With the development of renewable energy and electrified transportation, electrochemical energy storage will be more important in the future than it has ever been in the past. Although lithium-ion batteries (LIBs) are traditionally considered to be the most likeliest candidate thanks to their relatively long cycle life and high energy efficiency, their limited energy density as well as cost are still causing a bottleneck for their long-term application. Alternatively, metal-air batteries have been proposed as a very promising large-scale electricity storage technology with the replacement of the intercalation reaction mechanism by the catalytic redox reaction of a light weight metal-oxygen couple. Generally, based on the electrolyte, these metal-air batteries can be divided into aqueous and nonaqueous systems, corresponding to two typical batteries of Zn-air and Li-air, respectively. The prominent feature of both batteries are their extremely high theoretical energy density, especially for nonaqueous Li-air batteries, which far exceeds the best that can be achieved with LIBs. In this review, we focus on the major obstacle of sluggish kinetics of the cathode in both batteries, and summarize the fundamentals and recent advances related to the oxygen catalyst materials. According to the electrolyte, the aqueous and nonaqueous electrocatalytic mechanisms of the oxygen reduction and evolution reactions are discussed. Subsequently, seven groups of oxygen catalysts, which have played catalytic roles in both systems, are selectively reviewed, including transition metal oxides (single-metal oxides and mixed-metal oxides), functional carbon materials (nanostructured carbons and doped carbons), metal oxide-nanocarbon hybrid materials, metal-nitrogen complexes (non-pyrolyzed and pyrolyzed), transition metal nitrides, conductive polymers, and precious metals (alloys). Nonaqueous systems have the advantages of energy density and rechargeability over aqueous systems and have gradually become the research focus of metal-air batteries. However, there are considerable challenges beyond catalysts from aqueous to nonaqueous electrolytes, which are also discussed in this review. Finally, several future research directions are proposed based on the results achieved in this field, with emphasis on nonaqueous Li-air batteries.

Evaluation of mechanical properties in metal wire mesh supported selective catalytic reduction (SCR) catalyst structures

NASA Astrophysics Data System (ADS)

Rajath, S.; Siddaraju, C.; Nandakishora, Y.; Roy, Sukumar

2018-04-01

The objective of this research is to evaluate certain specific mechanical properties of certain stainless steel wire mesh supported Selective catalytic reduction catalysts structures wherein the physical properties of the metal wire mesh and also its surface treatments played vital role thereby influencing the mechanical properties. As the adhesion between the stainless steel wire mesh and the catalyst material determines the bond strength and the erosion resistance of catalyst structures, surface modifications of the metal- wire mesh structure in order to facilitate the interface bonding is therefore very important to realize enhanced level of mechanical properties. One way to enhance such adhesion properties, the stainless steel wire mesh is treated with the various acids, i.e., chromic acid, phosphoric acid including certain mineral acids and combination of all those in various molar ratios that could generate surface active groups on metal surface that promotes good interface structure between the metal- wire mesh and metal oxide-based catalyst material and then the stainless steel wire mesh is dipped in the glass powder slurry containing some amount of organic binder. As a result of which the said catalyst material adheres to the metal-wire mesh surface more effectively that improves the erosion profile of supported catalysts structure including bond strength.

Attrition resistant Fischer-Tropsch catalyst and support

DOEpatents

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

2004-05-25

A catalyst support having improved attrition resistance and a catalyst produced therefrom. The catalyst support is produced by a method comprising the step of treating calcined .gamma.-alumina having no catalytic material added thereto with an acidic aqueous solution having an acidity level effective for increasing the attrition resistance of the calcined .gamma.-alumina.

Non-conventional Pt-Cu alloy/carbon paper electrochemical catalyst formed by electrodeposition using hydrogen bubble as template

NASA Astrophysics Data System (ADS)

Kim, Youngkwang; Lee, Hyunjoon; Lim, Taeho; Kim, Hyun-Jong; Kwon, Oh Joong

2017-10-01

With emerging stability issues in fuel cell technology, a non-conventional catalyst not supported on carbon materials has been highlighted because it can avoid negative influences of carbon support materials on the stability, such as carbon corrosion. The nanostructured thin film catalyst is representative of non-conventional catalysts, which shows improved stability, enhanced mass specific activity, and fast mass transfer at high current densities. However, the nanostructured thin film catalyst usually requires multi-step processes for fabrication, making its mass production complex and irreproducible. We introduce a Pt-Cu alloy nanostructured thin film catalyst, which can be simply prepared by electrodeposition. By using hydrogen bubbles as a template, a three-dimensional free-standing foam of Cu was electrodeposited directly on the micro-porous layer/carbon paper and it was then displaced with Pt by simple immersion. The structure characterization revealed that a porous thin Pt-Cu alloy catalyst layer was successfully formed on the micro-porous layer/carbon paper. The synthesized Pt-Cu alloy catalyst exhibited superior durability compared to a conventional Pt/C in single cell test.

Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen

NASA Astrophysics Data System (ADS)

Luo, Si

Abstract of the Dissertation. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen. by. Si Luo. Doctor of Philosophy. in. Chemistry. Stony Brook University. 2017. The environmental impacts of fossil fuel consumption and the resulting global warming have attracted increasing attention to technologies and fuels that are both sustainable and renewable in the 21st century. To date, hydrogen has been proposed as an encouraging candidate of the next generation of chemical fuels, which meets all demands for carbon free and efficient chemistries that could be produced from a variety of sources. However, despite tremendous efforts, there is a clear need to develop new catalysts for the production of hydrogen through catalytic processes that are sustainable, such as in the photocatalytic splitting of water (PCS: H2O → H2 + 0.5O2) and the water-gas shift process (WGS: CO + H2O → H2 + CO2). This thesis is primarily motivated by this challenge and has focused on the photochemical and thermal production of H2 by the employment of novel TiO2 based catalysts. TiO2 is one of the most widely studied photocatalysts in all history, due to its relatively high activity, robust stability, safety and low cost. In this thesis, several TiO2-based mixed metal oxide nano catalysts (CeOx-TiO2, Ru-TiO2, Ga-TiO2) have been synthesized with carefully controlled morphology/structure and with inclusion of co-catalysts (Pt). These novel materials were comprehensively characterized to better understand their morphology, crystal structure, and electronic properties in an attempt to unravel phenomena responsible for high catalytic performance for the production of H2 from H2O. We have discovered the importance of low-dimensional metal oxide and interfacial stabilized nano-scaled mixed metal oxides for H2 production, while learning how best to tune such structure to optimize both thermal and photochemical conversion. Optimized structure and/or composition have been identified for TiO2 modified in different ways by another metal oxide (CeOx) or with dopants (Ga, Ru). In addition, we have also studied the water gas shift reaction on several TiO2 supported catalysts, where similar concepts can be applied. Advanced In situ characterization enabled the investigation of the catalyst structure, surface chemical intermediates and active species under reaction conditions. The influence of metal-oxide, oxide-oxide interactions has been further revealed for both the water-gas shift and the photocatalytic splitting of water.

Applications of Neutron Scattering in the Chemical Industry: Proton Dynamics of Highly Dispersed Materials, Characterization of Fuel Cell Catalysts, and Catalysts from Large-Scale Chemical Processes

NASA Astrophysics Data System (ADS)

Albers, Peter W.; Parker, Stewart F.

The attractiveness of neutron scattering techniques for the detailed characterization of materials of high degrees of dispersity and structural complexity as encountered in the chemical industry is discussed. Neutron scattering picks up where other analytical methods leave off because of the physico-chemical properties of finely divided products and materials whose absorption behavior toward electromagnetic radiation and electrical conductivity causes serious problems. This is demonstrated by presenting typical applications from large-scale production technology and industrial catalysis. These include the determination of the proton-related surface chemistry of advanced materials that are used as reinforcing fillers in the manufacture of tires, where interrelations between surface chemistry, rheological properties, improved safety, and significant reduction of fuel consumption are the focus of recent developments. Neutron scattering allows surface science studies of the dissociative adsorption of hydrogen on nanodispersed, supported precious metal particles of fuel cell catalysts under in situ loading at realistic gas pressures of about 1 bar. Insight into the occupation of catalytically relevant surface sites provides valuable information about the catalyst in the working state and supplies essential scientific input for tailoring better catalysts by technologists. The impact of deactivation phenomena on industrial catalysts by coke deposition, chemical transformation of carbonaceous deposits, and other processes in catalytic hydrogenation processes that result in significant shortening of the time of useful operation in large-scale plants can often be traced back in detail to surface or bulk properties of catalysts or materials of catalytic relevance. A better understanding of avoidable or unavoidable aspects of catalyst deactivation phenomena under certain in-process conditions and the development of effective means for reducing deactivation leads to more energy-efficient and, therefore, environmentally friendly processes and helps to save valuable resources. Even small or gradual improvements in all these fields are of considerable economic impact.

In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.

PubMed

Stefanidis, S D; Kalogiannis, K G; Iliopoulou, E F; Lappas, A A; Pilavachi, P A

2011-09-01

In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields. Copyright © 2011 Elsevier Ltd. All rights reserved.

Organic-inorganic hybrid polyionic liquid based polyoxometalate as nano porous material for selective oxidation of sulfides

NASA Astrophysics Data System (ADS)

Rafiee, Ezzat; Shahebrahimi, Shabnam

2017-07-01

Organic-inorganic hybrid nano porous materials based on poly(ionic liquid)-polyoxometalate (PIL-POM) were reported. These hybrid materials were synthesized by the reaction of 4-vinyl pyridine with 1,3-propanesultone, followed by the polymerization and also sulfonate-functionalized cross-linked poly(4-vinylpyridine) and combining these polymers with H5PMo10V2O40 (PMo10V2). Activity of prepared PIL-PMo10V2 hybrids were investigated as catalysts for oxidation of sulfides with H2O2 as oxidant. For understanding catalytic activities of the PIL-PMo10V2 hybrids in oxidation of sulfides, effect of catalyst composition, substrate, and reaction conditions were studied. The results show that the PIL-PMo10V2 hybrids are active as selective heterogeneous catalysts for oxidation of sulfides and can be recovered and reused. The catalyst was characterized by FT-IR, TGA-DSC, XRD, SEM/EDX, BET, CV and zeta potential measurement. Also, average molecular weight of prepared catalysts were measured.

A Nanopore-Structured Nitrogen-Doped Biocarbon Electrocatalyst for Oxygen Reduction from Two-Step Carbonization of Lemna minor Biomass

NASA Astrophysics Data System (ADS)

Guo, Chaozhong; Li, Zhongbin; Niu, Lidan; Liao, Wenli; Sun, Lingtao; Wen, Bixia; Nie, Yunqing; Cheng, Jing; Chen, Changguo

2016-05-01

So far, the development of highly active and stable carbon-based electrocatalysts for oxygen reduction reaction (ORR) to replace commercial Pt/C catalyst is a hot topic. In this study, a new nanoporous nitrogen-doped carbon material was facilely designed by two-step pyrolysis of the renewable Lemna minor enriched in crude protein under a nitrogen atmosphere. Electrochemical measurements show that the onset potential for ORR on this carbon material is around 0.93 V (versus reversible hydrogen electrode), slightly lower than that on the Pt/C catalyst, but its cycling stability is higher compared to the Pt/C catalyst in an alkaline medium. Besides, the ORR at this catalyst approaches to a four-electron transfer pathway. The obtained ORR performance can be basically attributed to the formation of high contents of pyridinic and graphitic nitrogen atoms inside this catalyst. Thus, this work opens up the path in the ORR catalysis for the design of nitrogen-doped carbon materials utilizing aquatic plants as starting precursors.

Synthesis of novel macrocycles carrying pincer-type ligands as future candidates for potential applications in size-selective, stereochemical and recyclable catalysts

NASA Astrophysics Data System (ADS)

Khan, Burhan; Shah, Muhammad Raza; Rabnawaz, Muhammad

2018-03-01

Macrocycles with ultra dense functionalities are very useful but are difficult to synthesize. In this study, we report six novel macrocycles bearing a pincer ligand alone or a combination of pincer-calixarenes, and pincer-fluorene moieties. Click chemistry was utilized to synthesize the desired macrocycles in good yields. These macrocycles were fully characterized using mass spectrometry (EI-MS, ESI-MS, and MALDI-TOF MS), and NMR spectroscopy. These macrocycles are under investigations as size-selective and recyclable catalysts for various chemical transformations.

Nano-catalysts: Bridging the gap between homogeneous and heterogeneous catalysis

EPA Science Inventory

Functionalized nanoparticles have emerged as sustainable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. We envisioned a catalyst system, which can bridge the homogenous and heterogeneous system. Postsynthetic surface modifica...

Develop and test fuel cell powered on-site integrated total energy systems. Phase 3: Full-scale power plant development

NASA Technical Reports Server (NTRS)

1983-01-01

Satisfactory performance is reported for the first three 12-cell sub-stacks of the 5 kW stack rebuild. Early general conclusions are presented from an economic study. Results are reported on a successful 700-hour test of a 3-cell stack in the full-sized configuration (0.33m x 0.56m). Construction of a 5 kW equivalent methanol/steam reformer based on a commercial shell-and-tube heat exchanger was completed. Several test runs are summarized. Preliminary conclusions are presented on the technical and economic aspects of fuel cell/HVAC interaction. Physical data are presented on several dense graphite materials which are candidates for gas-distribution plates. Performance of a new cathode catalyst is reported.

Chemo-Enzymatic Synthesis of Each Enantiomer of Orthogonally-Protected 4,4-Difluoroglutamic Acid – A Candidate Monomer for Chiral Brønsted-Acid Peptide-Based Catalysts

PubMed Central

Li, Yang

2011-01-01

We have accomplished an asymmetric synthesis of each enantiomer of 4,4-difluoroglutamic acid. This α-amino acid has been of interest in medicinal chemistry circles. Key features of the synthesis include highly scalable procedures, a Reformatsky-based coupling reaction, and straightforward functional group manipulations to make the parent amino acid. Enantioenrichment derives from an enzymatic resolution of the synthetic material. Conversion of the optically enriched compounds to orthogonally protected forms allows selective formation of peptide bonds. 4,4- Difluoroglutamic acid, in a suitably protected form, is also shown to exhibit enhanced catalytic activity in both an oxidation reaction and a reduction reaction, in comparison to the analogous glutamic acid derivative. PMID:22039908

Graphitic Carbon Nitride Supported Catalysts for Polymer Electrolyte Fuel Cells

PubMed Central

2014-01-01

Graphitic carbon nitrides are investigated for developing highly durable Pt electrocatalyst supports for polymer electrolyte fuel cells (PEFCs). Three different graphitic carbon nitride materials were synthesized with the aim to address the effect of crystallinity, porosity, and composition on the catalyst support properties: polymeric carbon nitride (gCNM), poly(triazine) imide carbon nitride (PTI/Li+Cl–), and boron-doped graphitic carbon nitride (B-gCNM). Following accelerated corrosion testing, all graphitic carbon nitride materials are found to be more electrochemically stable compared to conventional carbon black (Vulcan XC-72R) with B-gCNM support showing the best stability. For the supported catalysts, Pt/PTI-Li+Cl– catalyst exhibits better durability with only 19% electrochemical surface area (ECSA) loss versus 36% for Pt/Vulcan after 2000 scans. Superior methanol oxidation activity is observed for all graphitic carbon nitride supported Pt catalysts on the basis of the catalyst ECSA. PMID:24748912

Scaling-Relation-Based Analysis of Bifunctional Catalysis: The Case for Homogeneous Bimetallic Alloys

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

Andersen, Mie; Medford, Andrew J.; Norskov, Jens K.

Here, we present a generic analysis of the implications of energetic scaling relations on the possibilities for bifunctional gains at homogeneous bimetallic alloy catalysts. Such catalysts exhibit a large number of interface sites, where second-order reaction steps can involve intermediates adsorbed at different active sites. Using different types of model reaction schemes, we show that such site-coupling reaction steps can provide bifunctional gains that allow for a bimetallic catalyst composed of two individually poor catalyst materials to approach the activity of the optimal monomaterial catalyst. However, bifunctional gains cannot result in activities higher than the activity peak of the monomaterialmore » volcano curve as long as both sites obey similar scaling relations, as is generally the case for bimetallic catalysts. These scaling-relation-imposed limitations could be overcome by combining different classes of materials such as metals and oxides.« less

Scaling-Relation-Based Analysis of Bifunctional Catalysis: The Case for Homogeneous Bimetallic Alloys

DOE PAGES

Andersen, Mie; Medford, Andrew J.; Norskov, Jens K.; ...

2017-04-14

Here, we present a generic analysis of the implications of energetic scaling relations on the possibilities for bifunctional gains at homogeneous bimetallic alloy catalysts. Such catalysts exhibit a large number of interface sites, where second-order reaction steps can involve intermediates adsorbed at different active sites. Using different types of model reaction schemes, we show that such site-coupling reaction steps can provide bifunctional gains that allow for a bimetallic catalyst composed of two individually poor catalyst materials to approach the activity of the optimal monomaterial catalyst. However, bifunctional gains cannot result in activities higher than the activity peak of the monomaterialmore » volcano curve as long as both sites obey similar scaling relations, as is generally the case for bimetallic catalysts. These scaling-relation-imposed limitations could be overcome by combining different classes of materials such as metals and oxides.« less

Morphological investigation of nanostructured CoMo catalysts

NASA Astrophysics Data System (ADS)

Pawelec, B.; Castaño, P.; Zepeda, T. A.

2008-04-01

This work reports the morphological investigation of nanostructured sulfided CoMo catalysts by means of high-resolution transmission electron microscopy (HRTEM). The catalysts were supported on Ti-modified hexagonal mesoporous silica (HMS-Ti) and P-modified HMS-Ti (P/HMS-Ti) materials. The oxide precursors were characterized by specific surface area (S BET), temperature-programmed reduction (TPR), diffuse reflectance infrared Fourier transform spectroscopy in the OH region (DRIFTS-OH) and X-ray photoelectron spectroscopy (XPS) in order to elucidate the influence of the impregnation sequence (successive vs. simultaneous) and the effect of P-incorporation into HMS-Ti material on the morphology of calcined CoMo catalysts. Both TPR and XPS measurements indicate that the catalysts prepared by successive impregnation possess well-dispersed MoO 3 and CoO phases, whereas their counterparts prepared by simultaneous impregnation additionally possess the CoMoO 4 phase. For all sulfided catalysts, the presence of MoS 2 phase with particle size in the range 3.3-4.4 nm was confirmed by HRTEM. Catalytic activity was evaluated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) carried out in a flow reactor at 593 K and hydrogen pressure of 5.5 MPa. P-incorporation into the HMS-Ti material led to an overall increase in HDS activity and the hydrogenation ability of the sulfided catalysts. All catalysts proved to be stable during 10 h time-on-stream (TOS) operation. The activity of sulfide catalysts in the target reaction depends linearly on the surface exposure of Co species in the oxide precursors, as determined by XPS, and on the morphology of the sulfide form of catalysts (surface density of MoS 2 particles and their sizes) as determined by HRTEM.

Discovery of optimal zeolites for challenging separations and chemical transformations using predictive materials modeling

NASA Astrophysics Data System (ADS)

Bai, Peng; Jeon, Mi Young; Ren, Limin; Knight, Chris; Deem, Michael W.; Tsapatsis, Michael; Siepmann, J. Ilja

2015-01-01

Zeolites play numerous important roles in modern petroleum refineries and have the potential to advance the production of fuels and chemical feedstocks from renewable resources. The performance of a zeolite as separation medium and catalyst depends on its framework structure. To date, 213 framework types have been synthesized and >330,000 thermodynamically accessible zeolite structures have been predicted. Hence, identification of optimal zeolites for a given application from the large pool of candidate structures is attractive for accelerating the pace of materials discovery. Here we identify, through a large-scale, multi-step computational screening process, promising zeolite structures for two energy-related applications: the purification of ethanol from fermentation broths and the hydroisomerization of alkanes with 18-30 carbon atoms encountered in petroleum refining. These results demonstrate that predictive modelling and data-driven science can now be applied to solve some of the most challenging separation problems involving highly non-ideal mixtures and highly articulated compounds.

Metal nanoparticles as a conductive catalyst

DOEpatents

Coker, Eric N [Albuquerque, NM

2010-08-03

A metal nanocluster composite material for use as a conductive catalyst. The metal nanocluster composite material has metal nanoclusters on a carbon substrate formed within a porous zeolitic material, forming stable metal nanoclusters with a size distribution between 0.6-10 nm and, more particularly, nanoclusters with a size distribution in a range as low as 0.6-0.9 nm.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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.

Perovskite-nitrogen-doped carbon nanotube composite as bifunctional catalysts for rechargeable lithium-air batteries.

PubMed

Park, Hey Woong; Lee, Dong Un; Park, Moon Gyu; Ahmed, Raihan; Seo, Min Ho; Nazar, Linda F; Chen, Zhongwei

2015-03-01

Developing an effective bifunctional catalyst is a significant issue, as rechargeable metal-air batteries are very attractive for future energy systems. In this study, a facile one-pot process is introduced to prepare an advanced bifunctional catalyst (op-LN) incorporating nitrogen-doped carbon nanotubes (NCNTs) into perovskite La0.5 Sr0.5 Co0.8 Fe0.2 O3 nanoparticles (LSCF-NPs). Confirmed by half-cell testing, op-LN exhibits synergistic effects of LSCF-NP and NCNT with excellent bifunctionality for both the oxygen reduction reaction and the oxygen evolution reaction. Furthermore, op-LN exhibits comparable performances in these reactions to Pt/C and Ir/C, respectively, which highlights its potential for use as a commercially viable bifunctional catalyst. Moreover, the results obtained by testing op-LN in a practical Li-air battery demonstrate improved and complementary charge/discharge performance compared to those of LSCF-NP and NCNT, and this confirms that simply prepared op-LN is a promising candidate as a highly effective bifunctional catalyst for rechargeable metal-air batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic fast pyrolysis of white oak wood in-situ using a bubbling fluidized bed reactor

USDA-ARS?s Scientific Manuscript database

Catalytic fast pyrolysis was performed on white oak wood using two zeolite-type catalysts as bed material in a bubbling fluidized bed reactor. The two catalysts chosen, based on a previous screening study, were Ca2+ exchanged Y54 (Ca-Y54) and a proprietary ß-zeolite type catalyst (catalyst M) both ...

Effective rate constants for nanostructured heterogeneous catalysts

NASA Astrophysics Data System (ADS)

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

2012-02-01

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

Confined catalysis under two-dimensional materials

PubMed Central

Li, Haobo; Xiao, Jianping; Bao, Xinhe

2017-01-01

Confined microenvironments formed in heterogeneous catalysts have recently been recognized as equally important as catalytically active sites. Understanding the fundamentals of confined catalysis has become an important topic in heterogeneous catalysis. Well-defined 2D space between a catalyst surface and a 2D material overlayer provides an ideal microenvironment to explore the confined catalysis experimentally and theoretically. Using density functional theory calculations, we reveal that adsorption of atoms and molecules on a Pt(111) surface always has been weakened under monolayer graphene, which is attributed to the geometric constraint and confinement field in the 2D space between the graphene overlayer and the Pt(111) surface. A similar result has been found on Pt(110) and Pt(100) surfaces covered with graphene. The microenvironment created by coating a catalyst surface with 2D material overlayer can be used to modulate surface reactivity, which has been illustrated by optimizing oxygen reduction reaction activity on Pt(111) covered by various 2D materials. We demonstrate a concept of confined catalysis under 2D cover based on a weak van der Waals interaction between 2D material overlayers and underlying catalyst surfaces. PMID:28533413

Injectable biomaterials for minimally invasive orthopedic treatments.

PubMed

Jayabalan, M; Shalumon, K T; Mitha, M K

2009-06-01

Biodegradable and injectable hydroxy terminated-poly propylene fumarate (HT-PPF) bone cement was developed. The injectable formulation consisting HT-PPF and comonomer, n-vinyl pyrrolidone, calcium phosphate filler, free radical catalyst, accelerator and radiopaque agent sets rapidly to hard mass with low exothermic temperature. The candidate bone cement attains mechanical strength more than the required compressive strength of 5 MPa and compressive modulus 50 MPa. The candidate bone cement resin elicits cell adhesion and cytoplasmic spreading of osteoblast cells. The cured bone cement does not induce intracutaneous irritation and skin sensitization. The candidate bone cement is tissue compatible without eliciting any adverse tissue reactions. The candidate bone cement is osteoconductive and inductive and allow osteointegration and bone remodeling. HT-PPF bone cement is candidate bone cement for minimally invasive radiological procedures for the treatment of bone diseases and spinal compression fractures.

Hydrogen evolution reaction catalyst

DOEpatents

Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan

2016-02-09

Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.

Attrition resistant gamma-alumina catalyst support

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

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

2006-03-14

A .gamma.-alumina catalyst support having improved attrition resistance produced by a method comprising the steps of treating a particulate .gamma.-alumina material with an acidic aqueous solution comprising water and nitric acid and then, prior to adding any catalytic material thereto, calcining the treated .gamma.-alumina.

Apparatus for Screening Multiple Oxygen-Reduction Catalysts

NASA Technical Reports Server (NTRS)

Whitacre, Jay; Narayanan, Sekharipuram

2009-01-01

An apparatus that includes an array of multiple electrodes has been invented as a means of simultaneously testing multiple materials for their utility as oxygen-reduction catalysts in fuel cells. The apparatus ensures comparability of test results by exposing all the catalyst-material specimens to the same electrolytic test solution at the same potential. Heretofore, it has been possible to test only one specimen at a time, using a precise rotating disk electrode that provides a controlled flux of solution to the surface of the specimen.

Green Synthesis of Three-Dimensional Hybrid N-Doped ORR Electro-Catalysts Derived from Apricot Sap

PubMed Central

Karunagaran, Ramesh; Coghlan, Campbell; Gulati, Karan; Tung, Tran Thanh; Doonan, Christian

2018-01-01

Rapid depletion of fossil fuel and increased energy demand has initiated a need for an alternative energy source to cater for the growing energy demand. Fuel cells are an enabling technology for the conversion of sustainable energy carriers (e.g., renewable hydrogen or bio-gas) into electrical power and heat. However, the hazardous raw materials and complicated experimental procedures used to produce electro-catalysts for the oxygen reduction reaction (ORR) in fuel cells has been a concern for the effective implementation of these catalysts. Therefore, environmentally friendly and low-cost oxygen reduction electro-catalysts synthesised from natural products are considered as an attractive alternative to currently used synthetic materials involving hazardous chemicals and waste. Herein, we describe a unique integrated oxygen reduction three-dimensional composite catalyst containing both nitrogen-doped carbon fibers (N-CF) and carbon microspheres (N-CMS) synthesised from apricot sap from an apricot tree. The synthesis was carried out via three-step process, including apricot sap resin preparation, hydrothermal treatment, and pyrolysis with a nitrogen precursor. The nitrogen-doped electro-catalysts synthesised were characterised by SEM, TEM, XRD, Raman, and BET techniques followed by electro-chemical testing for ORR catalysis activity. The obtained catalyst material shows high catalytic activity for ORR in the basic medium by facilitating the reaction via a four-electron transfer mechanism. PMID:29382103

Green Synthesis of Three-Dimensional Hybrid N-Doped ORR Electro-Catalysts Derived from Apricot Sap.

PubMed

Karunagaran, Ramesh; Coghlan, Campbell; Shearer, Cameron; Tran, Diana; Gulati, Karan; Tung, Tran Thanh; Doonan, Christian; Losic, Dusan

2018-01-28

Rapid depletion of fossil fuel and increased energy demand has initiated a need for an alternative energy source to cater for the growing energy demand. Fuel cells are an enabling technology for the conversion of sustainable energy carriers (e.g., renewable hydrogen or bio-gas) into electrical power and heat. However, the hazardous raw materials and complicated experimental procedures used to produce electro-catalysts for the oxygen reduction reaction (ORR) in fuel cells has been a concern for the effective implementation of these catalysts. Therefore, environmentally friendly and low-cost oxygen reduction electro-catalysts synthesised from natural products are considered as an attractive alternative to currently used synthetic materials involving hazardous chemicals and waste. Herein, we describe a unique integrated oxygen reduction three-dimensional composite catalyst containing both nitrogen-doped carbon fibers (N-CF) and carbon microspheres (N-CMS) synthesised from apricot sap from an apricot tree. The synthesis was carried out via three-step process, including apricot sap resin preparation, hydrothermal treatment, and pyrolysis with a nitrogen precursor. The nitrogen-doped electro-catalysts synthesised were characterised by SEM, TEM, XRD, Raman, and BET techniques followed by electro-chemical testing for ORR catalysis activity. The obtained catalyst material shows high catalytic activity for ORR in the basic medium by facilitating the reaction via a four-electron transfer mechanism.

Method for hydrogen production and metal winning, and a catalyst/cocatalyst composition useful therefor

DOEpatents

Dhooge, Patrick M.

1987-10-13

A catalyst/cocatalyst/organics composition of matter is useful in electrolytically producing hydrogen or electrowinning metals. Use of the catalyst/cocatalyst/organics composition causes the anode potential and the energy required for the reaction to decrease. An electrolyte, including the catalyst/cocatalyst composition, and a reaction medium composition further including organic material are also described.

Commercialization of the Chevron FCC vanadium trap

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

Kennedy, J.V.; Kuehler, C.W.; Krishna, A.S.

1995-09-01

Vanadium, present to varying degrees in FCC feed, deposits on the catalyst virtually quantitatively in the cracking process. In resid operations, vanadium levels on catalyst can reach 10,000 ppm at typical catalyst make-up rates. Once on the catalyst, vanadium destroys the zeolite and restricts access to active sites. This reduces catalyst activity. A vanadium trap is a material that when introduced into the catalyst inventory selectively reacts with migrating vanadium, thus protecting the zeolite and other active components of the catalyst. The trap may be incorporated into the catalyst, or introduced as a separate particle. Only a limited amount ofmore » trap can be incorporated into the catalyst without limiting the amount of zeolite that can be included. Gulf began development of a vanadium trap during the early 1980`s. The work produced a variety of promising materials whose use as vanadium traps was subsequently patented. The work ultimately led to a formulation with a phase very active for trapping vanadium while still quite sulfur tolerant. Based on these results, an extensive pilot plant evaluation was undertaken by Chevron after the Chevron-Gulf merger to better simulate commercial operation. The paper describes pilot plant tests as well as 3 commercial tests of this vanadium trap.« less

Characteristics of Pt-K/MgAl2O4 lean NOx trap catalysts

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

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

2012-04-30

We report the various characteristics of Pt-K/MgAl{sub 2}O{sub 4} lean NOx trap (LNT) catalysts including the effect of K loading on nitrate formation/decomposition, NOx storage activity and durability. Upon the adsorption of NO{sub 2} on K/MgAl{sub 2}O{sub 4} samples, potassium nitrates formed on Mg-related sites in MgAl{sub 2}O{sub 4} support are observed, in addition to the typical two potassium nitrates (ionic and bidentate) formed also on Al{sub 2}O{sub 3} supported sample. Based on NO{sub 2} TPD and FTIR results, the Mg-bound KNO{sub 3} thermally decompose at higher temperature than Al-bound KNO{sub 3}, implying its superior thermal stability. At a potassiummore » loading of 5wt%, the temperature of maximum NOx uptake (T{sub max}) is 300 C. Increasing the potassium loading from 5wt% to 10 wt%, the T{sub max} gradually shifted from 300 C to 450 C, indicating the dependence of T{sub max} on the potassium loading. However, increase in potassium loading above 10 wt% only gives rise to the reduction in the overall NOx storage capacity. This work also underlines the obstacles these materials have prior to their practical application (e.g., durability and sulfur poisoning/ removal). This work provides fundamental understanding of Pt-K/MgAl{sub 2}O{sub 4}-based lean NOx trap catalysts, which could be good candidates for high temperature LNT applications.« less

Application of sodium carbonate prevents sulphur poisoning of catalysts in automated total mercury analysis

NASA Astrophysics Data System (ADS)

McLagan, David S.; Huang, Haiyong; Lei, Ying D.; Wania, Frank; Mitchell, Carl P. J.

2017-07-01

Analysis of high sulphur-containing samples for total mercury content using automated thermal decomposition, amalgamation, and atomic absorption spectroscopy instruments (USEPA Method 7473) leads to rapid and costly SO2 poisoning of catalysts. In an effort to overcome this issue, we tested whether the addition of powdered sodium carbonate (Na2CO3) to the catalyst and/or directly on top of sample material increases throughput of sulphur-impregnated (8-15 wt%) activated carbon samples per catalyst tube. Adding 5 g of Na2CO3 to the catalyst alone only marginally increases the functional lifetime of the catalyst (31 ± 4 g of activated carbon analyzed per catalyst tube) in relation to unaltered catalyst of the AMA254 total mercury analyzer (17 ± 4 g of activated carbon). Adding ≈ 0.2 g of Na2CO3 to samples substantially increases (81 ± 17 g of activated carbon) catalyst life over the unaltered catalyst. The greatest improvement is achieved by adding Na2CO3 to both catalyst and samples (200 ± 70 g of activated carbon), which significantly increases catalyst performance over all other treatments and enables an order of magnitude greater sample throughput than the unaltered samples and catalyst. It is likely that Na2CO3 efficiently sequesters SO2, even at high furnace temperatures to produce Na2SO4 and CO2, largely negating the poisonous impact of SO2 on the catalyst material. Increased corrosion of nickel sampling boats resulting from this methodological variation is easily resolved by substituting quartz boats. Overall, this variation enables an efficient and significantly more affordable means of employing automated atomic absorption spectrometry instruments for total mercury analysis of high-sulphur matrices.

Biomass-derived high-performance tungsten-based electrocatalysts on graphene for hydrogen evolution

DOE PAGES

Meng, Fanke; Hu, Enyuan; Zhang, Lihua; ...

2015-08-05

We report a new class of highly active and stable tungsten-based catalysts to replace noble metal materials for the hydrogen evolution reaction (HER) in an acidic electrolyte. The catalyst is produced by heating an earth-abundant and low-cost mixture of ammonium tungstate, soybean powder and graphene nanoplatelets (WSoyGnP). The catalyst compound consists of tungsten carbide (W₂C and WC) and tungsten nitride (WN) nanoparticles decorated on graphene nanoplatelets. The catalyst demonstrates an overpotential (η₁₀, the potential at a current density of 10 mA cm⁻²) of 0.105 V, which is the smallest among tungsten-based HER catalysts in acidic media. The coupling with graphenemore » significantly reduces the charge transfer resistance and increases the active surface area of the product, which are favorable for enhancing the HER activity. Therefore, the approach of employing biomass and other less expensive materials as precursors for the production of catalysts with high HER activity provides a new path for the design and development of efficient catalysts for the hydrogen production industry.« less

Life Support Catalyst Regeneration Using Ionic Liquids and In Situ Resources

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Karr, Laurel J.; Paley, Mark S.; Donovan, David N.; Kramer, Teersa J.

2016-01-01

Oxygen recovery from metabolic carbon dioxide is an enabling capability for long-duration manned space flight. Complete recovery of oxygen (100%) involves the production of solid carbon. Catalytic approaches for this purpose, such as Bosch technology, have been limited in trade analyses due in part to the mass penalty for high catalyst resupply caused by carbon fouling of the iron or nickel catalyst. In an effort to mitigate this challenge, several technology approaches have been proposed. These approaches have included methods to prolong the life of the catalysts by increasing the total carbon mass loading per mass catalyst, methods for simplified catalyst introduction and removal to limit the resupply container mass, methods of using in situ resources, and methods to regenerate catalyst material. Research and development into these methods is ongoing, but only use of in situ resources and/or complete regeneration of catalyst material has the potential to entirely eliminate the need for resupply. The use of ionic liquids provides an opportunity to combine these methods in a technology approach designed to eliminate the need for resupply of oxygen recovery catalyst. Here we describe the results of an initial feasibility study using ionic liquids and in situ resources for life support catalyst regeneration, we discuss the key challenges with the approach, and we propose future efforts to advance the technology.

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

Understanding low temperature oxidation activity of nanoarray-based monolithic catalysts: from performance observation to structural and chemical insights

DOE PAGES

Du, Shoucheng; Tang, Wenxiang; Guo, Yanbing; ...

2016-12-30

Monolithic catalysts have been widely used in automotive, chemical, and energy relevant industries. Nano-array based monolithic catalysts have been developed, demonstrating high catalyst utilization efficiency and good thermal/mechanical robustness. Compared with the conventional wash-coat based monolithic catalysts, they have shown advances in precise and optimum microstructure control and feasibility in correlating materials structure with properties. Recently, the nano-array based monolithic catalysts have been studied for low temperature oxidation of automotive engine exhaust and exhibited interesting and promising catalytic activities. Here, this review focuses on discussing the key catalyst structural parameters that affect the catalytic performance from the following aspects, (1)more » geometric shape and crystal planes, (2) guest atom doping and defects, (3) array size and size-assisted active species loading, and (4) the synergy effect of metal oxide in composite nano-arrays. Prior to the discussion, an overview of the current status of synthesis and development of the nano-array based monolithic catalysts is introduced. The performance of these materials in low temperature simulated engine exhaust oxidation is also demonstrated. Finally, we hope this review will elucidate the science and chemistry behind the good oxidation performance of the nanoarray- based monolithic catalysts, and serve as a timely and useful research guide for rational design and further improvement of the nano-array based monolithic catalysts for automobile emission control.« less

Understanding low temperature oxidation activity of nanoarray-based monolithic catalysts: from performance observation to structural and chemical insights

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

Du, Shoucheng; Tang, Wenxiang; Guo, Yanbing

Monolithic catalysts have been widely used in automotive, chemical, and energy relevant industries. Nano-array based monolithic catalysts have been developed, demonstrating high catalyst utilization efficiency and good thermal/mechanical robustness. Compared with the conventional wash-coat based monolithic catalysts, they have shown advances in precise and optimum microstructure control and feasibility in correlating materials structure with properties. Recently, the nano-array based monolithic catalysts have been studied for low temperature oxidation of automotive engine exhaust and exhibited interesting and promising catalytic activities. Here, this review focuses on discussing the key catalyst structural parameters that affect the catalytic performance from the following aspects, (1)more » geometric shape and crystal planes, (2) guest atom doping and defects, (3) array size and size-assisted active species loading, and (4) the synergy effect of metal oxide in composite nano-arrays. Prior to the discussion, an overview of the current status of synthesis and development of the nano-array based monolithic catalysts is introduced. The performance of these materials in low temperature simulated engine exhaust oxidation is also demonstrated. Finally, we hope this review will elucidate the science and chemistry behind the good oxidation performance of the nanoarray- based monolithic catalysts, and serve as a timely and useful research guide for rational design and further improvement of the nano-array based monolithic catalysts for automobile emission control.« less

Rambutan-like CNT-Al2O3 scaffolds for high-performance cathode catalyst layers of polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Chang, KwangHyun; Cho, Seonghun; Lim, Eun Ja; Park, Seok-Hee; Yim, Sung-Dae

2018-03-01

Rambutan-like CNT-Al2O3 scaffolds are introduced as a potential candidate for CNT-based catalyst supports to overcome the CNT issues, such as the easy bundling in catalyst ink and the poor pore structure of the CNT-based catalyst layers, and to achieve high MEA performance in PEFCs. Non-porous α-phase Al2O3 balls are introduced to enable the growth of multiwalled CNTs, and Pt nanoparticles are loaded onto the CNT surfaces. In a half-cell, the Pt/CNT-Al2O3 catalyst shows much higher durability than those of a commercial Pt/C catalyst even though it shows lower oxygen reduction reaction (ORR) activity than Pt/C. After using the decal process for MEA formation, the Pt/CNT-Al2O3 shows comparable initial performance characteristics to Pt/C, overcoming the lower ORR activity, mainly due to the facile oxygen transport in the cathode catalyst layers fabricated with the CNT-Al2O3 scaffolds. The Pt/CNT-Al2O3 also exhibits much higher durability against carbon corrosion than Pt/C owing to the durable characteristics of CNTs. Systematic analysis of single cell performance for both initial and after degradation is provided to understand the origin of the high initial performance and durable behavior of Pt/CNT-Al2O3-based catalyst layers. This will provide insights into the design of electrocatalysts for high-performance MEAs in PEFCs.

Current advances in precious metal core-shell catalyst design.

PubMed

Wang, Xiaohong; He, Beibei; Hu, Zhiyu; Zeng, Zhigang; Han, Sheng

2014-08-01

Precious metal nanoparticles are commonly used as the main active components of various catalysts. Given their high cost, limited quantity, and easy loss of catalytic activity under severe conditions, precious metals should be used in catalysts at low volumes and be protected from damaging environments. Accordingly, reducing the amount of precious metals without compromising their catalytic performance is difficult, particularly under challenging conditions. As multifunctional materials, core-shell nanoparticles are highly important owing to their wide range of applications in chemistry, physics, biology, and environmental areas. Compared with their single-component counterparts and other composites, core-shell nanoparticles offer a new active interface and a potential synergistic effect between the core and shell, making these materials highly attractive in catalytic application. On one hand, when a precious metal is used as the shell material, the catalytic activity can be greatly improved because of the increased surface area and the closed interfacial interaction between the core and the shell. On the other hand, when a precious metal is applied as the core material, the catalytic stability can be remarkably improved because of the protection conferred by the shell material. Therefore, a reasonable design of the core-shell catalyst for target applications must be developed. We summarize the latest advances in the fabrications, properties, and applications of core-shell nanoparticles in this paper. The current research trends of these core-shell catalysts are also highlighted.

Zinc-assisted hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran.

PubMed

Saha, Basudeb; Bohn, Christine M; Abu-Omar, Mahdi M

2014-11-01

2,5-Dimethylfuran (DMF), a promising cellulosic biofuel candidate from biomass derived intermediates, has received significant attention because of its low oxygen content, high energy density, and high octane value. A bimetallic catalyst combination containing a Lewis-acidic Zn(II) and Pd/C components is effective for 5-hydroxymethylfurfural (HMF) hydrodeoxygenation (HDO) to DMF with high conversion (99%) and selectivity (85% DMF). Control experiments for evaluating the roles of zinc and palladium revealed that ZnCl2 alone did not catalyze the reaction, whereas Pd/C produced 60% less DMF than the combination of both metals. The presence of Lewis acidic component (Zn) was also found to be beneficial for HMF HDO with Ru/C catalyst, but the synergistic effect between the two metal components is more pronounced for the Pd/Zn system than the Ru/Zn. A comparative analysis of the Pd/Zn/C catalyst to previously reported catalytic systems show that the Pd/Zn system containing at least four times less precious metal than the reported catalysts gives comparable or better DMF yields. The catalyst shows excellent recyclability up to 4 cycles, followed by a deactivation, which could be due to coke formation on the catalyst surface. The effectiveness of this combined bimetallic catalyst has also been tested for one-pot conversion of fructose to DMF. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DeNOx active iron sites in iron loaded ZSM-5 - a multitechnique analysis of a complex heterogeneous catalyst based on Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Padmalekha, K. G.; Huang, H.; Ellmers, I.; Pérez Vélez, R.; van Leusen, J.; Brückner, A.; Grünert, W.; Schünemann, V.

2017-11-01

Iron loaded zeolites like Fe-ZSM-5 are potent candidates for the catalytic abatement of nitrogen oxides from car exhaust, e.g. from Diesel engines. Recent problems in this field show that there is an urgent need in further improvement of such catalysts, for which a full analysis of Fe species present in them under different conditions is highly desirable. We have studied Fe-ZSM-5 catalysts prepared via solid-state ion exchange by using field dependent Mössbauer spectroscopy at low temperature in order to identify the different iron species present in this type of catalyst in the fresh state and after use in catalysis. Mössbauer spectroscopy proved to be the key technique for a full understanding of species structures, but due to the complexity of structures, guidance by parallel EPR experiments and control by SQUID magnetometry were essential to prove reliability of derived species distributions.

Vacuum-insulated catalytic converter

DOEpatents

Benson, David K.

2001-01-01

A catalytic converter has an inner canister that contains catalyst-coated substrates and an outer canister that encloses an annular, variable vacuum insulation chamber surrounding the inner canister. An annular tank containing phase-change material for heat storage and release is positioned in the variable vacuum insulation chamber a distance spaced part from the inner canister. A reversible hydrogen getter in the variable vacuum insulation chamber, preferably on a surface of the heat storage tank, releases hydrogen into the variable vacuum insulation chamber to conduct heat when the phase-change material is hot and absorbs the hydrogen to limit heat transfer to radiation when the phase-change material is cool. A porous zeolite trap in the inner canister absorbs and retains hydrocarbons from the exhaust gases when the catalyst-coated substrates and zeolite trap are cold and releases the hydrocarbons for reaction on the catalyst-coated substrate when the zeolite trap and catalyst-coated substrate get hot.

Method of producing pyrolysis gases from carbon-containing materials

DOEpatents

Mudge, Lyle K.; Brown, Michael D.; Wilcox, Wayne A.; Baker, Eddie G.

1989-01-01

A gasification process of improved efficiency is disclosed. A dual bed reactor system is used in which carbon-containing feedstock materials are first treated in a gasification reactor to form pyrolysis gases. The pyrolysis gases are then directed into a catalytic reactor for the destruction of residual tars/oils in the gases. Temperatures are maintained within the catalytic reactor at a level sufficient to crack the tars/oils in the gases, while avoiding thermal breakdown of the catalysts. In order to minimize problems associated with the deposition of carbon-containing materials on the catalysts during cracking, a gaseous oxidizing agent preferably consisting of air, oxygen, steam, and/or mixtures thereof is introduced into the catalytic reactor at a high flow rate in a direction perpendicular to the longitudinal axis of the reactor. This oxidizes any carbon deposits on the catalysts, which would normally cause catalyst deactivation.

Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

PubMed

Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

2017-12-01

Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

A Nanopore-Structured Nitrogen-Doped Biocarbon Electrocatalyst for Oxygen Reduction from Two-Step Carbonization of Lemna minor Biomass.

PubMed

Guo, Chaozhong; Li, Zhongbin; Niu, Lidan; Liao, Wenli; Sun, Lingtao; Wen, Bixia; Nie, Yunqing; Cheng, Jing; Chen, Changguo

2016-12-01

So far, the development of highly active and stable carbon-based electrocatalysts for oxygen reduction reaction (ORR) to replace commercial Pt/C catalyst is a hot topic. In this study, a new nanoporous nitrogen-doped carbon material was facilely designed by two-step pyrolysis of the renewable Lemna minor enriched in crude protein under a nitrogen atmosphere. Electrochemical measurements show that the onset potential for ORR on this carbon material is around 0.93 V (versus reversible hydrogen electrode), slightly lower than that on the Pt/C catalyst, but its cycling stability is higher compared to the Pt/C catalyst in an alkaline medium. Besides, the ORR at this catalyst approaches to a four-electron transfer pathway. The obtained ORR performance can be basically attributed to the formation of high contents of pyridinic and graphitic nitrogen atoms inside this catalyst. Thus, this work opens up the path in the ORR catalysis for the design of nitrogen-doped carbon materials utilizing aquatic plants as starting precursors.

ZrO2/bamboo leaves ash (BLA) Catalyst in Biodiesel Conversion of Rice Bran Oil

NASA Astrophysics Data System (ADS)

Fatimah, Is; Taushiyah, Ana; Badriatun Najah, Fitri; Azmi, Ulil

2018-04-01

Preparation, characterization and catalytic activity of ZrO2/bamboo leaves ash (BLA) catalyst for conversion of rice bran oil to biodiesel have been investigated. The catalyst was prepared by impregnation method of ZrOCl2 as ZrO2 precursor with BLA at a theoretical content of 20% wt. followed by calcination. The physicochemical properties of the catalyst material were characterized by x-ray diffraction (XRD), FTIR and surface acidity measurement. Activity test of materials in biodiesel conversion of rice bran oil was used by reflux method and microwave (MW) assisted method. Reaction variables studied in the investigation were the effect of catalyst weight and time of MW irradiation compared with the use reflux method. The results showed that ZrO2/BLA catalyst exhibited competitively effective and efficient processes for the production of biodiesel. The reflux method demonstrated an higher conversion (%) compared to MW method, however MW method showed the better reusable properties.

Microwave Deposition of Palladium Catalysts on Graphite Spheres and Reduced Graphene Oxide Sheets for Electrochemical Glucose Sensing.

PubMed

Xie, Jian-De; Gu, Siyong; Zhang, Houan

2017-09-21

This work outlines a synthetic strategy inducing the microwave-assisted synthesis of palladium (Pd) nanocrystals on a graphite sphere (GS) and reduced graphene oxide (rGO) supports, forming the Pd catalysts for non-enzymatic glucose oxidation reaction (GOR). The pulse microwave approach takes a short period (i.e., 10 min) to fast synthesize Pd nanocrystals onto a carbon support at 150 °C. The selection of carbon support plays a crucial role in affecting Pd particle size and dispersion uniformity. The robust design of Pd-rGO catalyst electrode displays an enhanced electrocatalytic activity and sensitivity toward GOR. The enhanced performance is mainly attributed to the synergetic effect that combines small crystalline size and two-dimensional conductive support, imparting high accessibility to non-enzymatic GOR. The rGO sheets serve as a conductive scaffold, capable of fast conducting electron. The linear plot of current response versus glucose concentration exhibits good correlations within the range of 1-12 mM. The sensitivity of the Pd-rGO catalyst is significantly enhanced by 3.7 times, as compared to the Pd-GS catalyst. Accordingly, the Pd-rGO catalyst electrode can be considered as a potential candidate for non-enzymatic glucose biosensor.

Microwave Deposition of Palladium Catalysts on Graphite Spheres and Reduced Graphene Oxide Sheets for Electrochemical Glucose Sensing

PubMed Central

Xie, Jian-De; Zhang, Houan

2017-01-01

This work outlines a synthetic strategy inducing the microwave-assisted synthesis of palladium (Pd) nanocrystals on a graphite sphere (GS) and reduced graphene oxide (rGO) supports, forming the Pd catalysts for non-enzymatic glucose oxidation reaction (GOR). The pulse microwave approach takes a short period (i.e., 10 min) to fast synthesize Pd nanocrystals onto a carbon support at 150 °C. The selection of carbon support plays a crucial role in affecting Pd particle size and dispersion uniformity. The robust design of Pd-rGO catalyst electrode displays an enhanced electrocatalytic activity and sensitivity toward GOR. The enhanced performance is mainly attributed to the synergetic effect that combines small crystalline size and two-dimensional conductive support, imparting high accessibility to non-enzymatic GOR. The rGO sheets serve as a conductive scaffold, capable of fast conducting electron. The linear plot of current response versus glucose concentration exhibits good correlations within the range of 1–12 mM. The sensitivity of the Pd-rGO catalyst is significantly enhanced by 3.7 times, as compared to the Pd-GS catalyst. Accordingly, the Pd-rGO catalyst electrode can be considered as a potential candidate for non-enzymatic glucose biosensor. PMID:28934104

Layered double hydroxide of Cd-Al/C for the Mineralization and De-coloration of Dyes in Solar and Visible Light Exposure

NASA Astrophysics Data System (ADS)

Khan, Shahid Ali; Khan, Sher Bahadar; Asiri, Abdullah M.

2016-11-01

Cd-Al/C layered double hydroxide (Cd-Al/C-LDH) and Cd-Sb/C nanocatalyst are reported here for the de-coloration and mineralization of organic dyes. These catalysts were largely characterized by FESEM, EDS, XRD, FTIR, XPS, PL and DRS. The diffuse reflectance data showed a band gap at 2.92 and 2.983 eV for Cd-Al/C-LDH and Cd-Sb/C respectively. The band gap suggested that both catalysts work well in visible range. The photoluminescence spectra indicated a peak at 623 nm for both the catalysts which further support the effectiveness of the respective catalyst in visible range. Both catalysts also showed good recyclability and durability till 4th cycle. Five dyes, acridine orange (AO), malachite green (MG), crystal violet (CV), congo red (CR) and methyl orange (MO) were used in this experiment. Various parameters of different light intensity such as visible, ultraviolet, sunlight and dark condition are observed for the de-coloration of these dyes. The de-coloration phenomenon was proceeded through adsorption assisted phot-degradation. The low cost, abundant nature, good recyclability and better dye removal efficiency make these catalysts suitable candidates for the de-coloration and mineralization of organic dyes.

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

NASA Astrophysics Data System (ADS)

Kim, Minjoong; Kwon, Chorong; Eom, Kwangsup; Kim, Jihyun; Cho, Eunae

2017-03-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2.

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability.

PubMed

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-03-14

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO 2 (Nb-TiO 2 ) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO 2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb 0.25 Ti 0.75 O 2 ). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO 2 -nanofibers (Pt/Nb-TiO 2 ) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO 2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO 2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO 2 nanofiber catalyst can be attributed to high corrosion resistance of TiO 2 and strong interaction between Pt and TiO 2 .

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

PubMed Central

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-01-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2. PMID:28290503

Catalyst and electrode research for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Antoine, A. C.; King, R. B.

1987-01-01

An account is given of the development status of phosphoric acid fuel cells' high performance catalyst and electrode materials. Binary alloys have been identified which outperform the baseline platinum catalyst; it has also become apparent that pressurized operation is required to reach the desired efficiencies, calling in turn for the use of graphitized carbon blacks in the role of catalyst supports. Efforts to improve cell performance and reduce catalyst costs have led to the investigation of a class of organometallic cathode catalysts represented by the tetraazaannulenes, and a mixed catalyst which is a mixture of carbons catalyzed with an organometallic and a noble metal.

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.

Catalyst design for enhanced sustainability through fundamental surface chemistry.

PubMed

Personick, Michelle L; Montemore, Matthew M; Kaxiras, Efthimios; Madix, Robert J; Biener, Juergen; Friend, Cynthia M

2016-02-28

Decreasing energy consumption in the production of platform chemicals is necessary to improve the sustainability of the chemical industry, which is the largest consumer of delivered energy. The majority of industrial chemical transformations rely on catalysts, and therefore designing new materials that catalyse the production of important chemicals via more selective and energy-efficient processes is a promising pathway to reducing energy use by the chemical industry. Efficiently designing new catalysts benefits from an integrated approach involving fundamental experimental studies and theoretical modelling in addition to evaluation of materials under working catalytic conditions. In this review, we outline this approach in the context of a particular catalyst-nanoporous gold (npAu)-which is an unsupported, dilute AgAu alloy catalyst that is highly active for the selective oxidative transformation of alcohols. Fundamental surface science studies on Au single crystals and AgAu thin-film alloys in combination with theoretical modelling were used to identify the principles which define the reactivity of npAu and subsequently enabled prediction of new reactive pathways on this material. Specifically, weak van der Waals interactions are key to the selectivity of Au materials, including npAu. We also briefly describe other systems in which this integrated approach was applied. © 2016 The Author(s).

Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO4 material phase transformations in direct methanol synthesis from methane

NASA Astrophysics Data System (ADS)

Dasireddy, Venkata D. B. C.; Khan, Faiza B.; Hanzel, Darko; Bharuth-Ram, Krish; Likozar, Blaž

2017-11-01

The effect of the FePO4 material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O2, H2O and N2O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO4 (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe2P2O7, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

Final Report of a CRADA Between Pacific Northwest National Laboratory and the Ford Motor Company (CRADA No. PNNL/265): “Deactivation Mechanisms of Base Metal/Zeolite Urea Selective Catalytic Reduction Materials, and Development of Zeolite-Based Hydrocarbon Adsorber Materials”

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

Gao, Feng; Kwak, Ja Hun; Lee, Jong H.

2013-02-14

Reducing NOx emissions and particulate matter (PM) are primary concerns for diesel vehicles required to meet current LEV II and future LEV III emission standards which require 90+% NOx conversion. Currently, urea SCR as the NOx reductant and a Catalyzed Diesel Particulate Filter (CDPF) are being used for emission control system components by Ford Motor Company for 2010 and beyond diesel vehicles. Because the use of this technology for vehicle applications is new, the relative lack of experience makes it especially challenging to satisfy durability requirements. Of particular concern is being able to realistically simulate actual field aging of themore » catalyst systems under laboratory conditions. This is necessary both as a rapid assessment tool for verifying improved performance and certifiability of new catalyst formulations, and to develop a good understanding of deactivation mechanisms that can be used to develop improved catalyst materials. In addition to NOx and PM, the hydrocarbon (HC) emission standards are expected to become much more stringent during the next few years. Meanwhile, the engine-out HC emissions are expected to increase and/or be more difficult to remove. Since HC can be removed only when the catalyst becomes warm enough for its oxidation, three-way catalyst (TWC) and diesel oxidation catalyst (DOC) formulations often contain proprietary zeolite materials to hold the HC produced during the cold start period until the catalyst reaches its operating temperature (e.g., >200°C). Unfortunately, much of trapped HC tends to be released before the catalyst reaches the operating temperature. Among materials effective for trapping HC during the catalyst warm-up period, siliceous zeolites are commonly used because of their high surface area and high stability under typical operating conditions. However, there has been little research on the physical properties of these materials related to the adsorption and release of various hydrocarbon species found in the engine exhaust. For these reasons, automakers and engine manufacturers have difficulty improving their catalytic converters for meeting the stringent HC emission standards. In this collaborative program, scientists and engineers in the Institute for Integrated Catalysis at Pacific Northwest National Laboratory and at Ford Motor Company have investigated laboratory- and engine-aged SCR catalysts, containing mainly base metal zeolites. These studies are leading to a better understanding of various aging factors that impact the long-term performance of SCR catalysts and improve the correlation between laboratory and engine aging, saving experimental time and cost. We have also studied materials effective for the temporary storage of HC species during the cold-start period. In particular, we have examined the adsorption and desorption of various HC species produced during the combustion with different fuels (e.g., gasoline, E85, diesel) over potential HC adsorber materials, and measured the kinetic parameters to update Ford’s HC adsorption model. Since this CRADA has now been completed, in this final report we will provide brief summaries of most of the work carried out on this CRADA over the last several years.« less

Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

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

Michling, R.; Braun, A.; Cristescu, I.

2015-03-15

Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during themore » H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)« less

Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: a selective and sustainable oxidation protocol with high turnover number

EPA Science Inventory

A magnetic nanoparticle-supported ruthenium hydroxide catalyst was readily prepared from inexpensive starting materials and shown to catalyze hydration of nitriles with excellent yield in benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity...

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.

40 CFR 1042.655 - Special certification provisions for-Category 3 engines with aftertreatment.

Code of Federal Regulations, 2010 CFR

2010-07-01

... demonstrating for certification that catalyst-equipped engines (or engines equipped with other aftertreatment... engine-out emissions comply with the Tier 2 standards. The catalyst material or other aftertreatment... points. This catalyst or aftertreatment testing may be performed on a benchscale. (c) Engineering...

Improved Anode for a Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Valdez, Thomas; Narayanan, Sekharipuram

2005-01-01

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Biosynthesis of rare hexoses using microorganisms and related enzymes

PubMed Central

Li, Zijie; Gao, Yahui; Nakanishi, Hideki

2013-01-01

Summary Rare sugars, referred to as monosaccharides and their derivatives that rarely exist in nature, can be applied in many areas ranging from foodstuffs to pharmaceutical and nutrition industry, or as starting materials for various natural products and drug candidates. Unfortunately, an important factor restricting the utilization of rare sugars is their limited availability, resulting from limited synthetic methods. Nowadays, microbial and enzymatic transformations have become a very powerful tool in this field. This article reviews the biosynthesis and enzymatic production of rare ketohexoses, aldohexoses and sugar alcohols (hexitols), including D-tagatose, D-psicose, D-sorbose, L-tagatose, L-fructose, 1-deoxy-L-fructose, D-allose, L-glucose, L-talose, D-gulose, L-galactose, L-fucose, allitol, D-talitol, and L-sorbitol. New systems and robust catalysts resulting from advancements in genomics and bioengineering are also discussed. PMID:24367410

Biosynthesis of rare hexoses using microorganisms and related enzymes.

PubMed

Li, Zijie; Gao, Yahui; Nakanishi, Hideki; Gao, Xiaodong; Cai, Li

2013-11-12

Rare sugars, referred to as monosaccharides and their derivatives that rarely exist in nature, can be applied in many areas ranging from foodstuffs to pharmaceutical and nutrition industry, or as starting materials for various natural products and drug candidates. Unfortunately, an important factor restricting the utilization of rare sugars is their limited availability, resulting from limited synthetic methods. Nowadays, microbial and enzymatic transformations have become a very powerful tool in this field. This article reviews the biosynthesis and enzymatic production of rare ketohexoses, aldohexoses and sugar alcohols (hexitols), including D-tagatose, D-psicose, D-sorbose, L-tagatose, L-fructose, 1-deoxy-L-fructose, D-allose, L-glucose, L-talose, D-gulose, L-galactose, L-fucose, allitol, D-talitol, and L-sorbitol. New systems and robust catalysts resulting from advancements in genomics and bioengineering are also discussed.

Combinatorial computational chemistry approach for materials design: applications in deNOx catalysis, Fischer-Tropsch synthesis, lanthanoid complex, and lithium ion secondary battery.

PubMed

Koyama, Michihisa; Tsuboi, Hideyuki; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Del Carpio, Carlos A; Miyamoto, Akira

2007-02-01

Computational chemistry can provide fundamental knowledge regarding various aspects of materials. While its impact in scientific research is greatly increasing, its contributions to industrially important issues are far from satisfactory. In order to realize industrial innovation by computational chemistry, a new concept "combinatorial computational chemistry" has been proposed by introducing the concept of combinatorial chemistry to computational chemistry. This combinatorial computational chemistry approach enables theoretical high-throughput screening for materials design. In this manuscript, we review the successful applications of combinatorial computational chemistry to deNO(x) catalysts, Fischer-Tropsch catalysts, lanthanoid complex catalysts, and cathodes of the lithium ion secondary battery.

Chemical signal activation of an organocatalyst enables control over soft material formation.

PubMed

Trausel, Fanny; Maity, Chandan; Poolman, Jos M; Kouwenberg, D S J; Versluis, Frank; van Esch, Jan H; Eelkema, Rienk

2017-10-12

Cells can react to their environment by changing the activity of enzymes in response to specific chemical signals. Artificial catalysts capable of being activated by chemical signals are rare, but of interest for creating autonomously responsive materials. We present an organocatalyst that is activated by a chemical signal, enabling temporal control over reaction rates and the formation of materials. Using self-immolative chemistry, we design a deactivated aniline organocatalyst that is activated by the chemical signal hydrogen peroxide and catalyses hydrazone formation. Upon activation of the catalyst, the rate of hydrazone formation increases 10-fold almost instantly. The responsive organocatalyst enables temporal control over the formation of gels featuring hydrazone bonds. The generic design should enable the use of a large range of triggers and organocatalysts, and appears a promising method for the introduction of signal response in materials, constituting a first step towards achieving communication between artificial chemical systems.Enzymes regulated by chemical signals are common in biology, but few such artificial catalysts exist. Here, the authors design an aniline catalyst that, when activated by a chemical trigger, catalyses formation of hydrazone-based gels, demonstrating signal response in a soft material.

Preparation of Supported Palladium Catalysts using Deep Eutectic Solvents.

PubMed

Iwanow, Melanie; Finkelmeyer, Jasmin; Söldner, Anika; Kaiser, Manuela; Gärtner, Tobias; Sieber, Volker; König, Burkhard

2017-09-12

Deep eutectic solvents (DESs) dissolve metal salts or oxides and are used as solvent and carbon source for the preparation of supported palladium catalysts. After dissolving of the palladium salt in the DES, the pyrolysis of the mixture under nitrogen atmosphere yields catalytically active palladium on supporting material composed of carbon, nitrogen and oxygen (CNO) by a simple single step preparation method without further activation. The catalysts were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and CHNS/O elementary analysis. The amount of functional groups on the surface of the supporting material was determined by Boehm titrations. Moreover, the activity of the prepared catalysts was evaluated in the hydrogenation of linear alkenes and compared with a commercial Pd/C catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

CO-oxidation catalysts: Low-temperature CO oxidation over Noble-Metal Reducible Oxide (NMRO) catalysts

NASA Technical Reports Server (NTRS)

Herz, Richard K.

1990-01-01

Oxidation of CO to CO2 is an important reaction technologically and environmentally and a complex and interesting reaction scientifically. In most cases, the reaction is carried out in order to remove CO as an environmental hazard. A major application of heterogeneous catalysts is catalytic oxidation of CO in the exhaust of combustion devices. The reaction over catalysts in exhaust gas is fast and often mass-transfer-limited since exhaust gases are hot and O2/CO ratios are high. The main challenges to catalyst designers are to control thermal sintering and chemical poisoning of the active materials. The effect of the noble metal on the oxide is discussed, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form unique catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

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

PubMed Central

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

2011-01-01

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

Wet air oxidation of cresylic spent caustic - A model compound study over graphene oxide (GO) and ruthenium/GO catalysts.

PubMed

Barge, Aditti S; Vaidya, Prakash D

2018-04-15

Wet air oxidation (WAO) is a candidate technique for the effective treatment of spent caustic wastewater. In this work, cresols were chosen as model compounds to represent cresylic spent caustic wash. Graphene oxide (GO) is a promising catalyst as well as support for the wet oxidation process, due to its unique structure and properties. For the first time, GO and ruthenium supported on graphene oxide (Ru/GO) were employed for WAO of cresylic isomers. The aforesaid materials were synthesized by modified Hummer's method and characterized using scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analysis. The performance of the investigated materials for WAO of cresols was studied in a slurry reactor. The best reaction conditions for GO were 175 °C and 0.69 MPa O 2 pressure. Total organic carbon (TOC) degradation achieved at these conditions was 54.9, 48.9 and 61.2% for o-cresol, m-cresol and p-cresol, respectively. The amount of TOC degradation obtained by using Ru/GO at the same reaction conditions was 66.4, 53.4 and 73.9% for o-cresol, m-cresol and p-cresol, respectively. It was found that the order of reactivity for cresols was p-cresol > o-cresol > m-cresol. Finally, kinetics of TOC destruction during CWAO of p-cresol over GO was described using a two-step power law model. Copyright © 2018 Elsevier Ltd. All rights reserved.

Nanotransfer and nanoreplication using deterministically grown sacrificial nanotemplates

DOEpatents

Melechko, Anatoli V [Oak Ridge, TN; McKnight, Timothy E. , Guillorn, Michael A.; Ilic, Bojan [Ithaca, NY; Merkulov, Vladimir I [Knoxville, TN; Doktycz, Mitchel J [Knoxville, TN; Lowndes, Douglas H [Knoxville, TN; Simpson, Michael L [Knoxville, TN

2011-05-17

Methods, manufactures, machines and compositions are described for nanotransfer and nanoreplication using deterministically grown sacrificial nanotemplates. A method includes depositing a catalyst particle on a surface of a substrate to define a deterministically located position; growing an aligned elongated nanostructure on the substrate, an end of the aligned elongated nanostructure coupled to the substrate at the deterministically located position; coating the aligned elongated nanostructure with a conduit material; removing a portion of the conduit material to expose the catalyst particle; removing the catalyst particle; and removing the elongated nanostructure to define a nanoconduit.

Catalysts for lean burn engine exhaust abatement

DOEpatents

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

2006-08-01

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

Catalysts For Lean Burn Engine Exhaust Abatement

DOEpatents

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

2004-04-06

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

Catalysts for lean burn engine exhaust abatement

DOEpatents

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

2003-01-01

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

Impact of initial catalyst form on the 3D structure and performance of ball-milled Ni-catalyzed MgH 2 for hydrogen storage

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

House, Stephen D.; Vajo, John J.; Ren, Chai

Although it has been shown that the hydrogen storage kinetics of metal hydrides can be significantly improved by the addition of transition metal-based catalysts, relatively little attention has been paid to the impact that the form in which these catalysts are introduced during synthesis has on the resulting structure and how this alters performance. Two mixtures of MgH 2 doped with Ni were prepared via high-energy ball-milling under identical conditions, one using a pure Ni nanopowder catalyst and the other using anhydrous NiCl 2. The resulting Ni catalyst particles of the NiCl 2-doped material were 10-100 times smaller, as wellmore » as more uniform in size and shape. Electron tomography revealed that the additive form also altered its incorporation and 3D spatial distribution, with Ni particles limited to the outer surface in the NiCl 2-doped case. The significantly lower desorption performance measured in the NiCl 2-doped material is attributed to regions of MgCl 2 acting as barriers between the MgH 2 and Ni, hindering the ability of the latter to effectively catalyze the reactions. Finally, this work demonstrates the hazards in assuming different catalyst forms produce similar final structures and highlights the potential of catalyst form as a synthesis tool for optimizing the material structure and performance.« less

Impact of initial catalyst form on the 3D structure and performance of ball-milled Ni-catalyzed MgH 2 for hydrogen storage

DOE PAGES

House, Stephen D.; Vajo, John J.; Ren, Chai; ...

2017-02-24

Although it has been shown that the hydrogen storage kinetics of metal hydrides can be significantly improved by the addition of transition metal-based catalysts, relatively little attention has been paid to the impact that the form in which these catalysts are introduced during synthesis has on the resulting structure and how this alters performance. Two mixtures of MgH 2 doped with Ni were prepared via high-energy ball-milling under identical conditions, one using a pure Ni nanopowder catalyst and the other using anhydrous NiCl 2. The resulting Ni catalyst particles of the NiCl 2-doped material were 10-100 times smaller, as wellmore » as more uniform in size and shape. Electron tomography revealed that the additive form also altered its incorporation and 3D spatial distribution, with Ni particles limited to the outer surface in the NiCl 2-doped case. The significantly lower desorption performance measured in the NiCl 2-doped material is attributed to regions of MgCl 2 acting as barriers between the MgH 2 and Ni, hindering the ability of the latter to effectively catalyze the reactions. Finally, this work demonstrates the hazards in assuming different catalyst forms produce similar final structures and highlights the potential of catalyst form as a synthesis tool for optimizing the material structure and performance.« less

Mesoporous Phosphorus-Doped g-C3N4 Nanostructured Flowers with Superior Photocatalytic Hydrogen Evolution Performance.

PubMed

Zhu, Yun-Pei; Ren, Tie-Zhen; Yuan, Zhong-Yong

2015-08-05

Graphitic carbon nitride (g-C3N4) has been deemed a promising heterogeneous metal-free catalyst for a wide range of applications, such as solar energy utilization toward water splitting, and its photocatalytic performance is reasonably adjustable through tailoring its texture and its electronic and optical properties. Here phosphorus-doped graphitic carbon nitride nanostructured flowers of in-plane mesopores are synthesized by a co-condensation method in the absence of any templates. The interesting structures, together with the phosphorus doping, can promote light trapping, mass transfer, and charge separation, enabling it to perform as a more impressive catalyst than its pristine carbon nitride counterpart for catalytic hydrogen evolution under visible light irradiation. The catalyst has low cost, is environmentally friendly, and represents a potential candidate in photoelectrochemistry.

Method for producing catalysis from coal

DOEpatents

Farcasiu, Malvina; Derbyshire, Frank; Kaufman, Phillip B.; Jagtoyen, Marit

1998-01-01

A method for producing catalysts from coal is provided comprising mixing an aqueous alkali solution with the coal, heating the aqueous mixture to treat the coal, drying the now-heated aqueous mixture, reheating the mixture to form carbonized material, cooling the mixture, removing excess alkali from the carbonized material, and recovering the carbonized material, wherein the entire process is carried out in controlled atmospheres, and the carbonized material is a hydrocracking or hydrodehalogenation catalyst for liquid phase reactions. The invention also provides for a one-step method for producing catalysts from coal comprising mixing an aqueous alkali solution with the coal to create a mixture, heating the aqueous mixture from an ambient temperature to a predetermined temperature at a predetermined rate, cooling the mixture, and washing the mixture to remove excess alkali from the treated and carbonized material, wherein the entire process is carried out in a controlled atmosphere.

Method for making oxygen-reducing catalyst layers

DOEpatents

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

2010-06-22

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

Catalyst Stability Benchmarking for the Oxygen Evolution Reaction: The Importance of Backing Electrode Material and Dissolution in Accelerated Aging Studies.

PubMed

Geiger, Simon; Kasian, Olga; Mingers, Andrea M; Nicley, Shannon S; Haenen, Ken; Mayrhofer, Karl J J; Cherevko, Serhiy

2017-09-18

In searching for alternative oxygen evolution reaction (OER) catalysts for acidic water splitting, fast screening of the material intrinsic activity and stability in half-cell tests is of vital importance. The screening process significantly accelerates the discovery of new promising materials without the need of time-consuming real-cell analysis. In commonly employed tests, a conclusion on the catalyst stability is drawn solely on the basis of electrochemical data, for example, by evaluating potential-versus-time profiles. Herein important limitations of such approaches, which are related to the degradation of the backing electrode material, are demonstrated. State-of-the-art Ir-black powder is investigated for OER activity and for dissolution as a function of the backing electrode material. Even at very short time intervals materials like glassy carbon passivate, increasing the contact resistance and concealing the degradation phenomena of the electrocatalyst itself. Alternative backing electrodes like gold and boron-doped diamond show better stability and are thus recommended for short accelerated aging investigations. Moreover, parallel quantification of dissolution products in the electrolyte is shown to be of great importance for comparing OER catalyst feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mussel-inspired approach to constructing robust cobalt-embedded N-doped carbon nanosheet toward enhanced sulphate radical-based oxidation

NASA Astrophysics Data System (ADS)

Zeng, Tao; Zhang, Haiyan; He, Zhiqiao; Chen, Jianmeng; Song, Shuang

2016-09-01

Heterogeneous sulphate radical based advanced oxidation processes (SR-AOPs) have lately been raised as a promising candidate for water treatment. Despite the progress made, either the stability or the performance of the current catalysts is still far from satisfactory for practical applications. Herein, using polydopamine-cobalt ion complex that inspired by mussel proteins as medium, we facilely fabricate a robust SR-AOPs catalyst with cobalt nanoparticles (NPs) embedded in nitrogen-doped reduced graphene oxide matrix (NRGO@Co). The NRGO scaffold with high porosity and surface area not only stabilizes the NPs but also greatly facilitates the accessibility and adsorption of substrates to the active sites. With the synergistic effect arising from the NRGO and Co NPs, the NRGO@Co hybrid catalyst exhibits enhanced catalytic activity for activation of peroxymonosulfate (PMS) to degrade organic pollutants in water. Furthermore, taking advantage of the favorable magnetic properties, the catalyst can be easily recycled and reused for at least 4 runs with negligible loss of activity. Coupled with systematic investigation in terms of influential factors, mineralization, and radicals identification, make the catalyst hold significant potential for application in remediation of organic pollutants in water.

Coating of porous carbon for use in lithium air batteries

DOEpatents

Amine, Khalil; Lu, Jun; Du, Peng; Lei, Yu; Elam, Jeffrey W

2015-04-14

A cathode includes a carbon material having a surface, the surface having a first thin layer of an inert material and a first catalyst overlaying the first thin layer, the first catalyst including metal or metal oxide nanoparticles, wherein the cathode is configured for use as the cathode of a lithium-air battery.

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.

Nanoparticle-supported and magnetically recoverable ruthenium hydroxide catalyst: efficient hydration of nitriles to amides in aqueous medium.

PubMed

Polshettiwar, Vivek; Varma, Rajender S

2009-01-01

Magnetic attraction not filtration: A magnetic nanoparticle-supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.

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.

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.

Hydrophilic TiO2 porous spheres anchored on hydrophobic polypropylene membrane for wettability induced high photodegrading activities.

PubMed

Niu, Fang; Zhang, Le-Sheng; Chen, Chao-Qiu; Li, Wei; Li, Lin; Song, Wei-Guo; Jiang, Lei

2010-08-01

TiO(2) porous nanospheres on polypropylene (PP) films (TiO(2)/PP composite) are produced at ambient temperature. Particle/pore size match up is the key anchoring point to overcome the low affinity between hydrophilic materials and hydrophobic materials. With the hydrophilic TiO(2) catalyst evenly dispersed on a hydrophobic surface, the aqueous solution will selectively skip the substrate and wet the catalysts. Such a wettability-induced smart system maximizes the degrading activity of the TiO(2) catalyst. In photodegrading reactions, the resulting TiO(2)/PP composite film exhibits a 10 times higher activity in flow-type setup than the same TiO(2) catalyst in a traditional batch-type setup.

Nano-Array Integrated Structured Catalysts: A New Paradigm upon Conventional Wash-Coated Monolithic Catalysts?

DOE PAGES

Weng, Junfei; Lu, Xingxu; Gao, Pu-Xian

2017-08-28

The monolithic catalyst, namely the structured catalyst, is one of the important categories of catalysts used in various fields, especially in catalytic exhaust after-treatment. Despite its successful application in conventional wash-coated catalysts in both mobile and stationary catalytic converters, washcoat-based technologies are facing multi-fold challenges, including: (1) high Pt-group metals (PGM) material loading being required, driving the market prices; (2) less-than ideal distribution of washcoats in typically square-shaped channels associated with pressure drop sacrifice; and (3) far from clear correlations between macroscopic washcoat structures and their catalytic performance. To tackle these challenges, the well-defined nanostructure array (nano-array)-integrated structured catalysts whichmore » we invented and developed recently have been proven to be a promising class of cost-effective and efficient devices that may complement or substitute wash-coated catalysts. This new type of structured catalysts is composed of honeycomb-structured monoliths, whose channel surfaces are grown in situ with a nano-array forest made of traditional binary transition metal oxide support such as Al 2O 3, CeO 2, Co 3O 4, MnO 2, TiO 2, and ZnO, or newer support materials including perovskite-type ABO3 structures, for example LaMnO 3, LaCoO 3, LaNiO, and LaFeO 3. The integration strategy parts from the traditional washcoat technique. Instead, an in situ nanomaterial assembly method is utilized, such as a hydro (solva-) thermal synthesis approach, in order to create sound structure robustness, and increase ease and complex-shaped substrate adaptability. Specifically, the critical fabrication procedures for nano-array structured catalysts include deposition of seeding layer, in situ growth of nano-array, and loading of catalytic materials. The generic methodology utilization in both the magnetic stirring batch process and continuous flow reactor synthesis offers the nano-array catalysts with great potential to be scaled up readily and cost-effectively. The tunability of the structure and catalytic performance could be achieved through morphology and geometry adjustment and guest atoms and defect manipulation, as well as composite nano-array catalyst manufacture. Excellent stabilities under various conditions were also present compared to conventional wash-coated catalysts.« less

Nano-Array Integrated Structured Catalysts: A New Paradigm upon Conventional Wash-Coated Monolithic Catalysts?

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

Weng, Junfei; Lu, Xingxu; Gao, Pu-Xian

The monolithic catalyst, namely the structured catalyst, is one of the important categories of catalysts used in various fields, especially in catalytic exhaust after-treatment. Despite its successful application in conventional wash-coated catalysts in both mobile and stationary catalytic converters, washcoat-based technologies are facing multi-fold challenges, including: (1) high Pt-group metals (PGM) material loading being required, driving the market prices; (2) less-than ideal distribution of washcoats in typically square-shaped channels associated with pressure drop sacrifice; and (3) far from clear correlations between macroscopic washcoat structures and their catalytic performance. To tackle these challenges, the well-defined nanostructure array (nano-array)-integrated structured catalysts whichmore » we invented and developed recently have been proven to be a promising class of cost-effective and efficient devices that may complement or substitute wash-coated catalysts. This new type of structured catalysts is composed of honeycomb-structured monoliths, whose channel surfaces are grown in situ with a nano-array forest made of traditional binary transition metal oxide support such as Al 2O 3, CeO 2, Co 3O 4, MnO 2, TiO 2, and ZnO, or newer support materials including perovskite-type ABO3 structures, for example LaMnO 3, LaCoO 3, LaNiO, and LaFeO 3. The integration strategy parts from the traditional washcoat technique. Instead, an in situ nanomaterial assembly method is utilized, such as a hydro (solva-) thermal synthesis approach, in order to create sound structure robustness, and increase ease and complex-shaped substrate adaptability. Specifically, the critical fabrication procedures for nano-array structured catalysts include deposition of seeding layer, in situ growth of nano-array, and loading of catalytic materials. The generic methodology utilization in both the magnetic stirring batch process and continuous flow reactor synthesis offers the nano-array catalysts with great potential to be scaled up readily and cost-effectively. The tunability of the structure and catalytic performance could be achieved through morphology and geometry adjustment and guest atoms and defect manipulation, as well as composite nano-array catalyst manufacture. Excellent stabilities under various conditions were also present compared to conventional wash-coated catalysts.« less

Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

NASA Astrophysics Data System (ADS)

Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

2017-02-01

In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

PubMed Central

Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

2017-01-01

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C–O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven. PMID:28621710

Covalent Heterogenization of a Discrete Mn(II) Bis-Phen Complex by a Metal-Template/Metal-Exchange Method: An Epoxidation Catalyst with Enhanced Reactivity

PubMed Central

Terry, Tracy J.; Stack, T. Daniel P.

2009-01-01

Considerable attention has been devoted to the immobilization of discrete epoxidation catalysts onto solid supports due to the possible benefits of site isolation such as increased catalyst stability, catalyst recycling, and product separation. A synthetic metal-template/metal-exchange method to imprint a covalently attached bis-1,10-phenanthroline coordination environment onto high-surface area, mesoporous SBA-15 silica is reported herein along with the epoxidation reactivity once reloaded with manganese. Comparisons of this imprinted material with material synthesized by random grafting of the ligand show that the template method creates more reproducible, solution-like bis-1,10-phenanthroline coordination at a variety of ligand loadings. Olefin epoxidation with peracetic acid shows the imprinted manganese catalysts have improved product selectivity for epoxides, greater substrate scope, more efficient use of oxidant, and higher reactivity than their homogeneous or grafted analogues independent of ligand loading. The randomly grafted manganese catalysts, however, show reactivity that varies with ligand loading while the homogeneous analogue degrades trisubstituted olefins and produces trans-epoxide products from cis-olefins. Efficient recycling behavior of the templated catalysts is also possible. PMID:18351763

A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

PubMed

Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

2017-06-16

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K₂CO₃ base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.

Materials for Energy Conversion: Materials for Energy Conversion and Storage

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

Atanassov, Plamen

2017-03-30

The main objective of this collaborative research project was to identify a formulation and develop a catalyst for electro-oxidation of ethanol. Ethanol is one of the most mass-produced biofuels, and such catalysts will enable the development of Direct Ethanol Fuel Cell technology and through it, will interconnect fuel cells with biofuels. Several catalysts for direct electrochemical oxidation of ethanol have been selected on the principles of rational desig from the knowledge build in studying aqueous oxidation of ethanol. The program involved fundamental study of ethanol oxidation in liquid media, and particularly in alakine solutions. The lessons learned from the heterogeneousmore » catalysis of ethanol thermal oxidation have been applied to the design of an electrocatalyst for direct ethanol fuel cells. The successful chemical compositions are based on PdZn and NiZn allows. The studies reveled the role of the transition metal oxide phase as a co-catalyst and the role of the active support material. To complete the set of materials for ethanol fuel cell, this program also invested n the development of ctalysts for oxygen reduction that are selective against alcohol oxidation. Non-platinum ctalysts based on pyrolyzed macrocycles or similar composites have been studied. This program included also the development of stuctured supports as an integral part of the catalyst development. A new family of materials has been designed based on mesoporous silica templating with synthetic carbon resulting in hierarchicaly porous structure. Structure-to-property relationship of catalysis and catalysts has been the center of this program. This have been engaged in both surface and bulk level and pursued with the tools avialble at the academic institutions and at LANSCE at LANL. The structural studies have been built in interaction with a computational effort on the basis of DFT approach to materials structure and reactivity.« less

Partial oxidation of liquid hydrocarbons in the presence of oxygen-conducting supports: Effect of catalyst layer deposition

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

Smith, M.; Berry, D.; Shekhawt, D.

2010-01-01

Ni-substituted barium hexaaluminate (BNHA) catalysts supported onto gadolinium-doped ceria (GDC), an oxygen-conductor, were prepared using two different methods: (1) conventional incipient wetness impregnation (IWI), in which a non-porous GDC support was impregnated in the conventional manner with aqueous precursors, then dried and calcined to form a supported hexaaluminate, and (2) solid-state mixing (SSM), in which solid hexaaluminate and GDC particles were mechanically ground together and thermally treated to produce a final catalyst. These catalysts were compared to bulk, unsupported BNHA; 3 wt% Ni/alumina; and 3 wt% Ni/GDC (the latter two prepared by conventional impregnation) for the partial oxidation (POX) ofmore » n-tetradecane. The reaction studies included examining the effect of 50 ppm S as dibenzothiophene (DBT) and 5 wt% 1-methylnaphthalene (MN) on the product yield under POX conditions. Temperature programmed oxidation (TPO) was used to characterize carbon formation in the reactor. The materials were characterized by BET, ICP-OES, XRD, and SEM/EDS prior to the reaction tests. Characterization of the two GDC-supported BNHA catalysts prior to the reaction studies indicated no significant differences in the bulk composition, surface area, and crystal structure. However, SEM images showed a larger amount of exposed GDC support surface area for the material prepared by IWI. Both of the GDC-supported BNHA materials demonstrated greatly reduced deactivation, with significantly reduced carbon formation compared to bulk BNHA. This was attributed to the oxygen-conducting property of the GDC, which reduced the rate of deactivation of the reaction sites by DBT and MN. The material prepared by IWI demonstrated more stable hydrogen and carbon monoxide yield than the material prepared by SSM. Although both catalysts deactivated in the presence of DBT and MN, the activity of the catalyst prepared by IWI recovered activity more quickly after the contaminants were removed. This material also maintained >50% of its initial hydrogen yield for more than 4 h after exposure to DBT and MN, while the hydrogen for the material prepared by SSM dropped to this same level within 2 h. Incipient wetness impregnation appears to provide a higher degree of interaction between the oxygenconducting GDC support and the hexaaluminate, resulting in less rapid deactivation, which appears to be due primarily to carbon deposition.« less

Flory-Stockmayer analysis on reprocessable polymer networks

NASA Astrophysics Data System (ADS)

Li, Lingqiao; Chen, Xi; Jin, Kailong; Torkelson, John

Reprocessable polymer networks can undergo structure rearrangement through dynamic chemistries under proper conditions, making them a promising candidate for recyclable crosslinked materials, e.g. tires. This research field has been focusing on various chemistries. However, there has been lacking of an essential physical theory explaining the relationship between abundancy of dynamic linkages and reprocessability. Based on the classical Flory-Stockmayer analysis on network gelation, we developed a similar analysis on reprocessable polymer networks to quantitatively predict the critical condition for reprocessability. Our theory indicates that it is unnecessary for all bonds to be dynamic to make the resulting network reprocessable. As long as there is no percolated permanent network in the system, the material can fully rearrange. To experimentally validate our theory, we used a thiol-epoxy network model system with various dynamic linkage compositions. The stress relaxation behavior of resulting materials supports our theoretical prediction: only 50 % of linkages between crosslinks need to be dynamic for a tri-arm network to be reprocessable. Therefore, this analysis provides the first fundamental theoretical platform for designing and evaluating reprocessable polymer networks. We thank McCormick Research Catalyst Award Fund and ISEN cluster fellowship (L. L.) for funding support.

Final Project Report: Development of Micro-Structural Mitigation Strategies for PEM Fuel Cells: Morphological Simulations and Experimental Approaches

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

Wessel, Silvia; Harvey, David

2013-06-28

The durability of PEM fuel cells is a primary requirement for large scale commercialization of these power systems in transportation and stationary market applications that target operational lifetimes of 5,000 hours and 40,000 hours by 2015, respectively. Key degradation modes contributing to fuel cell lifetime limitations have been largely associated with the platinum-based cathode catalyst layer. Furthermore, as fuel cells are driven to low cost materials and lower catalyst loadings in order to meet the cost targets for commercialization, the catalyst durability has become even more important. While over the past few years significant progress has been made in identifyingmore » the underlying causes of fuel cell degradation and key parameters that greatly influence the degradation rates, many gaps with respect to knowledge of the driving mechanisms still exist; in particular, the acceleration of the mechanisms due to different structural compositions and under different fuel cell conditions remains an area not well understood. The focus of this project was to address catalyst durability by using a dual path approach that coupled an extensive range of experimental analysis and testing with a multi-scale modeling approach. With this, the major technical areas/issues of catalyst and catalyst layer performance and durability that were addressed are: 1. Catalyst and catalyst layer degradation mechanisms (Pt dissolution, agglomeration, Pt loss, e.g. Pt in the membrane, carbon oxidation and/or corrosion). a. Driving force for the different degradation mechanisms. b. Relationships between MEA performance, catalyst and catalyst layer degradation and operational conditions, catalyst layer composition, and structure. 2. Materials properties a. Changes in catalyst, catalyst layer, and MEA materials properties due to degradation. 3. Catalyst performance a. Relationships between catalyst structural changes and performance. b. Stability of the three-phase boundary and its effect on performance/catalyst degradation. The key accomplishments of this project are: • The development of a molecular-dynamics based description of the carbon supported-Pt and ionomer system • The development of a composition-based, 1D-statistical Unit Cell Performance model • A modified and improved multi-pathway ORR model • An extension of the existing micro-structural catalyst model to transient operation • The coupling of a Pt Dissolution model to the modified ORR pathway model • The Development A Semi-empirical carbon corrosion model • The integration and release of an open-source forward predictive MEA performance and degradation model • Completion of correlations of BOT (beginning of test) and EOT (end of test) performance loss breakdown with cathode catalyst layer composition, morphology, material properties, and operational conditions • Catalyst layer durability windows and design curves • A design flow path of interactions from materials properties and catalyst layer effective properties to performance loss breakdown for virgin and degraded catalyst layers In order to ensure the best possible user experience we will perform a staged release of the software leading up to the webinar scheduled in October 2013. The release schedule will be as follows (please note that the manual will be released with the beta release as direct support is provided in Stage 1): • Stage 0 - Internal Ballard Release o Cross check of compilation and installation to ensure machine independence o Implement code on portable virtual machine to allow for non-UNIX use (pending) • Stage 1 - Alpha Release o The model code will be made available via a GIT, sourceforge, or other repository (under discussion at Ballard) for download and installation by a small pre-selected group of users o Users will be given three weeks to install, apply, and evaluate features of the code, providing feedback on issues or software bugs that require correction prior to beta release • Stage 2 - Beta Release o The model code repository is opened to the general public on a beta release concept, with a mechanism for bug tracking and feedback from a large user group o Code will be tracked and patched for any discovered bugs or relevant feedback from the user community, upon the completion of three months without a major bug submission the code will be moved to a full version release • Stage 3 - Full Version Release o Code is version to revision 1.0 and that version is frozen in development/patching« less

Self regulating formulations for safe hydrogen gettering

DOEpatents

Shepodd, Timothy Jon

2002-01-01

A method and composition are disclosed for preventing uncontrolled exothermic reaction in the presence of a catalyst. A catalyst deployed as a finely divided powder which is attached to the surface of a low melting point wax or wax-like material which is utilized as a carrier for the catalyst. During operation should the catalyst overheat due to uncontrolled conditions brought about by a run-away reaction the heat of reaction melts the low melting point wax which would itself wet the surface of the catalyst and prevent further catalysis.

Leadership Mentoring and Situated Learning: Catalysts for Principalship Readiness and Lifelong Mentoring

ERIC Educational Resources Information Center

Browne-Ferrigno, Tricia; Muth, Rodney

2006-01-01

Leadership mentoring and situated learning are important components in the effective preparation of candidates for school principalships. This study examined this assertion through responses to reflective writing prompts and to interview questions by students enrolled in three different closed cohorts in the same university-based preparation…

Organic Electronics: An El Dorado in the Quest of New Photocatalysts for Polymerization Reactions.

PubMed

Dumur, Frédéric; Gigmes, Didier; Fouassier, Jean-Pierre; Lalevée, Jacques

2016-09-20

Photoinitiated polymerization has been the subject of continued research efforts due to the numerous applications in which this polymerization technique is involved (coatings, inks, adhesives, optoelectronic, laser imaging, stereolithography, nanotechnology, etc.). More recently, photopolymerization has received renewed interest due to the emergence of 3D-printing technologies. However, despite current academic and industrial interest in photopolymerization methodologies, a major limitation lies in the slow rates of photopolymerization. The development of new photoinitiating systems aimed at addressing this limitation is an active area of research. Photopolymerization occurs through the exposure of a curable formulation to light, generating radical and/or cationic species to initiate polymerization. At present, photopolymerization is facing numerous challenges related to safety, economic and ecological concerns. Furthermore, practical considerations such as the curing depth and the competition for light absorption between the chromophores and other species in the formulation are key parameters drastically affecting the photopolymerization process. To address these issues, photoinitiating systems operating under low intensity visible light irradiation, in the absence of solvents are highly sought after. In this context, the use of photoredox catalysis can be highly advantageous; that is, photoredox catalysts can provide high reactivities with low catalyst loading, permitting access to high performance photoinitiating systems. However, to act as efficient photoredox catalysts, specific criteria have to be fulfilled. A strong absorption over the visible range, an ability to easily oxidize or reduce as well as sufficient photochemical stability are basic prerequisites to make these molecules desirable candidates for photoredox catalysis. Considering the similarity of requirements between organic electronics and photopolymerization, numerous materials initially designed for applications in organic electronics have been revisited in the context of photopolymerization. Organic electronics is a branch of electronics and materials science focusing on the development of semiconductors devoted to three main research fields; organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells (OSCs). The contribution of organic electronics to the field of electronics is important as it paves the way toward cheaper, lighter, and more energy efficient devices. In the present context of photopolymerization, materials that were investigated as photocatalysts were indifferently organic semiconductors used for transistors, charge-transport materials, and light-emitting materials used in electroluminescent devices or conjugated polymers and small molecule dyes for solar cells. In this Account, we summarize our latest developments in elaborating on photocatalytic systems based on these new classes of compounds. Through an in-depth understanding of the parameters governing their reactivities and our efforts to incorporate these materials into photoinitiating systems, we provide new knowledge and a valuable insight for future prospects.

Visible-light photochemical activity of heterostructured core-shell materials composed of selected ternary titanates and ferrites coated by tiO2.

PubMed

Li, Li; Liu, Xuan; Zhang, Yiling; Nuhfer, Noel T; Barmak, Katayun; Salvador, Paul A; Rohrer, Gregory S

2013-06-12

Heterostructured photocatalysts comprised of microcrystalline (mc-) cores and nanostructured (ns-) shells were prepared by the sol-gel method. The ability of titania-coated ATiO3 (A = Fe, Pb) and AFeO3 (A = Bi, La, Y) catalysts to degrade methylene blue in visible light (λ > 420 nm) was compared. The catalysts with the titanate cores had enhanced photocatalytic activities for methylene blue degradation compared to their components alone, whereas the catalysts with ferrite cores did not. The temperature at which the ns-titania shell is crystallized influences the photocatalytic dye degradation. mc-FeTiO3/ns-TiO2 annealed at 500 °C shows the highest reaction rate. Fe-doped TiO2, which absorbs visible light, did not show enhanced photocatalytic activity for methylene blue degradation. This result indicates that iron contamination is not a decisive factor in the reduced reactivity of the titania coated ferrite catalysts. The higher reactivity of materials with the titanate cores suggests that photogenerated charge carriers are more easily transported across the titanate-titanate interface than the ferrite-titanate interface and this provides guidance for materials selection in composite catalyst design.

Catalyst evaluation for high-purity H2 production by sorption-enhanced steam-methane reforming coupled to a Ca/Cu process

NASA Astrophysics Data System (ADS)

Navarro, M. V.; López, J. M.; García, T.; Grasa, G.; Murillo, R.

2017-09-01

The operational limits of a commercial nickel-based catalyst under the conditions of a sorption-enhanced steam-methane reforming process coupled to a Ca/Cu chemical loop are investigated for high-purity H2 production in a cyclic operation. The performance of the reforming catalyst is tested by means of a high number of oxidation-reduction-reforming cycles. After 100 oxidation-reduction cycles, this catalyst retains its exceptional reforming activity. The methane conversion values are close to the thermodynamic equilibrium under very demanding conditions: temperature between 500 °C - 700 °C and mass hourly space velocity of 8.8 kgCH4 h-1 kgcat-1. After 200 cycles, the sample shows reduction in its reforming activity in line with a lower dispersion of the Ni species. Sintering of Ni nanocrystals is evidenced during the oxidation-reduction multi-cycles. The performance of the catalyst after 200 oxidation-reduction cycles mixed with a CaO-based CO2 sorbent is studied under optimal conditions calculated for the sorption-enhanced reforming process coupled to a Ca/Cu cycle (temperature of 650 °C, steam/methane ratio of 4, sorbent/catalyst ratio of 4 and space velocity of 0.75 kgCH4 h-1 kgcat-1). Remarkably, an equilibrium value over 92 vol.% H2 concentration is achieved, highlighting this catalyst as a promising candidate for the next steps of the process development.

Synthesis and interface characterization of CNTs on graphene

NASA Astrophysics Data System (ADS)

Zhou, Changjian; Senegor, Richard; Baron, Zachary; Chen, Yihan; Raju, Salahuddin; Vyas, Anshul A.; Chan, Mansun; Chai, Yang; Yang, Cary Y.

2017-02-01

Carbon nanotubes (CNTs) and graphene are potential candidates for future interconnect materials. CNTs are promising on-chip via interconnect materials due to their readily formed vertical structures, their current-carrying capacity, which is much larger than existing on-chip interconnect materials such as copper and tungsten, and their demonstrated ability to grow in patterned vias with sub-50 nm widths; meanwhile, graphene is suitable for horizontal interconnects. However, they both present the challenge of having high-resistance contacts with other conductors. An all-carbon structure is proposed in this paper, which can be formed using the same chemical vapor deposition method for both CNTs and graphene. Vertically aligned CNTs are grown directly on graphene with an Fe or Ni catalyst. The structural characteristics of the graphene and the grown CNTs are analyzed using Raman spectroscopy and electron microscopy techniques. The CNT-graphene interface is studied in detail using transmission electron microscopic analysis of the CNT-graphene heterostructure, which suggests C-C bonding between the two materials. Electrical measurement results confirm the existence of both a lateral conduction path within graphene and a vertical conduction path in the CNT-graphene heterostructure, giving further support to the C-C bonding at the CNT-graphene interface and resulting in potential applications for all-carbon interconnects.

Synthesis and interface characterization of CNTs on graphene.

PubMed

Zhou, Changjian; Senegor, Richard; Baron, Zachary; Chen, Yihan; Raju, Salahuddin; Vyas, Anshul A; Chan, Mansun; Chai, Yang; Yang, Cary Y

2017-02-03

Carbon nanotubes (CNTs) and graphene are potential candidates for future interconnect materials. CNTs are promising on-chip via interconnect materials due to their readily formed vertical structures, their current-carrying capacity, which is much larger than existing on-chip interconnect materials such as copper and tungsten, and their demonstrated ability to grow in patterned vias with sub-50 nm widths; meanwhile, graphene is suitable for horizontal interconnects. However, they both present the challenge of having high-resistance contacts with other conductors. An all-carbon structure is proposed in this paper, which can be formed using the same chemical vapor deposition method for both CNTs and graphene. Vertically aligned CNTs are grown directly on graphene with an Fe or Ni catalyst. The structural characteristics of the graphene and the grown CNTs are analyzed using Raman spectroscopy and electron microscopy techniques. The CNT-graphene interface is studied in detail using transmission electron microscopic analysis of the CNT-graphene heterostructure, which suggests C-C bonding between the two materials. Electrical measurement results confirm the existence of both a lateral conduction path within graphene and a vertical conduction path in the CNT-graphene heterostructure, giving further support to the C-C bonding at the CNT-graphene interface and resulting in potential applications for all-carbon interconnects.

Distribution of Single-Wall Carbon Nanotubes in the Xenopus laevis Embryo after Microinjection

PubMed Central

Holt, Brian D.; Shawky, Joseph H.; Dahl, Kris Noel; Davidson, Lance A.; Islam, Mohammad F.

2016-01-01

Single-wall carbon nanotubes (SWCNTs) are advanced materials with the potential for a myriad of diverse applications, including biological technologies and largescale usage with the potential for environmental impacts. SWCNTs have been exposed to developing organisms to determine their effects on embryogenesis, and results have been inconsistent arising, in part, from differing material quality, dispersion status, material size, impurity from catalysts, and stability. For this study, we utilized highly purified SWCNT samples with short, uniform lengths (145 ± 17 nm) well dispersed in solution. To test high exposure doses, we microinjected > 500 μg mL-1 SWCNT concentrations into the well-established embryogenesis model, Xenopus laevis, and determined embryo compatibility and sub-cellular localization during development. SWCNTs localized within cellular progeny of the microinjected cells, but heterogeneously distributed throughout the target-injected tissue. Co-registering unique Raman spectral intensity of SWCNTs with images of fluorescently labelled sub-cellular compartments demonstrated that even at the regions of highest SWCNT concentration, there were no gross alterations to sub-cellular microstructures, including filamentous actin, endoplasmic reticulum and vesicles. Furthermore, SWCNTs did not aggregate or localize to the perinuclear sub-cellular region. Combined, these results suggest that purified and dispersed SWCNTs are not toxic to X. laevis animal cap ectoderm and may be suitable candidate materials for biological applications. PMID:26510384

Removal of sulphur-containing odorants from fuel gases for fuel cell-based combined heat and power applications

NASA Astrophysics Data System (ADS)

de Wild, P. J.; Nyqvist, R. G.; de Bruijn, F. A.; Stobbe, E. R.

Natural gas (NG) and liquefied petroleum gas (LPG) are important potential feedstocks for the production of hydrogen for fuel cell-based (e.g. proton exchange membrane fuel cells (PEMFC) or solid oxide fuel Cells (SOFC) combined heat and power (CHP) applications. To prevent detrimental effects on the (electro)catalysts in fuel cell-based combined heat and power installations (FC-CHP), sulphur removal from the feedstock is mandatory. An experimental bench-marking study of adsorbents has identified several candidates for the removal of sulphur containing odorants at low temperature. Among these adsorbents a new material has been discovered that offers an economically attractive means to remove TetraHydroThiophene (THT), the main European odorant, from natural gas at ambient temperature. The material is environmentally benign, easy to use and possesses good activity (residual sulphur levels below 20 ppbv) and capacity for the common odorant THT in natural gas. When compared to state-of-the-art metal-promoted active carbon the new material has a THT uptake capacity that is up to 10 times larger, depending on temperature and pressure. Promoted versions of the new material have shown potential for the removal of THT at higher temperatures and/or for the removal of other odorants such as mercaptans from natural gas or from LPG.

Magnetic nanocomposites for an efficient valorization of biomass

NASA Astrophysics Data System (ADS)

Kuncser, Victor; Coman, Simona M.; Kemnitz, Erhard; Parvulescu, Vasile I.

2015-05-01

The recovery of the catalysts from the reaction mixture and their recycling is important goals of the current applied catalysis. The stringent ecological and economical demands for sustainability made this concern even more important for the solid catalysts used in the area of biomass catalytic transformations where the raw material usually is not soluble in most of the organic solvents. Therefore, the solid catalyst cannot be easily separated from the mixture of untransformed raw material and by-products (e.g., humines). However, these goals can be achieved by using magnetic nanoparticles (MNPs) based catalysts. This study reports on the magnetic response of two types of new magnetic nanocomposite catalytic systems, Ru@MNP and Nb@AlF3, used in the synthesis of sorbitol/glycerol and of lactic acid, respectively, by direct cellulose degradation. The results showed that the recovering possibilities of the Nb@AlF3 catalysts, with a weaker magnetic response associated to the so called diluted magnetic oxide systems, are much diminished as compared to Ru@MNP, where the magnetic response is generated using MNP supported catalysts.

Characterization of three-way automotive catalysts

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

Kenik, E.A.; More, K.L.; LaBarge, W.

1997-04-01

The CRADA between Delphi Automotive Systems (Delphi; formerly General Motors - AC Delco, Systems) and Lockheed Martin Energy Research (LMER) on automotive catalysts was completed at the end of FY96, after a ten month, no-cost extension. The CRADA was aimed at improved performance and lifetime of noble metal based three-way-catalysts (TWC), which are the primary catalytic system for automotive emission control systems. While these TWC can meet the currently required emission standards, higher than optimum noble metal loadings are often required to meet lifetime requirements. In addition, more stringent emission standards will be imposed in the near future, demanding improvedmore » performance and service life from these catalysts. Understanding the changes of TWC conversion efficiency with ageing is a critical need in improving these catalysts. Initially in a fresh catalyst, the active material is often distributed on a very fine scale, approaching single atoms or small atomic clusters. As such, a wide range of analytical techniques have been employed to provide high spatial resolution characterization of the evolving state of the catalytic material.« less

Highly efficient transition metal and nitrogen co-doped carbide-derived carbon electrocatalysts for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Ratso, Sander; Kruusenberg, Ivar; Käärik, Maike; Kook, Mati; Puust, Laurits; Saar, Rando; Leis, Jaan; Tammeveski, Kaido

2018-01-01

The search for an efficient electrocatalyst for oxygen reduction reaction (ORR) to replace platinum in fuel cell cathode materials is one of the hottest topics in electrocatalysis. Among the many non-noble metal catalysts, metal/nitrogen/carbon composites made by pyrolysis of cheap materials are the most promising with control over the porosity and final structure of the catalyst a crucial point. In this work we show a method of producing a highly active ORR catalyst in alkaline media with a controllable porous structure using titanium carbide derived carbon as a base structure and dicyandiamide along with FeCl3 or CoCl2 as the dopants. The resulting transition metal-nitrogen co-doped carbide derived carbon (M/N/CDC) catalyst is highly efficient for ORR electrocatalysis with the activity in 0.1 M KOH approaching that of commercial 46.1 wt.% Pt/C. The catalyst materials are also investigated by scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy to characterise the changes in morphology and composition causing the raise in electrochemical activity. MEA performance of M/N/CDC cathode materials in H2/O2 alkaline membrane fuel cell is tested with the highest power density reached being 80 mW cm-2 compared to 90 mW cm-2 for Pt/C.

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

Synthesis and reactivity of ultra-fine coal liquefaction catalysts

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

Linehan, J.C.; Matson, D.W.; Fulton, J.L.

1992-10-01

The Pacific Northwest Laboratory is currently developing ultra-fine iron-based coal liquefaction catalysts using two new particle production technologies: (1) modified reverse micelles (MRM) and (2) rapid thermal decomposition of solutes (RTDS). These methodologies have been shown to allow control over both particle size (from 1 nm to 60 nm) and composition when used to produce ultra-fine iron-based materials. Powders produced using these methods are found to be selective catalysts for carbon-carbon bond scission using the naphthyl bibenzylmethane model compound, and to promote the production of THF soluble coal products during liquefaction studies. This report describes the materials produced by bothmore » MRM and the RTDS methods and summarizes the results of preliminary catalysis studies using these materials.« less

Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts.

PubMed

Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

2013-06-21

Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.

Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts

NASA Astrophysics Data System (ADS)

Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

2013-06-01

Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.

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

Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

Recently, carbonaceous materials including activated carbon were proven to be effective catalysts for hazardous waste gasification in supercritical water. Using coconut shell activated carbon catalyst, complete decomposition of industrial organic wastes including methanol and acetic acid was achieved. During this process, the total mass of the activated carbon catalyst changes by two competing processes: a decrease in weight via gasification of the carbon by supercritical water, or an increase in weight by deposition of carbonaceous materials generated by incomplete gasification of the biomass feedstocks. The deposition of carbonaceous materials does not occur when complete gasification is realized. Gasification of themore » activated carbon in supercritical water is often favored, resulting in changes in the quality and quantity of the catalyst. To thoroughly understand the hazardous waste decomposition process, a more complete understanding of the behavior of activated carbon in pure supercritical water is needed. The gasification rate of carbon by water vapor at subcritical pressures was studied in relation to coal gasification and generating activated carbon.« less

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

2011-01-01

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Thermal Decomposition Behaviors and Burning Characteristics of AN/RDX-Based Composite Propellants Supplemented with MnO2 and Fe2O3

NASA Astrophysics Data System (ADS)

Kohga, Makoto; Naya, Tomoki

2015-10-01

Ammonium nitrate (AN)-based composite propellants have gained popularity because of the clean burning nature of AN as an oxidizer. However, such propellants have several disadvantages such as poor ignition and low burning rate. The burning characteristics of the AN propellant were improved when a portion of this propellant was replaced by an energetic material and the addition of a catalyst. In this study, RDX (1,3,5-trinitroperhydro-1,3,5-triazine) was used as the energetic material, and Fe2O3 and MnO2 were used as catalysts. The burning characteristics of the AN/RDX propellants supplemented with catalysts were investigated, and the effects of the replacement of AN by RDX and the catalyst addition were evaluated.

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

Bosch Reactor Development for High Percentage Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Howard, David; Abney, Morgan

2015-01-01

This next Generation Life Support Project entails the development and demonstration of Bosch reaction technologies to improve oxygen recovery from metabolically generated oxygen and/or space environments. A primary focus was placed on alternate carbon formation reactor concepts to improve useful catalyst life for space vehicle applications, and make use of in situ catalyst resources for non-terrestrial surface missions. Current state-of-the-art oxygen recovery systems onboard the International Space Station are able to effectively recover approximately 45 percent of the oxygen consumed by humans and exhausted in the form of carbon dioxide (CO2). Excess CO2 is vented overboard and the oxygen contained in the molecules is lost. For long-duration missions beyond the reaches of Earth for resupply, it will be necessary to recover greater amounts of constituents such as oxygen that are necessary for sustaining life. Bosch technologies theoretically recover 100 percent of the oxygen from CO2, producing pure carbon as the sole waste product. Challenges with this technology revolve around the carbon product fouling catalyst materials, drastically limiting catalyst life. This project successfully demonstrated techniques to extend catalyst surface area exposure times to improve catalyst life for vehicle applications, and demonstrated the use of Martian and lunar regolith as viable catalyst Bosch Reactor Development for High Percentage Oxygen Recovery From Carbon Dioxide materials for surface missions. The Bosch process generates carbon nanotube formation within the regolith, which has been shown to improve mechanical properties of building materials. Production of bricks from post reaction regolith for building and radiation shielding applications were also explored.

Silica supported palladium nanoparticles for the decarboxylation of high-acid feedstocks: Design, deactivation and regeneration

NASA Astrophysics Data System (ADS)

Ping, Eric Wayne

2011-12-01

The major goals of this thesis were to (1) design and synthesize a supported catalyst with well-defined monodisperse palladium nanoparticles evenly distributed throughout an inorganic oxide substrate with tunable porosity characteristics, (2) demonstrate the catalytic activity of this material in the decarboxylation of long chain fatty acids and their derivatives to make diesel-length hydrocarbons, (3) elucidate the deactivation mechanism of supported palladium catalysts under decarboxylation conditions via post mortem catalyst characterization and develop a regeneration methodology thereupon, and (4) apply this catalytic system to a real low-value biofeedstock. Initial catalyst designs were based on the SBA-15 silica support, but in an effort to maximize loading and minimize mass transfer limitations, silica MCF was synthesized as catalyst support. Functionalization with various silane ligands yielded a surface that facilitated even distribution of palladium precursor salts throughout the catalyst particle, and, after reduction, monodisperse palladium nanoparticles approximately 2 nm in diameter. Complete characterization was performed on this Pd-MCF catalyst. The Pd-MCF catalyst showed high one-time activity in the decarboxylation of fatty acids to hydrocarbons in dodecane at 300°C. Hydrogen was found to be an unnecessary reactant in the absence of unsaturations, but was required in their presence---full hydrogenation of the double bonds occurs before any decarboxylation can take place. The Pd-MCF also exhibited good activity for alkyl esters and glycerol, providing a nice hypothetical description of a stepwise reaction pathway for catalytic decarboxylation of acids and their derivatives. As expected, the Pd-MCF catalyst experienced severe deactivation after only one use. Substantial effort was put into elucidating the nature of this deactivation via post mortem catalyst characterization. H2 chemisorption confirmed a loss of active surface area, but TEM and EXAFS ruled out morphological alterations in the supported nanoparticles. Significant decreases in pore volume and surface area via N2 physisorption put deposition under suspicion and TGA confirmed the presence of organic species in the material. Initial attempts to remove the deposits via calcination were successful, but at the expense of severe nanoparticle growth. GC-MS, NMR and FT-IR helped speciate the deposition, mainly confirming the presence of residual reactant acid. A regeneration scheme was developed to remove these compounds, and subsequent catalyst reuses exhibited high decarboxylation activity. Finally, the Pd-MCF catalyst was applied to a real feedstock: a wastewater-derived brown grease from a poultry rendering facility. Attempts at decarboxylating the raw material failed, so efforts to polish the material via dewaxing and degumming were undertaken. The treatments were able to optimize a three-phase separation, and the resultant polished brown grease was successfully decarboxylated to diesel-length hydrocarbons with high conversions and selectivities.

Enhanced development of a catalyst chamber for the decomposition of up to 1.0 kg/s hydrogen peroxide

NASA Astrophysics Data System (ADS)

Božić, Ognjan; Porrmann, Dennis; Lancelle, Daniel; May, Stefan

2016-06-01

A new innovative hybrid rocket engine concept is developed within the AHRES program of the German Aerospace Center (DLR). This rocket engine based on hydroxyl-terminated polybutadiene (HTPB) with metallic additives as solid fuel and high test peroxide (HTP) as liquid oxidizer. Instead of a conventional ignition system, a catalyst chamber with a silver mesh catalyst is designed to decompose the HTP. The newly modified catalyst chamber is able to decompose up to 1.0 kg/s of 87.5 wt% HTP. Used as a monopropellant thruster, this equals an average thrust of 1600 N. The catalyst chamber is designed using the self-developed software tool SHAKIRA. The applied kinetic law, which determines catalytic decomposition of HTP within the catalyst chamber, is given and commented. Several calculations are carried out to determine the appropriate geometry for complete decomposition with a minimum of catalyst material. A number of tests under steady state conditions are carried out, using 87.5 wt% HTP with different flow rates and a constant amount of catalyst material. To verify the decomposition, the temperature is measured and compared with the theoretical prediction. The experimental results show good agreement with the results generated by the design tool. The developed catalyst chamber provides a simple, reliable ignition system for hybrid rocket propulsion systems based on hydrogen peroxide as oxidizer. This system is capable for multiple reignition. The developed hardware and software can be used to design full scale monopropellant thrusters based on HTP and catalyst chambers for hybrid rocket engines.

Synthesis and characterizations of melamine-based epoxy resins.

PubMed

Ricciotti, Laura; Roviello, Giuseppina; Tarallo, Oreste; Borbone, Fabio; Ferone, Claudio; Colangelo, Francesco; Catauro, Michelina; Cioffi, Raffaele

2013-09-05

A new, easy and cost-effective synthetic procedure for the preparation of thermosetting melamine-based epoxy resins is reported. By this innovative synthetic method, different kinds of resins can be obtained just by mixing the reagents in the presence of a catalyst without solvent and with mild curing conditions. Two types of resins were synthesized using melamine and a glycidyl derivative (resins I) or by adding a silane derivative (resin II). The resins were characterized by means of chemical-physical and thermal techniques. Experimental results show that all the prepared resins have a good thermal stability, but differ for their mechanical properties: resin I exhibits remarkable stiffness with a storage modulus value up to 830 MPa at room temperature, while lower storage moduli were found for resin II, indicating that the presence of silane groups could enhance the flexibility of these materials. The resins show a pot life higher than 30 min, which makes these resins good candidates for practical applications. The functionalization with silane terminations can be exploited in the formulation of hybrid organic-inorganic composite materials.

Synthesis and Characterizations of Melamine-Based Epoxy Resins

PubMed Central

Ricciotti, Laura; Roviello, Giuseppina; Tarallo, Oreste; Borbone, Fabio; Ferone, Claudio; Colangelo, Francesco; Catauro, Michelina; Cioffi, Raffaele

2013-01-01

A new, easy and cost-effective synthetic procedure for the preparation of thermosetting melamine-based epoxy resins is reported. By this innovative synthetic method, different kinds of resins can be obtained just by mixing the reagents in the presence of a catalyst without solvent and with mild curing conditions. Two types of resins were synthesized using melamine and a glycidyl derivative (resins I) or by adding a silane derivative (resin II). The resins were characterized by means of chemical-physical and thermal techniques. Experimental results show that all the prepared resins have a good thermal stability, but differ for their mechanical properties: resin I exhibits remarkable stiffness with a storage modulus value up to 830 MPa at room temperature, while lower storage moduli were found for resin II, indicating that the presence of silane groups could enhance the flexibility of these materials. The resins show a pot life higher than 30 min, which makes these resins good candidates for practical applications. The functionalization with silane terminations can be exploited in the formulation of hybrid organic-inorganic composite materials. PMID:24013372

Synthesis and superconductivity of In-doped SnTe nanostructures

DOE PAGES

Kumaravadivel, Piranavan; Pan, Grace A.; Zhou, Yu; ...

2017-07-01

In xSn 1-xTe is a time-reversal invariant candidate 3D topological superconductor derived from doping the topological crystalline insulator SnTe with indium. The ability to synthesize low-dimensional nanostructures of indium-doped SnTe is key for realizing the promise they hold in future spintronic and quantum information processing applications. But hitherto only bulk synthesized crystals and nanoplates have been used to study the superconducting properties. Here for the first time we synthesize In xSn 1-xTe nanostructures including nanowires and nanoribbons, which show superconducting transitions. In some of the lower dimensional morphologies, we observe signs of more than one superconducting transition and the absencemore » of complete superconductivity. We propose that material inhomogeneity, such as indium inhomogeneity and possible impurities from the metal catalyst, is amplified in the transport characteristics of the smaller nanostructures and is responsible for this mixed behavior. Our work represents the first demonstration of In xSn 1-xTe nanowires with the onset of superconductivity, and points to the need for improving the material quality for future applications« less

Synthesis and superconductivity of In-doped SnTe nanostructures

NASA Astrophysics Data System (ADS)

Kumaravadivel, Piranavan; Pan, Grace A.; Zhou, Yu; Xie, Yujun; Liu, Pengzi; Cha, Judy J.

2017-07-01

InxSn1-xTe is a time-reversal invariant candidate 3D topological superconductor derived from doping the topological crystalline insulator SnTe with indium. The ability to synthesize low-dimensional nanostructures of indium-doped SnTe is key for realizing the promise they hold in future spintronic and quantum information processing applications. But hitherto only bulk synthesized crystals and nanoplates have been used to study the superconducting properties. Here for the first time we synthesize InxSn1-xTe nanostructures including nanowires and nanoribbons, which show superconducting transitions. In some of the lower dimensional morphologies, we observe signs of more than one superconducting transition and the absence of complete superconductivity. We propose that material inhomogeneity, such as indium inhomogeneity and possible impurities from the metal catalyst, is amplified in the transport characteristics of the smaller nanostructures and is responsible for this mixed behavior. Our work represents the first demonstration of InxSn1-xTe nanowires with the onset of superconductivity, and points to the need for improving the material quality for future applications.

Hollow core-shell structured Ni-Sn@C nanoparticles: a novel electrocatalyst for the hydrogen evolution reaction.

PubMed

Lang, Leiming; Shi, Yi; Wang, Jiong; Wang, Feng-Bin; Xia, Xing-Hua

2015-05-06

Pt-free electrocatalysts with high activity and low cost are highly pursued for hydrogen production by electrochemically splitting water. Ni-based alloy catalysts are potential candidates for the hydrogen evolution reaction (HER) and have been studied extensively. Here, we synthesized novel hollow core-shell structure Ni-Sn@C nanoparticles (NPs) by sol-gel, chemical vapor deposition, and etching processes. The prepared electrocatalysts with porous hollow carbon layers have a high conductivity and large active area, which exhibit good electrocatalytic activity toward HER. The Tafel slope of ∼35 millivolts per decade measured in acidic solution for Ni-Sn@C NPs is the smallest one to date for the Ni-Sn alloy catalysts, and exceeds those of the most non-noble metal catalysts, indicating a possible Volmer-Heyrovsky reaction mechanism. The synthetic method can be extended to prepare other hollow core-shell structure electrocatalysts for low-temperature fuel cells.

In-situ confined formation of NiFe layered double hydroxide quantum dots in expanded graphite for active electrocatalytic oxygen evolution

NASA Astrophysics Data System (ADS)

Guo, Jinxue; Li, Xiaoyan; Sun, Yanfang; Liu, Qingyun; Quan, Zhenlan; Zhang, Xiao

2018-06-01

Development of noble-metal-free catalysts towards highly efficient electrochemical oxygen evolution reaction (OER) is critical but challenging in the renewable energy area. Herein, we firstly embed NiFe LDHs quantum dots (QDs) into expanded graphite (NiFe LDHs/EG) via in-situ confined formation process. The interlayer spacing of EG layers acts as nanoreactors for spatially confined formation of NiFe LDHs QDs. The QDs supply huge catalytic sites for OER. The in-situ decoration endows the strong affinity between QDs with EG, thus inducing fast charge transfer. Based on the aforementioned benefits, the designed catalyst exhibits outstanding OER properties, in terms of small overpotential (220 mV required to generate 10 mA cm-2), low Tafel slope, and good durable stability, making it a promising candidate for inexpensive OER catalyst.

Biodiesel synthesis by TiO2-ZnO mixed oxide nanocatalyst catalyzed palm oil transesterification process.

PubMed

Madhuvilakku, Rajesh; Piraman, Shakkthivel

2013-12-01

Biodiesel is a promising alternating environmentally benign fuel to mineral diesel. For the development of easier transesterification process, stable and active heterogeneous mixed metal oxide of TiO2-ZnO and ZnO nanocatalysts were synthesized and exploited for the palm oil transesterification process. The synthesized catalysts were characterized by XRD, FT-IR, and FE-SEM studies for their structural and morphological characteristics. It was found that TiO2-ZnO nanocatalyst exhibits good catalytic activity and the catalytic performance was greatly depends on (i) catalyst concentration (ii) methanol to oil molar ratio (iii) reaction temperature and (iv) reaction time. A highest 98% of conversion was obtained at the optimum reaction parameters with 200 mg of catalyst loading and the biodiesel was analyzed by TLC and (1)H NMR techniques. The TiO2-ZnO nanocatalyst shows good catalytic performance over the ZnO catalyst, which could be a potential candidate for the large-scale biodiesel production from palm oil at the reduced temperature and time. Copyright © 2013. Published by Elsevier Ltd.

High Throughput Spectroscopic Catalyst Screening via Surface Plasmon Spectroscopy

DTIC Science & Technology

2014-05-10

this spectroscopic method can distinguish different catalysts . We also find we can directly investigate the role of different support materials. (ii...dispersed onto glass or within various oxide matrices (e.g. ZnO, silica , titania) as long as they do not scatter light. II. Preparation of Catalyst ...effectively, while gold on silica does not function as a catalyst . • Hydrogen does not dissociate on gold nanoaprticles on TiO2 in N2:H2 mixtures

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

Aldehyde-alcohol reactions catalyzed under mild conditions by chromium(III) terephthalate metal organic framework (MIL-101) and phosphotungstic acid composites.

PubMed

Bromberg, Lev; Hatton, T Alan

2011-12-01

Porous materials based on chromium(III) terephthalate metal organic frameworks (MIL-101) and their composites with phosphotungstic acid (PTA) were studied as heterogeneous acid catalysts in aldehyde-alcohol reactions exemplified by acetaldehyde-phenol (A-P) condensation and dimethylacetal formation from benzaldehyde and methanol (B-M reaction). The MIL-101 was synthesized solvothermically in water, and the MIL101/PTA composite materials were obtained by either impregnation of the already prepared MIL-101 porous matrix with phosphotungstic acid solution or by solvothermic treatment of aqueous mixtures of Cr(NO(3))(3), and terephthalic and phosphotungstic acids. The MIL101/PTA materials appeared to be effective catalysts for both A-P and B-M reactions occurring at room temperature, with half-lives ranging from 0.5 h (A-P) to 1.5-2 h (B-M) and turnover numbers over 600 for A-P and over 2900 for the B-M reaction, respectively. A synergistic effect of the strong acidic moieties (PTA) addition to mildly acidic Brønsted and Lewis acid cites of the MIL-101 was observed with the MIL101/PTA composites. The ability of the PTA and MIL101/PTA materials to strongly absorb and condense acetaldehyde vapors was discovered, with the MIL101/PTA absorbing over 10-fold its dry weight of acetaldehyde condensate at room temperature. The acetaldehyde was converted rapidly to crotonaldehyde and higher-molecular-weight compounds while in contact with MIL-101 and MIL101/PTA materials. The stability of the MIL-101 and MIL101/PTA catalysts was assessed within four cycles of the 1-day alcohol-aldehyde reactions in terms of the overall catalyst recovery, PTA or Cr content, and reaction rate constants in each cycle. The loss of the catalyst over 4 cycles was approximately 10 wt % for all tested catalysts due to the incomplete recovery and minute dissolution of the components. The reaction rates in all cycles remained unchanged and the catalyst losses stopped after the third cycle. The developed MIL101/PTA composites appear to be feasible for industrial catalytic applications. © 2011 American Chemical Society

Cure Schedule for Stycast 2651/Catalyst 9.

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

Kropka, Jamie Michael; McCoy, John D.

2017-11-01

The Emerson & Cuming technical data sheet (TDS) for Stycast 2651/Catalyst 9 lists three alternate cure schedules for the material, each of which would result in a different state of reaction and different material properties. Here, a cure schedule that attains full reaction of the material is defined. The use of this cure schedule will eliminate variance in material properties due to changes in the cure state of the material, and the cure schedule will serve as the method to make material prior to characterizing properties. The following recommendation uses one of the schedules within the TDS and adds amore » “post cure” to obtain full reaction.« less

Method for the catalytic conversion of organic materials into a product gas

DOEpatents

Elliott, D.C.; Sealock, L.J. Jr.; Baker, E.G.

1997-04-01

A method for converting organic material into a product gas includes: (a) providing a liquid reactant mixture containing liquid water and liquid organic material within a pressure reactor; (b) providing an effective amount of a reduced metal catalyst selected from the group consisting of ruthenium, rhodium, osmium and iridium or mixtures thereof within the pressure reactor; and (c) maintaining the liquid reactant mixture and effective amount of reduced metal catalyst in the pressure reactor at temperature and pressure conditions of from about 300 C to about 450 C; and at least 130 atmospheres for a period of time, the temperature and pressure conditions being effective to maintain the reactant mixture substantially as liquid, the effective amount of reduced metal catalyst and the period of time being sufficient to catalyze a reaction of the liquid organic material to produce a product gas composed primarily of methane, carbon dioxide and hydrogen. 5 figs.

Method for the catalytic conversion of organic materials into a product gas

DOEpatents

Elliott, Douglas C.; Sealock, Jr., L. John; Baker, Eddie G.

1997-01-01

A method for converting organic material into a product gas includes: a) providing a liquid reactant mixture containing liquid water and liquid organic material within a pressure reactor; b) providing an effective amount of a reduced metal catalyst selected from the group consisting of ruthenium, rhodium, osmium and iridium or mixtures thereof within the pressure reactor; and c) maintaining the liquid reactant mixture and effective amount of reduced metal catalyst in the pressure reactor at temperature and pressure conditions of from about 300.degree. C. to about 450.degree. C.; and at least 130 atmospheres for a period of time, the temperature and pressure conditions being effective to maintain the reactant mixture substantially as liquid, the effective amount of reduced metal catalyst and the period of time being sufficient to catalyze a reaction of the liquid organic material to produce a product gas composed primarily of methane, carbon dioxide and hydrogen.

Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts.

PubMed

Hu, Yang; Jensen, Jens Oluf; Zhang, Wei; Cleemann, Lars N; Xing, Wei; Bjerrum, Niels J; Li, Qingfeng

2014-04-01

Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low-temperature fuel cells. A novel type of catalysts prepared by high-pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting of uniform iron carbide (Fe3 C) nanoparticles encased by graphitic layers, with little surface nitrogen or metallic functionalities. In acidic media the outer graphitic layers stabilize the carbide nanoparticles without depriving them of their catalytic activity towards the oxygen reduction reaction (ORR). As a result the catalyst is highly active and stable in both acid and alkaline electrolytes. The synthetic approach, the carbide-based catalyst, the structure of the catalysts, and the proposed mechanism open new avenues for the development of ORR catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen-doped microporous carbon: An efficient oxygen reduction catalyst for Zn-air batteries

NASA Astrophysics Data System (ADS)

Zhang, Li-Yuan; Wang, Meng-Ran; Lai, Yan-Qing; Li, Xiao-Yan

2017-08-01

N-doped microporous carbon as an exceptional metal-free catalyst from waste biomass (banana peel as representative) was obtained via fast catalysis carbonization, followed by N-doping modification. The method achieves a relatively high C conversion efficiency of ∼41.9%. The final carbon materials are doped by N (∼3 at.%) and possess high surface area (∼1097 m2 g-1) and abundant micropores. Compared to commercial Pt/C materials, the as-prepared carbon catalyst exhibits a comparable electrocatalytic activity and much better stability. Furthermore, the metal-free catalyst loaded Zn-air battery possesses higher discharge voltage and power density as compared with that of commercial Pt/C. This novel technique can also be readily applied to produce metal-free carbon catalysts from other typical waste biomass (e.g., orange peel, leaves) as the carbon sources. The method can be developed as a potentially general and effective industrial route to transform waste biomass into high value-added microporous carbon with superior functionalities.

Realization of Both High-Performance and Enhanced Durability of Fuel Cells: Pt-Exoskeleton Structure Electrocatalysts.

PubMed

Kim, Ok-Hee; Cho, Yoon-Hwan; Jeon, Tae-Yeol; Kim, Jung Won; Cho, Yong-Hun; Sung, Yung-Eun

2015-07-01

Core-shell structure nanoparticles have been the subject of many studies over the past few years and continue to be studied as electrocatalysts for fuel cells. Therefore, many excellent core-shell catalysts have been fabricated, but few studies have reported the real application of these catalysts in a practical device actual application. In this paper, we demonstrate the use of platinum (Pt)-exoskeleton structure nanoparticles as cathode catalysts with high stability and remarkable Pt mass activity and report the outstanding performance of these materials when used in membrane-electrode assemblies (MEAs) within a polymer electrolyte membrane fuel cell. The stability and degradation characteristics of these materials were also investigated in single cells in an accelerated degradation test using load cycling, which is similar to the drive cycle of a polymer electrolyte membrane fuel cell used in vehicles. The MEAs with Pt-exoskeleton structure catalysts showed enhanced performance throughout the single cell test and exhibited improved degradation ability that differed from that of a commercial Pt/C catalyst.

Assessment of the Pozzolanic Activity of a Spent Catalyst by Conductivity Measurement of Aqueous Suspensions with Calcium Hydroxide

PubMed Central

Velázquez, Sergio; Monzó, José M.; Borrachero, María V.; Payá, Jordi

2014-01-01

The pozzolanic activity of the spent catalyst produced by fluid catalytic cracking (FCC) has been studied by various methods in recent years. However, no quick and easy method has been reported for this activity based on the associated studies. In this work, the pozzolanic activity of a spent catalyst was investigated by measuring its electrical conductivity in aqueous suspensions of pozzolan/calcium hydroxide. The behavior of the FCC catalyst residue was compared to that of reactive and inert materials of similar chemical compositions. Further, the influence of temperature on the suspension was studied, and also, a new method was proposed in which the pozzolan/calcium hydroxide ratio was varied (with the initial presence of solid Ca(OH)2 in the system). It was concluded that the method is effective, fast and simple for evaluating the high reactivity of the catalyst. Therefore, this method is an alternative for the evaluation of the reactivity of pozzolanic materials. PMID:28788583

Static and dynamic structural characterization of nanomaterial catalysts

NASA Astrophysics Data System (ADS)

Masiel, Daniel Joseph

Heterogeneous catalysts systems are pervasive in industry, technology and academia. These systems often involve nanostructured transition metal particles that have crucial interfaces with either their supports or solid products. Understanding the nature of these interfaces as well as the structure of the catalysts and support materials themselves is crucial for the advancement of catalysis in general. Recent developments in the field of transmission electron microscopy (TEM) including dynamic transmission electron microscopy (DTEM), electron tomography, and in situ techniques stand poised to provide fresh insight into nanostructured catalyst systems. Several electron microscopy techniques are applied in this study to elucidate the mechanism of silica nanocoil growth and to discern the role of the support material and catalyst size in carbon dioxide and steam reforming of methane. The growth of silica nanocoils by faceted cobalt nanoparticles is a process that was initially believed to take place via a vapor-liquid-solid growth mechanism similar to other nanowire growth techniques. The extensive TEM work described here suggests that the process may instead occur via transport of silicate and silica species over the nanoparticle surface. Electron tomography studies of the interface between the catalyst particles and the wire indicate that they grow from edges between facets. Studies on reduction of the Co 3O4 nanoparticle precursors to the faceted pure cobalt catalysts were carried out using DTEM and in situ heating. Supported catalyst systems for methane reforming were studied using dark field scanning TEM to better understand sintering effects and the increased activity of Ni/Co catalysts supported by carbon nanotubes. Several novel electron microscopy techniques are described including annular dark field DTEM and a metaheuristic algorithm for solving the phase problem of coherent diffractive imaging. By inserting an annular dark field aperture into the back focal plane of the objective lens in a DTEM, time-resolved dark field images can be produced that have vastly improved contrast for supported catalyst materials compared to bright field DTEM imaging. A new algorithm called swarm optimized phase retrieval is described that uses a population-based approach to solve for the missing phases of diffraction data from discrete particles.

Preparation of a Bimetal Using Mechanical Alloying for Environmental or Industrial Use

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline; Geiger, Cherie; Clausen, Christian

2013-01-01

Following the 1976 Toxic Substances Control Act ban on their manufacture, PCBs remain an environmental threat. PCBs are known to bio-accumulate and concentrate in fatty tissues. Further complications arise from the potential for contamination of commercial mixtures with other more toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Until recently, only one option was available for the treatment of PCB-contaminated materials: incineration. This may prove to be more detrimental to the environment than the PCBs themselves due to the potential for formation of PCDDs. Metals have been used for the past ten years for the remediation of halogenated solvents and other contaminants in the environment; however, zero-valent metals alone do not possess the activity required to dehalogenate PCBs. Palladium has been shown to act as an excellent catalyst for the dechlorination of PCBs with active metals. This invention is a method for the production of a palladium/magnesium bimetal capable of dechlorinating PCBs using mechanical milling/mechanical alloying. Other base metals and catalysts may also be alloyed together (e.g., nickel or zinc) to create a similarly functioning catalyst system. Several bimetal catalyst systems currently can be used for processes such as hydrogen peroxide synthesis, oxidation of ethane, selective oxidation, hydrogenation, and production of syngas for further conversion to clean fuels. The processes for making these bimetal catalysts often involve vapor deposition. This technology provides an alternative to vapor deposition that may provide equally active catalysts. A hydrogenation catalyst including a base material coated with a catalytic metal is made using mechanical milling techniques. The hydrogenation catalysts are used as an excellent catalyst for the dehalogenation of contaminated compounds and the remediation of other industrial compounds. The mechanical milling technique is simpler and cheaper than previously used methods for producing hydrogenation catalysts. Preferably, the hydrogenation catalyst is a bimetallic particle formed from a zero-valent iron or zero-valent magnesium particle coated with palladium that is impregnated onto a high-surface-area graphite support. The zero-valent metal particles should be microscale or nanoscale zero-valent magnesium or zero-valent iron particles. Other zero-valent metal particles and combinations may be used. Additionally, the base material may be selected from a variety of minerals including, but not limited to, alumina and zeolites. The catalytic metal is preferably selected from the group consisting of noble metals and transition metals, preferably palladium. The mechanical milling process includes milling the base material with a catalytic metal impregnated into a high-surface-area support to form the hydrogenation catalyst. In a preferred mechanical milling process, a zero-valent metal particle is provided as the base material, preferably having a particle size of less than about 10 microns, preferably 0.1 to 10 microns or smaller, prior to milling. The catalytic metal is supported on a conductive carbon support structure prior to milling. For example, palladium may be impregnated on a graphite support. Other support structures such as semiconductive metal oxides may also be used.

Halloysite-derived nitrogen doped carbon electrocatalysts for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Lu, Yaxiang; Wang, Lianqin; Preuß, Kathrin; Qiao, Mo; Titirici, Maria-Magdalena; Varcoe, John; Cai, Qiong

2017-12-01

Developing the low-cost, highly active carbonaceous materials for oxygen reduction reaction (ORR) catalysts has been a high-priority research direction for durable fuel cells. In this paper, two novel N-doped carbonaceous materials with flaky and rod-like morphology using the natural halloysite as template are obtained from urea nitrogen source as well as glucose (denoted as GU) and furfural (denoted as FU) carbon precursors, respectively, which can be directly applied as metal-free electrocatalysts for ORR in alkaline electrolyte. Importantly, compared with a benchmark Pt/C (20wt%) catalyst, the as-prepared carbon catalysts demonstrate higher retention in diffusion limiting current density (after 3000 cycles) and enhanced methanol tolerances with only 50-60mV negative shift in half-wave potentials. In addition, electrocatalytic activity, durability and methanol tolerant capability of the two N-doped carbon catalysts are systematically evaluated, and the underneath reasons of the outperformance of rod-like catalysts over the flaky are revealed. At last, the produced carbonaceous catalysts are also used as cathodes in the single cell H2/O2 anion exchange membrane fuel cell (AEMFC), in which the rod-like FU delivers a peak power density as high as 703 mW cm-2 (vs. 1106 mW cm-2 with a Pt/C benchmark cathode catalyst).

Unusual catalysts from molasses: synthesis, properties and application in obtaining biofuels from algae.

PubMed

Samorì, Chiara; Torri, Cristian; Fabbri, Daniele; Falini, Giuseppe; Faraloni, Cecilia; Galletti, Paola; Spera, Silvia; Tagliavini, Emilio; Torzillo, Giuseppe

2012-08-01

Acid catalysts were prepared by sulfonation of carbon materials obtained from the pyrolysis of sugar beet molasses, a cheap, viscous byproduct in the processing of sugar beets into sugar. Conditions for the pyrolysis of molasses (temperature and time) influenced catalyst performance; the best combination came from pyrolysis at low temperature (420 °C) for a relatively long time (8-15 h), which ensured better stability of the final material. The most effective molasses catalyst was highly active in the esterification of fatty acids with methanol (100 % yield after 3 h) and more active than common solid acidic catalysts in the transesterification of vegetable oils with 25-75 wt % of acid content (55-96 % yield after 8 h). A tandem process using a solid acid molasses catalyst and potassium hydroxide in methanol was developed to de-acidificate and transesterificate algal oils from Chlamydomonas reinhardtii, Nannochloropsis gaditana, and Phaeodactylum tricornutum, which contain high amounts of free fatty acids. The amount of catalyst required for the de-acidification step was influenced by the chemical composition of the algal oil, thus operational conditions were determined not only in relation to free fatty acids content in the oil, but according to the composition of the lipid extract of each algal species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

DOEpatents

Narula, Chaitanya K.; Yang, Xiaofan

2016-08-02

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Zeolite-based SCR catalysts and their use in diesel engine emission treatment

DOEpatents

Narula, Chaitanya K; Yang, Xiaofan

2015-03-24

A catalyst comprising a zeolite loaded with copper ions and at least one trivalent metal ion other than Al.sup.+3, wherein the catalyst decreases NO.sub.x emissions in diesel exhaust. The trivalent metal ions are selected from, for example, trivalent transition metal ions, trivalent main group metal ions, and/or trivalent lanthanide metal ions. In particular embodiments, the catalysts are selected from Cu--Fe-ZSM5, Cu--La-ZSM-5, Fe--Cu--La-ZSM5, Cu--Sc-ZSM-5, and Cu--In-ZSM5. The catalysts are placed on refractory support materials and incorporated into catalytic converters.

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

Chapter 19: Catalysis by Metal Carbides and Nitrides

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

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

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

Semiconductor-Based Photoelectrochemical Conversion of Carbon Dioxide: Stepping Towards Artificial Photosynthesis.

PubMed

Pang, Hong; Masuda, Takuya; Ye, Jinhua

2018-01-18

The photoelectrochemical (PEC) carbon dioxide reduction process stands out as a promising avenue for the conversion of solar energy into chemical feedstocks, among various methods available for carbon dioxide mitigation. Semiconductors derived from cheap and abundant elements are interesting candidates for catalysis. Whether employed as intrinsic semiconductors or hybridized with metallic cocatalysts, biocatalysts, and metal molecular complexes, semiconductor photocathodes exhibit good performance and low overpotential during carbon dioxide reduction. Apart from focusing on carbon dioxide reduction materials and chemistry, PEC cells towards standalone devices that use photohybrid electrodes or solar cells have also been a hot topic in recent research. An overview of the state-of-the-art progress in PEC carbon dioxide reduction is presented and a deep understanding of the catalysts of carbon dioxide reduction is also given. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxyhydrochlorination catalyst

DOEpatents

Taylor, Charles E.; Noceti, Richard P.

1992-01-01

An improved catalyst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HCl and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

Long life hydrocarbon conversion catalyst and method of making

DOEpatents

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

2002-11-12

The present invention includes a catalyst that has at least four layers, (1) porous support, (2) buffer layer, (3) interfacial layer, and optionally (4) catalyst layer. The buffer layer provides a transition of thermal expansion coefficient from the porous support to the interfacial layer thereby reducing thermal expansion stress as the catalyst is heated to high operating temperatures. The method of the present invention for making the at least three layer catalyst has the steps of (1) selecting a porous support, (2) solution depositing an interfacial layer thereon, and optionally (3) depositing a catalyst material onto the interfacial layer; wherein the improvement comprises (4) depositing a buffer layer between the porous support and the interfacial layer.

Combinatorial Search for High-Activity Hydrogen Catalysts Based on Transition-Metal-Embedded Graphitic Carbons

DOE PAGES

Choi, Woon Ih; Wood, Brandon C.; Schwegler, Eric; ...

2015-09-22

Transition metal (TM) atoms in porphyrin–like complexes play important roles in many protein and enzymetic systems, where crystal–field effects are used to modify d–orbital levels. Inspired by the tunable electronic structure of these motifs, a high–throughput computational search for synthetic hydrogen catalysts is performed based on a similar motif of TM atoms embedded into the lattice of graphene. Based on an initial list of 300 possible embedding geometries, binders, and host atoms, descriptors for stability and catalytic activity are applied to extract ten promising candidates for hydrogen evolution, two of which are expected to exhibit high activity for hydrogen oxidation.more » In several instances, the active TM atoms are earth–abundant elements that show no activity in the bulk phase, highlighting the importance of the coordination environment in tuning the d–orbitals. In conclusion, it is found that the most active candidates involve a hitherto unreported surface reaction pathway that involves a Kubas–complex intermediate, which significantly lowers the kinetic barrier associated with hydrogen dissociation and association.« less

Alternative catalysts for low-temperature CO-oxidation

NASA Technical Reports Server (NTRS)

Gardner, Steven D.; Hoflund, Gar B.; Schryer, David R.; Schryer, Jacqueline; Upchurch, Billy T.; Brown, David R.

1990-01-01

MnO sub x, Ag/MnO sub x, Cu/MnO sub x, Pt/MnO sub x, Ru/MnO sub x, Au/CeO sub x, and Au/Fe2O3 were synthesized and tested for CO oxidation activity in low concentrations of stoichiometric CO and O2 at 30 to 75 C. Catalytic activity was measured for periods as long as 18000 minutes. At 75 deg Au/MnO sub x is most active sustaining nearly 100 percent CO conversion for 10000 minutes. It also retains high activity at 50 and 30 C with negligible decay in activity. A direct comparison between an unpretreated 10 percent Au/MnO sub x catalyst and an optimized 19.5 percent Pt/SnO sub 2 (pretreated) catalyst shows that the Au/MnO sub x catalyst exhibits much higher catalytic activity and far superior decay characteristics. Other catalysts including Au/CeO sub x and Au/Fe2O3 also perform well. The Cu/MnO sub x exhibits a high initial activity which decays rapidly. After the decay period the activity remains very stable making Cu/MnO sub x a potential candidate for long-term applications such as CO2 lasers in space.

Engineering Single-Atom Cobalt Catalysts toward Improved Electrocatalysis.

PubMed

Wan, Gang; Yu, Pengfei; Chen, Hangrong; Wen, Jianguo; Sun, Cheng-Jun; Zhou, Hua; Zhang, Nian; Li, Qianru; Zhao, Wanpeng; Xie, Bing; Li, Tao; Shi, Jianlin

2018-04-01

The development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiple use of waste catalysts with and without regeneration for waste polymer cracking.

PubMed

Salmiaton, A; Garforth, A A

2011-06-01

Waste plastics contain a substantial number of valuable chemicals. The wastes from post-consumer as well as from industrial production can be recycled to valuable chemical feedstock, which can be used in refineries and/or petrochemical industries. This chemical recycling process is an ideal approach in recycling the waste for a better environment. Polymer cracking using a laboratory fluidized bed reactor concentrated on the used highly contaminated catalyst, E-Cat 2. Even though E-Cat 2 had low activity due to fewer acid sites, the products yielded were similar with amorphous ASA and were far better than thermal cracking. The high levels of heavy metals, namely nickel and vanadium, deposited during their lifetime as an FCC catalyst, did not greatly affect on the catalyst activity. It was also shown that E-Cat 2 could be used with and without regeneration. Although there was more deactivation when there was no regeneration step, the yield of gases (C(2)-C(7)) remained fairly constant. For the first time, these results indicate that "waste" FCC catalyst (E-Cat) is a good candidate for future feedstock recycling of polymer waste. The major benefits of using E-Cat are a low market price, the ability to tolerate reuse and regeneration capacity. Copyright © 2011 Elsevier Ltd. All rights reserved.

Platinum-Promoted Ga/Al2O3 as Highly Active, Selective, and Stable Catalyst for the Dehydrogenation of Propane**

PubMed Central

Sattler, Jesper J H B; Gonzalez-Jimenez, Ines D; Luo, Lin; Stears, Brien A; Malek, Andrzej; Barton, David G; Kilos, Beata A; Kaminsky, Mark P; Verhoeven, Tiny W G M; Koers, Eline J; Baldus, Marc; Weckhuysen, Bert M

2014-01-01

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a promoter. PMID:24989975

Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

NASA Astrophysics Data System (ADS)

Guzman Blas, Rolando Pedro

This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the carbon-platinum-cerium has better catalytic activity than platinum-carbon. Due to the hybridization behavior of C and Ce could arise charge transfer, both carbon and cerium to the Platinum. Ce-C→Pt charge transfer could occur at the Ce-C/Pt interface. Thus, results in an increase in the catalytic activity of platinum-cerium-carbon when compared with carbon-platinum.

Engineering of Transition Metal Catalysts Confined in Zeolites

PubMed Central

2018-01-01

Transition metal–zeolite composites are versatile catalytic materials for a wide range of industrial and lab-scale processes. Significant advances in fabrication and characterization of well-defined metal centers confined in zeolite matrixes have greatly expanded the library of available materials and, accordingly, their catalytic utility. In this review, we summarize recent developments in the field from the perspective of materials chemistry, focusing on synthesis, postsynthesis modification, (operando) spectroscopy characterization, and computational modeling of transition metal–zeolite catalysts. PMID:29861546

Solid oxide fuel cells having porous cathodes infiltrated with oxygen-reducing catalysts

DOEpatents

Liu, Meilin; Liu, Ze; Liu, Mingfei; Nie, Lifang; Mebane, David Spencer; Wilson, Lane Curtis; Surdoval, Wayne

2014-08-12

Solid-oxide fuel cells include an electrolyte and an anode electrically coupled to a first surface of the electrolyte. A cathode is provided, which is electrically coupled to a second surface of the electrolyte. The cathode includes a porous backbone having a porosity in a range from about 20% to about 70%. The porous backbone contains a mixed ionic-electronic conductor (MIEC) of a first material infiltrated with an oxygen-reducing catalyst of a second material different from the first material.

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

PubMed

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

2018-06-18

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

Catalyst containing oxygen transport membrane

DOEpatents

Christie, Gervase Maxwell; Wilson, Jamie Robyn; van Hassel, Bart Antonie

2012-12-04

A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a high average pore diameter and the intermediate porous layer has a lower permeability and lower pore diameter than the porous support layer. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts

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

Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie

The nanoscale compositional mapping of fresh HZSM-5 catalyst synthesized using hydrothermal process as well as after just steaming and after ethanol conversion reaction for 72 hours at realistic catalytic conditions was investigated using atom probe tomography. Atom probe tomography permitted direct atomic scale imaging of non-uniform distribution of Al within the HZSM-5 as well as for the first time image the hydrocarbon coking after ethanol reaction. Clear evidences for existence of multiple C-H molecular species which appear to aggregate as clusters within the pores of spent HZSM-5 catalyst materials is provided. These results provide evidence for the ability of atommore » probe tomography, a powerful 3D characterization tool in interrogating the atomic scale chemistry of zeolite catalyst materials at industrially relevant catalytic conditions.« less

Highly efficient and durable TiN nanofiber electrocatalyst supports.

PubMed

Kim, Hyun; Cho, Min Kyung; Kwon, Jeong An; Jeong, Yeon Hun; Lee, Kyung Jin; Kim, Na Young; Kim, Min Jung; Yoo, Sung Jong; Jang, Jong Hyun; Kim, Hyoung-Juhn; Nam, Suk Woo; Lim, Dong-Hee; Cho, EunAe; Lee, Kwan-Young; Kim, Jin Young

2015-11-28

To date, carbon-based materials including various carbon nanostructured materials have been extensively used as an electrocatalyst support for proton exchange membrane fuel cell (PEMFC) applications due to their practical nature. However, carbon dissolution or corrosion caused by high electrode potential in the presence of O2 and/or water has been identified as one of the main failure modes for the device operation. Here, we report the first TiN nanofiber (TNF)-based nonwoven structured materials to be constructed via electrospinning and subsequent two-step thermal treatment processes as a support for the PEMFC catalyst. Pt catalyst nanoparticles (NPs) deposited on the TNFs (Pt/TNFs) were electrochemically characterized with respect to oxygen reduction reaction (ORR) activity and durability in an acidic medium. From the electrochemical tests, the TNF-supported Pt catalyst was better and more stable in terms of its catalytic performance compared to a commercially available carbon-supported Pt catalyst. For example, the initial oxygen reduction performance was comparable for both cases, while the Pt/TNF showed much higher durability from an accelerated degradation test (ADT) configuration. It is understood that the improved catalytic roles of TNFs on the supported Pt NPs for ORR are due to the high electrical conductivity arising from the extended connectivity, high inertness to the electrochemical environment and strong catalyst-support interactions.

Bimetallic magnetic PtPd-nanoparticles as efficient catalyst for PAH removal from liquid media

NASA Astrophysics Data System (ADS)

Zanato, A. F. S.; Silva, V. C.; Lima, D. A.; Jacinto, M. J.

2017-11-01

Monometallic Pd- and bimetallic PtPd-nanoparticles supported on a mesoporous magnetic magnetite@silica matrix resembling a core-shell structure (Fe3O4@mSiO2) have been fabricated. The material was characterized by transmission electron microscope (TEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectra (XPS), energy dispersive spectroscopy (EDS) and inductively coupled plasma mass spectrometry (ICP-MS). The catalysts were applied in the removal of anthracene from liquid phase via catalytic hydrogenation. It was found that anthracene as a model compound could be completely converted into the partially hydrogenated species by the monometallic and bimetallic solids. However, during the recycling study the bimetallic material (Fe3O4@mSiO2PtPd-) showed an enhanced activity towards anthracene removal compared with the monometallic materials. A single portion of the PtPd-based catalyst can be used up to 11 times in the hydrogenation of anthracene under mild conditions (6 atm of H2, 75 °C, 20 min). Thanks to the presence of a dense magnetic core, the catalysts were capable of responding to an applied external magnetic field and once the reaction was completed, catalyst/product separation was straightforward.

New catalysts for coal liquefaction and new nanocrystalline catalysts synthesis methods

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

Linehan, J.C.; Matson, D.W.; Darab, J.G.

1994-09-01

The use of coal as a source of transportation fuel is currently economically unfavorable due to an abundant world petroleum supply and the relatively high cost of coal liquefaction. Consequently, a reduction in the cost of coal liquefaction, for example by using less and/or less costly catalysts or lower liquefaction temperatures, must be accomplished if coal is to play an significant role as a source of liquid feedstock for the petrochemical industry. The authors and others have investigated the applicability of using inexpensive iron-based catalysts in place of more costly and environmentally hazardous metal catalysts for direct coal liquefaction. Iron-basedmore » catalysts can be effective in liquefying coal and in promoting carbon-carbon bond cleavage in model compounds. The authors have been involved in an ongoing effort to develop and optimize iron-based powders for use in coal liquefaction and related petrochemical applications. Research efforts in this area have been directed at three general areas. The authors have explored ways to optimize the effectiveness of catalyst precursor species through use of nanocrystalline materials and/or finely divided powders. In this effort, the authors have developed two new nanophase material production techniques, Modified Reverse Micelle (MRM) and the Rapid Thermal Decomposition of precursors in Solution (RTDS). A second effort has been aimed at optimizing the effectiveness of catalysts by variations in other factors. To this, the authors have investigated the effect that the crystalline phase has on the capacity of iron-based oxide and oxyhydroxide powders to be effectively converted to an active catalyst phase under liquefaction conditions. And finally, the authors have developed methods to produce active catalyst precursor powders in quantities sufficient for pilot-scale testing. Major results in these three areas are summarized.« less

MicroChannel Reactors for ISRU Applications Using Nanofabricated Catalysts

NASA Astrophysics Data System (ADS)

Carranza, Susana; Makel, Darby B.; Vander Wal, Randall L.; Berger, Gordon M.; Pushkarev, Vladimir V.

2006-01-01

With the new direction of NASA to emphasize the exploration of the Moon, Mars and beyond, quick development and demonstration of efficient systems for In-Situ Resources Utilization (ISRU) is more critical and timely than ever before. Affordable planning and execution of prolonged manned space missions depend upon the utilization of local resources and the waste products which are formed in manned spacecraft and surface bases. This paper presents current development of miniaturized chemical processing systems that combine microchannel reactor design with nanofabricated catalysts. Carbon nanotubes (CNT) are used to produce a nanostructure within microchannel reactors, as support for catalysts. By virtue of their nanoscale dimensions, nanotubes geometrically restrict the catalyst particle size that can be supported upon the tube walls. By confining catalyst particles to sizes smaller than the CNT diameter, a more uniform catalyst particle size distribution may be maintained. The high dispersion permitted by the vast surface area of the nanoscale material serves to retain the integrity of the catalyst by reducing sintering or coalescence. Additionally, catalytic efficiency increases with decreasing catalyst particle size (reflecting higher surface area per unit mass) while chemical reactivity frequently is enhanced at the nanoscale. Particularly significant is the catalyst exposure. Rather than being confined within a porous material or deposited upon a 2-d surface, the catalyst is fully exposed to the reactant gases by virtue of the nanofabricated support structure. The combination of microchannel technology with nanofabricated catalysts provides a synergistic effect, enhancing both technologies with the potential to produce much more efficient systems than either technology alone. The development of highly efficient microchannel reactors will be applicable to multiple ISRU programs. By selection of proper nanofabricated catalysts, the microchannel reactors can be designed for the processes that generate the most benefit for each mission, from early demonstration missions to long term settlements.

Foamed-metal-based catalytic afterburners in automotive exhaust systems

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

Pestryakov, A.N.; Ametov, V.A.

1994-08-10

Properties of exhaust afterburning catalysts based on porous cellular materials (foamed metals) have been investigated. Catalysts containing oxides of base metals provide a two-to-threefold reduction of CO emission. Platinum-containing foamed catalysts lower the toxicity of exhaust by 85-90%. A favorable effect is demonstrated by the combined use of afterburners and a motor oil additive based on ultradispersed copper.

PdCo supported on multiwalled carbon nanotubes as an anode catalyst in a microfluidic formic acid fuel cell

NASA Astrophysics Data System (ADS)

Morales-Acosta, D.; Morales-Acosta, M. D.; Godinez, L. A.; Álvarez-Contreras, L.; Duron-Torres, S. M.; Ledesma-García, J.; Arriaga, L. G.

This work reports the synthesis of Pd-based alloys of Co and their evaluation as anode materials in a microfluidic formic acid fuel cell (μFAFC). The catalysts were prepared using the impregnation method followed by thermal treatment. The synthesized catalysts contain 22 wt.% Pd on multiwalled carbon nanotubes (Pd/MWCNT) and its alloys with two Co atomic percent in the sample with 4 at.% Co (PdCo1/MWCNT) and 10 at.% Co (PdCo2/MWCNT). The role of the alloying element was determined by XRD and XPS techniques. Both catalysts were evaluated as anode materials in a μFAFC operating with different concentrations of HCOOH (0.1 and 0.5 M), and the results were compared to those obtained with Pd/MWCNT. A better performance was obtained for the cell using PdCo1/MWCNT (1.75 mW cm -2) compared to Pd/MWCNT (0.85 mW cm -2) in the presence of 0.5 M HCOOH. By means of external electrode measurements, it was also possible to observe shifts in the formic acid oxidation potential due to a fuel concentration increment (ca. 0.05 V for both PdCo1/MWCNT and PdCo2/MWCNT catalysts and 0.23 V for Pd/MWCNT) that was attributed to deactivation of the catalyst material. The maximum current densities obtained were 8 mA cm -2 and 5.2 mA cm -2 for PdCo2/MWCNT and Pd/MWCNT, respectively. In this way, the addition of Co to the Pd catalyst was shown to improve the tolerance of intermediates produced during formic acid oxidation that tend to poison Pd, thus improving the catalytic activity and stability of the cell.

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.

Application of a mixed metal oxide catalyst to a metallic substrate

NASA Technical Reports Server (NTRS)

Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

2009-01-01

A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

Self-healing polymers---The importance of choosing an adequate healing monomer, and the olefin metathesis polymerization of agricultural oils

NASA Astrophysics Data System (ADS)

Mauldin, Timothy C.

Modern society's immense and ill-fated reliance on petrochemical-based polymeric materials will likely necessitate a shift in polymer production paradigms in the near future. The work presented herein attempts to address this issue via a two-pronged approach. First, efforts to improve the duration of composite materials by incorporation of a self-healing function are discussed, the fruitful application of which can potentially reduce or eliminate the massive carbon footprints associated with the repair/replacement of damaged materials. And second, polymeric materials derived predominately from natural and renewable feedstock---namely vegetable oils---are developed. Early microcapsule-based self-healing materials utilized dicyclopentadiene-filled microcapsules and Grubbs' olefin metathesis catalyst to initiate the healing mechanism. However, the patent-protected catalyst, made from the precious metal ruthenium and sometimes costly ligands, will likely never be inexpensive and therefore limit large-scale applications. Hence, clever approaches to reduce the healing catalyst loading in self-healing polymers are of great interest. To this end, our efforts have revolved around solving the problem of the relatively inefficient use of Grubbs' catalyst during the healing mechanism. Given that the mismatch of the olefin metathesis polymerization and Grubbs' catalyst dissolution (in monomer) kinetics is a known cause of this inefficient use of the catalyst, we attempted to tune the "latency" (i.e. pot life) of the olefin metathesis polymerization to ensure more complete dissolution of catalyst in monomer. In an alternative approach to improving efficient catalyst dissolution, we developed a simple model to predict relative dissolution rates of Grubbs' catalyst in a small library of healing monomers. This model was shown experimentally to be able to aid in the selection of, for example, reactive monomer additives that can yield impressive improvements in catalyst dissolution at small loadings. Furthermore, we have recently developed a novel rheokinetic technique designed to mimic the self-healing mechanism. This new analytical technique allows for collection of copious amounts of information related to the self-healing mechanism (e.g. healing kinetics, rheological and mechanical changes of polymerizing healing agents, adhesive interactions between healing agent and polymer matrix, etc.) to be extracted from a single experiment. New polymers derived from renewable feeds were synthesized via olefin metathesis polymerization techniques, which are ideally suited to react with the unactivated olefins (i.e. non-styrenic, non-acrylated, non-conjugated, etc.) prominent in most vegetable oils. Various vegetable oils were modified to contain norbornenyl functional groups via the high-pressure Diels-Alder addition of cyclopentadiene to their olefins to yield ROMP-reactive monomers. These monomers, polymerized in the presence of Grubbs' catalyst and the occasional comonomer, were able to yield highly crosslinked thermosets with ambient temperature storage moduli, glass transition temperatures and decomposition temperatures comparable to their currently-used, petrochemical-based counterparts. Other research thrusts in this area have focused on the development of renewable thermoplastic polymers. Vegetable oils were chemically modified to yield a series of alpha,o-dienes, from which polymers were formed via acyclic diene metathesis (ADMET). The resulting polymers were shown to have unique material properties, comparable to that of other biopolyesters (poly(lactic acid), poly(glycolides), poly(caprolactones), etc.) and common, petrochemical-derived polyesters.

Advanced Materials by Atom Transfer Radical Polymerization.

PubMed

Matyjaszewski, Krzysztof

2018-06-01

Atom transfer radical polymerization (ATRP) has been successfully employed for the preparation of various advanced materials with controlled architecture. New catalysts with strongly enhanced activity permit more environmentally benign ATRP procedures using ppm levels of catalyst. Precise control over polymer composition, topology, and incorporation of site specific functionality enables synthesis of well-defined gradient, block, comb copolymers, polymers with (hyper)branched structures including stars, densely grafted molecular brushes or networks, as well as inorganic-organic hybrid materials and bioconjugates. Examples of specific applications of functional materials include thermoplastic elastomers, nanostructured carbons, surfactants, dispersants, functionalized surfaces, and biorelated materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

PubMed

Zhou, Min; Weng, Qunhong; Popov, Zakhar I; Yang, Yijun; Antipina, Liubov Yu; Sorokin, Pavel B; Wang, Xi; Bando, Yoshio; Golberg, Dmitri

2018-05-22

Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni 3 N nanostructure (Ni 3 N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni 3 N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm -2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni 3 N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni 3 N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

Cyclic Catalytic Upgrading of Chemical Species Using Metal Oxide Materials

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Rolfe, Sara L. (Inventor); Schutte, Erick J. (Inventor)

2013-01-01

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce(sub x)B(sub y)B'(sub z)B''O(sub gamma; wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Cyclic catalytic upgrading of chemical species using metal oxide materials

DOEpatents

White, James H; Schutte, Erick J; Rolfe, Sara L

2013-05-07

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Synthesis of low cost organometallic-type catalysts for their application in microbial fuel cell technology.

PubMed

Zerrouki, A; Salar-García, M J; Ortiz-Martínez, V M; Guendouz, S; Ilikti, H; de Los Ríos, A P; Hernández-Fernández, F J; Kameche, M

2018-03-05

Microbial fuel cells (MFCs) are a promising technology that generates electricity from several biodegradable substrates and wastes. The main drawback of these devices is the need of using a catalyst for the oxygen reduction reaction at the cathode, which makes the process relatively expensive. In this work, two low cost materials are tested as catalysts in MFCs. A novel iron complex based on the ligand n-phenyledenparaethoxy aniline has been synthesized and its performance as catalyst in single chamber MFCs containing ionic liquids has been compared with a commercial inorganic material such as Raney nickel. The results show that both materials are suitable for bioenergy production and wastewater treatment in the systems. Raney nickel cathodes allow MFCs to reach a maximum power output of 160 mW.m -3 anode , while the iron complex offers lower values. Regarding the wastewater treatment capacity, MFCs working with Raney nickel-based cathodes reach higher values of chemical oxygen demand removal (76%) compared with the performance displayed by the cathodes based on Fe-complex (56%).

Catalyst design with atomic layer deposition

DOE PAGES

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

2015-02-06

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

Catalyst design with atomic layer deposition

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

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

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

Efficient photo-catalytic degradation of malachite green using nickel tungstate material as photo-catalyst.

PubMed

Helaïli, N; Boudjamaa, A; Kebir, M; Bachari, K

2017-03-01

The present study focused on the evaluation of photo-catalytic and photo-electrochemical properties of the photo-catalyst based on nickel tungstate material prepared by a nitrate method through the degradation of malachite green (MG) dye's. The effect of catalyst loading and dye concentration was examined. Physico-chemical, optical, electrical, electrochemical, and photo-electrochemical properties of the prepared material were analyzed by X-ray diffraction (XRD), fourier transform-infrared spectroscopy (FTIR), BET analysis, optical reflectance diffuse (DR), scanning electron microscopy (SEM/EDX), electrical conductivity, cyclic voltammetry (CV), current intensity, mott-shottky, and nyquist. XRD revealed the formation of monoclinic structure with a small particle size. BET surface area of the sample was around 10 m 2 /g. The results show that the degradation of MG was more than 80%, achieved after 3 h of irradiation at pH 4.6 and with a catalyst loading of 75 mg. Also, it was found that the dye photo-degradation obeyed the pseudo-first order kinetic via Langmuir Hinshelwood model.

Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

PubMed

Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

2014-01-01

The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

Highly dispersed catalysts for coal liquefaction. Quarterly report No. 9, August 23, 1993--November 22, 1993

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

Hirschon, A.S.; Wilson, R.B.

We analyzed two sets of liquefaction experiments, one involved the liquefaction of Black Thunder Coal with the corresponding recycle vehicle, and the second set of liquefaction runs involved the liquefaction of Argonne North Dakota Lignite. We compared coal conversions of Black Thunder coal and recycle solvent using Fe(CO){sub 5} and carbon monoxide/hydrogen atmospheres and a MolyVanL molybdenum catalyst under a hydrogen atmosphere. We also continued our investigation of the effect of water on the conversions. We found that addition of water seemed to decrease the amount of oils; we determined the effect of water with the recycle solvent alone, (nomore » coal added) under similar conditions, and again produced a decrease in oil yields. FIMS analyses of the hexane and toluene soluble fractions seem to indicate that in the experiment when water was added, a considerable amount of light material remained behind in the toluene layer, suggesting that somehow the addition of water decreased the amount of extracted material, perhaps by increasing the amount of polarity of the product. When the conversion was conducted with the MolyVanL molybdenum catalyst a good quality product in terms of lower viscosity was produced; however, conversions to THF soluble material was not increased. We believe the molybdenum catalyst hydrogenated the recycle vehicle rather than effectively converted the coal. In order to eliminate the effect of solvent we have often conducted experiments in an inert solvent with Argonne coals. We conducted several coal conversions experiments using an Argonne North Dakota lignite. We compared several dispersed Fe catalysts and in addition, a nickel catalyst. We investigated nickel as a catalyst since we believe this metal may be more effective in decarboxylating low rank coals. Consistent with this premise we found that the nickel catalyst gave the highest conversions.« less

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

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

Dong, Xinbo; Wang, Danjun; College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an 716000

2014-09-15

Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalystmore » is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.« less

Hydrogen gettering packing material, and process for making same

DOEpatents

LeMay, James D.; Thompson, Lisa M.; Smith, Henry Michael; Schicker, James R.

2001-01-01

A hydrogen gettering system for a sealed container is disclosed comprising packing material for use within the sealed container, and a coating film containing hydrogen gettering material on at least a portion of the surface of such packing material. The coating film containing the hydrogen gettering material comprises a mixture of one or more organic materials capable of reacting with hydrogen and one or more catalysts capable of catalyzing the reaction of hydrogen with such one or more organic materials. The mixture of one or more organic materials capable of reacting with hydrogen and the one or more catalysts is dispersed in a suitable carrier which preferably is a curable film-forming material. In a preferred embodiment, the packing material comprises a foam material which is compatible with the coating film containing hydrogen gettering material thereon.

Nucleation Control for Large, Single Crystalline Domains of Monolayer Hexagonal Boron Nitride via Si-Doped Fe Catalysts

PubMed Central

2015-01-01

The scalable chemical vapor deposition of monolayer hexagonal boron nitride (h-BN) single crystals, with lateral dimensions of ∼0.3 mm, and of continuous h-BN monolayer films with large domain sizes (>25 μm) is demonstrated via an admixture of Si to Fe catalyst films. A simple thin-film Fe/SiO2/Si catalyst system is used to show that controlled Si diffusion into the Fe catalyst allows exclusive nucleation of monolayer h-BN with very low nucleation densities upon exposure to undiluted borazine. Our systematic in situ and ex situ characterization of this catalyst system establishes a basis for further rational catalyst design for compound 2D materials. PMID:25664483

On-demand Hydrogen Production from Organosilanes at Ambient Temperature Using Heterogeneous Gold Catalysts

NASA Astrophysics Data System (ADS)

Mitsudome, Takato; Urayama, Teppei; Kiyohiro, Taizo; Maeno, Zen; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi

2016-11-01

An environmentally friendly (“green”), H2-generation system was developed that involved hydrolytic oxidation of inexpensive organosilanes as hydrogen storage materials with newly developed heterogeneous gold nanoparticle catalysts. The gold catalyst functioned well at ambient temperature under aerobic conditions, providing efficient production of pure H2. The newly developed size-selective gold nanoparticle catalysts could be separated easily from the reaction mixture containing organosilanes, allowing an on/off-switchable H2-production by the introduction and removal of the catalyst. This is the first report of an on/off-switchable H2-production system employing hydrolytic oxidation of inexpensive organosilanes without requiring additional energy.

Computational Chemistry-Based Identification of Ultra-Low Temperature Water-Gas-Shift Catalysts

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

Manos Mavrikakis

2008-08-31

The current work seeks to identify novel, catalytically-active, stable, poison-resistant LWGS catalysts that retain the superior activity typical of conventional Cu catalysts but can be operated at similar or lower temperatures. A database for the Binding Energies (BEs) of the LWGS relevant species, namely CO, O and OH on the most-stable, close-packed facets of a set of 17 catalytically relevant transition metals was established. This BE data and a database of previously established segregation energies was utilized to predict the stability of bimetallic NSAs that could be synthesized by combinations of the 17 parent transition metals. NSAs that were potentiallymore » stable both in vacuo and under the influence of strong-binding WGS intermediates were then selected for adsorption studies. A set of 40 NSAs were identified that satisfied all three screener criteria and the binding energies of CO, O and OH were calculated on a set of 66, 43 and 79 NSA candidates respectively. Several NSAs were found that bound intermediates weaker than the monometallic catalysts and were thus potentially poison-resistant. Finally, kinetic studies were performed and resulted in the discovery of a specific NSA-based bimetallic catalyst Cu/Pt that is potentially a promising LWGS catalyst. This stable Cu/Pt subsurface alloy is expected to provide facile H{sub 2}O activation and remain relatively resistant from the poisoning by CO, S and formate intermediates.« less

Nitrogen-doped graphene/CoNi alloy encased within bamboo-like carbon nanotube hybrids as cathode catalysts in microbial fuel cells

NASA Astrophysics Data System (ADS)

Hou, Yang; Yuan, Heyang; Wen, Zhenhai; Cui, Shumao; Guo, Xiaoru; He, Zhen; Chen, Junhong

2016-03-01

Cost-effective catalysts are of key importance to the successful deployment of microbial fuel cells (MFCs) for electricity generation from organic wastes. Herein, a novel catalyst prepared by one-step synthesis strategy is reported. The catalyst features N-doped bamboo-like carbon nanotube (BCNT) in which CoNi-alloy is encapsulated at the end and/or the middle section of the tube with many graphene layers inside inner cavities of BCNT (N-G@CoNi/BCNT). The prepared N-G@CoNi/BCNT exhibits a high oxygen reduction reaction (ORR) activity with an early onset potential of 0.06 V vs. Ag/AgCl and a comparable exchange current density to that of commercial Pt/C. The excellent catalytic activity is further evidenced by a high electron transfer number of 3.63. When being applied in MFCs, the N-G@CoNi/BCNT yields an average current density of 6.7 A m-2, slightly lower than that of Pt/C but with a less mass transfer potential loss. The cost of the N-G@CoNi/BCNT for constructing a 1-m2 cathode electrode is 200 times lower than that of Pt/C. With such a competitive price and excellent electrocatalytic-activity resulting from its unique morphology, CoNi-alloy/nitrogen dopants, considerable specific surface area, and carbon-coated alloy/graphene hybridization, the present catalyst is a promising candidate for ORR catalysts in MFCs for energy recovery from wastes.

Computational designing and screening of solid materials for CO2capture

NASA Astrophysics Data System (ADS)

Duan, Yuhua

In this presentation, we will update our progress on computational designing and screening of solid materials for CO2 capture. By combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations, a theoretical screening methodology to identify the most promising CO2 sorbent candidates from the vast array of possible solid materials have been proposed and validated at NETL. The advantage of this method is that it identifies the thermodynamic properties of the CO2 capture reaction as a function of temperature and pressure without any experimental input beyond crystallographic structural information of the solid phases involved. The calculated thermodynamic properties of different classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO2 adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO2 capture reactions by the solids of interest, we were able to identify only those solid materials for which lower capture energy costs are expected at the desired working conditions. In addition, we present a simulation scheme to increase and decrease the turnover temperature (Tt) of solid capturing CO2 reaction by mixing other solids. Our results also show that some solid sorbents can serve as bi-functional materials: CO2 sorbent and CO oxidation catalyst. Such dual functionality could be used for removing both CO and CO2 after water-gas-shift to obtain pure H2.

Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

DOE PAGES

Perras, Frederic A.; Wang, Zhuoran; Naik, Pranjali; ...

2017-05-12

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O–H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. As a result, experiments performed on materials impregnated with pyridine also allow for the direct detection ofmore » intermolecular hydrogen bonding interactions through the lengthening of O–H bonds.« less

Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

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

Perras, Frederic A.; Wang, Zhuoran; Naik, Pranjali

Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17O DNP surface-enhanced NMR spectroscopy (SENS). We additionally show that the O–H bond length in these catalysts can be measured with sub-picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. As a result, experiments performed on materials impregnated with pyridine also allow for the direct detection ofmore » intermolecular hydrogen bonding interactions through the lengthening of O–H bonds.« less

Visible light photoreduction of CO.sub.2 using heterostructured catalysts

DOEpatents

Matranga, Christopher; Thompson, Robert L; Wang, Congjun

2015-03-24

The method provides for use of sensitized photocatalyst for the photocatalytic reduction of CO.sub.2 under visible light illumination. The photosensitized catalyst is comprised of a wide band gap semiconductor material, a transition metal co-catalyst, and a semiconductor sensitizer. The semiconductor sensitizer is photoexcited by visible light and forms a Type II band alignment with the wide band gap semiconductor material. The wide band gap semiconductor material and the semiconductor sensitizer may be a plurality of particles, and the particle diameters may be selected to accomplish desired band widths and optimize charge injection under visible light illumination by utilizing quantum size effects. In a particular embodiment, CO.sub.2 is reduced under visible light illumination using a CdSe/Pt/TiO2 sensitized photocatalyst with H.sub.2O as a hydrogen source.

A new Keggin-type polyoxometalate catalyst for degradation of aqueous organic contaminants

NASA Astrophysics Data System (ADS)

Olgun, Asim; Çolak, Alper Tolga; Gübbük, İ. Hilal; Şahin, Onur; Kanar, Ebru

2017-04-01

In this study, a new polyoxometalate, K16[Ni(H2O)6]2[BW12O40]4·48H2O (1) was synthesized at room temperature and characterized by X-ray single crystal diffractions, elemental analyses, IR spectra, and thermo gravimetric analyses (TGA). Crystal structure analysis reveals that compound 1 exhibits a supramolecular structure containing one Keggin-type [BW12O40]4 heteropoly anion. The catalytic properties of this molecule for the degradation of Methyl red (MR), Rhodamine B (RhB), Methyl orange (MO) and Congo red (CR) were investigated. The results show that the compound 1 is a promising catalyst candidate for dye degradation.

Direct methanol feed fuel cell with reduced catalyst loading

NASA Technical Reports Server (NTRS)

Kindler, Andrew (Inventor)

1999-01-01

Improvements to direct feed methanol fuel cells include new protocols for component formation. Catalyst-water repellent material is applied in formation of electrodes and sintered before application of ionomer. A membrane used in formation of an electrode assembly is specially pre-treated to improve bonding between catalyst and membrane. The improved electrode and the pre-treated membrane are assembled into a membrane electrode assembly.

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

NASA Astrophysics Data System (ADS)

Jin, Lei

2011-12-01

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

Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO 2

DOE PAGES

Hod, Idan; Sampson, Matthew D.; Deria, Pravas; ...

2015-09-18

Realization of heterogeneous electrochemical CO 2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO 2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~10 15 sites/cm 2). The chemical products of the reduction, obtained withmore » ~100% Faradaic efficiency, are mixtures of CO and H 2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.« less

Imidazolium-Functionalized Carbon Nanohorns for the Conversion of Carbon Dioxide: Unprecedented Increase of Catalytic Activity after Recycling.

PubMed

Calabrese, Carla; Liotta, Leonarda F; Carbonell, Esther; Giacalone, Francesco; Gruttadauria, Michelangelo; Aprile, Carmela

2017-03-22

Six new hybrid materials composed of carbon nanohorns (CNHs) and highly cross-linked imidazolium salts were easily synthesized using a one-step procedure based on the radical oligomerization of bis-vinylimidazolium salts (bVImiX) in the presence of pristine CNHs. The hybrid materials were characterized and employed as the sole catalysts for the conversion of carbon dioxide into cyclic carbonate by reaction with epoxides. The solids displayed excellent turnover number and productivity. Moreover, four catalysts were investigated in recycling experiments. Two catalysts containing an octyl linker between the imidazolium units and a bromide or an iodide anion showed no loss in activity after three cycles. The other two catalysts containing a p-xylyl linker and a bromide anion and different CNHs/bVImiX ratios showed an unprecedented increase of activity after recycling. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

DOEpatents

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

2012-03-13

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

Pyrochlore catalysts for hydrocarbon fuel reforming

DOEpatents

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

2012-08-14

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

Pyrolysis of triglyceride materials for the production of renewable fuels and chemicals.

PubMed

Maher, K D; Bressler, D C

2007-09-01

Conversion of vegetable oils and animal fats composed predominantly of triglycerides using pyrolysis type reactions represents a promising option for the production of renewable fuels and chemicals. The purpose of this article was to collect and review literature on the thermo-chemical conversion of triglyceride based materials. The literature was divided and discussed as (1) direct thermal cracking and (2) combination of thermal and catalytic cracking. Typically, four main catalyst types are used including transition metal catalysts, molecular sieve type catalysts, activated alumina, and sodium carbonate. Reaction products are heavily dependant on the catalyst type and reaction conditions and can range from diesel like fractions to gasoline like fractions. Research in this area is not as advanced as bio-oil and bio-diesel research and there is opportunity for further study in the areas of reaction optimization, detailed characterization of products and properties, and scale-up.

Methods for dehydration of sugars and sugar alcohols

DOEpatents

Holladay, Johnathan E [Kennewick, WA; Hu, Jianli [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

2010-08-10

The invention includes a method of dehydration of a sugar using a dehydration catalyst and a co-catalyst within a reactor. A sugar is introduced and H.sub.2 is flowed through the reactor at a pressure of less than or equal to about 300 psig to convert at least some of the sugar into an anhydrosugar product. The invention includes a process for producing isosorbide. A starting material comprising sorbitol is flowed into a reactor. H.sub.2 is counter flowed through the reactor. The starting material is exposed to a catalyst in the presence of a co-catalyst which comprises at least one metal. The exposing is conducted at a hydrogen pressure of less than or equal to 300 psig within the reactor and the hydrogen removes at least some of any water present during the exposing and inhibits formation of colored byproducts.

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

Hydrogen sulfide conversion with nanophase titania

DOEpatents

Beck, Donald D.; Siegel, Richard W.

1996-01-01

A process for disassociating H.sub.2 S in a gaseous feed using an improved catalytic material in which the feed is contacted at a temperature of at least about 275.degree. C. with a catalyst of rutile nanocrystalline titania having grain sizes in the range of from about 1 to about 100 nanometers. Other transition metal catalysts are disclosed, each of nanocrystalline material with grain sizes in the 1-100 nm range.

Catalyst design for enhanced sustainability through fundamental surface chemistry

DOE PAGES

Personick, Michelle L.; Montemore, Matthew M.; Kaxiras, Efthimios; ...

2016-01-11

Decreasing energy consumption in the production of platform chemicals is necessary to improve the sustainability of the chemical industry, which is the largest consumer of delivered energy. The majority of industrial chemical transformations rely on catalysts, and therefore designing new materials that catalyse the production of important chemicals via more selective and energy-efficient processes is a promising pathway to reducing energy use by the chemical industry. Efficiently designing new catalysts benefits from an integrated approach involving fundamental experimental studies and theoretical modelling in addition to evaluation of materials under working catalytic conditions. In this paper, we outline this approach inmore » the context of a particular catalyst—nanoporous gold (npAu)—which is an unsupported, dilute AgAu alloy catalyst that is highly active for the selective oxidative transformation of alcohols. Fundamental surface science studies on Au single crystals and AgAu thin-film alloys in combination with theoretical modelling were used to identify the principles which define the reactivity of npAu and subsequently enabled prediction of new reactive pathways on this material. Specifically, weak van der Waals interactions are key to the selectivity of Au materials, including npAu. Finally, we also briefly describe other systems in which this integrated approach was applied.« less

Oxygen tolerance of an in silico-designed bioinspired hydrogen-evolving catalyst in water.

PubMed

Sit, Patrick H-L; Car, Roberto; Cohen, Morrel H; Selloni, Annabella

2013-02-05

Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production from water as large as 10(4)/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production from water. In earlier work, our group has reported the computational design of [FeFe](P)/FeS(2), a hydrogenase-inspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe](P)/FeS(2) is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant.

From small molecules to polymeric catalysts in the oscillatory carbonylation reaction: multiple effects of adding HI.

PubMed

Isakova, Anna; Murdoch, Billy J; Novakovic, Katarina

2018-04-04

The oscillatory palladium-catalysed carbonylation reaction opens new horizons for applications in smart materials due to the versatility of its conditions and substrates, as well as the adjustability of amplitude and period of pH oscillations. A variety of viable substrates have been demonstrated, including polymeric alkyne-terminated substrates. However, so far, there have not been any reports of polymer-based palladium catalysts in oscillatory mode. In this paper, we demonstrate pH oscillations in various systems, using commercially available palladium acetate, a triphenylphosphine palladium acetate complex and a polymer-bound palladium catalyst. While palladium acetate was able to generate oscillations under the conditions already established in our previous research on PdI2-catalysed oscillators, the other two catalysts needed the addition of HI to induce oscillations. HI forced an initial pH drop, bringing pH into the range where oscillations generally occur. Addition of HI had a significant effect on all catalysts, modifying the amplitude and period of oscillations, oscillation mode, as well as starting material conversion and product distribution.

Economical and green biodiesel production process using river snail shells-derived heterogeneous catalyst and co-solvent method.

PubMed

Roschat, Wuttichai; Siritanon, Theeranun; Kaewpuang, Teadkait; Yoosuk, Boonyawan; Promarak, Vinich

2016-06-01

River snail shells-derived CaO was used as a heterogeneous catalyst to synthesize biodiesel via transesterification of palm oil with methanol. The shell materials were calcined in air at 600-1000°C for 3h. Physicochemical properties of the resulting catalysts were characterized by TGA-DTG, XRD, SEM, BET, XRF, FT-IR and TPD. CaO catalyzed transesterification mechanism of palm oil into biodiesel was verified. The effects of adding a co-solvent on kinetic of the reaction and %FAME yield were investigated. %FAME yield of 98.5%±1.5 was achieved under the optimal conditions of catalyst/oil ratio of 5wt.%; methanol/oil molar ratio of 12:1; reaction temperature of 65°C; 10%v/v of THF in methanol and reaction time of 90min. The results ascertained that river snail shells is a novel raw material for preparation of CaO catalyst and the co-solvent method successfully decreases the reaction time and biodiesel production cost. Copyright © 2016 Elsevier Ltd. All rights reserved.

Oxygen tolerance of an in silico-designed bioinspired hydrogen-evolving catalyst in water

PubMed Central

Sit, Patrick H.-L.; Car, Roberto; Cohen, Morrel H.; Selloni, Annabella

2013-01-01

Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production from water as large as 104/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production from water. In earlier work, our group has reported the computational design of [FeFe]P/FeS2, a hydrogenase-inspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe]P/FeS2 is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant. PMID:23341607

Rate and Selectivity Control in Thioether and Alkene Oxidation with H 2 O 2 over Phosphonate-Modified Niobium(V)-Silica Catalysts

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

Thornburg, Nicholas E.; Notestein, Justin M.

Supported metal oxide catalysts are versatile materials for liquid-phase oxidations, including alkene epoxidation and thioether sulfoxidation with H2O2. Periodic trends in H2O2 activation was recently demonstrated for alkene epoxidation, highlighting Nb-SiO2 as a more active and selective catalyst than Ti-SiO2. Three representative catalysts are studied consisting of NbV, TiIV, and ZrIV on silica, each made through a molecular precursor approach that yields highly dispersed oxide sites, for thioanisole oxidation by H2O2. Initial rates trend Nb>Ti>>Zr, as for epoxidation, and Nb outperforms Ti for a number of other thioethers. In contrast, selectivity to sulfoxide vs. sulfone trends Ti>Nb>>Zr at all conversions.more » Modifying the Nb-SiO2 catalyst with phenylphosphonic acid does not completely remove sulfoxidation reactivity, as it did for photooxidation and epoxidation, and results in an unusual material active for sulfoxidation but neither epoxidation nor overoxidation to the sulfone.« less

Low-grade oils and fats: effect of several impurities on biodiesel production over sulfonic acid heterogeneous catalysts.

PubMed

Morales, Gabriel; Bautista, L Fernando; Melero, Juan A; Iglesias, Jose; Sánchez-Vázquez, Rebeca

2011-10-01

Different lipidic wastes and low-grade oils and fats have been characterized and evaluated as feedstocks for the acid-catalyzed production of FAME. The characterization of these materials has revealed significant contents of free fatty acids, Na, K, Ca, Mg, P, unsaponifiable matter and humidity. Arenesulfonic acid-functionalized SBA-15 silica catalyst has provided yields to FAME close to 80% in the simultaneous esterification-transesterification of the different feedstocks, regardless of their nature and properties, using methanol under the following reaction conditions: 160 °C, 2 h, methanol to oil molar ratio of 30, 8 wt.% catalyst loading, and 2000 rpm stirring rate. Nevertheless, reutilization of the catalyst is compromised by high levels of impurities, especially because of deactivation by strong interaction of unsaponifiable matter with the catalytic sites. The conditioning of these materials by aqueous washing in the presence of cationic-exchange resin Amberlyst-15, followed by a drying step, resulted in a lower deactivation of the catalyst. Copyright © 2011 Elsevier Ltd. All rights reserved.

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.

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

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

Chaleshtori, Maryam Zarei, E-mail: mzarei@utep.edu; Hosseini, Mahsa; Edalatpour, Roya

2013-10-15

Graphical abstract: The photocatalytic activity of different porous titanium–niobium oxides was evaluated toward degradation of bromocresol green (BG) under UV light. A better catalytic activity was observed for all samples at lower pH. Catalysts have a stronger ability for degradation of BG in acid media than in alkaline media. - Highlights: • Different highly structured titanium–niobium oxides have been prepared using improved methods of synthesis. • Photo-degradation of bromocresol green dye (BG) with nanostructure titanium–niobium oxide catalysts was carried out under UV light. • The photo-catalytic activity of all catalysts was higher in lower pH. • Titanium–niobium oxide catalysts aremore » considerably stable and reusable. - Abstract: In this study, high surface area semiconductors, non porous and porous titanium–niobium oxides derived from KTiNbO{sub 5} were synthesized, characterized and developed for their utility as photocatalysts for decontamination with sunlight. These materials were then used in the photocatalytic degradation of bromocresol green dye (BG) in aqueous solution using UV light and their catalytic activities were evaluated at various pHs. For all catalysts, the photocatalytic degradation of BG was most efficient in acidic solutions. Results show that the new porous oxides have large porous and high surface areas and high catalytic activity. A topotactic dehydration treatment greatly improves catalyst performance at various pHs. Stability and long term activity of porous materials (topo and non-topo) in photocatalysis reactions was also tested. These results suggest that the new materials can be used to efficiently purify contaminated water.« less

Tuning the surface properties of novel ternary iron(III) fluoride-based catalysts using the template effect of the matrix.

PubMed

Guo, Ying; Lippitz, Andreas; Saftien, Paul; Unger, Wolfgang E S; Kemnitz, Erhard

2015-03-21

Sol-gel prepared ternary FeF3-MgF2 materials have become promising heterogeneous catalysts due to their porosity and surface Lewis/Brønsted acidity (bi-acidity). Despite the good catalytic performance, nanoscopic characterisations of this type of material are still missing and the key factors controlling the surface properties have not yet been identified, impeding both a better understanding and further development of ternary fluoride catalysts. In this study, we characterised the interaction between the bi-acidic component (FeF3) and the matrix (MgF2) on the nano-scale. For the first time, the formation pathway of FeF3-MgF2 was profiled and the template effect of MgF2 during the synthesis process was discovered. Based on these new insights two novel materials, FeF3-CaF2 and FeF3-SrF2, were established, revealing that with decreasing the atomic numbers (from Sr to Mg), the ternary fluorides exhibited increasing surface acidity and surface area but decreasing pore size. These systematic changes gave rise to a panel of catalysts with tuneable surface and bulk properties either by changing the matrix alkaline earth metal fluoride or by adjusting their ratios to Fe or both. The template effect of the alkaline earth metal fluoride matrix was identified as the most probable key factor determining the surface properties and further influencing the catalytic performance in ternary fluoride based catalysts, and paves the way to targeted design of next-generation catalysts with tunable properties.

Nanostructured material-based biofuel cells: recent advances and future prospects.

PubMed

Zhao, Cui-E; Gai, Panpan; Song, Rongbin; Chen, Ying; Zhang, Jianrong; Zhu, Jun-Jie

2017-03-06

During the past decade, biofuel cells (BFCs) have emerged as an emerging technology on account of their ability to directly generate electricity from biologically renewable catalysts and fuels. Due to the boost in nanotechnology, significant advances have been accomplished in BFCs. Although it is still challenging to promote the performance of BFCs, adopting nanostructured materials for BFC construction has been extensively proposed as an effective and promising strategy to achieve high energy production. In this review, we presented the major novel nanostructured materials applied for BFCs and highlighted the breakthroughs in this field. Based on different natures of the bio-catalysts and electron transfer process at the bio-electrode surfaces, the fundamentals of BFC systems, including enzymatic biofuel cells (EBFCs) and microbial fuel cells (MFCs), have been elucidated. In particular, the principle of electrode materials design has been detailed in terms of enhancing electrical communications between biological catalysts and electrodes. Furthermore, we have provided the applications of BFCs and potential challenges of this technology.

Atomically dispersed metal sites in MOF-based materials for electrocatalytic and photocatalytic energy conversion.

PubMed

Liang, Zibin; Qu, Chong; Xia, Dingguo; Zou, Ruqiang; Xu, Qiang

2018-02-19

Metal sites play an essential role for both electrocatalytic and photocatalytic energy conversion applications. The highly ordered arrangements of the organic linkers and metal nodes and the well-defined pore structures of metal-organic frameworks (MOFs) make them ideal substrates to support atomically dispersed metal sites (ADMSs) located in their metal nodes, linkers, and pores. Besides, porous carbon materials doped with ADMSs can be derived from these ADMS-incorporated MOF precursors through controlled treatments. These ADMSs incorporated in pristine MOFs and MOF-derived carbon materials possess unique merits over the molecular or the bulk metal-based catalysts, bridging the gap between homogeneous and heterogeneous catalysts for energy conversion applications. In this review, recent progress and perspective of design and incorporation of ADMSs in pristine MOFs and MOF-derived materials for energy conversion applications are highlighted, which will hopefully promote further developments of advanced MOF-based catalysts in foreseeable future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composition and method for polymer moderated catalytic water formation

DOEpatents

Shepodd, Timothy Jon

1999-01-01

A composition suitable for safely removing hydrogen from gaseous mixtures containing hydrogen and oxygen, particularly those mixtures wherein the hydrogen concentration is within the explosive range. The composition comprises a hydrogenation catalyst, preferably Pd dispersed on carbon, wherein the concentration of Pd is from about 1-10 wt %, dispersed in a polymeric material matrix. As well as serving as a matrix to contain the hydrogenation catalyst, the polymeric material, which is substantially unreactive to hydrogen, provides both a diffusion restriction to hydrogen and oxygen, thereby limiting the rate at which the reactants (hydrogen and oxygen) can diffuse to the catalyst surface and thus, the production of heat from the recombination reaction and as a heat sink.

Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

2000-01-01

This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

Industrial Catalysis: A Practical Guide

NASA Astrophysics Data System (ADS)

Farrauto, Robert J.

Every student of chemistry, material science, and chemical engineering should be schooled in catalysis and catalytic reactions. The reason is quite simple; most products produced in the chemical and petroleum industry utilize catalysts to enhance the rate of reaction and selectivity to desired products. Catalysts are also extensively used to minimize harmful byproduct pollutants in environmental applications. Enhanced reaction rates translate to higher production volumes at lower temperatures with smaller and less exotic materials of construction necessary. When a highly selective catalyst is used, large volumes of desired products are produced with virtually no undesirable byproducts. Gasoline, diesel, home heating oil, and aviation fuels owe their performance quality to catalytic processing used to upgrade crude oil.

Direct liquid-feed fuel cell with membrane electrolyte and manufacturing thereof

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1999-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Improvements in interfacing of the catalyst layer and the membrane and activating catalyst materials are disclosed.

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.

Method for generating a highly reactive plasma for exhaust gas after treatment and enhanced catalyst reactivity

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

Whealton, John H.; Hanson, Gregory R.; Storey, John M.

This patent application describes a method and apparatus of exhaust gas remediation that enhance the reactivity of the material catalysts found within catalytic converters of cars, trucks, and power stations.

Series-Bosch Technology for Oxygen Recovery During Lunar or Martian Surface Missions

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Mansell, J. Matthew; Rabenberg, Ellen; Stanley, Christine M.; Edmunson, Jennifer; Alleman, James E.; Chen, Kevin; Dumez, Sam

2014-01-01

Long-duration surface missions to the Moon or Mars will require life support systems that maximize resource recovery to minimize resupply from Earth. To address this need, NASA previously proposed a Series-Bosch (S-Bosch) oxygen recovery system, based on the Bosch process, which can theoretically recover 100% of the oxygen from metabolic carbon dioxide. Bosch processes have the added benefits of the potential to recover oxygen from atmospheric carbon dioxide and the use of regolith materials as catalysts, thereby eliminating the need for catalyst resupply from Earth. In 2012, NASA completed an initial design for an S-Bosch development test stand that incorporates two catalytic reactors in series including a Reverse Water-Gas Shift (RWGS) Reactor and a Carbon Formation Reactor (CFR). In 2013, fabrication of system components, with the exception of a CFR, and assembly of the test stand was initiated. Stand-alone testing of the RWGS reactor was completed to compare performance with design models. Continued testing of Lunar and Martian regolith simulants provided sufficient data to design a CFR intended to utilize these materials as catalysts. Finally, a study was conducted to explore the possibility of producing bricks from spent regolith catalysts. The results of initial demonstration testing of the RWGS reactor, results of continued catalyst performance testing of regolith simulants, and results of brick material properties testing are reported. Additionally, design considerations for a regolith-based CFR are discussed.

Series-Bosch Technology for Oxygen Recovery During Lunar or Martian Surface Missions

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Mansell, James M.; Stanley, Christine; Edmunson, Jennifer; Dumez, Samuel; Chen, Kevin; Alleman, James E.

2014-01-01

Long-duration surface missions to the Moon or Mars will require life support systems that maximize resource recovery to minimize resupply from Earth. To address this need, NASA previously proposed a Series-Bosch (S-Bosch) oxygen recovery system, based on the Bosch process, which can theoretically recover 100% of the oxygen from metabolic carbon dioxide. Bosch processes have the added benefits of the potential to recover oxygen from atmospheric carbon dioxide and the use of regolith materials as catalysts, thereby eliminating the need for catalyst resupply from Earth. In 2012, NASA completed an initial design for an S-Bosch development test stand that incorporates two catalytic reactors in series including a Reverse Water-Gas Shift (RWGS) Reactor and a Carbon Formation Reactor (CFR). In 2013, fabrication of system components, with the exception of a CFR, and assembly of the test stand was initiated. Stand-alone testing of the RWGS reactor was completed to compare performance with design models. Continued testing of Lunar and Martian regolith simulants provided sufficient data to design a CFR intended to utilize these materials as catalysts. Finally, a study was conducted to explore the possibility of producing bricks from spend regolith catalysts. The results of initial demonstration testing of the RWGS reactor, results of continued catalyst performance testing of regolith simulants, and results of brick material properties testing are reported. Additionally, design considerations for a regolith-based CFR are discussed.

Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

DOE PAGES

Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; ...

2016-03-08

The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities comparedmore » to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.« less

Practical, economical, and eco-friendly starch-supported palladium catalyst for Suzuki coupling reactions.

PubMed

Baran, Talat

2017-06-15

In catalytic systems, the support materials need to be both eco friendly and low cost as well as having high thermal and chemical stability. In this paper, a novel starch supported palladium catalyst, which had these outstanding properties, was designed and its catalytic activity was evaluated in a Suzuki coupling reaction under microwave heating with solvent-free and mild reaction conditions. The starch supported catalyst gave remarkable reaction yields after only 5min as a result of the coupling reaction of the phenyl boronic acid with 23 different substrates, which are bearing aril bromide, iodide, and chloride. The longevity of the catalyst was also investigated, and the catalyst could be reused for 10 runs. The starch supported Pd(II) catalyst yielded remarkable TON (up to 25,000) and TOF (up to 312,500) values by using a simple, fast and eco-friendly method. In addition, the catalytic performance of the catalyst was tested against different commercial palladium catalysts, and the green starch supported catalyst had excellent selectivity. The catalytic tests showed that the novel starch based palladium catalyst proved to be an economical and practical catalyst for the synthesis of biaryl compounds. Copyright © 2017 Elsevier Inc. All rights reserved.

Biodiesel production from palm oil using calcined waste animal bone as catalyst.

PubMed

Obadiah, Asir; Swaroopa, Gnanadurai Ajji; Kumar, Samuel Vasanth; Jeganathan, Kenthorai Raman; Ramasubbu, Alagunambi

2012-07-01

Waste animal bones was employed as a cost effective catalyst for the transesterification of palm oil. The catalyst was calcined at different temperatures to transform the calcium phosphate in the bones to hydroxyapatite and 800 °C was found to give the best yield of biodiesel. The catalyst was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectrometry (EDS) and Fourier transform infrared spectrometry (FT-IR). Under the optimal reaction conditions of 20 wt.% of catalyst, 1:18 oil to methanol molar ratio, 200 rpm of stirring of reactants and at a temperature of 65 °C, the methyl ester conversion was 96.78% and it was achieved in 4h. The catalyst performed equally well as the laboratory-grade CaO. Animal bone is therefore a useful raw material for the production of a cheap catalyst for transesterification. Copyright © 2012 Elsevier Ltd. All rights reserved.

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.

Enhancing substrate utilization and power production of a microbial fuel cell with nitrogen-doped carbon aerogel as cathode catalyst.

PubMed

Tardy, Gábor Márk; Lóránt, Bálint; Lóka, Máté; Nagy, Balázs; László, Krisztina

2017-07-01

Catalytic efficiency of a nitrogen-doped, mesoporous carbon aerogel cathode catalyst was investigated in a two-chambered microbial fuel cell (MFC) applying graphite felt as base material for cathode and anode, utilizing peptone as carbon source. This mesoporous carbon aerogel containing catalyst layer on the cathode increased the maximum power density normalized to the anode volume to 2.7 times higher compared to the maximum power density obtained applying graphite felt cathode without the catalyst layer. At high (2 and 3) cathode/anode volume ratios, maximum power density exceeded 40 W m -3 . At the same time, current density and specific substrate utilization rate increased by 58% resulting in 31.9 A m -3 and 18.8 g COD m -3  h -1 , respectively (normalized to anode volume). Besides the increase of the power and the rate of biodegradation, the investigated catalyst decreased the internal resistance from the range of 450-600 to 350-370 Ω. Although Pt/C catalyst proved to be more efficient, a considerable decrease in the material costs might be achieved by substituting it with nitrogen-doped carbon aerogel in MFCs. Such cathode still displays enhanced catalytic effect.

Evaluation of Silica-Supported Metal and Metal Phosphide Nanoparticle Catalysts for the Hydrodeoxygenation of Guaiacol Under Ex Situ Catalytic Fast Pyrolysis Conditions

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

Griffin, Michael B.; Baddour, Frederick G.; Habas, Susan E.

A series of metal and metal phosphide catalysts were investigated for the hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis (CFP) conditions (350 °C, 0.5 MPa, 12 H 2:1 guaiacol, weight hourly space velocity 5 h $-$1). Ligand-capped Ni, Pt, Rh, Ni 2P, and Rh 2P nanoparticles (NPs) were prepared using solution-phase synthesis techniques and dispersed on a silica support. For the metal phosphide NP-catalysts, a synthetic route that relies on the decomposition of a single molecular precursor was employed. The reactivity of the NP-catalysts was compared to a series of reference materials including Ni/SiO 2 and Pt/SiO 2more » prepared using incipient wetness (IW) impregnation and a commercial (com) Pt/SiO 2 catalyst. The NP-Ni/SiO 2 catalyst exhibited the largest reduction in the oxygen mol% of the organic phase and outperformed the IW-Ni/SiO 2 material. Although it was less active for guaiacol conversion than NP-Ni/SiO 2, NP-Rh2P/SiO 2 demonstrated the largest production of completely deoxygenated products and the highest selectivity to anisole, benzene, and cyclohexane, suggesting that it is a promising catalyst for deoxygenation of aryl-OH bonds. Finally, the com-Pt/SiO 2 and IW-Pt/SiO 2 catalyst exhibited the highest normalized rate of guaiacol conversion per m 2 and per gram of active phase, respectively, but did not produce any completely deoxygenated products.« less

Evaluation of Silica-Supported Metal and Metal Phosphide Nanoparticle Catalysts for the Hydrodeoxygenation of Guaiacol Under Ex Situ Catalytic Fast Pyrolysis Conditions

DOE PAGES

Griffin, Michael B.; Baddour, Frederick G.; Habas, Susan E.; ...

2015-09-30

A series of metal and metal phosphide catalysts were investigated for the hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis (CFP) conditions (350 °C, 0.5 MPa, 12 H 2:1 guaiacol, weight hourly space velocity 5 h $-$1). Ligand-capped Ni, Pt, Rh, Ni 2P, and Rh 2P nanoparticles (NPs) were prepared using solution-phase synthesis techniques and dispersed on a silica support. For the metal phosphide NP-catalysts, a synthetic route that relies on the decomposition of a single molecular precursor was employed. The reactivity of the NP-catalysts was compared to a series of reference materials including Ni/SiO 2 and Pt/SiO 2more » prepared using incipient wetness (IW) impregnation and a commercial (com) Pt/SiO 2 catalyst. The NP-Ni/SiO 2 catalyst exhibited the largest reduction in the oxygen mol% of the organic phase and outperformed the IW-Ni/SiO 2 material. Although it was less active for guaiacol conversion than NP-Ni/SiO 2, NP-Rh2P/SiO 2 demonstrated the largest production of completely deoxygenated products and the highest selectivity to anisole, benzene, and cyclohexane, suggesting that it is a promising catalyst for deoxygenation of aryl-OH bonds. Finally, the com-Pt/SiO 2 and IW-Pt/SiO 2 catalyst exhibited the highest normalized rate of guaiacol conversion per m 2 and per gram of active phase, respectively, but did not produce any completely deoxygenated products.« less

Bifunctional catalyst of graphite-encapsulated iron compound nanoparticle for magnetic carbon nanotubes growth by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Saraswati, Teguh Endah; Prasiwi, Oktaviana Dewi Indah; Masykur, Abu; Anwar, Miftahul

2017-01-01

The carbon nanotube has widely taken great attractive in carbon nanomaterial research and application. One of its preparation methods is catalytic chemical vapor deposition (CCVD) using catalyst i.e. iron, nickel, etc. Generally, except the catalyst, carbon source gasses as the precursor are still required. Here, we report the use of the bifunctional material of Fe3O4/C which has an incorporated core/shell structures of carbon-encapsulated iron compound nanoparticles. The bifunctional catalyst was prepared by submerged arc discharge that simply performed using carbon and carbon/iron oxide electrodes in ethanol 50%. The prepared material was then used as a catalyst in thermal chemical vapor deposition at 800°C flown with ethanol vapor as the primer carbon source in a low-pressure condition. This catalyst might play a dual role as a catalyst and secondary carbon source for growing carbon nanotubes at the time. The synthesized products were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The successful formation of carbon nanotubes was assigned by the shifted X-ray diffracted peak of carbon C(002), the iron oxides of Fe3O4 and γ-Fe2O3, and the other peaks which were highly considered to the other carbon allotropes with sp2 hybridization structures. The other assignment was studied by electron microscopy which successfully observed the presence of single-wall carbon nanotubes. In addition, the as-prepared carbon nanotubes have a magnetic property which was induced by the remaining of metal catalyst inside the CNT.

Density controlled carbon nanotube array electrodes

DOEpatents

Ren, Zhifeng F [Newton, MA; Tu, Yi [Belmont, MA

2008-12-16

CNT materials comprising aligned carbon nanotubes (CNTs) with pre-determined site densities, catalyst substrate materials for obtaining them and methods for forming aligned CNTs with controllable densities on such catalyst substrate materials are described. The fabrication of films comprising site-density controlled vertically aligned CNT arrays of the invention with variable field emission characteristics, whereby the field emission properties of the films are controlled by independently varying the length of CNTs in the aligned array within the film or by independently varying inter-tubule spacing of the CNTs within the array (site density) are disclosed. The fabrication of microelectrode arrays (MEAs) formed utilizing the carbon nanotube material of the invention is also described.

Varied morphology carbon nanotubes and method for their manufacture

DOEpatents

Li, Wenzhi; Wen, Jian Guo; Ren, Zhi Feng

2007-01-02

The present invention describes the preparation of carbon nanotubes of varied morphology, catalyst materials for their synthesis. The present invention also describes reactor apparatus and methods of optimizing and controlling process parameters for the manufacture carbon nanotubes with pre-determined morphologies in relatively high purity and in high yields. In particular, the present invention provides methods for the preparation of non-aligned carbon nanotubes with controllable morphologies, catalyst materials and methods for their manufacture.

Hydrogen sulfide conversion with nanophase titania

DOEpatents

Beck, D.D.; Siegel, R.W.

1996-08-20

A process is described for disassociating H{sub 2}S in a gaseous feed using an improved catalytic material in which the feed is contacted at a temperature of at least about 275 C with a catalyst of rutile nanocrystalline titania having grain sizes in the range of from about 1 to about 100 nanometers. Other transition metal catalysts are disclosed, each of nanocrystalline material with grain sizes in the 1-100 nm range. 5 figs.

An Integrated Computational and Experimental Approach Toward the Design of Materials for Fuel Cell Systems

DTIC Science & Technology

2012-10-01

13 Based on the limited work done, the best reported ORR chalcogenide electrocatalysts for PEMFC applications can be ranked as follows: MoRuSe... PEMFC catalysts is the durability of the catalyst particles. Particle size distribution tends to shift towards larger particles during the...the design of new materials for applications in PEMFCs . Reference: A more detailed treatment of the topics of this section, Experimental Target 11

Graphene Nanowalls as Ingenious Material for Catalysts and Superconductors

DTIC Science & Technology

2011-03-12

whole transferred graphene films by using ECOPIA Hall measurement system HMS-3000 with silver paint used as electrodes at the four corners of graphene ...introduced for 15 min during growth stage. On the right: (a) A picture of the transferred graphene on SiO2/Si wafer with silver paint as electrodes at...Final Report for AOARD Grant 104057 “ Graphene Nanowalls as Ingenious Material for Catalysts and Superconductors” March 12, 2011 Name of

Electrode assembly for use in a solid polymer electrolyte fuel cell

DOEpatents

Raistrick, Ian D.

1989-01-01

A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

Phenomenological modelling of self-healing polymers based on integrated healing agents

NASA Astrophysics Data System (ADS)

Mergheim, Julia; Steinmann, Paul

2013-09-01

The present contribution introduces a phenomenological model for self-healing polymers. Self-healing polymers are a promising class of materials which mimic nature by their capability to autonomously heal micro-cracks. This self-healing is accomplished by the integration of microcapsules containing a healing agent and a dispersed catalyst into the matrix material. Propagating microcracks may then break the capsules which releases the healing agent into the microcracks where it polymerizes with the catalyst, closes the crack and 'heals' the material. The present modelling approach treats these processes at the macroscopic scale, the microscopic details of crack propagation and healing are thus described by means of continuous damage and healing variables. The formulation of the healing model accounts for the fact that healing is directly associated with the curing process of healing agent and catalyst. The model is implemented and its capabilities are studied by means of numerical examples.

Acid-functionalized polyolefin materials and their use in acid-promoted chemical reactions

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

Oyola, Yatsandra; Tian, Chengcheng; Bauer, John Christopher

An acid-functionalized polyolefin material that can be used as an acid catalyst in a wide range of acid-promoted chemical reactions, wherein the acid-functionalized polyolefin material includes a polyolefin backbone on which acid groups are appended. Also described is a method for the preparation of the acid catalyst in which a precursor polyolefin is subjected to ionizing radiation (e.g., electron beam irradiation) of sufficient power and the irradiated precursor polyolefin reacted with at least one vinyl monomer having an acid group thereon. Further described is a method for conducting an acid-promoted chemical reaction, wherein an acid-reactive organic precursor is contacted inmore » liquid form with a solid heterogeneous acid catalyst comprising a polyolefin backbone of at least 1 micron in one dimension and having carboxylic acid groups and either sulfonic acid or phosphoric acid groups appended thereto.« less

Synthesis Methods, Microscopy Characterization and Device Integration of Nanoscale Metal Oxide Semiconductors for Gas Sensing

PubMed Central

Vander Wal, Randy L.; Berger, Gordon M.; Kulis, Michael J.; Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura

2009-01-01

A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. Both nanostructures possess a one-dimensional morphology. Different synthesis methods are used to produce these materials: thermal evaporation-condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed. Practical issues associated with harvesting, purification, and integration of these materials into sensing devices are detailed. For comparison to the nascent form, these sensing materials are surface coated with Pd and Pt nanoparticles. Gas sensing tests, with respect to H2, are conducted at ambient and elevated temperatures. Comparative normalized responses and time constants for the catalyst and noncatalyst systems provide a basis for identification of the superior metal-oxide nanostructure and catalyst combination. With temperature-dependent data, Arrhenius analyses are made to determine activation energies for the catalyst-assisted systems. PMID:22408484

A Unique 3D Nitrogen-Doped Carbon Composite as High-Performance Oxygen Reduction Catalyst

PubMed Central

Karunagaran, Ramesh; Tung, Tran Thanh; Tran, Diana; Coghlan, Campbell; Doonan, Christian

2017-01-01

The synthesis and properties of an oxygen reduction catalyst based on a unique 3-dimensional (3D) nitrogen doped (N-doped) carbon composite are described. The composite material is synthesised via a two-step hydrothermal and pyrolysis method using bio-source low-cost materials of galactose and melamine. Firstly, the use of iron salts and galactose to hydrothermally produceiron oxide (Fe2O3) magnetic nanoparticle clusters embedded carbon spheres. Secondly, magnetic nanoparticles diffused out of the carbon sphere when pyrolysed in the presence of melamine as nitrogen precursor. Interestingly, many of these nanoparticles, as catalyst-grown carbon nanotubes (CNTs), resulted in the formation of N-doped CNTs and N-doped carbon spheres under the decomposition of carbon and a nitrogen environment. The composite material consists of integrated N-doped carbon microspheres and CNTs show high ORR activity through a predominantly four-electron pathway. PMID:28792432

Overview of Photocatalysis, Photocatalytic Surface Materials Studies, and Demonstration of Self-Cleaning Materials for Space and Terrestrial Based Applications at the Infinity Science Center at NASA Stennis Space Center

NASA Technical Reports Server (NTRS)

Underwood, Lauren W.

2012-01-01

Research into photocatalytic technology has been progressing for over three decades in the early 1990s Japanese and European companies initiate research into photocatalytic technology. In the 1996 specific focus on the technology with the first large-scale application: the construction of a church in Rome (Jubilee Church). And in 2000 Europe and Japan research into the benefits of photocatalytic technology. Currently, photocatalytic technology continues to improve, and with time development is becoming more efficient and effective. What is Photocatalysis? Photo: phenomenon induced by the light, having specifically a wavelength around 320-400 nm (artificial or natural sunlight). Catalyst: a material that induces a reaction but is not consumed or transformed by it. The catalyst remains constantly available. In this case, the catalyst is made with nano-particles of titanium oxide (Ti02).

Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition

NASA Astrophysics Data System (ADS)

Lubers, Alia Marie

Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most successful hydrogen pumping catalysts, comparable to a commercial Pt/C catalyst. Synthesized Pt/C materials were also used as PEMFC catalysts. We found the ALD catalysts with lower platinum loading to be competitive with a commercial fuel cell catalyst, especially when exhibiting similar platinum particle characteristics. The functionalized carbon helped produce smaller and more dispersed platinum particles; however, it encouraged carbon corrosion within an electrode, severing electrical connections and lowering energy production. The most suitable chemistry for competitive Pt/C catalysts was produced by platinum ALD on unmodified carbon using hydrogen as a reactant. ALD is a promising method for fabricating electrocatalysts, which could help fuel cells become an economically viable alternative to fossil fuels.

SULFUR TOLERANT CATALYSTS FOR BIOMASS TAR REMOVAL - PHASE I

EPA Science Inventory

In this Small Business Innovation Research (SBIR) project, NexTech Materials proposes a catalytic reforming approach to remove waste tar from gasified biomass on nickel-based catalysts. Biomass gasification is a potential renewable route to producing electricity, liquid fue...

Discovery of Novel NOx Catalysts for CIDI Applications by High-throughput Methods

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

Blint, Richard J.

DOE project DE-PS26-00NT40758 has developed very active, lean exhaust, NOx reduction catalysts that have been tested on the discovery system, laboratory reactors and engine dynamometer systems. The goal of this project is the development of effective, affordable NOx reduction catalysts for lean combustion engines in the US light duty vehicle market which can meet Tier II emission standards with hydrocarbons based reductants for reducing NOx. General Motors (prime contractor) along with subcontractors BASF (Engelhard) (a catalytic converter developer) and ACCELRYS (an informatics supplier) carried out this project which began in August of 2002. BASF (Engelhard) has run over 16,000 testsmore » of 6100 possible catalytic materials on a high throughput discovery system suitable for automotive catalytic materials. Accelrys developed a new database informatics system which allowed material tracking and data mining. A program catalyst was identified and evaluated at all levels of the program. Dynamometer evaluations of the program catalyst both with and without additives show 92% NOx conversions on the HWFET, 76% on the US06, 60% on the cold FTP and 65% on the Set 13 heavy duty test using diesel fuel. Conversions of over 92% on the heavy duty FTP using ethanol as a second fluid reductant have been measured. These can be competitive with both of the alternative lean NOx reduction technologies presently in the market. Conversions of about 80% were measured on the EUDC for lean gasoline applications without using active dosing to adjust the C:N ratio for optimum NOx reduction at all points in the certification cycle. A feasibility analysis has been completed and demonstrates the advantages and disadvantages of the technology using these materials compared with other potential technologies. The teaming agreements among the partners contain no obstacles to commercialization of new technologies to any potential catalyst customers.« less

Electrochemical and Structural Study of a Chemically Dealloyed PtCu Oxygen Reduction Catalyst

PubMed Central

Dutta, Indrajit; Carpenter, Michael K; Balogh, Michael P; Ziegelbauer, Joseph M; Moylan, Thomas E; Atwan, Mohammed H; Irish, Nicholas P

2013-01-01

A carbon-supported, dealloyed platinum-copper (Pt-Cu) oxygen reduction catalyst was prepared using a multi-step synthetic procedure. Material produced at each step was characterized using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), electron energy loss spectroscopy (EELS) mapping, x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and cyclic voltammetry (CV), and its oxygen reduction reaction (ORR) activity was measured by a thin-film rotating disk electrode (TF-RDE) technique. The initial synthetic step, a co-reduction of metal salts, produced a range of poorly crystalline Pt, Cu, and Pt-Cu alloy nanoparticles that nevertheless exhibited good ORR activity. Annealing this material alloyed the metals and increased particle size and crystallinity. TEM shows the annealed catalyst to include particles of various sizes, large (>25 nm), medium (12–25 nm), and small (<12 nm). Most of the small and medium-sized particles exhibited a partial or complete coreshell (Cu-rich core and Pt shell) structure with the smaller particles typically having more complete shells. The appearance of Pt shells after annealing indicates that they are formed by a thermal diffusion mechanism. Although the specific activity of the catalyst material was more than doubled by annealing, the concomitant decrease in Pt surface area resulted in a drop in its mass activity. Subsequent dealloying of the catalyst by acid treatment to partially remove the copper increased the Pt surface area by changing the morphology of the large and some medium particles to a “Swiss cheese” type structure having many voids. The smaller particles retained their core-shell structure. The specific activity of the catalyst material was little reduced by dealloying, but its mass activity was more than doubled due to the increase in surface area. The possible origins of these results are discussed in this report. PMID:23807900

Adsorption properties of regenerative materials for removal of low concentration of toluene.

PubMed

Xie, Zhen-Zhen; Wang, Lin; Cheng, Ge; Shi, Lei; Zhang, Yi-Bo

2016-12-01

A specific type of material, activated carbon fiber (ACF), was modified by SiO 2 , and the final products ACF-x were obtained as ACF-12.5, ACF-20, ACF-40, and ACF-80 according to different dosages of tetraethoxysilane (TEOS). The modified material on the ACF surface had a significant and smooth cover layer with low content of silica from scanning electron microscope (SEM) image. The modified ACF-x showed the stronger hydrophobicity, thermal stability, and adsorption capacity, which had almost no effect in the presence of water vapor and no destruction in multiple cycles. ACF-20 was proven as the most efficient adsorbent in humid conditions. The dual-function system composed of the regenerative adsorbents and the combustion catalyst would be efficient in consecutive toluene adsorption/oxidation cycles, in which the combustion catalyst was prepared by the displacement reaction of H 2 PtCl 6 with foam Ni. Therefore, the adsorption/catalytic oxidation could be a promising technique in the indoor air purification, especially in the case of very low volatile organic compound (VOC; toluene) concentration levels. Exploring highly effective adsorptive materials with less expensive costs becomes an urgent issue in the indoor air protection. ACF-20 modified by SiO 2 with Pt/Ni catalysts shows stronger hydrophobicity, thermal stability, and adsorption capacity. This dual-function system composed of the regenerative materials and the combustion catalyst would be a promising technique in the indoor air purification, especially in the case of removal of very low concentration of toluene.

Materials and systems for unassisted photoelectrochemical solar fuels production (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lee, Jae Sung

2016-10-01

About 400 semiconductor solids are known to have photocatalytic activity for water splitting. Yet there is no single material that could satisfy all the requirements for desired photocatalysts: i) suitable band gap energy (1.7 eV< Eg < 2.3 eV) for high efficiency, ii) proper band position for reduction and/or oxidation of water, iii) long-term stability in aqueous solutions, iv) low cost, v) high crystallinity, and vi) high conductivity. Hence, in the selection of photocatalytic materials, we better start from intrinsically stable materials made of earth-abundant elements. The band bap energy is also the primary consideration to absorb ample amount of solar energy of wide wavelength spectrum. It sets the limit of theoretically maximum efficiency and it could also be extended by band engineering techniques. Upon selection of the candidate materials, we can also modify the materials for full utilization their potentials. The main path of efficiency loss in PEC water splitting process is recombination of photoelectrons and holes. We discuss the material designs including i) p-n heterojunction photoanodes for effective electron-hole separation, ii) electron highway to facilitate interparticle electron transfer, iii) metal or anion doping to improve conductivity of the semiconductor and to extend the range of light absorption, iv) one-dimensional nanomaterials to secure a short hole diffusion distance and vectoral electron transfer, and v) loading co-catalysts for facile charge separation. High efficiency has been demonstrated for all these examples due to efficient electron-hole separation. Finally, total systems for unassisted solar fuel production are demonstrated.

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

A Hybrid Co Quaterpyridine Complex/Carbon Nanotube Catalytic Material for CO2 Reduction in Water.

PubMed

Wang, Min; Chen, Lingjing; Lau, Tai-Chu; Robert, Marc

2018-06-25

Associating a metal-based catalyst to a carbon-based nanomaterial is a promising approach for the production of solar fuels from CO 2 . Upon appending a Co II quaterpyridine complex [Co(qpy)] 2+ at the surface of multi-walled carbon nanotubes, CO 2 conversion into CO was realized in water at pH 7.3 with 100 % catalytic selectivity and 100 % Faradaic efficiency, at low catalyst loading and reduced overpotential. A current density of 0.94 mA cm -2 was reached at -0.35 V vs. RHE (240 mV overpotential), and 9.3 mA cm -2 could be sustained for hours at only 340 mV overpotential with excellent catalyst stability (89 095 catalytic cycles in 4.5 h), while 19.9 mA cm -2 was met at 440 mV overpotential. Such a hybrid material combines the high selectivity of a homogeneous molecular catalyst to the robustness of a heterogeneous material. Catalytic performances compare well with those of noble-metal-based nano-electrocatalysts and atomically dispersed metal atoms in carbon matrices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafine Pt Nanoparticles and Amorphous Nickel Supported on 3D Mesoporous Carbon Derived from Cu-Metal-Organic Framework for Efficient Methanol Oxidation and Nitrophenol Reduction.

PubMed

Wu, Xue-Qian; Zhao, Jun; Wu, Ya-Pan; Dong, Wen-Wen; Li, Dong-Sheng; Li, Jian-Rong; Zhang, Qichun

2018-04-18

The development of novel strategy to produce new porous carbon materials is extremely important because these materials have wide applications in energy storage/conversion, mixture separation, and catalysis. Herein, for the first time, a novel 3D carbon substrate with hierarchical pores derived from commercially available Cu-MOF (metal-organic framework) (HKUST-1) through carbonization and chemical etching has been employed as the catalysts' support. Highly dispersed Pt nanoparticles and amorphous nickel were evenly dispersed on the surface or embedded within carbon matrix. The corresponding optimal composite catalyst exhibits a high mass-specific peak current of 1195 mA mg -1 Pt and excellent poison resistance capacity ( I F / I B = 1.58) for methanol oxidation compared to commercial Pt/C (20%). Moreover, both composite catalysts manifest outstanding properties in the reduction of nitrophenol and demonstrate diverse selectivities for 2/3/4-nitrophenol, which can be attributed to different integrated forms between active species and carbon matrix. This attractive route offers broad prospects for the usage of a large number of available MOFs in fabricating functional carbon materials as well as highly active carbon-based electrocatalysts and heterogeneous organic catalysts.

Development of a Stochastically-driven, Forward Predictive Performance Model for PEMFCs

NASA Astrophysics Data System (ADS)

Harvey, David Benjamin Paul

A one-dimensional multi-scale coupled, transient, and mechanistic performance model for a PEMFC membrane electrode assembly has been developed. The model explicitly includes each of the 5 layers within a membrane electrode assembly and solves for the transport of charge, heat, mass, species, dissolved water, and liquid water. Key features of the model include the use of a multi-step implementation of the HOR reaction on the anode, agglomerate catalyst sub-models for both the anode and cathode catalyst layers, a unique approach that links the composition of the catalyst layer to key properties within the agglomerate model and the implementation of a stochastic input-based approach for component material properties. The model employs a new methodology for validation using statistically varying input parameters and statistically-based experimental performance data; this model represents the first stochastic input driven unit cell performance model. The stochastic input driven performance model was used to identify optimal ionomer content within the cathode catalyst layer, demonstrate the role of material variation in potential low performing MEA materials, provide explanation for the performance of low-Pt loaded MEAs, and investigate the validity of transient-sweep experimental diagnostic methods.

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.

One-step chemical vapor deposition synthesis and supercapacitor performance of nitrogen-doped porous carbon–carbon nanotube hybrids

PubMed Central

Bulusheva, Lyubov G; Fedorovskaya, Ekaterina O; Shubin, Yury V; Plyusnin, Pavel E; Lonchambon, Pierre; Senkovskiy, Boris V; Ismagilov, Zinfer R; Flahaut, Emmanuel; Okotrub, Alexander V

2017-01-01

Novel nitrogen-doped carbon hybrid materials consisting of multiwalled nanotubes and porous graphitic layers have been produced by chemical vapor deposition over magnesium-oxide-supported metal catalysts. CNx nanotubes were grown on Co/Mo, Ni/Mo, or Fe/Mo alloy nanoparticles, and MgO grains served as a template for the porous carbon. The simultaneous formation of morphologically different carbon structures was due to the slow activation of catalysts for the nanotube growth in a carbon-containing gas environment. An analysis of the obtained products by means of transmission electron microscopy, thermogravimetry and X-ray photoelectron spectroscopy methods revealed that the catalyst's composition influences the nanotube/porous carbon ratio and concentration of incorporated nitrogen. The hybrid materials were tested as electrodes in a 1M H2SO4 electrolyte and the best performance was found for a nitrogen-enriched material produced using the Fe/Mo catalyst. From the electrochemical impedance spectroscopy data, it was concluded that the nitrogen doping reduces the resistance at the carbon surface/electrolyte interface and the nanotubes permeating the porous carbon provide fast charge transport in the cell. PMID:29354339

Co- and defect-rich carbon nanofiber films as a highly efficient electrocatalyst for oxygen reduction

NASA Astrophysics Data System (ADS)

Kim, Il To; Song, Myeong Jun; Shin, Seoyoon; Shin, Moo Whan

2018-03-01

Many efforts are continuously devoted to developing high-efficiency, low-cost, and highly scalable oxygen reduction reaction (ORR) electrocatalysts to replace precious metal catalysts. Herein, we successfully synthesize Co- and defect-rich carbon nanofibers (CNFs) using an efficient heat treatment approach involving the pyrolysis of electrospun fibers at 370 °C under air. The heat treatment process produces Co-decorated CNFs with a high Co mass ratio, enriched pyridinic N, Co-pyridinic Nx clusters, and defect-rich carbon structures. The synergistic effects from composition and structural changes in the designed material increase the number of catalytically active sites for the ORR in an alkaline solution. The prepared Co- and defect-rich CNFs exhibit excellent ORR activities with a high ORR onset potential (0.954 V vs. RHE), a large reduction current density (4.426 mA cm-2 at 0.40 V), and a nearly four-electron pathway. The catalyst also exhibits a better long-term durability than commercial Pt/C catalysts. This study provides a novel hybrid material as an efficient ORR catalyst and important insight into the design strategy for CNF-based hybrid materials as electrochemical electrodes.

Shape Fixing via Salt Recrystallization: A Morphology-Controlled Approach To Convert Nanostructured Polymer to Carbon Nanomaterial as a Highly Active Catalyst for Oxygen Reduction Reaction.

PubMed

Ding, Wei; Li, Li; Xiong, Kun; Wang, Yao; Li, Wei; Nie, Yao; Chen, Siguo; Qi, Xueqiang; Wei, Zidong

2015-04-29

Herein, we report a "shape fixing via salt recrystallization" method to efficiently synthesize nitrogen-doped carbon material with a large number of active sites exposed to the three-phase zones, for use as an ORR catalyst. Self-assembled polyaniline with a 3D network structure was fixed and fully sealed inside NaCl via recrystallization of NaCl solution. During pyrolysis, the NaCl crystal functions as a fully sealed nanoreactor, which facilitates nitrogen incorporation and graphitization. The gasification in such a closed nanoreactor creates a large number of pores in the resultant samples. The 3D network structure, which is conducive to mass transport and high utilization of active sites, was found to have been accurately transferred to the final N-doped carbon materials, after dissolution of the NaCl. Use of the invented cathode catalyst in a proton exchange membrane fuel cell produces a peak power of 600 mW cm(-2), making this among the best nonprecious metal catalysts for the ORR reported so far. Furthermore, N-doped carbon materials with a nanotube or nanoshell morphology can be realized by the invented method.

The use of mixed pyrrhotite/pyrite catalysts for co-liquefaction of coal and waste rubber tires

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

Dadyburjor, D.B.; Zondlo, J.W.; Sharma, R.K.

1995-12-31

The overall objective of this research program is to determine the optimum processing conditions for tire/coal co-liquefaction. The catalysts used will be a ferric-sulfide-based materials, as well as promising catalysts from other consortium laboratories. The intent here is to achieve the maximum coal+tire conversion at the mildest conditions of temperature and pressure. Specific objectives include an investigation of the effects of time, temperature, pressure, catalyst and co-solvent on the conversion and product slate of the co-liquefaction. Accomplishments and conclusions are discussed.

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

PubMed

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

2018-05-21

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

Encapsulating Reactive Nanoparticles in Carbon Nanotubes Using Flame-Based Synthesis

DTIC Science & Technology

2008-12-22

Results from the Aerosol Catalyst Method using Ferrocene as Precursor Running the experiment using a rich premixed flame seeded with ferrocene allows...flames with ferrocene seeding. There is significant catalyst nanoparticle production, encased within carbon material, namely CNTs. Resonant Raman

Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

DOE PAGES

Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; ...

2016-05-19

This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g –1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

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

Choi, Jae -Soon; Zacher, Alan; Wang, Huamin

This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g –1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

Magnetic nanoparticles conjugated to chiral imidazolidinone as recoverable catalyst

NASA Astrophysics Data System (ADS)

Mondini, Sara; Puglisi, Alessandra; Benaglia, Maurizio; Ramella, Daniela; Drago, Carmelo; Ferretti, Anna M.; Ponti, Alessandro

2013-11-01

The immobilization of an ad hoc designed chiral imidazolidin-4-one onto iron oxide magnetic nanoparticles (MNPs) is described, to afford MNP-supported MacMillan's catalyst. Morphological and structural analysis of the materials, during preparation, use, and recycle, has been carried out by transmission electron microscopy. The supported catalyst was tested in the Diels-Alder reaction of cyclopentadiene with cinnamic aldehyde, affording the products in good yields and enantiomeric excesses up to 93 %, comparable to those observed with the non-supported catalyst. Recovery of the chiral catalyst has been successfully performed by simply applying an external magnet to achieve a perfect separation of the MNPs from the reaction product. The recycle of the catalytic system has been also investigated. Noteworthy, this immobilized MacMillan's catalyst proved to be able to efficiently promote the reaction in pure water.

Hydrodeoxygenation of Pyrolysis Bio-Oil Over Ni Impregnated Mesoporous Materials.

PubMed

Lee, In-Gu; Lee, Heejin; Kang, Bo Sung; Kim, Young-Min; Kim, Sang Chai; Jung, Sang-Chul; Ko, Chang Hyun; Park, Young-Kwon

2018-02-01

The catalytic hydrodeoxygenation (HDO) of bio-oil over Ni-supported mesoporous materials was performed using a high pressure autoclave reactor. The actual pyrolysis oil of cork oak wood was used as a sample, and Ni/Al-SBA-15 and Ni/Al-MSU-F were used as catalysts. In addition, supercritical ethanol was added as solvent. Both Ni-supported mesoporous catalysts showed efficient HDO reaction ability. A higher heating value and pH of bio-oil were achieved by the HDO reaction over both catalysts and upgraded bio-oil had a lower viscosity. Compared to Ni/Al-MSU-F, Ni/Al- SBA-15 produced more upgraded bio-oil with a lower oxygen content and higher heating value via a catalytic HDO process.

Catalyst for hydrotreating carbonaceous liquids

DOEpatents

Berg, Lloyd; McCandless, Frank P.; Ramer, Ronald J.

1982-01-01

A catalyst for denitrogenating and desulfurating carbonaceous liquid such as solvent refined coal includes catalytic metal oxides impregnated within a porous base of mostly alumina with relatively large pore diameters, surface area and pore volume. The base material includes pore volumes of 0.7-0.85 ml/g, surface areas of 200-350 m.sup.2 /g and pore diameters of 85-200 Angstroms. The catalytic metals impregnated into these base materials include the oxides of Group VI metals, molybdenum and tungsten, and the oxides of Group VIII metals, nickel and cobalt, in various combinations. These catalysts and bases in combination have effectively promoted the removal of chemically combined sulfur and nitrogen within a continuous flowing mixture of carbonaceous liquid and hydrogen gas.

Controlling interfacial properties in supported metal oxide catalysts through metal–organic framework templating

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

Abney, Carter W.; Patterson, Jacob T.; Gilhula, James C.

Precise control over the chemical structure of hard-matter materials is a grand challenge of basic science and a prerequisite for the development of advanced catalyst systems. In this work we report the application of a sacrificial metal-organic framework (MOF) template for the synthesis of a porous supported metal oxide catalyst, demonstrating proof-of-concept for a highly generalizable approach to the preparation new catalyst materials. Application of 2,2’-bipyridine-5,5’-dicarboxylic acid as the organic strut in the Ce MOF precursor results in chelation of Cu 2+ and affords isolation of the metal oxide precursor. Following pyrolysis of the template, homogeneously dispersed CuO nanoparticles aremore » formed in the resulting porous CeO 2 support. By partially substituting non-chelating 1,1’-biphenyl-4,4’-dicarboxylic acid, the Cu 2+ loading and dispersion can be finely tuned, allowing precise control over the CuO/CeO 2 interface in the final catalyst system. Characterization by x-ray diffraction, x-ray absorption fine structure spectroscopy, and in situ IR spectroscopy/mass spectrometry confirm control over interface formation to be a function of template composition, constituting the first report of a MOF template being used to control interfacial properties in a supported metal oxide. Using CO oxidation as a model reaction, the system with the greatest number of interfaces possessed the lowest activation energy and better activity under differential conditions, but required higher temperature for catalytic onset and displayed inferior efficiency at 100 °C than systems with higher Cu-loading. This finding is attributable to greater CO adsorption in the more heavily-loaded systems, and indicates catalyst performance for these supported oxide systems to be a function of at least two parameters: size of adsorption site and extent of interface. In conclusion, optimization of catalyst materials thus requires precise control over synthesis parameters, such as is demonstrated by this MOF-templating method.« less

Promoting Ethylene Selectivity from CO2 Electroreduction on CuO Supported onto CO2 Capture Materials.

PubMed

Yang, Hui-Juan; Yang, Hong; Hong, Yu-Hao; Zhang, Peng-Yang; Wang, Tao; Chen, Li-Na; Zhang, Feng-Yang; Wu, Qi-Hui; Tian, Na; Zhou, Zhi-You; Sun, Shi-Gang

2018-03-09

Cu is a unique catalyst for CO 2 electroreduction, since it can catalyze CO 2 reduction to a series of hydrocarbons, alcohols, and carboxylic acids. Nevertheless, such Cu catalysts suffer from poor selectivity. High pressure of CO 2 is considered to facilitate the activity and selectivity of CO 2 reduction. Herein, a new strategy is presented for CO 2 reduction with improved C 2 H 4 selectivity on a Cu catalyst by using CO 2 capture materials as the support at ambient pressure. N-doped carbon (N x C) was synthesized through high-temperature carbonization of melamine and l-lysine. We observed that the CO 2 uptake capacity of N x C depends on both the microporous area and the content of pyridinic N species, which can be controlled by the carbonization temperature (600-800 °C). The as-prepared CuO/N x C catalysts exhibit a considerably higher C 2 H 4 faradaic efficiency (36 %) than CuO supported on XC-72 carbon black (19 %), or unsupported CuO (20 %). Moreover, there is a good linear relationship between the C 2 H 4 faradaic efficiency and CO 2 uptake capacity of the supports for CuO. The local high CO 2 concentration near Cu catalysts, created by CO 2 capture materials, was proposed to increase the coverage of CO intermediate, which is favorable for the coupling of two CO units in the formation of C 2 H 4 . This study demonstrates that pairing Cu catalysts with CO 2 capture supports is a promising approach for designing highly effective CO 2 reduction electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

IR-doped ruthenium oxide catalyst for oxygen evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

2012-01-01

A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

Surface properties of lead-free halide double perovskites: Possible visible-light photo-catalysts for water splitting

NASA Astrophysics Data System (ADS)

Volonakis, George; Giustino, Feliciano

2018-06-01

Halide double perovskites based on combinations of monovalent and trivalent cations have been proposed as promising lead-free alternatives to lead halide perovskites. Among the newly synthesized compounds Cs2BiAgCl6, Cs2BiAgBr6, Cs2SbAgCl6, and Cs2InAgCl6, some exhibit bandgaps in the visible range and all have low carrier effective masses; therefore, these materials constitute potential candidates for various opto-electronic applications. Here, we use first-principles calculations to investigate the electronic properties of the surfaces of these four compounds and determine, for the first time, their ionization potential and electron affinity. We find that the double perovskites Cs2BiAgCl6 and Cs2BiAgBr6 are potentially promising materials for photo-catalytic water splitting, while Cs2InAgCl6 and Cs2SbAgCl6 would require controlling their surface termination to obtain energy levels appropriate for water splitting. The energy of the halogen p orbitals is found to control the conduction band level; therefore, we propose that mixed halides could be used to fine-tune the electronic affinity.

Long-life high performance fuel cell program

NASA Technical Reports Server (NTRS)

Martin, R. E.

1985-01-01

A multihundred kilowatt Regenerative Fuel Cell for use in a space station is envisioned. Three 0.508 sq ft (471.9 cm) active area multicell stacks were assembled and endurance tested. The long term performance stability of the platinum on carbon catalyst configuration suitability of the lightweight graphite electrolyte reservoir plate, the stability of the free standing butyl bonded potassium titanate matrix structure, and the long life potential of a hybrid polysulfone cell edge frame construction were demonstrated. A 18,000 hour demonstration test of multicell stack to a continuous cyclical load profile was conducted. A total of 12,000 cycles was completed, confirming the ability of the alkaline fuel cell to operate to a load profile simulating Regenerative Fuel Cell operation. An orbiter production hydrogen recirculation pump employed in support of the cyclical load profile test completed 13,000 hours of maintenance free operation. Laboratory endurance tests demonstrated the suitability of the butyl bonded potassium matrix, perforated nickel foil electrode substrates, and carbon ribbed substrate anode for use in the alkaline fuel cell. Corrosion testing of materials at 250 F (121.1 C) in 42% wgt. potassium identified ceria, zirconia, strontium titanate, strontium zirconate and lithium cobaltate as candidate matrix materials.

Facile synthesis of sewage sludge-derived in-situ multi-doped nanoporous carbon material for electrocatalytic oxygen reduction

NASA Astrophysics Data System (ADS)

Yuan, Shi-Jie; Dai, Xiao-Hu

2016-06-01

Developing efficient, low-cost, and stable carbon-based catalysts for oxygen reduction reaction (ORR) to replace the expensive platinum-based electrocatalysts remains a major challenge that hamper the practical application of fuel cells. Here, we report that N, Fe, and S co-doped nanoporous carbon material, derived via a facile one-step pyrolysis of sewage sludge, the major byproduct of wastewater treatment, can serve as an effective electrocatalyst for ORR. Except for the comparable catalytic activity with commercial 20% Pt/C via a nearly four-electron transfer pathway in both alkaline and acid medium, the as-synthesized co-doped electrocatalyst also exhibits excellent methanol crossover resistance and outstanding long-term operation stability. The organic compounds in sewage sludge act as the carbon source and the in-situ N and S dopant in the fabrication, while the inorganic compounds serve as the in-built template and the in-situ Fe dopant. Our protocol demonstrates a new approach in the economic and eco-friendly benign reuse of sewage sludge, and also provides a straightforward route for synthesizing excellent carbon-based electrocatalysts as promising candidates for ORR directly from a type of waste/pollution.

Peculiar behavior of MWW materials in aldol condensation of furfural and acetone.

PubMed

Kikhtyanin, Oleg; Chlubná, Pavla; Jindrová, Tereza; Kubička, David

2014-07-21

MWW family of different structural types (MCM-22, MCM-49, MCM-56 and MCM-36) was used as catalysts for aldol condensation of furfural and acetone studied in a batch reactor at 100 °C, autogenous pressure and a reaction time of 0-4 h. To establish a relation between physico-chemical and catalytic properties of microporous materials, the samples were characterized by XRD, SEM, N2 adsorption, FTIR and TGA. It was found that the acidic solids possessed appreciable activity in the reaction and resulted in the formation of products of aldehyde-ketone interaction. Surprisingly, MCM-22 and MCM-49, i.e. three-dimensional materials containing internal supercages, exhibited higher activity than two MCM-36 catalysts with two-dimensional character having larger accessible external surface area due to expansion of the interlayer space by swelling and pillaring treatments. Moreover, all MWW family catalysts gave higher conversion than the large-pore zeolite BEA. Nevertheless, furfural conversion decreased rapidly for all the studied materials due to coke formation. Unexpectedly, the deactivation was found to be more severe for MCM-36 catalysts than for MCM-22 and MCM-49, which was attributed to the reaction taking place also in supercages that are protected by 10-ring channels from severe coking. In contrast the cups located on the external surface were coked rapidly.

A new hydrocarbon material based on seabuckthorn ( Hippophae rhamnoides) sawdust: A structural promoter of cobalt catalyst for Fischer-Tropsch synthesis

NASA Astrophysics Data System (ADS)

Pankina, G. V.; Chernavskii, P. A.; Lunin, V. V.

2016-09-01

Aspects of the physicochemical properties of a hydrocarbon material based on seabuckthorn ( Hippophae rhamnoides) sawdust are studied. The use of a hydrocarbon material based on sea buckthorn sawdust as a structural promoter of Co/CHip cobalt catalyst in the reaction of CO hydrogenation is shown to require an additional cycling stage in the mode of reduction and oxidation. The resulting mean size of the Co particles is found to be 18-19 nm and is considered acceptable for the synthesis of C5+ liquid hydrocarbons.

Evaluation of malt spent rootlets biochar as catalyst for biodiesel production.

NASA Astrophysics Data System (ADS)

Pantiora, Dimitra

2014-05-01

Evaluation of malt spent rootlets biochar as catalyst for biodiesel production. Dimitra Pantiora1, Hrissi K. Karapanagioti1, Ioannis D. Manariotis2, Alexis Lycourghiotis1, Christos Kordulis1,3 (1) University of Patras, Department of Chemistry, GR 26500, Patras, Greece, (2) University of Patras, Department of Civil Engineering, Patras, Greece, (3) Institute of Chemical Engineering Science (FORTH/ ICE-HT), Stadiou Str., Platani, GR 26500, Patras, Greece Biodiesel is an attractive renewable fuel, environmentally friendly, and can readily be synthesized from the triglycerides found in animal fats and vegetable oils. It can be used in existing engines. Biodiesel consists of fatty acid alkyl esters. Conversion of triglycerides to biodiesel fuel is commonly achieved through a series of transesterification reactions involving the reaction of an alkoxy group of an ester (i.e., mono-, di-, or triglyceride) with that of a small alcohol (usually methanol). This reaction is traditionally catalyzed by homogeneous catalysts, such as bases or mineral acids. Basic catalysts have been proved to be much more active than acidic ones. However, due to environmental (waste water) and economic concerns (catalyst separation and product and by-product cleaning), heterogeneous catalysts are much more desirable. In the present study we have evaluated the use of biochar, produced from malt spent rootlets, as a potential basic catalyst, for transesterification of triglycerides using triacetin as a probe molecule. The biochar used in this study was prepared by heating malt spent rootlets in an oxygen-limited environment. It is a carbon rich material, containing 66% C, 22% O, 0.45% Mg, 0.86% Si, 5.7% K, 1.5% Cl, 0.61% Ca, and 2.4% P. Aqueous suspension of this material equilibrates at pH= 10. This is probably due to high K content. Furthermore, it exhibits high specific surface area (SSA= 183 m2g-1). The above described characteristics make this material very promising catalyst for transesterification reactions. Indeed, the corresponding catalytic tests showed that 100% transesterification of triacetin can be achieved into 0.5 hour. This activity was maintained at least for 4 successive catalytic runs.

Carbon nanotube-like materials in the exhaust from a diesel engine using gas oil/ethanol mixing fuel with catalysts and sulfur.

PubMed

Suzuki, Shunsuke; Mori, Shinsuke

2017-08-01

Particulate matter from a diesel engine, including soot and carbon nanomaterials, was collected on a sampling holder and the structure of the materials was studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). As a result of employing gas oil/ethanol mixing fuel with sulfur and ferrocene/molybdenum as catalyst sources, formation of carbon nanotubes (CNT)-like materials in addition to soot was observed in the exhaust gas from a diesel engine. It was revealed that CNT-like materials were included among soot in our system only when the following three conditions were satisfied simultaneously: high ethanol fraction in fuel, high sulfur loading, and presence of catalyst sources in fuel. This study confirmed that if at least one of these three conditions was not satisfied, CNT-like materials were not observed in the exhaust from a diesel engine. These experimental results shown in this work provide insights into understanding CNT-like material formation mechanism in a diesel engine. Recent papers reported that carbon nanotube-like materials were included in the exhaust gas from engines, but conditions for carbon nanotube-like material formation have not been well studied. This work provides the required conditions for carbon nanotube-like material growth in a diesel engine, and this will be helpful for understanding the carbon nanotube-like material formation mechanism and taking countermeasures to preventing carbon nanotube-like material formation in a diesel engine.

Electronically conducting hybrid material as high performance catalyst support for electrocatalytic application

NASA Astrophysics Data System (ADS)

Rajesh, B.; Ravindranathan Thampi, K.; Bonard, J.-M.; Mathieu, H. J.; Xanthopoulos, N.; Viswanathan, B.

The electronically conducting hybrid material based on transition metal oxide and conducting polymer has been used as the catalyst support for Pt nanoparticles. The Pt nanoparticles loaded hybrid organic (polyaniline)-inorganic (vanadium pentoxide) composite has been used as the electrode material for methanol oxidation, a reaction of importance for the development of direct methanol fuel cells (DMFC). The hybrid material exhibited excellent electrochemical and thermal stability in comparison to the physical mixture of conducting polymer and transition metal oxide. The Pt nanoparticles loaded hybrid material exhibited high electrocatalytic activity and stability for methanol oxidation in comparison to the Pt supported on the Vulcan XC 72R carbon support. The higher activity and stability is attributed to the better CO tolerance of the composite material.

Atomic level study of water-gas shift catalysts via transmission electron microscopy and x-ray spectroscopy

NASA Astrophysics Data System (ADS)

Akatay, Mehmed Cem

Water-gas shift (WGS), CO + H2O ⇆ CO2 + H2 (DeltaH° = -41 kJ mol -1), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2O3 catalysts are employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism. In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy and X-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors of the catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization of nanostructures. Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety of nanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo2C is explored by forming Mo 2C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.

Anion permselective membrane

NASA Technical Reports Server (NTRS)

Hodgdon, R. B.; Waite, W. A.

1982-01-01

The synthesis and fabrication of polymeric anion permselective membranes for redox systems are discussed. Variations of the prime candidate anion membrane formulation to achieve better resistance and/or lower permeability were explored. Processing parameters were evaluated to lower cost and fabricate larger sizes. The processing techniques to produce more membranes per batch were successfully integrated with the fabrication of larger membranes. Membranes of about 107 cm x 51 cm were made in excellent yield. Several measurements were made on the larger sample membranes. Among the data developed were water transport and transference numbers for these prime candidate membranes at 20 C. Other work done on this system included characterization of a number of specimens of candidate membranes which had been returned after service lives of up to sixteen months. Work with new polymer constituents, with new N.P.'s, catalysts and backing fabrics is discussed. Some work was also done to evaluate other proportions of the ingredients of the prime candidate system. The adoption of a flow selectivity test at elevated temperature was explored.

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

Barroo, Cedric; Janvelyan, Nare; Zugic, Branko

To improve the understanding of catalytic processes, the surface structure and composition of the active materials need to be determined before and after reaction. Morphological changes may occur under reaction conditions and can dramatically influence the reactivity and/or selectivity of a catalyst. Goldbased catalysts with different architectures are currently being developed for selective oxidation reactions at low temperatures. Specifically, nanoporous Au (npAu) with a composition of Au 97-Ag 3 is obtained by dealloying a Ag 70-Au 30 bulk alloy. Recent studies highlight the efficiency of npAu catalysts for methanol oxidation using ozone to activate the catalysts before methanol oxidation. Inmore » this paper, we studied the morphological and compositional changes occurring at the surface of Au-based catalysts in certain conditions.« less

Catalysts and method

DOEpatents

Taylor, Charles E.; Noceti, Richard P.

1991-01-01

An improved catlayst and method for the oxyhydrochlorination of methane is disclosed. The catalyst includes a pyrogenic porous support on which is layered as active material, cobalt chloride in major proportion, and minor proportions of an alkali metal chloride and of a rare earth chloride. On contact of the catalyst with a gas flow of methane, HC1 and oxygen, more than 60% of the methane is converted and of that converted more than 40% occurs as monochloromethane. Advantageously, the monochloromethane can be used to produce gasoline boiling range hydrocarbons with the recycle of HCl for further reaction. This catalyst is also of value for the production of formic acid as are analogous catalysts with lead, silver or nickel chlorides substituted for the cobalt chloride.

Perovskites in catalysis and electrocatalysis

NASA Astrophysics Data System (ADS)

Hwang, Jonathan; Rao, Reshma R.; Giordano, Livia; Katayama, Yu; Yu, Yang; Shao-Horn, Yang

2017-11-01

Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.

Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

NASA Astrophysics Data System (ADS)

Li, Yuanchao; Nguyen, Trung Van

2018-04-01

Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.

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 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.

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

PubMed

Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong

2013-06-01

Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.

Durability of template-free Fe-N-C foams for electrochemical oxygen reduction in alkaline solution

NASA Astrophysics Data System (ADS)

Mufundirwa, Albert; Harrington, George F.; Smid, Břetislav; Cunning, Benjamin V.; Sasaki, Kazunari; Lyth, Stephen M.

2018-01-01

Due to the high cost and limited availability of platinum, the development of non-platinum-group metals (non-PGM) catalysts is of paramount importance. A promising alternative to Pt are Fe-N-C-based materials. Here we present the synthesis, characterization and electrochemistry of a template-free nitrogen-doped carbon foam, impregnated with iron. This low-cost and gram-scale method results in materials with micron-scale pore size and large surface area (1600 m2g-1). When applied as an oxygen reduction reaction (ORR) electrocatalyst in alkaline solution, the Fe-N-C foams display extremely high initial activity, slightly out-performing commercially available non-PGM catalysts (NCP-2000, Pajarito Powder). The load-cycle durability in alkaline solution is investigated, and the performance steadily degrades over 60,000 potential cycles, whilst the commercial catalyst is remarkably stable. The post-operation catalyst microstructure is elucidated by transmission electron microscopy (TEM), to provide insight into the degradation processes. The resulting images suggest that potential cycling leads to leaching of atomically dispersed Fe-N2/4 sites in all the catalysts, whereas encapsulated iron nanoparticles are protected.

Microgravity Effects on Chronoamperometric Ammonia Oxidation Reaction at Platinum Nanoparticles on Modified Mesoporous Carbon Supports

NASA Astrophysics Data System (ADS)

Poventud-Estrada, Carlos M.; Acevedo, Raúl; Morales, Camila; Betancourt, Luis; Diaz, Diana C.; Rodriguez, Manuel A.; Larios, Eduardo; José-Yacaman, Miguel; Nicolau, Eduardo; Flynn, Michael; Cabrera, Carlos R.

2017-10-01

The effect of microgravity on the electrochemical oxidation of ammonia at platinum nanoparticles supported on modified mesoporous carbons (MPC) with three different pore diameters (64, 100, and 137 Å) was studied via the chronoamperometric technique in a half-cell. The catalysts were prepared by a H2 reductive process of PtCl6^{4-} in presence of the mesoporous carbon support materials. A microgravity environment was obtained with an average gravity of less than 0.02 g created aboard an airplane performing parabolic maneuvers. Results show the chronoamperommetry of the ammonia oxidation reaction in 1.0 M NH4OH at 0.60 V vs. RHE under microgravity conditions. The current density, in all three catalysts, decreased while in microgravity conditions when compared to ground based experiments. Under microgravity, all three catalysts yielded a decrease in ammonia oxidation reaction current density between 25 to 63% versus terrestrial experimental results, in time scales between 1 and 15 s. The Pt catalyst prepared with mesoporous carbon of 137 Å porous showed the smallest changes, between 25 to 48%. Nanostructuring catalyst materials have an effect on the level of current density decrease under microgravity conditions.

Zinc sulfide liquefaction catalyst

DOEpatents

Garg, Diwakar

1984-01-01

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

The degradation of wheat straw lignin

NASA Astrophysics Data System (ADS)

Liang, Jiaqi

2017-03-01

Lignin is a kind of formed by polymerization of aromatic alcohol, prices are lower and sources of renewable resources. Using lignin as raw material, through the push to resolve together preparation phenolic high value-added fine chemicals alkanes and aromatic hydrocarbons, such as the high grade biofuels, can partly replace fossil fuels as raw material to the production process, biomass resources is an important part of the comprehensive utilization of effective components. In lignin push solve clustering method, catalytic hydrogenolysis can directly to the lignin into liquid fuels, low oxygen content in the use of biofuels shows great potential. In this paper, through the optimization of the reaction time, reaction temperature, catalyst type and solvent type, dosage of catalyst, etc factors, determines the alcoholysis - hydrogen solution two-step degradation of lignin, the optimal process conditions: lignin alcoholysis under 50% methanol and NaOH catalyst in the solution, the lignin in methanol solution and 50% hydrogen solution under the Pd/C catalyst. In this process, the degradation of lignin yield can reach 42%.

Catalysts for the hydrodenitrogenation of organic materials and process for the preparation of the catalysts

DOEpatents

Laine, R.M.; Hirschon, A.S.; Wilson, R.B. Jr.

1987-12-29

A process is described for the preparation of a multimetallic catalyst for the hydrodenitrogenation of an organic feedstock, which process comprises: (a) forming a precatalyst itself comprising: (1) a first metal compound selected from compounds of nickel, cobalt or mixtures thereof; (2) a second metal compound selected from compounds of chromium, molybdenum, tungsten, or mixtures thereof; and (3) an inorganic support; (b) heating the precatalyst of step (a) with a source of sulfide in a first non-oxidizing gas at a temperature and for a time effective to presulfide the precatalyst; (c) adding in a second non-oxidizing gas to the sulfided precatalyst of step (b) an organometallic transition metal moiety selected from compounds of iridium, rhodium, iron, ruthenium, tungsten or mixtures thereof for a time and at a temperature effective to chemically combine the metal components; and (d) optionally heating the chemically combined catalyst of step (b) in vacuum at a temperature and for a time effective to remove residual volatile organic materials. 12 figs.

Redox-Active Nitroxide Radical Polymers: From Green Catalysts to Energy Storage Devices

NASA Astrophysics Data System (ADS)

Waskitoaji, Wihatmoko; Suga, Takeo; Nishide, Hiroyuki

2009-09-01

Robust but redox-active radical polymers bearing 2, 2, 6, 6-tetramethylpiperidin-N-oxy (TEMPO) were investigated as a metal-free, green mediator/catalyst for the oxidation of alcohol derivatives, and as a new electrode-active and charge-storage material. The TEMPO-mediated oxidation of the primary alcohol group of the natural cellulose improved the water-dispersivity of cellulose, and the polymer-supported catalysts or redox resins allow facile removal of catalysts from products by simple filtration. Other radical molecule (e.g. galvinoxyl) was also used as a mediator, which is coupled with the molecular oxygen. A reversible one-electron redox reaction of TEMPO allowed its application as an electrode-active material featuring high cyclability (>500 cycles), relatively high battery electrode capacity (100-135 mAh/g), and fast electrode kinetics, leading to the high power rate capability of the battery. The radical polymer-based electrodes also provided good processability and shape flexibility, which promised the paper-like and wearable energy-storage devices.

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.

Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals

PubMed Central

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-01-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)–(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized. PMID:27877800

Development of Metal-impregnated Single Walled Carbon Nanotubes for Toxic Gas Contaminant Control in Advanced Life Support Systems

NASA Technical Reports Server (NTRS)

Pisharody, Suresh A.; Fisher, John W.; Wignarajah, K.

2002-01-01

The success of physico-chemical waste processing and resource recovery technologies for life support application depends partly on the ability of gas clean-up systems to efficiently remove trace contaminants generated during the process with minimal use of expendables. Carbon nanotubes promise superior performance over conventional approaches to gas clean-up due to their ability to direct the selective uptake of gaseous species based on their controlled pore size, high surface area, ordered chemical structure that allows functionalization and their effectiveness also as catalyst support materials for toxic gas conversion. We present results and findings from a preliminary study on the effectiveness of metal impregnated single walled nanotubes as catalyst/catalyst support materials for toxic gas contaminate control. The study included the purification of single walled nanotubes, the catalyst impregnation of the purified nanotubes, the experimental characterization of the surface properties of purified single walled nanotubes and the characterization of physisorption and chemisorption of uptake molecules.

Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals.

PubMed

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-06-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)-(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized.

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

Gewirth, Andrew A.; Kenis, Paul J.; Nuzzo, Ralph G.

In this research, we prosecuted a comprehensive plan of research directed at developing new catalysts and new understandings relevant to the operation of low temperature hydrogen-oxygen fuel cells. The focal point of this work was one centered on the Oxygen Reduction Reaction (ORR), the electrochemical process that most fundamentally limits the technological utility of these environmentally benign energy conversion devices. Over the period of grant support, we developed new ORR catalysts, based on Cu dimers and multimers. In this area, we developed substantial new insight into design rules required to establish better ORR materials, inspired by the three-Cu active sitemore » in laccase which has the highest ORR onset potential of any material known. We also developed new methods of characterization for the ORR on conventional (metal-based) catalysts. Finally, we developed a new platform to study the rate of proton transfer relevant to proton coupled electron transfer (PCET) reactions, of which the ORR is an exemplar. Other aspects of work involved theory and prototype catalyst testing.« less

An initial analysis of short- and medium-range correlations potential non-Pt catalysts in CoNx

NASA Astrophysics Data System (ADS)

Peterson, Joe

2009-10-01

A potential show stopper for the development of fuel cells for the commercial automotive industry is the design of low-cost catalysts. The best catalysts are based on platinum, which is a rare and expensive noble metal. Our group has been involved in the characterization of potential materials for non-Pt catalysts. In this presentation, I will present some preliminary neutron scattering data from a nanocrystalline powder sample of CoNx. It is apparent that the diffraction data cannot be analyzed with standard Riedveld refinement, and we have to invoke pair distribution function (PDF) analysis. The PDF provides insight into short-range correlations, as it measures the probabilities of short- and mid-range interatomic distances in a material. The analysis reveals a strong incoherent scattering response, which is indicative of the presence of hydrogen in the sample. After correcting for the incoherent scattering, one obtains the normalized scattering function S(Q), whose Fourier transform yields the PDF.

An initial analysis of short- and medium-range correlations potential non-Pt catalysts in CoNx

NASA Astrophysics Data System (ADS)

Peterson, Joe

2010-03-01

A potential show stopper for the development of fuel cells for the commercial automotive industry is the design of low-cost catalysts. The best catalysts are based on platinum, which is a rare and expensive noble metal. Our group has been involved in the characterization of potential materials for non-Pt catalysts. In this presentation, I will present some preliminary neutron scattering data from a nanocrystalline powder sample of CoNx. It is apparent that the diffraction data cannot be analyzed with standard Riedveld refinement, and we have to invoke pair distribution function (PDF) analysis. The PDF provides insight into short-range correlations, as it measures the probabilities of short- and mid-range interatomic distances in a material. The analysis reveals a strong incoherent scattering response, which is indicative of the presence of hydrogen in the sample. After correcting for the incoherent scattering, one obtains the normalized scattering function S(Q), whose Fourier transform yields the PDF.

Mesopore quality determines the lifetime of hierarchically structured zeolite catalysts

NASA Astrophysics Data System (ADS)

Milina, Maria; Mitchell, Sharon; Crivelli, Paolo; Cooke, David; Pérez-Ramírez, Javier

2014-05-01

Deactivation due to coking limits the lifetime of zeolite catalysts in the production of chemicals and fuels. Superior performance can be achieved through hierarchically structuring the zeolite porosity, yet no relation has been established between the mesopore architecture and the catalyst lifetime. Here we introduce a top-down demetallation strategy to locate mesopores in different regions of MFI-type crystals with identical bulk porous and acidic properties. In contrast, well-established bottom-up strategies as carbon templating and seed silanization fail to yield materials with matching characteristics. Advanced characterization tools capable of accurately discriminating the mesopore size, distribution and connectivity are applied to corroborate the concept of mesopore quality. Positron annihilation lifetime spectroscopy proves powerful to quantify the global connectivity of the intracrystalline pore network, which, as demonstrated in the conversions of methanol or of propanal to hydrocarbons, is closely linked to the lifetime of zeolite catalysts. The findings emphasize the need to aptly tailor hierarchical materials for maximal catalytic advantage.

Hexagonal mesoporous silica modified with copper phthalocyanine as a photocatalyst for pesticide 2,4-dichlorophenoxiacetic acid degradation.

PubMed

DeOliveira, Edimar; Neri, Cláudio R; Ribeiro, Anderson O; Garcia, Vinícius S; Costa, Leonardo L; Moura, Aline O; Prado, Alexandre G S; Serra, Osvaldo A; Iamamoto, Yassuko

2008-07-01

A new mesoporous catalyst was prepared by the reaction between 3-aminopropyltrimethoxisylane and Cu(II)-hexadecafluorophthalocyanine, followed by co-condensation of tetraethylorthosilicate around a micelle formed by n-dodecylamine. The surfactant was removed from the pores by continuous extraction with ethanol, giving the Si-CuF16Pc catalyst. This catalyst was characterized by SEM, FTIR, TGA, 29Si NMR, N2 adsorption and X-ray diffraction. SEM images confirmed that the catalyst material is formed by nanoaggregates with a diameter of 100 nm. N2 adsorption isotherms showed that Si-CuF16Pc has a surface area of approximately 200 m2 g(-1) and a porous diameter of 7.7 nm, characterizing the mesoporosity of this product. This novel material shows an excellent photocatalytic activity, degrading almost 90% of 2,4-dichlorophenoxyacetic acid (2,4-D) up to 30 min, while only approximately 40% of photodegradation was obtained in its absence.

Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals

NASA Astrophysics Data System (ADS)

Hara, Michikazu; Nakajima, Kiyotaka; Kamata, Keigo

2015-06-01

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)-(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized.

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

PubMed

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

2017-12-01

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

Designing supported palladium-on-gold bimetallic nano-catalysts for controlled hydrogenation of acetylene in large excess of ethylene

NASA Astrophysics Data System (ADS)

Malla, Pavani

Ethylene is used as a starting point for many chemical intermediates in the petrochemical industry. It is predominantly produced through steam cracking of higher hydrocarbons (ethane, propane, butane, naphtha, and gas oil). During the cracking process, a small amount of acetylene is produced as a side product. However, acetylene must be removed since it acts as a poison for ethylene polymerization catalysts at even ppm concentrations (>5 ppm). Thus, the selective hydrogenation of acetylene to ethylene is an important process for the purification of ethylene. Conventional, low weight loading Pd catalysts are used for this selective reaction in high concentration ethylene streams. Gold was initially considered to be catalytically inactive for a long time. This changed when gold was seen in the context of the nanometric scale, which has indeed shown it to have excellent catalytic activity as a homogeneous or a heterogeneous catalyst. Gold is proved to have high selectivity to ethylene but poor at conversion. Bimetallic Au and Pd catalysts have exhibited superior activity as compared to Pd particles in semi-hydrogenation. Hydrogenation of acetylene was tested using this bimetallic combination. The Pd-on-Au bimetallic catalyst structure provides a new synthesis approach in improving the catalytic properties of monometallic Pd materials. TiO 2 as a support material and 0.05%Pd loading on 1%Au on titania support and used different treatment methods like washing plasma and reduction between the two metal loadings and was observed under 2:1 ratio. In my study there were two set of catalysts which were prepared by a modified incipient wetness impregnation technique. Out of all the reaction condition the catalyst which was reduced after impregnating gold and then impregnating palladium which was further treated in non-thermal hydrogen plasma and then pretreated in hydrogen till 250°C for 1 hour produced the best activity of 76% yield at 225°C. Stability tests were conducted on the catalysts which were followed by TGA analysis to analyze the coke formation on the catalyst in a period of time at a particular temperature. The catalysts were characterized by the hydrogen chemisorption and atomic absorption spectroscopy.

Oxygen reduction reaction on highly-durable Pt/nanographene fuel cell catalyst synthesized employing in-liquid plasma

NASA Astrophysics Data System (ADS)

Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Kano, Hiroyuki; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

2016-09-01

We recently have established ultrahigh-speed synthesis method of nanographene materials employing in-liquid plasma, and reported high durability of Pt/nanographene composites as a fuel cell catalyst. Crystallinity and domain size of nanographene materials were essential to their durability. However, their mechanism is not clarified yet. In this study, we investigated the oxygen reduction reaction using three-types of nanographene materials with different crystallinity and domain sizes, which were synthesized using ethanol, 1-propanol and 1-butanol, respectively. According to our previous studies, the nanographene material synthesized using the lower molecular weight alcohol has the higher crystallinity and larger domain size. Pt nanoparticles were supported on the nanographene surfaces by reducing 8 wt% H2PtCl6 diluted with H2O. Oxygen reduction current densities at a potential of 0.2 V vs. RHE were 5.43, 5.19 and 3.69 mA/cm2 for the samples synthesized using ethanol, 1-propanol and 1-butanol, respectively. This means that the higher crystallinity nanographene showed the larger oxygen reduction current density. The controls of crystallinity and domain size of nanographene materials are essential to not only their durability but also highly efficiency as catalyst electrodes.

Catalysts and methods for converting carbonaceous materials to fuels

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

Hensley, Jesse; Ruddy, Daniel A.; Schaidle, Joshua A.

Catalysts and processes designed to convert DME and/or methanol and hydrogen (H.sub.2) to desirable liquid fuels are described. These catalysts produce the fuels efficiently and with a high selectivity and yield, and reduce the formation of aromatic hydrocarbons by incorporating H.sub.2 into the products. Also described are process methods to further upgrade these fuels to higher molecular weight liquid fuel mixtures, which have physical properties comparable with current commercially used liquid fuels.

Phenol hydroxylation on Al-Fe modified-bentonite: Effect of Fe loading, temperature and reaction time

NASA Astrophysics Data System (ADS)

Widi, R. K.; Budhyantoro, A.; Christianto, A.

2017-11-01

The present work reflects the study of the phenol hydroxylation reactions to synthesize hydroquinone and catechol on Al-Fe modified-bentonite. This study started with synthesizes the catalyst material based on the modified bentonite. Natural bentonite from Pacitan, Indonesia was intercalated with Cetyl-TetramethylammoniumBromida (CTMA-Br) followed by pillarization using Alumina. The pillared bentonite was then impregnated with Fe solution (0.01 M, 0.05 M, and 0.1 M). The solid material obtained was calcined at 723 K for 4 hours. All the materials were characterized using BET N2 adsorption. Their catalytic activity and selectivity were studied for phenol hydroxylation using H2O2 (30%). The reaction conditions of this reaction were as follows: ratio of phenol/H2O2 = 1:1 (molar ratio), concentration of phenol = 1 M and ratio of catalyst/phenol was 1:10. Reaction temperatures were varied at 333, 343 and 353 K. The reaction time was also varied at 3, 4 and 5 hours. The result shows that the materials have potential catalyst activity.

Reliability of Scores Obtained from Self-, Peer-, and Teacher-Assessments on Teaching Materials Prepared by Teacher Candidates

ERIC Educational Resources Information Center

Nalbantoglu Yilmaz, Funda

2017-01-01

This study aims to determine the reliability of scores obtained from self-, peer-, and teacher-assessments in terms of teaching materials prepared by teacher candidates. The study group of this research constitutes 56 teacher candidates. In the scope of research, teacher candidates were asked to develop teaching material related to their study.…

Fe2 PO5 -Encapsulated Reverse Energetic ZnO/Fe2 O3 Heterojunction Nanowire for Enhanced Photoelectrochemical Oxidation of Water.

PubMed

Qin, Dong-Dong; He, Cai-Hua; Li, Yang; Trammel, Antonio C; Gu, Jing; Chen, Jing; Yan, Yong; Shan, Duo-Liang; Wang, Qiu-Hong; Quan, Jing-Jing; Tao, Chun-Lan; Lu, Xiao-Quan

2017-07-10

Zinc oxide is regarded as a promising candidate for application in photoelectrochemical water oxidation due to its higher electron mobility. However, its instability under alkaline conditions limits its application in a practical setting. Herein, we demonstrate an easily achieved wet-chemical route to chemically stabilize ZnO nanowires (NWs) by protecting them with a thin layer Fe 2 O 3 shell. This shell, in which the thickness can be tuned by varying reaction times, forms an intact interface with ZnO NWs, thus protecting ZnO from corrosion in a basic solution. The reverse energetic heterojunction nanowires are subsequently activated by introducing an amorphous iron phosphate, which substantially suppressed surface recombination as a passivation layer and improved photoelectrochemical performance as a potential catalyst. Compared with pure ZnO NWs (0.4 mA cm -2 ), a maximal photocurrent of 1.0 mA cm -2 is achieved with ZnO/Fe 2 O 3 core-shell NWs and 2.3 mA cm -2 was achieved for the PH 3 -treated NWs at 1.23 V versus RHE. The PH 3 low-temperature treatment creates a dual function, passivation and catalyst layer (Fe 2 PO 5 ), examined by X-ray photoelectron spectroscopy, TEM, photoelectrochemical characterization, and impedance measurements. Such a nano-composition design offers great promise to improve the overall performance of the photoanode material. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perovskite-type catalytic materials for environmental applications.

PubMed

Labhasetwar, Nitin; Saravanan, Govindachetty; Kumar Megarajan, Suresh; Manwar, Nilesh; Khobragade, Rohini; Doggali, Pradeep; Grasset, Fabien

2015-06-01

Perovskites are mixed-metal oxides that are attracting much scientific and application interest owing to their low price, adaptability, and thermal stability, which often depend on bulk and surface characteristics. These materials have been extensively explored for their catalytic, electrical, magnetic, and optical properties. They are promising candidates for the photocatalytic splitting of water and have also been extensively studied for environmental catalysis applications. Oxygen and cation non-stoichiometry can be tailored in a large number of perovskite compositions to achieve the desired catalytic activity, including multifunctional catalytic properties. Despite the extensive uses, the commercial success for this class of perovskite-based catalytic materials has not been achieved for vehicle exhaust emission control or for many other environmental applications. With recent advances in synthesis techniques, including the preparation of supported perovskites, and increasing understanding of promoted substitute perovskite-type materials, there is a growing interest in applied studies of perovskite-type catalytic materials. We have studied a number of perovskites based on Co, Mn, Ru, and Fe and their substituted compositions for their catalytic activity in terms of diesel soot oxidation, three-way catalysis, N 2 O decomposition, low-temperature CO oxidation, oxidation of volatile organic compounds, etc. The enhanced catalytic activity of these materials is attributed mainly to their altered redox properties, the promotional effect of co-ions, and the increased exposure of catalytically active transition metals in certain preparations. The recent lowering of sulfur content in fuel and concerns over the cost and availability of precious metals are responsible for renewed interest in perovskite-type catalysts for environmental applications.

Perovskite-type catalytic materials for environmental applications

PubMed Central

Labhasetwar, Nitin; Saravanan, Govindachetty; Kumar Megarajan, Suresh; Manwar, Nilesh; Khobragade, Rohini; Doggali, Pradeep; Grasset, Fabien

2015-01-01

Perovskites are mixed-metal oxides that are attracting much scientific and application interest owing to their low price, adaptability, and thermal stability, which often depend on bulk and surface characteristics. These materials have been extensively explored for their catalytic, electrical, magnetic, and optical properties. They are promising candidates for the photocatalytic splitting of water and have also been extensively studied for environmental catalysis applications. Oxygen and cation non-stoichiometry can be tailored in a large number of perovskite compositions to achieve the desired catalytic activity, including multifunctional catalytic properties. Despite the extensive uses, the commercial success for this class of perovskite-based catalytic materials has not been achieved for vehicle exhaust emission control or for many other environmental applications. With recent advances in synthesis techniques, including the preparation of supported perovskites, and increasing understanding of promoted substitute perovskite-type materials, there is a growing interest in applied studies of perovskite-type catalytic materials. We have studied a number of perovskites based on Co, Mn, Ru, and Fe and their substituted compositions for their catalytic activity in terms of diesel soot oxidation, three-way catalysis, N2O decomposition, low-temperature CO oxidation, oxidation of volatile organic compounds, etc. The enhanced catalytic activity of these materials is attributed mainly to their altered redox properties, the promotional effect of co-ions, and the increased exposure of catalytically active transition metals in certain preparations. The recent lowering of sulfur content in fuel and concerns over the cost and availability of precious metals are responsible for renewed interest in perovskite-type catalysts for environmental applications. PMID:27877813

An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911

L-Lactide Ring-Opening Polymerization with Tris(acetylacetonate)Titanium(IV) for Renewable Material.

PubMed

Kim, Da Hee; Yoo, Ji Yun; Ko, Young Soo

2016-05-01

A new Ti-type of catalyst for L-lactide polymerization was synthesized by reaction of titanium(IV) isopropoxide (TTIP) with acetylacetone (AA). Moreover, PLA was prepared by the bulk ring-opening polymerization using synthesized Ti catalyst. Polymerization behaviors were examined depending on monomer/catalyst molar ratio, polymerization temperature and time. The structure of synthesized catalysts was verified with FT-IR and 1H NMR and the properties of poly(L-lactide) (PLLA) were examined by GPC, DSC and FT-IR. There existed about 30 minutes of induction time at the monomer/catalyst molar ratio of 300. The molecular weight (MW) increased as monomer/catalyst molar ratio increased. The MW increased almost linearly as polymerization progressed. Increasing polymerization temperature increased the molecular weight of PLLA as well as monomer/catalyst molar ratio. The melting point (T(m)) of polymers was in the range of 142 to 167 degrees C. Lower T(m) was expected to be resulted from relatively lower molecular weight.

Catalytic conversion of xylose and corn stalk into furfural over carbon solid acid catalyst in γ-valerolactone.

PubMed

Zhang, Tingwei; Li, Wenzhi; Xu, Zhiping; Liu, Qiyu; Ma, Qiaozhi; Jameel, Hasan; Chang, Hou-min; Ma, Longlong

2016-06-01

A novel carbon solid acid catalyst was synthesized by the sulfonation of carbonaceous material which was prepared by carbonization of sucrose using 4-BDS as a sulfonating agent. TEM, N2 adsorption-desorption, elemental analysis, XPS and FT-IR were used to characterize the catalyst. Then, the catalyst was applied for the conversion of xylose and corn stalk into furfural in GVL. The influence of the reaction time, temperature and dosage of catalyst on xylose dehydration were also investigated. The Brønsted acid catalyst exhibited high activity in the dehydration of xylose, with a high furfural yield of 78.5% at 170°C in 30min. What's more, a 60.6% furfural yield from corn stalk was achieved in 100min at 200°C. The recyclability of the sulfonated carbon catalyst was perfect, and it could be reused for 5times without the loss of furfural yields. Copyright © 2016 Elsevier Ltd. All rights reserved.

Conversion of glycerol to polyglycerol over waste duck-bones as a catalyst in solvent free etherification process

NASA Astrophysics Data System (ADS)

Ayoub, Muhammad; Sufian, Suriati; Mekuria Hailegiorgis, Sintayehu; Ullah, Sami; Uemura, Yoshimitsu

2017-08-01

The alkaline catalyst derived from the duck-bones was used for conversion of glycerol to polyglycerol via solvent free etherification process. The physicochemical properties of prepared materials were duck-bones were systematically investigated as a catalyst by latest techniques of Thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface properties. TGA showed different trends of duck-bones decomposition from room temperature to 1000C. XRD pattern showed a clear and sharp peaks of a crystalline phase of CaO. The activity of the catalysts was in line with the basic amount of the strong base sites, surface area, and crystalline phase in the catalysts. The prepared catalyst derived from duck-bones provided high activity (99 %) for glycerol conversion and around 68 % yield for polyglycerol production. These ample wastes of duck-bones have good potential to be used as polyglycerol production catalysts due to have high quantity of Ca compare to other types of bones like cow, chicken and fish bones.

Generation of reactive oxygen species and oxidative stress in Escherichia coli and Staphylococcus aureus by a novel semiconductor catalyst

NASA Astrophysics Data System (ADS)

Chow, K. L.; Mak, N. K.; Wong, M. H.; Zhou, X. F.; Liang, Y.

2011-03-01

The objective of this study was to investigate antimicrobial mechanisms of a new catalytic material (charge transfer auto oxidation-reduction type catalyst, CT catalyst) that may have great potential for application in water/wastewater treatment. Generation of reactive oxygen species (ROS) in bacteria-free solution, induction of ROS and oxidative damage in bacteria (including E. coli and S. aureus) were examined for the CT catalyst. The results showed that significantly higher ( p < 0.05, via t-test) amount of hydroxyl radicals was generated by the CT catalyst compared with the control, particularly after 6 h of contact time that more than twice of the amount of the control was produced. The generation of ROS in the bacteria was greater under higher pH and temperature levels, which closely related with the oxidative damage in cells. The results indicated that CT catalyst induced oxidative damage in the bacteria might serve as an important mechanism interpreting the anti-microbial function of the CT catalyst.

Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

DOEpatents

Sachtler, W.M.H.; Huang, Y.Y.

1998-07-28

Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

DOEpatents

Sachtler, Wolfgang M. H.; Huang, Yin-Yan

1998-01-01

Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics.

Hydrodesulfurization reactions of atmospheric gas oil over CoMo/alumina-aluminum borate catalysts

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

Chiuping Li; Jungchung Wu; Yuwen Chen

1993-08-01

A precipitation technique at constant pH value was used to prepare a series of alumina-aluminum borates (AABs) with various Al/B atomic ratios. These materials were used as the supports of Co-Mo catalysts. Hydrodesulfurization (HDS) of Kuwait atmospheric gas (AGO) oil was carried out over these presulfided catalysts in a bench-scale trickle bed reactor at 400 psi and 340 C. All CoMo/AAB catalysts are much more active than the conventional CoMo/Al[sub 2]O[sub 3] catalyst on HDS reactions. A correlation exists between the acidity and the HDS activity of the catalysts. The high activities of the CoMo/AAB catalysts can be rationalized onmore » the presence of boron. On one hand, it can increase the metal dispersions and hydrogenation capabilities. On the other hand, it can enhance the acidities and cracking abilities of the catalysts. The desulfurization data can be fitted with a pseudo-second-order rate equation. The activation energy for desulfurization is found to be 26 kcal/mol.« less

Metal catalysts for steam reforming of tar derived from the gasification of lignocellulosic biomass.

PubMed

Li, Dalin; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

2015-02-01

Biomass gasification is one of the most important technologies for the conversion of biomass to electricity, fuels, and chemicals. The main obstacle preventing the commercial application of this technology is the presence of tar in the product gas. Catalytic reforming of tar appears a promising approach to remove tar and supported metal catalysts are among the most effective catalysts. Nevertheless, improvement of catalytic performances including activity, stability, resistance to coke deposition and aggregation of metal particles, as well as catalyst regenerability is greatly needed. This review focuses on the design and catalysis of supported metal catalysts for the removal of tar in the gasification of biomass. The recent development of metal catalysts including Rh, Ni, Co, and their alloys for steam reforming of biomass tar and tar model compounds is introduced. The role of metal species, support materials, promoters, and their interfaces is described. Copyright © 2014 Elsevier Ltd. All rights reserved.

Takovite-aluminosilicate-Cr materials prepared by adsorption of Cr3+ from industrial effluents as catalysts for hydrocarbon oxidation reactions.

PubMed

Ciuffi, Katia J; de Faria, Emerson H; Marçal, Liziane; Rocha, Lucas A; Calefi, Paulo S; Nassar, Eduardo J; Pepe, Iuri; da Rocha, Zênis N; Vicente, Miguel A; Trujillano, Raquel; Gil, Antonio; Korili, Sophia A

2012-05-01

The catalytic efficiency of takovite-aluminosilicate-chromium catalysts obtained by adsorption of Cr(3+) ions from aqueous solutions by a takovite-aluminosilicate nanocomposite adsorbent is reported. The adsorbent was synthesized by the coprecipitation method. The catalytic activity of the final Cr-catalysts depended on the amount of adsorbed chromium. (Z)-cyclooctene conversion up to 90% with total selectivity for the epoxide was achieved when the oxidation was carried out with hydrogen peroxide, at room temperature. After five consecutive runs, the catalysts maintained high activity, although after the sixth reuse, the epoxide yields strongly decreased to 35%. The catalysts were also efficient for cyclohexane oxidation, reaching up to 18% conversion, with cyclohexanone/cyclohexanol selectivity close to 1.2. On the whole, their use as catalysts gives a very interesting application for the solids obtained by adsorption of a contaminant cation such as Cr(3+).

Comparison of real waste (MSW and MPW) pyrolysis in batch reactor over different catalysts. Part II: contaminants, char and pyrolysis oil properties.

PubMed

Miskolczi, Norbert; Ateş, Funda; Borsodi, Nikolett

2013-09-01

Pyrolysis of real wastes (MPW and MSW) has been investigated at 500°C, 550°C and 600°C using Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3 as catalysts. The viscosity of pyrolysis oils could be decreased by the using of catalysts, especially by β-zeolite and MoO3. Both carbon frame and double bound isomerization was found in case of thermo-catalytic pyrolysis. Char morphology and texture analysis showed more coke deposits on the catalyst surface using MSW raw material. Pyrolysis oils had K, S, P Cl, Ca, Zn, Fe, Cr, Br and Sb as contaminants; and the concentrations of K, S, P, Cl and Br could be decreased by the using of catalysts. Copyright © 2013 Elsevier Ltd. All rights reserved.

Process for magnetic beneficiating petroleum cracking catalyst

DOEpatents

Doctor, R.D.

1993-10-05

A process is described for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded. 1 figures.

Process for magnetic beneficiating petroleum cracking catalyst

DOEpatents

Doctor, Richard D.

1993-01-01

A process for beneficiating a particulate zeolite petroleum cracking catalyst having metal values in excess of 1000 ppm nickel equivalents. The particulate catalyst is passed through a magnetic field in the range of from about 2 Tesla to about 5 Tesla generated by a superconducting quadrupole open-gradient magnetic system for a time sufficient to effect separation of said catalyst into a plurality of zones having different nickel equivalent concentrations. A first zone has nickel equivalents of about 6,000 ppm and greater, a second zone has nickel equivalents in the range of from about 2000 ppm to about 6000 ppm, and a third zone has nickel equivalents of about 2000 ppm and less. The zones of catalyst are separated and the second zone material is recycled to a fluidized bed of zeolite petroleum cracking catalyst. The low nickel equivalent zone is treated while the high nickel equivalent zone is discarded.

Graphene supported heterogeneous catalysts for Li-O2 batteries

NASA Astrophysics Data System (ADS)

Alaf, M.; Tocoglu, U.; Kartal, M.; Akbulut, H.

2016-09-01

In this study production and characterization of free-standing and flexible (i) graphene, (ii) α-MnO2/graphene, (iii) Pt/graphene (iv) α-MnO2/Pt/graphene composite cathodes for Li-air batteries were reported. Graphene supported heterogeneous catalysts were produced by a facile method. In order to prevent aggregation of graphene sheets and increase not only interlayer distance but also surface area, a trace amount multi-wall carbon nano tube (MWCNT) was introduced to the composite structure. The obtained composite catalysts were characterized by SEM, X-ray diffraction, N2 adsorption-desorption analyze and Raman spectroscopy. The electrochemical characterization tests including galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) measurement of catalyst were carried out by using an ECC-Air test cell. These highly active graphene supported heterogeneous composite catalysts provide competitive properties relative to other catalyst materials for Li-air batteries.

Pulse electrodeposition of CoFe thin films covered with layered double hydroxides as a fast route to prepare enhanced catalysts for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Sakita, Alan M. P.; Noce, Rodrigo Della; Vallés, Elisa; Benedetti, Assis V.

2018-03-01

A novel, ultra-fast, and one-step method for obtaining an effective catalyst for oxygen evolution reaction is proposed. The procedure consists in direct electrodeposition, in a free-nitrate bath, of CoFe alloy films covered with layered double hydroxides (LDH), by potentiostatic mode, in continuous or pulsed regime. The catalyst is directly formed on glassy carbon substrates. The best-prepared catalyst material reveals a mixed morphology with granular and dendritic CoFe alloy covered with a sponge of CoFe-LDH containing a Cl interlayer. An overpotential of η10 mA = 286 mV, with a Tafel slope of 48 mV dec-1, is obtained for the OER which displays the enhanced properties of the catalyst. These improved results demonstrate the competitiveness and efficacy of our proposal for the production of OER catalysts.

Facile approach to prepare Pt decorated SWNT/graphene hybrid catalytic ink

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

Mayavan, Sundar, E-mail: sundarmayavan@cecri.res.in; Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, Daejeon, 305-701; Mandalam, Aditya

Highlights: • Pt NPs were in situ synthesized onto CNT–graphene support in aqueous solution. • The as-prepared material was used directly as a catalyst ink without further treatment. • Catalyst ink is active toward methanol oxidation. • This approach realizes both scalable and greener production of hybrid catalysts. - Abstract: Platinum nanoparticles were in situ synthesized onto hybrid support involving graphene and single walled carbon nanotube in aqueous solution. We investigate the reduction of graphene oxide, and platinum nanoparticle functionalization on hybrid support by X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The as-preparedmore » platinum on hybrid support was used directly as a catalyst ink without further treatment and is active toward methanol oxidation. This work realizes both scalable and greener production of highly efficient hybrid catalysts, and would be valuable for practical applications of graphene based fuel cell catalysts.« less

Recent Progress on Transition Metal Catalyst Separation and Recycling in ATRP.

PubMed

Ding, Mingqiang; Jiang, Xiaowu; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2015-10-01

Atom transfer radical polymerization (ATRP) is a versatile and robust tool to synthesize a wide spectrum of monomers with various designable structures. However, it usually needs large amounts of transition metal as the catalyst to mediate the equilibrium between the dormant and propagating species. Unfortunately, the catalyst residue may contaminate or color the resultant polymers, which limits its application, especially in biomedical and electronic materials. How to efficiently and economically remove or reduce the catalyst residue from its products is a challenging and encouraging task. Herein, recent advances in catalyst separation and recycling are highlighted with a focus on (1) highly active ppm level transition metal or metal free catalyzed ATRP; (2) post-purification method; (3) various soluble, insoluble, immobilized/soluble, and reversible supported catalyst systems; and (4) liquid-liquid biphasic catalyzed systems, especially thermo-regulated catalysis systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activity Tests of Macro-Meso Porous Catalysts over Metal Foam Plate for Steam Reforming of Bio-Ethanol.

PubMed

Park, No-Kuk; Jeong, Yong Han; Kang, Misook; Lee, Tae Jin

2018-09-01

The catalytic activity of a macro-mesoporous catalyst coated on a metal foam plate in the reforming of bio-ethanol to synthesis gas was investigated. The catalysts were prepared by coating a support with a noble metal and transition metal. The catalytic activity for the production of synthetic gas by the reforming of bio-ethanol was compared according to the support material, reaction temperature, and steam/carbon ratio. The catalysts coated on the metal foams were prepared using a template method, in which macro-pores and meso-pores were formed by mixing polymer beads. In particular, the thermodynamic equilibrium composition of bio-ethanol reforming with the reaction temperature and steam/carbon ratio to produce synthetic gas was examined using the HSC (Enthalpy-Entropy-Heat capacity) chemistry program in this study. The composition of hydrogen and carbon monoxide in the reformate gas produced by steam reforming over the Rh/Ni-Ce-Zr/Al2O3-based pellet type catalysts and metal foam catalysts that had been coated with the Rh/Al-Ce-Zr-based catalysts was investigated by experimental activity tests. The activity of the metal foam catalyst was higher than that of the pellet type catalyst.

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

Lercher, Johannes

PNNL’s catalysis research is serving as a catalyst for changing how our nation will secure a strong, clean energy future. Senior Physical Chemist Johannes Lercher leads an award-winning team that is developing catalysts that efficiently make fuels from alternate feedstocks, such as biomass, and can store electrical energy in chemical bonds. The researchers are also creating catalysts that can increase vehicle fuel efficiency, while simultaneously cutting emissions. About 80 percent of all man-made materials — from plastics to pharmaceuticals — are made using catalysts. Through PNNL’s Institute for Integrated Catalysis, Johannes and colleagues study how to speed the catalysis reactionmore » process for manufacturers, which ultimately cuts costs and production time.« less

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.

Ship-in-a-bottle catalysts

DOEpatents

Haw, James F.; Song, Weiguo

2006-07-18

In accordance with the present invention there is provided a novel catalyst system in which the catalytic structure is tailormade at the nanometer scale using the invention's novel ship-in-a-bottle synthesis techniques. The invention describes modified forms of solid catalysts for use in heterogeneous catalysis that have a microporous structure defined by nanocages. Examples include zeolites, SAPOs, and analogous materials that have the controlled pore dimensions and hydrothermal stability required for many industrial processes. The invention provides for modification of these catalysts using reagents that are small enough to pass through the windows used to access the cages. The small reagents are then reacted to form larger molecules in the cages.

Growth of 2D Materials and Application in Electrochemical Energy Conversion

NASA Astrophysics Data System (ADS)

Ye, Gonglan

The discovery of graphene in 2004 has generated numerous interests among scientists for graphene's versatile potentials. The enthusiasm for graphene has recently been extended to other members of two-dimensional (2D) materials for applications in electronics, optoelectronics, and catalysis. Different from graphene, atomically-thin transition metal dichalcogenides (TMDs) have varied band gaps and would benefit for applications in the semiconductor industry. One of the promising applications of 2D TMDs is for 2D integrated circuits to replace current Si based electronics. In addition to electronic applications, 2D materials are also good candidates for electrochemical energy storage and conversion due to their large surface area and atomic thickness. This thesis mainly focuses on the synthesis of 2D materials and their application in energy conversion. Firstly, we focus on the synthesis of two-dimensional Tin Disulfide (SnS2). SnS2 is considered to be a novel material in 2D family. 2D SnS2 has a large band gap ( 2.8 eV) and high carrier mobility, which makes it a potential applicant for electronics. Monolayer SnS2 with large scale and high crystal quality was successfully synthesized by chemical vapor deposition (CVD), and its performance as a photodetector was examined. The next chapter demonstrated a generic method for growing millimeter-scale single crystals as well as wafer-scale thin films of TMDs. This generic method was obtained by studying the precursors' behavior and the flow dynamics during the CVD process of growing MoSe2, and was extended to other TMD layers such as millimeter-scale WSe2 single crystals. Understanding the growth processes of high quality large area monolayers of TMDs is crucial for further fundamental research as well as future development for scalable complex electronics. Besides the synthesis of 2D materials with high qualities, we further explored the relationship between defects and electrochemical properties. By directly observing and correlating the microscale structural changes of TMD monolayers such as MoS2 to the catalytic properties, we were able to provide insight on the fundamental catalytic mechanism for hydrogen evolution reaction. Finally, we used the 2D materials to build up 3D architectures, showing excellent performance in energy storage and conversion. For example, we used graphene as a conductive scaffold to support vanadium oxide (V 2O5) on nanoscale, and achieved high performances for supercapacitors. Also, we applied the Pt anchored N-doped graphene nanoribbons as the catalyst for methanol electro oxidation, and reported the best performance among Pt/Carbon-based catalysts.

In-Situ Sampling Analysis of a Jupiter Trojan Asteroid by High Resolution Mass Spectrometry in the Solar Power Sail Mission

NASA Astrophysics Data System (ADS)

Kebukawa, Y.; Aoki, J.; Ito, M.; Kawai, Y.; Okada, T.; Matsumoto, J.; Yano, H.; Yurimoto, H.; Terada, K.; Toyoda, M.; Yabuta, H.; Nakamura, R.; Cottin, H.; Grand, N.; Mori, O.

2017-12-01

The Solar Power Sail (SPS) mission is one of candidates for the upcoming strategic middle-class space exploration to demonstrate the first outer Solar System journey of Japan. The mission concept includes in-situ sampling analysis of the surface and subsurface (up to 1 m) materials of a Jupiter Trojan asteroid using high resolution mass spectrometry (HRMS). The candidates for the HRMS are multi-turn time-of-flight mass spectrometer (MULTUM) type and Cosmorbitrap type. We plan to analyze isotopic and elemental compositions of volatile materials from organic matter, hydrated minerals, and ice (if any), in order to understand origin and evolution of the Jupiter Trojan asteroids. It will provide insights into planet formation/migration theories, evolution and distribution of volatiles in the Solar System, and missing link between asteroids and comets on evolutional. The HRMS system allows to measure H, N, C, O isotopic compositions and elemental compositions of molecules prepared by various pre-MS procedures including stepwise heating up to 600ºC, gas chromatography (GC), and high-temperature pyrolysis with catalyst to decompose the samples into simple gaseous molecules (e.g., H2, CO, and N2) for isotopic ratio analysis. The required mass resolution should be at least 30,000 for analyzing isotopic ratios for simple gaseous molecules. For elemental compositions, mass accuracy of 10 ppm is required to determine elemental compositions for molecules with m/z up to 300 (as well as compound specific isotopic compositions for smaller molecules). Our planned analytical sequences consist of three runs for both surface and subsurface samples. In addition, `sniff mode' which simply introduces environmental gaseous molecules into a HRMS will be done by the system.

Synthesis and Characterization of Biodegradable Polyurethane for Hypopharyngeal Tissue Engineering

PubMed Central

Shen, Zhisen; Lu, Dakai; Li, Qun; Zhang, Zongyong

2015-01-01

Biodegradable crosslinked polyurethane (cPU) was synthesized using polyethylene glycol (PEG), L-lactide (L-LA), and hexamethylene diisocyanate (HDI), with iron acetylacetonate (Fe(acac)3) as the catalyst and PEG as the extender. Chemical components of the obtained polymers were characterized by FTIR spectroscopy, 1H NMR spectra, and Gel Permeation Chromatography (GPC). The thermodynamic properties, mechanical behaviors, surface hydrophilicity, degradability, and cytotoxicity were tested via differential scanning calorimetry (DSC), tensile tests, contact angle measurements, and cell culture. The results show that the synthesized cPU possessed good flexibility with quite low glass transition temperature (T g, −22°C) and good wettability. Water uptake measured as high as 229.7 ± 18.7%. These properties make cPU a good candidate material for engineering soft tissues such as the hypopharynx. In vitro and in vivo tests showed that cPU has the ability to support the growth of human hypopharyngeal fibroblasts and angiogenesis was observed around cPU after it was implanted subcutaneously in SD rats. PMID:25839041

Biotemplated synthesis of PZT nanowires.

PubMed

Cung, Kellye; Han, Booyeon J; Nguyen, Thanh D; Mao, Sheng; Yeh, Yao-Wen; Xu, Shiyou; Naik, Rajesh R; Poirier, Gerald; Yao, Nan; Purohit, Prashant K; McAlpine, Michael C

2013-01-01

Piezoelectric nanowires are an important class of smart materials for next-generation applications including energy harvesting, robotic actuation, and bioMEMS. Lead zirconate titanate (PZT), in particular, has attracted significant attention, owing to its superior electromechanical conversion performance. Yet, the ability to synthesize crystalline PZT nanowires with well-controlled properties remains a challenge. Applications of common nanosynthesis methods to PZT are hampered by issues such as slow kinetics, lack of suitable catalysts, and harsh reaction conditions. Here we report a versatile biomimetic method, in which biotemplates are used to define PZT nanostructures, allowing for rational control over composition and crystallinity. Specifically, stoichiometric PZT nanowires were synthesized using both polysaccharide (alginate) and bacteriophage templates. The wires possessed measured piezoelectric constants of up to 132 pm/V after poling, among the highest reported for PZT nanomaterials. Further, integrated devices can generate up to 0.820 μW/cm(2) of power. These results suggest that biotemplated piezoelectric nanowires are attractive candidates for stimuli-responsive nanosensors, adaptive nanoactuators, and nanoscale energy harvesters.

Synthesis and characterization of biodegradable polyurethane for hypopharyngeal tissue engineering.

PubMed

Shen, Zhisen; Lu, Dakai; Li, Qun; Zhang, Zongyong; Zhu, Yabin

2015-01-01

Biodegradable crosslinked polyurethane (cPU) was synthesized using polyethylene glycol (PEG), L-lactide (L-LA), and hexamethylene diisocyanate (HDI), with iron acetylacetonate (Fe(acac)3) as the catalyst and PEG as the extender. Chemical components of the obtained polymers were characterized by FTIR spectroscopy, (1)H NMR spectra, and Gel Permeation Chromatography (GPC). The thermodynamic properties, mechanical behaviors, surface hydrophilicity, degradability, and cytotoxicity were tested via differential scanning calorimetry (DSC), tensile tests, contact angle measurements, and cell culture. The results show that the synthesized cPU possessed good flexibility with quite low glass transition temperature (T g , -22°C) and good wettability. Water uptake measured as high as 229.7 ± 18.7%. These properties make cPU a good candidate material for engineering soft tissues such as the hypopharynx. In vitro and in vivo tests showed that cPU has the ability to support the growth of human hypopharyngeal fibroblasts and angiogenesis was observed around cPU after it was implanted subcutaneously in SD rats.

Geomaterials: their application to environmental remediation

PubMed Central

Yamada, Hirohisa; Tamura, Kenji; Watanabe, Yujiro; Iyi, Nobuo; Morimoto, Kazuya

2011-01-01

Geomaterials are materials inspired by geological systems originating from the billion years long history of the Earth. This article reviews three important classes of geomaterials. The first one is smectites—layered silicates with a cation-exchange capacity. Smectites are useful for removing pollutants and as intercalation compounds, catalysts and polymer nanocomposites. The second class is layered double hydroxides (LDHs). They have an anion-exchange capacity and are used as catalysts, catalyst precursors, sorbents and scavengers for halogens. The third class of geomaterials is zeolites—microporous materials with a cation-exchange capacity which are used for removing harmful cations. Zeolite composites with LDHs can absorb ammonium and phosphate ions in rivers and lakes, whereas zeolite/apatite composites can immobilize the radioactive iodine. These geomaterials are essential for environmental remediation. PMID:27877455

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

Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

Recently, carbonaceous materials were proved to be effective catalysts for hazardous waste decomposition in supercritical water. Gasification of the carbonaceous catalyst itself is also expected, however, under supercritical conditions. Thus, it is essential to determine the gasification rate of the carbonaceous materials during this process to determine the active lifetime of the catalysts. For this purpose, the gasification characteristics of granular coconut shell activated carbon in supercritical water alone (600-650{degrees}C, 25.5-34.5 MPa) were investigated. The gasification rate at subatmospheric pressure agreed well with the gasification rate at supercritical conditions, indicating the same reaction mechanism. Methane generation under these conditions ismore » via pyrolysis, and thus is not affected by the water pressure. An iodine number increase of 25% was observed as a result of the supercritical water gasification.« less

Refractory Ceramic Foams for Novel Applications

NASA Technical Reports Server (NTRS)

Stackpoole, M.

2008-01-01

Workers at NASA Ames Research center are endeavoring to develop durable, oxidation-resistant, foam thermal protection systems (TPSs) that would be suitable for covering large exterior spacecraft surfaces, would have low to moderate densities, and would have temperature capabilities comparable to those of carbon-based TPSs [reusable at 3,000 F (.1,650 C)] with application of suitable coatings. These foams may also be useful for repairing TPSs while in orbit. Moreover, on Earth as well as in outer space, these foams might be useful as catalyst supports and filters. Preceramic polymers are obvious candidates for use in making the foams in question. The use of these polymers offers advantages over processing routes followed in making conventional ceramics. Among the advantages are the ability to plastically form parts, the ability to form pyrolized ceramic materials at lower temperatures, and the ability to form high-purity microstructures having properties that can be tailored to satisfy requirements. Heretofore, preceramic polymers have been used mostly in the production of such low-dimensional products as fibers because the loss of volatiles during pyrolysis of the polymers leads to porosity and large shrinkage (in excess of 30 percent). In addition, efforts to form bulk structures from preceramic polymers have resulted in severe cracking during pyrolysis. However, because the foams in question would consist of networks of thin struts (in contradistinction to nonporous dense solids), these foams are ideal candidates for processing along a preceramic-polymer route.

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.

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

None

During this time period, at WVU, we tried several methods to eliminate problems related to condensation of heavier products when 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 (TPR) spectra for C-supported Mo-based catalysts. We have completed the kinetic study for the sulfided Co-K-MoS /C catalyst. We have compared the results of methanol synthesis 2 using the membrane reactor with those using a simple plug-flow reactor. At UCC, the complete characterization of selected catalystsmore » has been completed. The results suggest that catalyst pretreatment under different reducing conditions yield different surface compositions and thus different catalytic reactivities.« less

Method for removing soot from exhaust gases

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

Suib, Steven L.; Dharmarathna, D. A. Saminda; Pahalagedara, Lakshitha R.

A method for oxidizing soot from diesel exhaust gas from a diesel engine. The method involves providing a diesel particulate filter for receiving the diesel exhaust gas; coating a catalyst composition on the diesel particulate filter; and contacting the soot from the diesel exhaust gas with the catalyst coated diesel particulate filter at a temperature sufficient to oxidize the soot to carbon dioxide. The catalyst composition is a doped or undoped manganese oxide octahedral molecular sieve (OMS-2) material. A diesel exhaust gas treatment system that includes a diesel particulate filter for receiving diesel exhaust gas from a diesel engine andmore » collecting soot; and a catalyst composition coated on the diesel particulate filter. The catalyst composition is a doped or undoped manganese oxide octahedral molecular sieve (OMS-2).« less

Hydrogen storage material and related processes

DOEpatents

Soloveichik, Grigorii Lev [Latham, NY; Andrus, Matthew John [Cape Canaveral, FL

2012-06-05

Disclosed herein is a composition comprising a complex hydride and a borohydride catalyst wherein the borohydride catalyst comprises a BH.sub.4 group, and a group IV metal, a group V metal, or a combination of a group IV and a group V metal. Also disclosed herein are methods of making the composition.

Hydrogen storage material and related processes

DOEpatents

Soloveichik; Grigorii Lev , Andrus; Matthew John

2010-07-13

Disclosed herein is a composition comprising a complex hydride and a borohydride catalyst wherein the borohydride catalyst comprises a BH.sub.4 group, and a group IV metal, a group V metal, or a combination of a group IV and a group V metal. Also disclosed herein are methods of making the composition.

Oxygen reduction reaction: A framework for success

DOE PAGES

Allendorf, Mark D.

2016-05-06

Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Here, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

76 FR 75950 - Hazardous Materials: Emergency Restriction/Prohibition Order

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-05

.... This Order is issued to Rainbow of Hope, Strategic Sciences, Inc., Realm Industries AKA Realm Catalyst... company of Rainbow of Hope. This explosion was also linked to TyLar. In light of these facts, PHMSA... of Hope, Strategic Sciences, Inc., Realm Industries (Realm Catalyst, Inc.), any other alias or...

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

Catalytic Synthesis of n-Butyl Oleate by Cerium Complex Doped Y/SBA-15 Composite Molecular Sieve

NASA Astrophysics Data System (ADS)

Shi, Chunwei; Bian, Xue; Wu, Yongfu; Cong, Yufeng; Pei, Mingyuan

2018-01-01

Cerium ion was successfully incorporated into Y/SBA-15 micro-mesoporous molecular sieves via the hydrothermal synthesis method to give a series of composite materials. The prepared materials were thoroughly characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and differential thermo gravimetric analysis (TG-DTG). The results showed that the prepared composite materials retained the highly ordered mesoporous two-dimensional hexagonal structure of SBA-15 and the octagonal structure of Y. The catalyst Ce-Y/SBA-15 was prepared and characterized, then the esterification of n-butanol and oleic acid was studied with bismuth phosphotungstate as a catalyst. Using this model reaction, the effects of Ce-HY/SBA-15, molar ratio of alcohol to oleic acid, amount of catalysts, reaction time and reaction temperature were investigated. The experimental results show that the optimal reaction conditions were: 1.8:1 molar ratio of alcohol to acid, 5 % catalyst amount (based on weight of oleic acid), 4 h reaction time and reflux conditions. Under these conditions, the yield of esterification was 90.6 %. The results suggest that the addition of Ce can effectively improve the catalytic properties of composite molecular sieves.

Synthesis Methods, Microscopy Characterization and Device Integration of Nanoscale Metal Oxide Semiconductors for Gas Sensing in Aerospace Applications

NASA Technical Reports Server (NTRS)

VanderWal, Randy L.; Berger, Gordon M.; Kulis, Michael J.; Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.

2009-01-01

A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. Both nanostructures possess a one-dimensional morphology. Different synthesis methods are used to produce these materials: thermal evaporation-condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed. Practical issues associated with harvesting, purification, and integration of these materials into sensing devices are detailed. For comparison to the nascent form, these sensing materials are surface coated with Pd and Pt nanoparticles. Gas sensing tests, with respect to H2, are conducted at ambient and elevated temperatures. Comparative normalized responses and time constants for the catalyst and noncatalyst systems provide a basis for identification of the superior metal-oxide nanostructure and catalyst combination. With temperature-dependent data, Arrhenius analyses are made to determine an activation energy for the catalyst-assisted systems.

Heteroatom-Doped Carbon Materials for Electrocatalysis.

PubMed

Asefa, Tewodros; Huang, Xiaoxi

2017-08-10

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

Nanocrystalline ZnO as a Visible Active Photocatalyst for the Degradation of Benzene-1,4-diol

NASA Astrophysics Data System (ADS)

Ramachandran, Saranya; Sivasamy, A.

We have synthesized nanocrystalline ZnO by a simple precipitation method. The prepared ZnO was found to be highly phase pure and nanocrystalline hexagonal wurtzite structure. UV-Visible-DRS spectroscopy showed the material to have bandgap energy of 3.22eV. HR-SEM image revealed the material to be made up of distinct hexagonal particles with a highly porous surface. AFM analysis was employed to confirm the high surface roughness and porosity of the material. The photocatalytic activity of the prepared ZnO was evaluated by the degradation of benzene-1,4-diol (hydroquinone), under visible light irradiation. Preliminary experiments showed the catalyst to be effective at neutral pH with an optimum catalyst dosage of 4g/L. Kinetic studies showed the degradation reaction to follow pseudo-first-order kinetics. In the presence of commonly used industrial electrolytes, the catalyst exhibited a decrease in efficiency. Reusability studies showed the catalytic efficiency of ZnO to diminish marginally after the third cycle of reuse.