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

Partridge Jr, William P.; Choi, Jae-Soon

By directly resolving spatial and temporal species distributions within operating honeycomb monolith catalysts, spatially resolved capillary inlet mass spectrometry (SpaciMS) provides a uniquely enabling perspective for advancing automotive catalysis. Specifically, the ability to follow the spatiotemporal evolution of reactions throughout the catalyst is a significant advantage over inlet-and-effluent-limited analysis. Intracatalyst resolution elucidates numerous catalyst details including the network and sequence of reactions, clarifying reaction pathways; the relative rates of different reactions and impacts of operating conditions and catalyst state; and reaction dynamics and intermediate species that exist only within the catalyst. These details provide a better understanding of how themore » catalyst functions and have basic and practical benefits; e.g., catalyst system design; strategies for on-road catalyst state assessment, control, and on-board diagnostics; and creating robust and accurate predictive catalyst models. Moreover, such spatiotemporally distributed data provide for critical model assessment, and identification of improvement opportunities that might not be apparent from effluent assessment; i.e., while an incorrectly formulated model may provide correct effluent predictions, one that can accurately predict the spatiotemporal evolution of reactions along the catalyst channels will be more robust, accurate, and reliable. In such ways, intracatalyst diagnostics comprehensively enable improved design and development tools, and faster and lower-cost development of more efficient and durable automotive catalyst systems. Beyond these direct contributions, SpaciMS has spawned and been applied to enable other analytical techniques for resolving transient distributed intracatalyst performance. This chapter focuses on SpaciMS applications and associated catalyst insights and improvements, with specific sections related to lean NOx traps, selective catalytic reduction catalysts, oxidation catalysts, and particulate filters. The objective is to promote broader use and development of intracatalyst analytical methods, and thereby expand the insights resulting from this detailed perspective for advancing automotive catalyst technologies.« less

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

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

PubMed

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

2016-11-05

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

Chiral catalysts immobilized on achiral polymers: effect of the polymer support on the performance of the catalyst.

PubMed

Altava, Belén; Burguete, M Isabel; García-Verdugo, Eduardo; Luis, Santiago V

2018-04-23

Positive effects of the polymeric support on the performance of supported chiral catalysts, in terms of activity, stability and selectivity-enantioselectivity, have been reported when the support is properly selected and optimized opening the way to the design of more efficient catalytic systems.

Conceptual process design and techno-economic assessment of ex situ catalytic fast pyrolysis of biomass: A fixed bed reactor implementation scenario for future feasibility

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

Dutta, Abhijit; Schaidle, Joshua A.; Humbird, David

Ex situ catalytic fast pyrolysis of biomass is a promising route for the production of fungible liquid biofuels. There is significant ongoing research on the design and development of catalysts for this process. However, there are a limited number of studies investigating process configurations and their effects on biorefinery economics. Herein we present a conceptual process design with techno-economic assessment; it includes the production of upgraded bio-oil via fixed bed ex situ catalytic fast pyrolysis followed by final hydroprocessing to hydrocarbon fuel blendstocks. This study builds upon previous work using fluidized bed systems, as detailed in a recent design reportmore » led by the National Renewable Energy Laboratory (NREL/TP-5100-62455); overall yields are assumed to be similar, and are based on enabling future feasibility. Assuming similar yields provides a basis for easy comparison and for studying the impacts of areas of focus in this study, namely, fixed bed reactor configurations and their catalyst development requirements, and the impacts of an inline hot gas filter. A comparison with the fluidized bed system shows that there is potential for higher capital costs and lower catalyst costs in the fixed bed system, leading to comparable overall costs. The key catalyst requirement is to enable the effective transformation of highly oxygenated biomass into hydrocarbons products with properties suitable for blending into current fuels. Potential catalyst materials are discussed, along with their suitability for deoxygenation, hydrogenation and C–C coupling chemistry. This chemistry is necessary during pyrolysis vapor upgrading for improved bio-oil quality, which enables efficient downstream hydroprocessing; C–C coupling helps increase the proportion of diesel/jet fuel range product. One potential benefit of fixed bed upgrading over fluidized bed upgrading is catalyst flexibility, providing greater control over chemistry and product composition. Since this study is based on future projections, the impacts of uncertainties in the underlying assumptions are quantified via sensitivity analysis. As a result, this analysis indicates that catalyst researchers should prioritize by: carbon efficiency > catalyst cost > catalyst lifetime, after initially testing for basic operational feasibility.« less

Conceptual process design and techno-economic assessment of ex situ catalytic fast pyrolysis of biomass: A fixed bed reactor implementation scenario for future feasibility

DOE PAGES

Dutta, Abhijit; Schaidle, Joshua A.; Humbird, David; ...

2015-10-06

Ex situ catalytic fast pyrolysis of biomass is a promising route for the production of fungible liquid biofuels. There is significant ongoing research on the design and development of catalysts for this process. However, there are a limited number of studies investigating process configurations and their effects on biorefinery economics. Herein we present a conceptual process design with techno-economic assessment; it includes the production of upgraded bio-oil via fixed bed ex situ catalytic fast pyrolysis followed by final hydroprocessing to hydrocarbon fuel blendstocks. This study builds upon previous work using fluidized bed systems, as detailed in a recent design reportmore » led by the National Renewable Energy Laboratory (NREL/TP-5100-62455); overall yields are assumed to be similar, and are based on enabling future feasibility. Assuming similar yields provides a basis for easy comparison and for studying the impacts of areas of focus in this study, namely, fixed bed reactor configurations and their catalyst development requirements, and the impacts of an inline hot gas filter. A comparison with the fluidized bed system shows that there is potential for higher capital costs and lower catalyst costs in the fixed bed system, leading to comparable overall costs. The key catalyst requirement is to enable the effective transformation of highly oxygenated biomass into hydrocarbons products with properties suitable for blending into current fuels. Potential catalyst materials are discussed, along with their suitability for deoxygenation, hydrogenation and C–C coupling chemistry. This chemistry is necessary during pyrolysis vapor upgrading for improved bio-oil quality, which enables efficient downstream hydroprocessing; C–C coupling helps increase the proportion of diesel/jet fuel range product. One potential benefit of fixed bed upgrading over fluidized bed upgrading is catalyst flexibility, providing greater control over chemistry and product composition. Since this study is based on future projections, the impacts of uncertainties in the underlying assumptions are quantified via sensitivity analysis. As a result, this analysis indicates that catalyst researchers should prioritize by: carbon efficiency > catalyst cost > catalyst lifetime, after initially testing for basic operational feasibility.« 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.

Rational approach to polymer-supported catalysts: synergy between catalytic reaction mechanism and polymer design.

PubMed

Madhavan, Nandita; Jones, Christopher W; Weck, Marcus

2008-09-01

Supported catalysis is emerging as a cornerstone of transition metal catalysis, as environmental awareness necessitates "green" methodologies and transition metal resources become scarcer and more expensive. Although these supported systems are quite useful, especially in their capacity for transition metal catalyst recycling and recovery, higher activity and selectivity have been elusive compared with nonsupported catalysts. This Account describes recent developments in polymer-supported metal-salen complexes, which often surpass nonsupported analogues in catalytic activity and selectivity, demonstrating the effectiveness of a systematic, logical approach to designing supported catalysts from a detailed understanding of the catalytic reaction mechanism. Over the past few decades, a large number of transition metal complex catalysts have been supported on a variety of materials ranging from polymers to mesoporous silica. In particular, soluble polymer supports are advantageous because of the development of controlled and living polymerization methods that are tolerant to a wide variety of functional groups, including controlled radical polymerizations and ring-opening metathesis polymerization. These methods allow for tuning the density and structure of the catalyst sites along the polymer chain, thereby enabling the development of structure-property relationships between a catalyst and its polymer support. The fine-tuning of the catalyst-support interface, in combination with a detailed understanding of catalytic reaction mechanisms, not only permits the generation of reusable and recyclable polymer-supported catalysts but also facilitates the design and realization of supported catalysts that are significantly more active and selective than their nonsupported counterparts. These superior supported catalysts are accessible through the optimization of four basic variables in their design: (i) polymer backbone rigidity, (ii) the nature of the linker, (iii) catalyst site density, and (iv) the nature of the catalyst attachment. Herein, we describe the design of polymer supports tuned to enhance the catalytic activity or decrease, or even eliminate, decomposition pathways of salen-based transition metal catalysts that follow either a monometallic or a bimetallic reaction mechanism. These findings result in the creation of some of the most active and selective salen catalysts in the literature.

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.

Engineering of solar photocatalytic detoxification and disinfection process

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

Goswami, D.Y.

1995-12-31

Use of solar radiation for photocatalytic detoxification and disinfection is a very fascinating and fast-developing area. Although scientific research on these processes, especially photocatalytic oxidation, has been conducted for at least the last three decades, the development of industrial/commercial applications, engineering systems and engineering design methodologies have occurred only recently. A number of reactor concepts and designs, including concentrating and non-concentrating types and various methods of catalyst deployment have been developed. Some of these reactors have been used in field demonstrations of groundwater and wastewater remediation. Recent research has been focused on improvements of catalysts to increase the reaction rates,more » as well as finding new applications of the process. This paper reviews the latest developments of solar detoxification and disinfection including catalyst development, industrial/commercial applications, reactor design and engineering system design methodologies. 80 refs., 20 figs., 3 tabs.« less

ECUT: Energy Conversion and Utilization Technologies program. Heterogeneous catalysis modeling program concept

NASA Technical Reports Server (NTRS)

Voecks, G. E.

1983-01-01

Insufficient theoretical definition of heterogeneous catalysts is the major difficulty confronting industrial suppliers who seek catalyst systems which are more active, selective, and stable than those currently available. In contrast, progress was made in tailoring homogeneous catalysts to specific reactions because more is known about the reaction intermediates promoted and/or stabilized by these catalysts during the course of reaction. However, modeling heterogeneous catalysts on a microscopic scale requires compiling and verifying complex information on reaction intermediates and pathways. This can be achieved by adapting homogeneous catalyzed reaction intermediate species, applying theoretical quantum chemistry and computer technology, and developing a better understanding of heterogeneous catalyst system environments. Research in microscopic reaction modeling is now at a stage where computer modeling, supported by physical experimental verification, could provide information about the dynamics of the reactions that will lead to designing supported catalysts with improved selectivity and stability.

Performance and life cycle environmental benefits of recycling spent ion exchange brines by catalytic treatment of nitrate.

PubMed

Choe, Jong Kwon; Bergquist, Allison M; Jeong, Sangjo; Guest, Jeremy S; Werth, Charles J; Strathmann, Timothy J

2015-09-01

Salt used to make brines for regeneration of ion exchange (IX) resins is the dominant economic and environmental liability of IX treatment systems for nitrate-contaminated drinking water sources. To reduce salt usage, the applicability and environmental benefits of using a catalytic reduction technology to treat nitrate in spent IX brines and enable their reuse for IX resin regeneration were evaluated. Hybrid IX/catalyst systems were designed and life cycle assessment of process consumables are used to set performance targets for the catalyst reactor. Nitrate reduction was measured in a typical spent brine (i.e., 5000 mg/L NO3(-) and 70,000 mg/L NaCl) using bimetallic Pd-In hydrogenation catalysts with variable Pd (0.2-2.5 wt%) and In (0.0125-0.25 wt%) loadings on pelletized activated carbon support (Pd-In/C). The highest activity of 50 mgNO3(-)/(min - g(Pd)) was obtained with a 0.5 wt%Pd-0.1 wt%In/C catalyst. Catalyst longevity was demonstrated by observing no decrease in catalyst activity over more than 60 days in a packed-bed reactor. Based on catalyst activity measured in batch and packed-bed reactors, environmental impacts of hybrid IX/catalyst systems were evaluated for both sequencing-batch and continuous-flow packed-bed reactor designs and environmental impacts of the sequencing-batch hybrid system were found to be 38-81% of those of conventional IX. Major environmental impact contributors other than salt consumption include Pd metal, hydrogen (electron donor), and carbon dioxide (pH buffer). Sensitivity of environmental impacts of the sequencing-batch hybrid reactor system to sulfate and bicarbonate anions indicate the hybrid system is more sustainable than conventional IX when influent water contains <80 mg/L sulfate (at any bicarbonate level up to 100 mg/L) or <20 mg/L bicarbonate (at any sulfate level up to 100 mg/L) assuming 15 brine reuse cycles. The study showed that hybrid IX/catalyst reactor systems have potential to reduce resource consumption and improve environmental impacts associated with treating nitrate-contaminated water sources. Copyright © 2015 Elsevier Ltd. All rights reserved.

Highly Durable Supportless Pt Hollow Spheres Designed for Enhanced Oxygen Transport in Cathode Catalyst Layers of Proton Exchange Membrane Fuel Cells.

PubMed

Dogan, Didem C; Cho, Seonghun; Hwang, Sun-Mi; Kim, Young-Min; Guim, Hwanuk; Yang, Tae-Hyun; Park, Seok-Hee; Park, Gu-Gon; Yim, Sung-Dae

2016-10-10

Supportless Pt catalysts have several advantages over conventional carbon-supported Pt catalysts in that they are not susceptible to carbon corrosion. However, the need for high Pt loadings in membrane electrode assemblies (MEAs) to achieve state-of-the-art fuel cell performance has limited their application in proton exchange membrane fuel cells. Herein, we report a new approach to the design of a supportless Pt catalyst in terms of catalyst layer architecture, which is crucial for fuel cell performance as it affects water management and oxygen transport in the catalyst layers. Large Pt hollow spheres (PtHSs) 100 nm in size were designed and prepared using a carbon template method. Despite their large size, the unique structure of the PtHSs, which are composed of a thin-layered shell of Pt nanoparticles (ca. 7 nm thick), exhibited a high surface area comparable to that of commercial Pt black (PtB). The PtHS structure also exhibited twice the durability of PtB after 2000 potential cycles (0-1.3 V, 50 mV/s). A MEA fabricated with PtHSs showed significant improvement in fuel cell performance compared to PtB-based MEAs at high current densities (>800 mA/cm 2 ). This was mainly due to the 2.7 times lower mass transport resistance in the PtHS-based catalyst layers compared to that in PtB, owing to the formation of macropores between the PtHSs and high porosity (90%) in the PtHS catalyst layers. The present study demonstrates a successful example of catalyst design in terms of catalyst layer architecture, which may be applied to a real fuel cell system.

Ionic Attachment as a Feasible Approach to Heterogenizing Anionic Solution Catalysts. The Carbonylation of Methanol,

DTIC Science & Technology

1980-08-01

carbonylation of methanol to acetic acid reaction is well suited for a demonstration of the feasibility and value of ionically binding a catalyst to a...approximate doubling of the reaction rate. This result suggests that a liquid flow system design in which there is a large catalyst to methanol ratio could...Heterogenizing Anionic Solution Catalysts . The Carbonylation of Methanol by Russell S. Drago, Eric D. Nyberg, Anton El A’mma and Alan Zombeck ABSTRACT -’Few

Ionic Liquids Enabling Revolutionary Closed-Loop Life Support

NASA Technical Reports Server (NTRS)

Brown, Brittany R.; Abney, Morgan B.; Karr, Laurel; Stanley, Christine M.; Paley, Steve

2017-01-01

Minimizing resupply from Earth is essential for future long duration manned missions. The current oxygen recovery system aboard the International Space Station is capable of recovering approximately 50% of the oxygen from metabolic carbon dioxide. For long duration manned missions, a minimum of 75% oxygen recovery is targeted with a goal of greater than 90%. Theoretically, the Bosch process can recover 100% of oxygen, making it a promising technology for oxygen recovery for long duration missions. However, the Bosch process produces elemental carbon which ultimately fouls the catalyst. Once the catalyst performance is compromised, it must be replaced resulting in undesired resupply mass. Based on the performance of a Bosch system designed by NASA in the 1990's, a three year Martian mission would require approximately 1315 kg (2850 lbs) of catalyst resupply. It may be possible to eliminate catalyst resupply with a fully regenerable system using an Ionic Liquid (IL)-based Bosch system. In 2016, we reported the feasibility of using ILs to produce an iron catalyst on a copper substrate and to regenerate the iron catalyst by extracting the iron from the copper substrate and product carbon. Additionally, we described a basic system concept for an IL-based Bosch. Here we report the results of efforts to scale catalyst preparation, to scale catalyst regeneration, and to scale the carbon formation processing rate of a single reactor.

Ionic Liquids Enabling Revolutionary Closed-Loop Life Support

NASA Technical Reports Server (NTRS)

Brown, Brittany R.; Abney, Morgan B.; Karr, Laurel J.; Stanley, Christine M.; Donovan, Dave N.; Palsey, Mark S.

2017-01-01

Minimizing resupply from Earth is essential for future long duration manned missions. The current oxygen recovery system aboard the International Space Station is capable of recovering approximately 50% of the oxygen from metabolic carbon dioxide. For long duration manned missions, a minimum of 75% oxygen recovery is targeted with a goal of greater than 90%. Theoretically, the Bosch process can recover 100% of oxygen, making it a promising technology for oxygen recovery for long duration missions. However, the Bosch process produces elemental carbon which ultimately fouls the catalyst. Once the catalyst performance is compromised, it must be replaced resulting in undesired resupply mass. Based on the performance of a Bosch system designed by NASA in the 1990's, a three year Martian mission would require approximately 1315 kg (2850 lbs) of catalyst resupply. It may be possible to eliminate catalyst resupply with a fully regenerable system using an Ionic Liquid (IL)-based Bosch system. In 2016, we reported the feasibility of using ILs to produce an iron catalyst on a copper substrate and to regenerate the iron catalyst by extracting the iron from the copper substrate and product carbon. Additionally, we described a basic system concept for an IL-based Bosch. Here we report the results of efforts to scale catalyst preparation, catalyst regeneration, and to scale the carbon formation processing rate of a single reactor.

Advancing Fenton and photo-Fenton water treatment through the catalyst design.

PubMed

Vorontsov, Alexander V

2018-04-20

The review is devoted to modern Fenton, photo-Fenton, as well as Fenton-like and photo-Fenton-like reactions with participation of iron species in liquid phase and as heterogeneous catalysts. Mechanisms of these reactions were considered that include hydroxyl radical and oxoferryl species as the reactive intermediates. The barriers in the way of application of these reactions to wastewater treatment were discussed. The following fundamental problems need further research efforts: inclusion of more mechanism steps and quantum calculations of all rate constants lacking in the literature, checking the outer sphere electron transfer contribution, determination of the causes for the key changes in the homogeneous Fenton reaction mechanism with a change in the reagents concentration. The key advances for Fenton reactions implementation for the water treatment are related to tremendous hydrodynamical effects on the catalytic activity, design of ligands for high rate and completeness of mineralization in short time, and design of highly active heterogeneous catalysts. While both homogeneous and heterogeneous Fenton and photo-Fenton systems are open for further improvements, heterogeneous photo-Fenton systems are most promising for practical applications because of the inherent higher catalyst stability. Modern methods of quantum chemistry are expected to play a continuously increasing role in development of such catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.

Design and fabrication of a four-man capacity urine wick evaporator system

NASA Technical Reports Server (NTRS)

1979-01-01

The integrated system was tested to determine the performance characteristics and limitations of the dual catalyst concept. The primary objective of the dual catalyst concept is to remove ammonia and other noxious substances in the gas phase and thereby eliminate the need for and current practice of chemically or electrochemically pretreating urine prior to distillation.

Progress in the Development of Oxygen Reduction Reaction Catalysts for Low-Temperature Fuel Cells

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

Li, Dongguo; Lv, Haifeng; Kang, Yijin

2016-04-06

In this paper, we present a brief summary on the most recent progress in the design of catalysts for electrochemical reduction of oxygen. The main challenge in the wide spread of fuel cell technology is to lower the content of, or even eliminate, Pt and other precious metals in catalysts without sacrificing their performance. Pt-based nanosized catalysts with novel and refined architectures continue to dominate in catalytic performance, and formation of Pt-skin-like surfaces is key to achieving the highest values in activity. Moreover, durability has also been improved in Pt-based systems with addition of Au, which plays an important rolemore » in stabilizing the Pt topmost layers against dissolution. However, various carbon-based materials without precious metal have shown improvement in activity and durability and have been explored to serve as catalyst supports. Finally, understanding how the doped elements interact with each other and/or carbon is challenging and necessary in the design of robust fuel cell catalysts.« less

LaRC-developed catalysts for CO2 lasers

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Kielin, Erik J.; Miller, Irvin M.

1990-01-01

Pulsed CO2 lasers have many remote sensing applications from space, airborne, and ground platforms. The NASA Laser Atmospheric Wind Sounder (LAWS) system will be designed to measure wind velocities from polar earth orbit for a period of up to three years. Accordingly, this and other applications require a closed-cycle pulsed CO2 laser which necessitates the use of an efficient CO-O2 recombination catalyst for these dissociation products which otherwise would degrade the laser operation. The required catalyst must not only operate at low temperatures but also must operate efficiently for long time periods. The research effort at NASA LaRC has centered around development and testing of CO oxidation catalysts for closed-cycle, pulsed, common and rare-isotope CO2 lasers. Researchers examined available commercial catalysts both in a laser and under simulated closed-cycle laser conditions with efforts aimed toward a thorough understanding of the fundamental catalytic reaction. These data were used to design and synthesize new catalyst compositions to better meet the catalyst requirements for closed-cycle pulsed CO2 lasers. Syntheses and test results for catalysts developed at Langley Research Center which have significantly better long-term decay characteristics than previously available catalysts and at the same time operate quite well under lower temperature conditions are discussed.

Catalysts for cleaner combustion of coal, wood and briquettes sulfur dioxide reduction options for low emission sources

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

Smith, P.V.

1995-12-31

Coal fired, low emission sources are a major factor in the air quality problems facing eastern European cities. These sources include: stoker-fired boilers which feed district heating systems and also meet local industrial steam demand, hand-fired boilers which provide heat for one building or a small group of buildings, and masonary tile stoves which heat individual rooms. Global Environmental Systems is marketing through Global Environmental Systems of Polane, Inc. catalysts to improve the combustion of coal, wood or fuel oils in these combustion systems. PCCL-II Combustion Catalysts promotes more complete combustion, reduces or eliminates slag formations, soot, corrosion and somemore » air pollution emissions and is especially effective on high sulfur-high vanadium residual oils. Glo-Klen is a semi-dry powder continuous acting catalyst that is injected directly into the furnace of boilers by operating personnel. It is a multi-purpose catalyst that is a furnace combustion catalyst that saves fuel by increasing combustion efficiency, a cleaner of heat transfer surfaces that saves additional fuel by increasing the absorption of heat, a corrosion-inhibiting catalyst that reduces costly corrosion damage and an air pollution reducing catalyst that reduces air pollution type stack emissions. The reduction of sulfur dioxides from coal or oil-fired boilers of the hand fired stoker design and larger, can be controlled by the induction of the Glo-Klen combustion catalyst and either hydrated lime or pulverized limestone.« less

Potential technology transfers of research on low-temperature carbon monoxide-oxygen recombination catalysts

NASA Technical Reports Server (NTRS)

Poziomek, Edward J.

1990-01-01

Results from research on catalytic recombination of CO-O2 for stable closed-cycle operation of CO2 lasers hold much promise for a variety of technology transfer. Expansion of CO2 laser remote sensing applications toward chemical detection and pollution monitoring would certainly be expected. However, the catalysts themselves may be especially effective in low-temperature oxidation of a number of chemicals in addition to CO. It is therefore of interest to compare the CO-O2 catalysts with chemical systems designed for chemical sensing, air purification and process catalysis. Success in understanding the catalytic mechanisms of the recombination of CO-O2 could help to shed light on how catalyst systems operate. New directions in low-temperature oxidation catalysts, coatings for chemical sensors and sorbents for air purification could well emerge.

The development of a non-cryogenic nitrogen/oxygen supply system

NASA Technical Reports Server (NTRS)

Greenough, B. M.

1972-01-01

Development of the hydrazine/water electrolysis process in a manned spacecraft to provide metabolic oxygen and both oxygen and nitrogen for cabin leakage makeup was studied. Electrode development efforts were directed to stability, achieved with catalyst additives and improved processing techniques, and a higher hydrazine conversion efficiency, achieved by reducing catalyst loading on the cathodes. Extensive testing of the one-man breadboard N2/02 system provided complete characterization of cabin atmosphere control aspects. A detailed design of a prototype modular N2/02 unit was conducted. The contact heat exchanger which is an integral component of this design was fabricated and sucessfully design-verification tested.

Fuel Processing System for a 5kW Methanol Fuel Cell Power Unit.

DTIC Science & Technology

1985-11-27

report documents the development and design of a 5kW neat methanol reformer for phosphoric acid fuel cell power plants . The reformer design was based...VAPORIZATION OF METHANOL ........... 4.3 REFORMING/SHIFT CATALYST BED ......... 2 5.0 COMPONENT TESTING............... 5.1 COMBUSTION TUBE...69 36 Catalyst Bed Temperature Profile Before and After Transient ................. 70 37 Assembly -5kw Neat Methanol Reformer. ......... 72 Page No

Approaches to Polymer Curing and Imaging Via the In Situ Generation of a Catalyst

DTIC Science & Technology

1992-04-20

polyimide can be formulated from a polyamic acid derivative and a photo- precursor of base. Of particular interest are systems that incorporate chemical...amplification. In these systems the initial radiation induced proc- ess, photogeneration of the acid or base catalyst within the polymer film, is...different, new systems better suited for the high demands of modem microlithography have been developed. Issues of particular relevance in the design of

Janus structured Pt–FeNC nanoparticles as a catalyst for the oxygen reduction reaction

DOE PAGES

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Park, Gu -Gon; ...

2017-01-03

Here, we present a new Janus structured catalyst consisting of Pt nanoparticles on Fe–N–C nanoparticles encapsulated by graphene layers for the ORR. The ORR activity of the catalyst increases under potential cycling as the unique Janus nanostructure is further bonded due to a synergetic effect. The present study describes an important advanced approach for the future design of efficient, stable, and low-cost Pt-based electrocatalytic systems.

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

From Rockets to Racecars

NASA Technical Reports Server (NTRS)

2005-01-01

NASA s Langley Research Center scientists developed a family of catalysts for low- temperature oxidation of carbon monoxide and other gases. The catalysts provide oxidation of both carbon monoxide and formaldehyde at room temperature without requiring any energy input, just a suitable flow of gas through them. Originally designed as part of an atmospheric satellite project, where the catalysts were intended to recycle and recapture carbon dioxide to enhance the operational life of carbon dioxide lasers, the entire system was made to be rugged, long-lived, and fail-safe. The low-temperature oxidation catalysts can be produced and coated onto various catalyst supports, including porous ceramic monoliths and beads, which means that they can be integrated into existing designs, made to fit in limited space, and fashioned into a variety of geometrically different products. Although the satellite project was never launched, the resulting catalysts are doing great things here on Earth, with current applications in the high-speed motor sports arena as air purifiers, so professional racecar drivers do not get carbon monoxide poisoning. Future benefits may extend even further.

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

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

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

PubMed Central

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; Cullen, David A.; Toops, Todd J.; Green, Johney B.; Mench, Matthew M.; Zhang, Feng-Yuan

2016-01-01

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. This discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices. PMID:28138516

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

DOE PAGES

Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; ...

2016-11-18

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

Design and fabrication of miniaturized PEM fuel cell combined microreactor with self-regulated hydrogen mechanism

NASA Astrophysics Data System (ADS)

Balakrishnan, A.; Frei, M.; Kerzenmacher, S.; Reinecke, H.; Mueller, C.

2015-12-01

In this work we present the design and fabrication of the miniaturized PEM fuel cell combined microreactor system with hydrogen regulation mechanism and testing of prototype microreactor. The system consists of two components (i) fuel cell component and (ii) microreactor component. The fuel cell component represents the miniaturized PEM fuel cell system (combination of screen printed fuel cell assembly and an on-board hydrogen storage medium). Hydrogen production based on catalytic hydrolysis of chemical hydride takes place in the microreactor component. The self-regulated hydrogen mechanism based on the gaseous hydrogen produced from the catalytic hydrolysis of sodium borohydride (NaBH4) gets accumulated as bubbles at the vicinity of the hydrophobic coated hydrogen exhaust holes. When the built up hydrogen bubbles pressure exceeds the burst pressure at the hydrogen exhaust holes the bubble collapses. This collapse causes a surge of fresh NaBH4 solution onto the catalyst surface leading to the removal of the reaction by-products formed at the active sites of the catalyst. The catalyst used in the system is platinum deposited on a base substrate. Nickel foam, carbon porous medium (CPM) and ceramic plate were selected as candidates for base substrate for developing a robust catalyst surface. For the first time the platinum layer fabricated by pulsed electrodeposition and dealloying (EPDD) technique is used for hydrolysis of NaBH4. The major advantages of such platinum catalyst layers are its high surface area and their mechanical stability. Prototype microreactor system with self-regulated hydrogen mechanism is demonstrated.

Design of electrolyzer for carbon dioxide conversion to fuels and chemicals

NASA Astrophysics Data System (ADS)

Rosen, Jonathan S.

The stabilization of global atmospheric CO2 levels requires a transition towards a renewable energy based economy as well as methods for handling current CO2 output from fossil fuels. Challenges with renewable energy intermittency have thus far limited the use of these alternative energy sources to only a fraction of the current energy portfolio. To enable more widespread use of renewable energy systems, methods of large scale energy storage must be developed to store excess renewable energy when demand is low and allow for combined use of energy storage and renewable systems when demand is high. To date, no one technique has demonstrated energy storage methods on the gigawatt scale needed for integration with renewable sources; therefore the development of suitable energy storage technologies, such as CO2 electrolysis to fuels is needed. In this work, research efforts have focused on two major thrusts related to electrochemical methods of CO 2 conversion to fuels. The first thrust focuses on the synthesis and design of highly efficient anode and cathode catalysts with emphasis on understanding structure-property relationships. A second thrust focuses on the design of novel electrochemical devices for CO2 conversion and integration of synthesized materials into flow cell systems. On the anode side, the synthesis of highly active catalysts using abundant transition metals is crucial to reducing capital costs and enabling widespread use of electrochemical CO2 conversion devices. Highly active mesoporous Co3O4 and metal-substituted Co3O4 water oxidation catalysts were designed to investigate the role of the spinel structure on water oxidation activity. Further analysis of metal substituted samples reveal the importance of the octahedral sites in the spinel structure, which was later used to design an Mg-Co3O4 sample with improved water oxidation activity. The design of efficient cathode materials which can selectivity reduce CO2 to fuels and chemicals is critical to the widespread use of CO2 electrolysis. A nanoporous Ag material was synthesized through a dealloying technique able to operate with less than 0.5 V overpotential and high selectivity towards CO. CO is a valuable intermediate chemical which can used in Fischer-Tropsch or Gas-to-liquids technologies to produce liquids fuels. A detailed investigation of nanostructured Ag catalysts found stepped sites to be responsible for enhanced CO2 reduction activity due to improved stabilization of the COOH intermediate on the catalyst surface. In addition, an low-cost Zn dendrite electrocatalyst was developed using an electroplating technique. Low coordinated sites formed through electrodeposition demonstrated the suppression of hydrogen evolution while maintaining CO activity. The Zn dendrite electrocatalyst was further examined using a newly developed in situ X-ray absorption technique able to probe catalyst stability and crystalline structure under CO2 reduction operating conditions. A final hurdle in the realization of CO2 electrolysis technologies is the integration of catalysts into working flow cell devices. To address this issue and enable testing in a practical system, a highly efficient and robust CO2 electrolysis flow cell was designed including the scale up of the previous nanoporous Ag synthesis procedure. Using the modified porous Ag catalyst, currents in the Amp regime were demonstrated approaching rates needed for energy storage applications. Stability on the order of days was successfully demonstrated due to use of robust system components and conditions suitable for process scale up.

Development and Testing of a Methane/Oxygen Catalytic Microtube Ignition System for Rocket Propulsion

NASA Technical Reports Server (NTRS)

Deans, Matthew

2012-01-01

This study sought to develop a catalytic ignition advanced torch system with a unique catalyst microtube design that could serve as a low energy alternative or redundant system for the ignition of methane and oxygen rockets. Development and testing of iterations of hardware was carried out to create a system that could operate at altitude and produce a torch. A unique design was created that initiated ignition via the catalyst and then propagated into external staged ignition. This system was able to meet the goals of operating across a range of atmospheric and altitude conditions with power inputs on the order of 20 to 30 watts with chamber pressures and mass flow rates typical of comparable ignition systems for a 100 lbf engine.

Development and Testing of a Methane/Oxygen Catalytic Microtube Ignition System for Rocket Propulsion

NASA Technical Reports Server (NTRS)

Deans, Matthew C.; Schneider, Steven J.

2012-01-01

This study sought to develop a catalytic ignition advanced torch system with a unique catalyst microtube design that could serve as a low energy alternative or redundant system for the ignition of methane and oxygen rockets. Development and testing of iterations of hardware was carried out to create a system that could operate at altitude and produce a torch. A unique design was created that initiated ignition via the catalyst and then propagated into external staged ignition. This system was able to meet the goals of operating across a range of atmospheric and altitude conditions with power inputs on the order of 20 to 30 watts with chamber pressures and mass flow rates typical of comparable ignition systems for a 100 Ibf engine.

A BGO detector for Positron Emission Profiling in catalysts

NASA Astrophysics Data System (ADS)

Mangnus, A. V. G.; van Ijzendoorn, L. J.; de Goeij, J. J. M.; Cunningham, R. H.; van Santen, R. A.; de Voigt, M. J. A.

1995-05-01

As part of a project to study the reaction kinetics in catalysts, a detector system has been designed and built. The detector will measure in one dimension the activity distribution of positron emitters in catalyst reactors under operational conditions as a function of time. The detector consists of two arrays of ten BGO crystals each and has the flexibility to measure with high sensitivity the activity profile in various reactor sizes; the position resolution that can be reached is 3 mm.

High throughput operando studies using Fourier transform infrared imaging and Raman spectroscopy.

PubMed

Li, Guosheng; Hu, Dehong; Xia, Guanguang; White, J M; Zhang, Conrad

2008-07-01

A prototype high throughput operando (HTO) reactor designed and built for catalyst screening and characterization combines Fourier transform infrared (FT-IR) imaging and Raman spectroscopy in operando conditions. Using a focal plane array detector (HgCdTe focal plane array, 128x128 pixels, and 1610 Hz frame rate) for the FT-IR imaging system, the catalyst activity and selectivity of all parallel reaction channels can be simultaneously followed. Each image data set possesses 16 384 IR spectra with a spectral range of 800-4000 cm(-1) and with an 8 cm(-1) resolution. Depending on the signal-to-noise ratio, 2-20 s are needed to generate a full image of all reaction channels for a data set. Results on reactant conversion and product selectivity are obtained from FT-IR spectral analysis. Six novel Raman probes, one for each reaction channel, were specially designed and house built at Pacific Northwest National Laboratory, to simultaneously collect Raman spectra of the catalysts and possible reaction intermediates on the catalyst surface under operando conditions. As a model system, methanol partial oxidation reaction on silica-supported molybdenum oxide (MoO3SiO2) catalysts has been studied under different reaction conditions to demonstrate the performance of the HTO reactor.

Recent progress in asymmetric bifunctional catalysis using multimetallic systems.

PubMed

Shibasaki, Masakatsu; Kanai, Motomu; Matsunaga, Shigeki; Kumagai, Naoya

2009-08-18

The concept of bifunctional catalysis, wherein both partners of a bimolecular reaction are simultaneously activated, is very powerful for designing efficient asymmetric catalysts. Catalytic asymmetric processes are indispensable for producing enantiomerically enriched compounds in modern organic synthesis, providing more economical and environmentally benign results than methods requiring stoichiometric amounts of chiral reagents. Extensive efforts in this field have produced many asymmetric catalysts, and now a number of reactions can be rendered asymmetric. We have focused on the development of asymmetric catalysts that exhibit high activity, selectivity, and broad substrate generality under mild reaction conditions. Asymmetric catalysts based on the concept of bifunctional catalysis have emerged as a particularly effective class, enabling simultaneous activation of multiple reaction components. Compared with conventional catalysts, bifunctional catalysts generally exhibit enhanced catalytic activity and higher levels of stereodifferentiation under milder reaction conditions, attracting much attention as next-generation catalysts for prospective practical applications. In this Account, we describe recent advances in enantioselective catalysis with bifunctional catalysts. Since our identification of heterobimetallic rare earth-alkali metal-BINOL (REMB) complexes, we have developed various types of bifunctional multimetallic catalysts. The REMB catalytic system is effective for catalytic asymmetric Corey-Chaykovsky epoxidation and cyclopropanation. A dinucleating Schiff base has emerged as a suitable multidentate ligand for bimetallic catalysts, promoting catalytic syn-selective nitro-Mannich, anti-selective nitroaldol, and Mannich-type reactions. The sugar-based ligand GluCAPO provides a suitable platform for polymetallic catalysts; structural elucidation revealed that their higher order polymetallic structures are a determining factor for their function in the catalytic asymmetric Strecker reaction. Rational design identified a related ligand, FujiCAPO, which exhibits superior performance in catalytic asymmetric conjugate addition of cyanide to enones and a catalytic asymmetric Diels-Alder-type reaction. The combination of an amide-based ligand with a rare earth metal constitutes a unique catalytic system: the ligand-metal association is in equilibrium because of structural flexibility. These catalytic systems are effective for asymmetric amination of highly coordinative substrate as well as for Mannich-type reaction of alpha-cyanoketones, in which hydrogen bonding cooperatively contributes to substrate activation and stereodifferentiation. Most of the reactions described here generate stereogenic tetrasubstituted carbons or quaternary carbons, noteworthy accomplishments even with modern synthetic methods. Several reactions have been incorporated into the asymmetric synthesis of therapeutics (or their candidate molecules) such as Tamiflu, AS-3201 (ranirestat), GRL-06579A, and ritodrine, illustrating the usefulness of bifunctional asymmetric catalysis.

Rapid starting methanol reactor system

DOEpatents

Chludzinski, Paul J.; Dantowitz, Philip; McElroy, James F.

1984-01-01

The invention relates to a methanol-to-hydrogen cracking reactor for use with a fuel cell vehicular power plant. The system is particularly designed for rapid start-up of the catalytic methanol cracking reactor after an extended shut-down period, i.e., after the vehicular fuel cell power plant has been inoperative overnight. Rapid system start-up is accomplished by a combination of direct and indirect heating of the cracking catalyst. Initially, liquid methanol is burned with a stoichiometric or slightly lean air mixture in the combustion chamber of the reactor assembly. The hot combustion gas travels down a flue gas chamber in heat exchange relationship with the catalytic cracking chamber transferring heat across the catalyst chamber wall to heat the catalyst indirectly. The combustion gas is then diverted back through the catalyst bed to heat the catalyst pellets directly. When the cracking reactor temperature reaches operating temperature, methanol combustion is stopped and a hot gas valve is switched to route the flue gas overboard, with methanol being fed directly to the catalytic cracking reactor. Thereafter, the burner operates on excess hydrogen from the fuel cells.

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.

Designing Artificial Enzymes by Intuition and Computation

PubMed Central

Nanda, Vikas; Koder, Ronald L.

2012-01-01

The rational design of artificial enzymes either by applying physio-chemical intuition of protein structure and function or with the aid of computation methods is a promising area of research with the potential to tremendously impact medicine, industrial chemistry and energy production. Designed proteins also provide a powerful platform for dissecting enzyme mechanisms of natural systems. Artificial enzymes have come a long way, from simple α-helical peptide catalysts to proteins that facilitate multi-step chemical reactions designed by state-of-the-art computational methods. Looking forward, we examine strategies employed by natural enzymes which could be used to improve the speed and selectivity of artificial catalysts. PMID:21124375

A Dual-Catalysis Approach to Enantioselective [2+2] Photocycloadditions Using Visible Light

PubMed Central

Du, Juana; Skubi, Kazimer L.; Schultz, Danielle M.; Yoon, Tehshik P.

2015-01-01

In contrast to the wealth of catalytic systems that are available to control the stereochemistry of thermally promoted cycloadditions, few similarly effective methods exist for the stereocontrol of photochemical cycloadditions. A major unsolved challenge in the design of enantioselective catalytic photocycloaddition reactions has been the difficulty of controlling racemic background reactions that occur by direct photoexcitation of substrates while unbound to catalyst. Here we describe a strategy for eliminating the racemic background reaction in asymmetric [2+2] photocycloadditions of α,β-unsaturated ketones to the corresponding cyclobutanes by employing a dual-catalyst system consisting of a visible light-absorbing transition metal photocatalyst and a stereocontrolling Lewis acid co-catalyst. The independence of these two catalysts enables broader scope, greater stereochemical flexibility, and better efficiency than previously reported methods for enantioselective photochemical cycloadditions. PMID:24763585

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.

Hydrogen Generation from Biomass-Derived Surgar Alcohols via the Aqueous-Phase Carbohydrate Reforming (ACR) Process

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

Randy Cortright

2006-06-30

This project involved the investigation and development of catalysts and reactor systems that will be cost-effective to generate hydrogen from potential sorbitol streams. The intention was to identify the required catalysts and reactors systems as well as the design, construction, and operation of a 300 grams per hour hydrogen system. Virent was able to accomplish this objective with a system that generates 2.2 kgs an hour of gas containing both hydrogen and alkanes that relied directly on the work performed under this grant. This system, funded in part by the local Madison utility, Madison, Gas & Electric (MGE), is describedmore » further in the report. The design and development of this system should provide the necessary scale-up information for the generation of hydrogen from corn-derived sorbitol.« less

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

NONE

During this time period, at WVU, the authors have obtained models for the kinetics of the HAS (higher alcohol synthesis) reaction over the Co-K-MoS{sub 2}/C catalyst. The Rotoberty reactor was then replaced in the reactor system by a plug-flow tubular reactor. Accordingly, the authors re-started the investigations on sulfide catalysts. The authors encountered and solved the leak problem from the sampling valve for the non-sulfided reactor system. They also modified the system to eliminate the condensation problem. Accordingly, they are continuing their kinetic studies on the reduced Mo-Ni-K/C catalysts. They have set up an apparatus for temperature-programmed reduction (TPR) studies,more » and have obtained some interesting results on TPR characterizations. At UCC, the complete characterization of selected catalysts has been started. The authors sent nine selected types of ZnO, Zn/CrO and Zn/Cr/MnO catalysts and supports for BET surface area, SEM, XRD and ICP. They also sent fresh and spent samples of the Engelhard Zn/CrO catalyst impregnated with 3 wt% potassium for ISS and XPS testing. In Task 2, work on the design and optimization portion of this task, as well as on the fuel testing, is completed. All funds have been expended and there are no personnel working on this project.« less

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).

Quantifying ligand effects in high-oxidation-state metal catalysis

NASA Astrophysics Data System (ADS)

Billow, Brennan S.; McDaniel, Tanner J.; Odom, Aaron L.

2017-09-01

Catalysis by high-valent metals such as titanium(IV) impacts our lives daily through reactions like olefin polymerization. In any catalysis, optimization involves a careful choice of not just the metal but also the ancillary ligands. Because these choices dramatically impact the electronic structure of the system and, in turn, catalyst performance, new tools for catalyst development are needed. Understanding ancillary ligand effects is arguably one of the most critical aspects of catalyst optimization and, while parameters for phosphines have been used for decades with low-valent systems, a comparable system does not exist for high-valent metals. A new electronic parameter for ligand donation, derived from experiments on a high-valent chromium species, is now available. Here, we show that the new parameters enable quantitative determination of ancillary ligand effects on catalysis rate and, in some cases, even provide mechanistic information. Analysing reactions in this way can be used to design better catalyst architectures and paves the way for the use of such parameters in a host of high-valent processes.

Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2017-09-24

Here, a critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s –1, faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L) 2] (bpH 2cH = 2,2'-bipyridine-6-phosphonic acid-6'-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediatesmore » O–O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.« less

Lability and Basicity of Bipyridine-Carboxylate-Phosphonate Ligand Accelerate Single-Site Water Oxidation by Ruthenium-Based Molecular Catalysts

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

Shaffer, David W.; Xie, Yan; Szalda, David J.

Here, a critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s –1, faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L) 2] (bpH 2cH = 2,2'-bipyridine-6-phosphonic acid-6'-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediatesmore » O–O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.« less

Computational Modeling of Cobalt-Based Water Oxidation: Current Status and Future Challenges

PubMed Central

Schilling, Mauro; Luber, Sandra

2018-01-01

A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context, mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysts. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability toward real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions. PMID:29721491

Supramolecular water oxidation with Ru-bda-based catalysts.

PubMed

Richmond, Craig J; Matheu, Roc; Poater, Albert; Falivene, Laura; Benet-Buchholz, Jordi; Sala, Xavier; Cavallo, Luigi; Llobet, Antoni

2014-12-22

Extremely slow and extremely fast new water oxidation catalysts based on the Ru-bda (bda=2,2'-bipyridine-6,6'-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s(-1) , respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cooperative dual catalysis: application to the highly enantioselective conjugate cyanation of unsaturated imides.

PubMed

Sammis, Glenn M; Danjo, Hiroshi; Jacobsen, Eric N

2004-08-18

Cooperative heterobimetallic catalysis was used as a design principle to achieve a highly reactive system for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides. A dual-catalyst pathway involving chiral (salen)Al complex 1b and chiral (pybox)Er complex 4b provides measurable improvements in rates and enantioselectivities relative to single-catalyst systems. Mechanistic studies point to a cooperative bimetallic mechanism involving activation of the imide by the Al complex and activation of cyanide by the Er complex.

Colloid Science of Metal Nanoparticle Catalysts in 2D and 3D Structures. Challenges of Nucleation, Growth, Composition, Particle Shape, Size Control and their Influence on Activity and Selectivity

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

Somorjai, Gabor A.; Park, Jeong Y.

2008-02-13

Recent breakthroughs in synthesis in nanosciences have achieved control of size and shapes of nanoparticles that are relevant for catalyst design. In this article, we review the advance of synthesis of nanoparticles, fabrication of two and three dimensional model catalyst system, characterization, and studies of activity and selectivity. The ability to synthesize monodispersed platinum and rhodium nanoparticles in the 1-10 nm range permitted us to study the influence of composition, structure, and dynamic properties of monodispersed metal nanoparticle on chemical reactivity and selectivity. We review the importance of size and shape of nanoparticles to determine the reaction selectivity in multi-pathmore » reactions. The influence of metal-support interaction has been studied by probing the hot electron flows through the metal-oxide interface in catalytic nanodiodes. Novel designs of nanoparticle catalytic systems are discussed.« less

Methyl chloride via oxyhydrochlorination of methane: A building block for chemicals and fuels from natural gas

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

Benson, R.L.; Brown, S.S.D.; Ferguson, S.P.

1995-12-31

The objectives of this program are to (a) develop a process for converting natural gas to methyl chloride via an oxyhydrochlorination route using highly selective, stable catalysts in a fixed-bed, (b) design a reactor capable of removing the large amount of heat generated in the process so as to control the reaction, (c) develop a recovery system capable of removing the methyl chloride from the product stream and (d) determine the economics and commercial viability of the process. The general approach has been as follows: (a) design and build a laboratory scale reactor, (b) define and synthesize suitable OHC catalystsmore » for evaluation, (c) select first generation OHC catalyst for Process Development Unit (PDU) trials, (d) design, construct and startup PDU, (e) evaluate packed bed reactor design, (f) optimize process, in particular, product recovery operations, (g) determine economics of process, (h) complete preliminary engineering design for Phase II and (i) make scale-up decision and formulate business plan for Phase II. Conclusions regarding process development and catalyst development are presented.« less

Flexibility Matters: Cooperative Active Sites in Covalent Organic Framework and Threaded Ionic Polymer.

PubMed

Sun, Qi; Aguila, Briana; Perman, Jason; Nguyen, Nicholas; Ma, Shengqian

2016-12-07

The combination of two or more reactive centers working in concert on a substrate to facilitate the reaction is now considered state of the art in catalysis, yet there still remains a tremendous challenge. Few heterogeneous systems of this sort have been exploited, as the active sites spatially separated within the rigid framework are usually difficult to cooperate. It is now shown that this roadblock can be surpassed. The underlying principle of the strategy presented here is the integration of catalytic components with excellent flexibility and porous heterogeneous catalysts, as demonstrated by the placement of linear ionic polymers in close proximity to surface Lewis acid active sites anchored on the walls of a covalent organic framework (COF). Using the cycloaddition of the epoxides and CO 2 as a model reaction, dramatic activity improvements have been achieved for the composite catalysts in relation to the individual catalytic component. Furthermore, they also clearly outperform the benchmark catalytic systems formed by the combination of the molecular organocatalysts and heterogeneous Lewis acid catalysts, while affording additional recyclability. The extraordinary flexibility and enriched concentration of the catalytically active moieties on linear polymers facilitate the concerted catalysis, thus leading to superior catalytic performance. This work therefore uncovers an entirely new strategy for designing bifunctional catalysts with double-activation behavior and opens a new avenue in the design of multicapable systems that mimic biocatalysis.

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

James K. Neathery; Gary Jacobs; Burtron H. Davis

In this reporting period, a fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of production since the reaction is highly exothermic. Consequently, heavy wax products must be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase FTS. The separation problem is further compounded by catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbonmore » particles. Existing pilot-scale equipment was modified to include a filtration test apparatus. After undergoing an extensive plant shakedown period, filtration tests with cross-flow filter modules using simulant FTS wax slurry were conducted. The focus of these early tests was to find adequate mixtures of polyethylene wax to simulate FTS wax. Catalyst particle size analysis techniques were also developed. Initial analyses of the slurry and filter permeate particles will be used by the research team to design improved filter media and cleaning strategies.« less

Design of template-stabilized active and earth-abundant oxygen evolution catalysts in acid† †Electronic supplementary information (ESI) available: CVs for unary metal oxides deposition, electrochemical stability at higher current densities for unary metal oxides at pH 2.5, EDS maps for CoMnOx and CoPbOx, STEM images and PXRD of CoMnOx and CoFePbOx, high-resolution XPS of Fe 2p for CoFePbOx, Pourbaix diagrams (of Mn, Co, Pb, and Fe), and elemental analysis. See DOI: 10.1039/c7sc01239j Click here for additional data file.

PubMed Central

Huynh, Michael; Ozel, Tuncay; Liu, Chong; Lau, Eric C.

2017-01-01

Oxygen evolution reaction (OER) catalysts that are earth-abundant and are active and stable in acid are unknown. Active catalysts derived from Co and Ni oxides dissolve at low pH, whereas acid stable systems such as Mn oxides (MnOx) display poor OER activity. We now demonstrate a rational approach for the design of earth-abundant catalysts that are stable and active in acid by treating activity and stability as decoupled elements of mixed metal oxides. Manganese serves as a stabilizing structural element for catalytically active Co centers in CoMnOx films. In acidic solutions (pH 2.5), CoMnOx exhibits the OER activity of electrodeposited Co oxide (CoOx) with a Tafel slope of 70–80 mV per decade while also retaining the long-term acid stability of MnOx films for OER at 0.1 mA cm–2. Driving OER at greater current densities in this system is not viable because at high anodic potentials, Mn oxides convert to and dissolve as permanganate. However, by exploiting the decoupled design of the catalyst, the stabilizing structural element may be optimized independently of the Co active sites. By screening potential–pH diagrams, we replaced Mn with Pb to prepare CoFePbOx films that maintained the high OER activity of CoOx at pH 2.5 while exhibiting long-term acid stability at higher current densities (at 1 mA cm–2 for over 50 h at pH 2.0). Under these acidic conditions, CoFePbOx exhibits OER activity that approaches noble metal oxides, thus establishing the viability of decoupling functionality in mixed metal catalysts for designing active, acid-stable, and earth-abundant OER catalysts. PMID:29163926

Modularized and water-cooled photo-catalyst cleaning devices for aquaponics based on ultraviolet light-emitting diodes

NASA Astrophysics Data System (ADS)

Yang, Henglong; Lung, Louis; Wei, Yu-Chien; Huang, Yi-Bo; Chen, Zi-Yu; Chou, Yu-Yang; Lin, Anne-Chin

2017-08-01

The feasibility of applying ultraviolet light-emitting diodes (UV-LED's) as triggering sources of photo-catalyst based on titanium dioxide (TiO2) nano-coating specifically for water-cleaning process in an aquaponics system was designed and proposed. The aquaponics system is a modern farming system to integrate aquaculture and hydroponics into a single system to establish an environmental-friendly and lower-cost method for farming fish and vegetable all together in urban area. Water treatment in an aquaponics system is crucial to avoid mutual contamination. we proposed a modularized watercleaning device composed of all commercially available components and parts to eliminate organic contaminants by using UV-LED's for TiO2 photo-catalyst reaction. This water-cleaning module consisted of two coaxial hollowed cylindrical pipes can be submerged completely in water for water treatment and cooling UV-LED's. The temperature of the UV-LED after proper thermal management can be reduced about 16% to maintain the optimal operation condition. Our preliminary experimental result by using Methylene Blue solution to simulate organic contaminants indicated that TiO2 photo-catalyst triggered by UV-LED's can effectively decompose organic compound and decolor Methylene Blue solution.

A Facile Strategy for Catalyst Separation and Recycling Suitable for ATRP of Hydrophilic Monomers Using a Macroligand.

PubMed

Jiang, Xiaowu; Wu, Jian; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2016-01-01

How to simply and efficiently separate and recycle catalyst has still been a constraint for the wide application of atom transfer radical polymerization (ATRP), especially for the polymerization systems with hydrophilic monomers because the polar functional groups may coordinate with transition metal salts, resulting in abundant catalyst residual in the resultant water-soluble polymers. In order to overcome this problem, a latent-biphasic system is developed, which can be successfully used for ATRP catalyst separation and recycling in situ for various kinds of hydrophilic monomers for the first time, such as poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), N,N-dimethyl acrylamide (DMA), and N-isopropylacrylamide (NIPAM). Herein, random copolymer of octadecyl acrylate (OA), MA-Ln (2-(bis(pyridin-2-ylmethyl)amino)ethyl acrylate), and POA-ran-P(MA-Ln) is designed as the macroligand, and heptane/ethanol is selected as the biphasic solvent. Copper(II) bromide (CuBr2 ) is employed as the catalyst, PEG-bound 2-bromo-2-methylpropanoate (PEG350 -Br) as the water-soluble ATRP initiator and 2,2'-azobis(isobutyronitrile) (AIBN) as the azo-initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP system. Importantly, well-defined water-soluble polymers are obtained even though the recyclable catalyst is used for sixth times. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Challenging nickel-catalysed amine arylations enabled by tailored ancillary ligand design

PubMed Central

Lavoie, Christopher M.; MacQueen, Preston M.; Rotta-Loria, Nicolas L.; Sawatzky, Ryan S.; Borzenko, Andrey; Chisholm, Alicia J.; Hargreaves, Breanna K. V.; McDonald, Robert; Ferguson, Michael J.; Stradiotto, Mark

2016-01-01

Palladium-catalysed C(sp2)–N cross-coupling (that is, Buchwald–Hartwig amination) is employed widely in synthetic chemistry, including in the pharmaceutical industry, for the synthesis of (hetero)aniline derivatives. However, the cost and relative scarcity of palladium provides motivation for the development of alternative, more Earth-abundant catalysts for such transformations. Here we disclose an operationally simple and air-stable ligand/nickel(II) pre-catalyst that accommodates the broadest combination of C(sp2)–N coupling partners reported to date for any single nickel catalyst, without the need for a precious-metal co-catalyst. Key to the unprecedented performance of this pre-catalyst is the application of the new, sterically demanding yet electron-poor bisphosphine PAd-DalPhos. Featured are the first reports of nickel-catalysed room temperature reactions involving challenging primary alkylamine and ammonia reaction partners employing an unprecedented scope of electrophiles, including transformations involving sought-after (hetero)aryl mesylates for which no capable catalyst system is known. PMID:27004442

DE-FG02-08ER64658 (OASIS) - Final Technical Report

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

Sharman, Jonathan

Project OASIS (Operation of Advanced Structures, Interfaces and Sub-components for MEAs) was a 12 month project that ran from 1st September 2008 to 31st August 2009, and was managed by the Department of Energy Office of Science, Chicago Office, as Award No DE-FG02-08ER64658, with Johnson Matthey Fuel Cells Inc. as the sole contractor. The project was completed on schedule, with technical successes (details below) and payment of the full grant award made by DOE. The aim of the project was the development of membrane electrode assemblies (MEAs) for H2/air polymer electrolyte membrane (PEM) fuel cells that would give higher performancemore » under hot/dry and dry operating conditions, ideally with no loss of performance under wet conditions. Reducing or eliminating the need for humidifying the incoming gases will allow significant system cost and size reduction for many fuel cell applications including automotive, stationary and back-up power, and portable systems. Portable systems are also of particular interest in military markets. In previous work Johnson Matthey Fuel Cells had developed very stable, corrosion-resistant catalysts suitable for resisting degradation by carbon corrosion in particular. These materials were applied within the OASIS project as they are considered necessary for systems such as automotive where multiple start-stop events are experienced. These catalysts were contrasted with more conventional materials in the design of catalyst layers and novel microporous layers (MPLs) and gas diffusion layer (GDL) combinations were also explored. Early on in the work it was shown how much more aggressive high temperature operation is than dry operation. At the same humidity, tests at 110?C caused much more dehydration than tests at 80?C and the high temperature condition was much more revealing of improvements made to MEA design. Alloy catalysts were introduced and compared with Pt catalysts with a range of particle sizes. It was apparent that the larger particle sizes of the alloy catalysts led to a reduction in performance that offset much of their kinetic advantage. The Pt-only materials clearly showed that small particles are beneficial to good performance under hot/dry conditions, because of their higher surface area, although they are known to be less stable to cyclic operation. An ex-situ water vapour sorption technique was developed that showed a very clear correlation with in-cell performance: catalyst powders that absorbed more water gave better performance in-cell. It was shown that alloy catalysts could give a 25 mV advantage over Pt-only at 1 Acm-2. GDL design was also shown to influence performance and more permeable GDLs on the anode allowed better membrane hydration and therefore conductivity. A very impermeable GDL on the cathode caused cathode flooding even under dry conditions, but a novel cathode MPL incorporating ionomer and operating at 110?C, 33/17% RH showed a 150 mV gain at 800 mAcm-2 over the conventional MPL. This project has increased the understanding of the factors that influence performance loss under dry conditions, including the development of an insightful ex-situ characterisation technique (Dynamic Vapour Sorption). All the approaches investigated can be readily implemented in state-of the-art MEAs, although optimisation would be needed to integrate the new designs with existing MEA types and to tune to the exact range of operating conditions. The work is thus expected to benefit the public by feeding through more condition-tolerant production MEAs to a range of applications and thereby accelerate the commercialisation of fuel cell technology. In summary, a number of specific catalyst, catalyst layer, MPL and GDL improvements were made during this project. Often the best designs under dry conditions translated to some performance loss under wet conditions, but compromise situations were also found where dry performance was improved with no loss of wet performance.« less

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.

Fe1-xZnxS ternary solid solution as an efficient Fenton-like catalyst for ultrafast degradation of phenol.

PubMed

Gao, Jing; Liu, Yutang; Xia, Xinnian; Wang, Longlu; Dong, Wanyue

2018-07-05

Heterogeneous Fenton-like system has been proved to be an promising alternative to Fenton system due to its easy separation. However, it's a challenge to design heterogeneous Fenton-like catalysts with high activity and great durability. Here, ternary solid solution Fe 1-x Zn x S were prepared via hydrothermal synthesis as heterogeneous Fenton-like catalysts. The Fe 0.7 Zn 0.3 S sample exhibited state of the art activity for yielding OH by H 2 O 2 decomposition, and the ultrafast degradation of phenol was achieved in 4 min at initial acidic condition under room temperature. The phenol degradation rate constant of Fe 0.7 Zn 0.3 S was 99 and 70 times of ZnS and FeS, respectively. Further, we show that the unique structural configuration of iron atoms, the formation of FeS 2 -pyrite with (200) plane, are responsible for the excellent activity. The intermediate products were identified by LC-MS and a possible pathway was accordingly proposed to elucidate the mechanism of phenol degradation by OH. Overall, this work provides an idea for the rational design of the relevant heterogeneous Fenton-like catalysts. Copyright © 2018 Elsevier B.V. All rights reserved.

Recent Advances in the Synthesis, Characterization and Application of Zn+-containing Heterogeneous Catalysts.

PubMed

Chen, Guangbo; Zhao, Yufei; Shang, Lu; Waterhouse, Geoffrey I N; Kang, Xiaofeng; Wu, Li-Zhu; Tung, Chen-Ho; Zhang, Tierui

2016-07-01

Monovalent Zn + (3d 10 4s 1 ) systems possess a special electronic structure that can be exploited in heterogeneous catalysis and photocatalysis, though it remains challenge to synthesize Zn + -containing materials. By careful design, Zn + -related species can be synthesized in zeolite and layered double hydroxide systems, which in turn exhibit excellent catalytic potential in methane, CO and CO 2 activation. Furthermore, by utilizing advanced characterization tools, including electron spin resonance, X-ray absorption fine structure and density functional theory calculations, the formation mechanism of the Zn + species and their structure-performance relationships can be understood. Such advanced characterization tools guide the rational design of high-performance Zn + -containing catalysts for efficient energy conversion.

Recent Advances in the Synthesis, Characterization and Application of Zn+‐containing Heterogeneous Catalysts

PubMed Central

Chen, Guangbo; Zhao, Yufei; Shang, Lu; Waterhouse, Geoffrey I. N.; Kang, Xiaofeng; Wu, Li‐Zhu; Tung, Chen‐Ho

2016-01-01

Monovalent Zn+ (3d104s1) systems possess a special electronic structure that can be exploited in heterogeneous catalysis and photocatalysis, though it remains challenge to synthesize Zn+‐containing materials. By careful design, Zn+‐related species can be synthesized in zeolite and layered double hydroxide systems, which in turn exhibit excellent catalytic potential in methane, CO and CO2 activation. Furthermore, by utilizing advanced characterization tools, including electron spin resonance, X‐ray absorption fine structure and density functional theory calculations, the formation mechanism of the Zn+ species and their structure‐performance relationships can be understood. Such advanced characterization tools guide the rational design of high‐performance Zn+‐containing catalysts for efficient energy conversion. PMID:27818902

Small-volume, ultrahigh-vacuum-compatible high-pressure reaction cell for combined kinetic and in situ IR spectroscopic measurements on planar model catalysts

NASA Astrophysics Data System (ADS)

Zhao, Z.; Diemant, T.; Häring, T.; Rauscher, H.; Behm, R. J.

2005-12-01

We describe the design and performance of a high-pressure reaction cell for simultaneous kinetic and in situ infrared reflection (IR) spectroscopic measurements on model catalysts at elevated pressures, between 10-3 and 103mbars, which can be operated both as batch reactor and as flow reactor with defined gas flow. The cell is attached to an ultrahigh-vacuum (UHV) system, which is used for sample preparation and also contains facilities for sample characterization. Specific for this design is the combination of a small cell volume, which allows kinetic measurements with high sensitivity under batch or continuous flow conditions, the complete isolation of the cell from the UHV part during UHV measurements, continuous temperature control during both UHV and high-pressure operation, and rapid transfer between UHV and high-pressure stage. Gas dosing is performed by a designed gas-handling system, which allows operation as flow reactor with calibrated gas flows at adjustable pressures. To study the kinetics of reactions on the model catalysts, a quadrupole mass spectrometer is connected to the high-pressure cell. IR measurements are possible in situ by polarization-modulation infrared reflection-absorption spectroscopy, which also allows measurements at elevated pressures. The performance of the setup is demonstrated by test measurements on the kinetics for CO oxidation and the CO adsorption on a Au /TiO2/Ru(0001) model catalyst film at 1-50 mbar total pressure.

'Design of CO-O2 recombination catalysts for closed-cycle CO2 lasers'

NASA Technical Reports Server (NTRS)

Guinn, K.; Goldblum, S.; Noskowski, E.; Herz, R.

1989-01-01

Pulsed CO2 lasers have many applications in aeronautics, space research, weather monitoring and other areas. Full exploitation of the potential of these lasers is hampered by the dissociation of CO2 that occurs during laser operation. The development of closed-cycle CO2 lasers requires active CO-O2 recombination (CO oxidation) catalysts and design methods for implementation of catalysts inside lasers. This paper will discuss the performance criteria and constraints involved in the design of monolith catalyst configurations for use in a closed-cycle laser and will present a design study performed with a computerized design program that had been written. Trade-offs between catalyst activity and dimensions, flow channel dimensions, pressure drop, O2 conversion and other variables will be discussed.

Visible-Light-Responsive Photocatalysis: Ag-Doped TiO2 Catalyst Development and Reactor Design Testing

NASA Technical Reports Server (NTRS)

Coutts, Janelle L.; Hintze, Paul E.; Meier, Anne; Shah, Malay G.; Devor, Robert W.; Surma, Jan M.; Maloney, Phillip R.; Bauer, Brint M.; Mazyck, David W.

2016-01-01

In recent years, the alteration of titanium dioxide to become visible-light-responsive (VLR) has been a major focus in the field of photocatalysis. Currently, bare titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Hg-vapor fluorescent light sources are used in photocatalytic oxidation (PCO) reactors to provide adequate levels of ultraviolet light for catalyst activation; these mercury-containing lamps, however, hinder the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. VLR-TiO2 would allow for use of ambient visible solar radiation or highly efficient visible wavelength LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Over the past three years, Kennedy Space Center has developed a VLR Ag-doped TiO2 catalyst with a band gap of 2.72 eV and promising photocatalytic activity. Catalyst immobilization techniques, including incorporation of the catalyst into a sorbent material, were examined. Extensive modeling of a reactor test bed mimicking air duct work with throughput similar to that seen on the International Space Station was completed to determine optimal reactor design. A bench-scale reactor with the novel catalyst and high-efficiency blue LEDs was challenged with several common volatile organic compounds (VOCs) found in ISS cabin air to evaluate the system's ability to perform high-throughput trace contaminant removal. The ultimate goal for this testing was to determine if the unit would be useful in pre-heat exchanger operations to lessen condensed VOCs in recovered water thus lowering the burden of VOC removal for water purification systems.

High-Flux, High Performance H2O2 Catalyst Bed for ISTAR

NASA Technical Reports Server (NTRS)

Ponzo, J.

2005-01-01

On NASA's ISTAR RBCC program packaging and performance requirements exceeded traditional H2O2 catalyst bed capabilities. Aerojet refined a high performance, monolithic 90% H202 catalyst bed previously developed and demonstrated. This approach to catalyst bed design and fabrication was an enabling technology to the ISTAR tri-fluid engine. The catalyst bed demonstrated 55 starts at throughputs greater than 0.60 lbm/s/sq in for a duration of over 900 seconds in a physical envelope approximately 114 of traditional designs. The catalyst bed uses photoetched plates of metal bonded into a single piece monolithic structure. The precise control of the geometry and complete mixing results in repeatable, quick starting, high performing catalyst bed. Three different beds were designed and tested, with the best performing bed used for tri-fluid engine testing.

A dual-catalysis approach to enantioselective [2 + 2] photocycloadditions using visible light.

PubMed

Du, Juana; Skubi, Kazimer L; Schultz, Danielle M; Yoon, Tehshik P

2014-04-25

In contrast to the wealth of catalytic systems that are available to control the stereochemistry of thermally promoted cycloadditions, few similarly effective methods exist for the stereocontrol of photochemical cycloadditions. A major unsolved challenge in the design of enantioselective catalytic photocycloaddition reactions has been the difficulty of controlling racemic background reactions that occur by direct photoexcitation of substrates while unbound to catalyst. Here, we describe a strategy for eliminating the racemic background reaction in asymmetric [2 + 2] photocycloadditions of α,β-unsaturated ketones to the corresponding cyclobutanes by using a dual-catalyst system consisting of a visible light-absorbing transition-metal photocatalyst and a stereocontrolling Lewis acid cocatalyst. The independence of these two catalysts enables broader scope, greater stereochemical flexibility, and better efficiency than previously reported methods for enantioselective photochemical cycloadditions.

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

Support effects in single atom iron catalysts on adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S)

NASA Astrophysics Data System (ADS)

Gao, Zhengyang; Yang, Weijie; Ding, Xunlei; Lv, Gang; Yan, Weiping

2018-04-01

The effects of support on gas adsorption is crucial for single atom catalysts design and optimization. To gain insight into support effects on gas adsorption characteristics, a comprehensive theoretical study was performed to investigate the adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S) by utilizing single atom iron catalysts with three graphene-based supports. The adsorption geometry, adsorption energy, electronic and magnetic properties of the adsorption system have been explored. Additionally, the support effects have been analyzed through d-band center and Fermi softness, and thermodynamic analysis has been performed to consider the effect of temperature on gas adsorption. The support effects have a remarkable influence on the adsorption characteristics of four types of toxic gases which is determined by the electronic structure of graphene-based support, and the electronic structure can be characterized by Fermi softness of catalysts. Fermi softness and uplift height of Fe atom could be good descriptors for the adsorption activity of single atom iron catalysts with graphene-based supports. The findings can lay a foundation for the further study of graphene-based support effects in single atom catalysts and provide a guideline for development and design of new graphene-based support materials utilizing the idea of Fermi softness.

Oxidation catalyst

DOEpatents

Ceyer, Sylvia T.; Lahr, David L.

2010-11-09

The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

Investigation of NO(x) Removal from Small Engine Exhaust

NASA Technical Reports Server (NTRS)

Akyurtlu, Ates; Akyurtlu, Jale F.

1999-01-01

Contribution of emissions from small engines to the air pollution is significant. Due to differences in operating conditions and economics, the pollution control systems designed for automobiles will be neither suitable nor economically feasible for use on small engines. The objective of this project was to find a catalyst for the removal of NOx from the exhaust of small engines which use a rich air to fuel ratio. The desired catalyst should be inexpensive so that the cost of the pollution control unit will be only a small fraction of the total equipment cost. The high cost of noble metals makes them too expensive for use as NOx catalyst for small engines. Catalytic reduction of NO can also be accomplished by base-metal oxide catalysts. The main disadvantage of base-metal catalysts is their deactivation by poisons and high temperatures. Requirements for the length of the life of the small engine exhaust catalysts are much less than those for automobile exhaust catalysts. Since there is no oxygen in the exhaust gases, reduction selectivity is not a problem. Also, the reducing exhaust gases might help prevent the harmful interactions of the catalyst with the support. For these reasons only the supported metal oxide catalysts were investigated in this project.

Investigation of NOx Removal from Small Engine Exhaust

NASA Technical Reports Server (NTRS)

Akyurtlu, Ates; Akyurtlu, Jale F.

1999-01-01

Contribution of emissions from small engines to the air pollution is significant. Due to differences in operating conditions and economics, the pollution control systems designed for automobiles will be neither suitable nor economically feasible for use on small engines. The objective of this project was to find a catalyst for the removal of NOx from the exhaust of small engines which use a rich air to fuel ratio. The desired catalyst should be inexpensive so that the cost of the pollution control unit will be only a small fraction of the total equipment cost. The high cost of noble metals makes them too expensive for use as NOx catalyst for small engines. Catalytic reduction of Nitrogen Oxide (NO) can also be accomplished by base-metal oxide catalysts. The main disadvantage of base-metal catalysts is their deactivation by poisons and high temperatures. Requirements for the length of the life of the small engine exhaust catalysts are much less than those for automobile exhaust catalysts. Since there is no oxygen in the exhaust gases, reduction selectivity is not a problem. Also, the reducing exhaust gases might help prevent the harmful interactions of the catalyst with the support. For these reasons only the supported metal oxide catalysts were investigated in this project.

Fibrous Catalyst-Enhanced Acanthamoeba Disinfection by Hydrogen Peroxide.

PubMed

Kilvington, Simon; Winterton, Lynn

2017-11-01

Hydrogen peroxide (H2O2) disinfection systems are contact-lens-patient problem solvers. The current one-step, criterion-standard version has been widely used since the mid-1980s, without any significant improvement. This work identifies a potential next-generation, one-step H2O2, not based on the solution formulation but rather on a case-based peroxide catalyst. One-step H2O2 systems are widely used for contact lens disinfection. However, antimicrobial efficacy can be limited because of the rapid neutralization of the peroxide from the catalytic component of the systems. We studied whether the addition of an iron-containing catalyst bound to a nonfunctional propylene:polyacryonitrile fabric matrix could enhance the antimicrobial efficacy of these one-step H2O2 systems. Bausch + Lomb PeroxiClear and AOSept Plus (both based on 3% H2O2 with a platinum-neutralizing disc) were the test systems. These were tested with and without the presence of the catalyst fabric using Acanthamoeba cysts as the challenge organism. After 6 hours' disinfection, the number of viable cysts was determined. In other studies, the experiments were also conducted with biofilm formed by Stenotrophomonas maltophilia and Elizabethkingia meningoseptica bacteria. Both control systems gave approximately 1-log10 kill of Acanthamoeba cysts compared with 3.0-log10 kill in the presence of the catalyst (P < .001). In the biofilm studies, no viable bacteria were recovered following disinfection in the presence of the catalyst compared with ≥3.0-log10 kill when it was omitted. In 30 rounds' recurrent usage, the experiments, in which the AOSept Plus system was subjected to 30 rounds of H2O2 neutralization with or without the presence of catalytic fabric, showed no loss in enhanced biocidal efficacy of the material. The catalytic fabric was also shown to not retard or increase the rate of H2O2 neutralization. We have demonstrated the catalyst significantly increases the efficacy of one-step H2O2 disinfection systems using highly resistant Acanthamoeba cysts and bacterial biofilm. Incorporating the catalyst into the design of these one-step H2O2 disinfection systems could improve the antimicrobial efficacy and provide a greater margin of safety for contact lens users.

Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

PubMed

Gao, Wenpei; Hood, Zachary D; Chi, Miaofang

2017-04-18

Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell, between separate phases and twinned grains, between the catalyst surface and gas, and between metal and support are discussed. We also provide an outlook on how emerging electron microscopy techniques, such as vibrational spectroscopy and electron ptychography, will impact future catalysis research.

Novel micro-reactor flow cell for investigation of model catalysts using in situ grazing-incidence X-ray scattering

PubMed Central

Kehres, Jan; Pedersen, Thomas; Masini, Federico; Andreasen, Jens Wenzel; Nielsen, Martin Meedom; Diaz, Ana; Nielsen, Jane Hvolbæk; Hansen, Ole

2016-01-01

The design, fabrication and performance of a novel and highly sensitive micro-reactor device for performing in situ grazing-incidence X-ray scattering experiments of model catalyst systems is presented. The design of the reaction chamber, etched in silicon on insulator (SIO), permits grazing-incidence small-angle X-ray scattering (GISAXS) in transmission through 10 µm-thick entrance and exit windows by using micro-focused beams. An additional thinning of the Pyrex glass reactor lid allows simultaneous acquisition of the grazing-incidence wide-angle X-ray scattering (GIWAXS). In situ experiments at synchrotron facilities are performed utilizing the micro-reactor and a designed transportable gas feed and analysis system. The feasibility of simultaneous in situ GISAXS/GIWAXS experiments in the novel micro-reactor flow cell was confirmed with CO oxidation over mass-selected Ru nanoparticles. PMID:26917133

Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, Robert J.; Gao, Hanrong

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

Catalyst system comprising a first catalyst system tethered to a supported catalyst

DOEpatents

Angelici, R.J.; Gao, H.

1998-08-04

The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilication, olefin oxidation, isomerization, hydrocyanidation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical. 2 figs.

Oxidative Dehydrogenation on Nanocarbon: Insights into the Reaction Mechanism and Kinetics via in Situ Experimental Methods.

PubMed

Qi, Wei; Yan, Pengqiang; Su, Dang Sheng

2018-03-20

Sustainable and environmentally benign catalytic processes are vital for the future to supply the world population with clean energy and industrial products. The replacement of conventional metal or metal oxide catalysts with earth abundant and renewable nonmetallic materials has attracted considerable research interests in the field of catalysis and material science. The stable and efficient catalytic performance of nanocarbon materials was discovered at the end of last century, and these materials are considered as potential alternatives for conventional metal-based catalysts. With its rapid development in the past 20 years, the research field of carbon catalysis has been experiencing a smooth transition from the discovery of novel nanocarbon materials or related new reaction systems to the atomistic-level mechanistic understanding on the catalytic process and the subsequent rational design of the practical catalytic reaction systems. In this Account, we summarize the recent progress in the kinetic and mechanistic studies on nanocarbon catalyzed alkane oxidative dehydrogenation (ODH) reactions. The paper attempts to extract general concepts and basic regularities for carbon catalytic process directing us on the way for rational design of novel efficient metal-free catalysts. The nature of the active sites for ODH reactions has been revealed through microcalorimetric analysis, ambient pressure X-ray photoelectron spectroscopy (XPS) measurement, and in situ chemical titration strategies. The detailed kinetic analysis and in situ catalyst structure characterization suggests that carbon catalyzed ODH reactions involve the redox cycles of the ketonic carbonyl-hydroxyl pairs, and the key physicochemical parameters (activation energy, reaction order, and rate/equilibrium constants, etc.) of the carbon catalytic systems are proposed and compared with conventional transition metal oxide catalysts. The proposal of the intrinsic catalytic activity (TOF) provides the possibility for the fair comparisons of different nanocarbon catalysts and the consequent structure-function relation regularity. Surface modification and heteroatom doping are proved as the most effective strategies to adjust the catalytic property (activity and product selectivity etc.) of the nanocarbon catalysts. Nanocarbon is actually a proper candidate platform helping us to understand the classical catalytic reaction mechanism better, since there is no lattice oxygen and all the catalytic process happens on nanocarbon surface. This Account also exhibits the importance of the in situ structural characterizations for heterogeneous nanocarbon catalysis. The research strategy and methods proposed for carbon catalysts may also shed light on other complicated catalytic systems or fields concerning the applications of nonmetallic materials, such as energy storage and environment protection etc.

Superstructure-based Design and Optimization of Batch Biodiesel Production Using Heterogeneous Catalysts

NASA Astrophysics Data System (ADS)

Nuh, M. Z.; Nasir, N. F.

2017-08-01

Biodiesel as a fuel comprised of mono alkyl esters of long chain fatty acids derived from renewable lipid feedstock, such as vegetable oil and animal fat. Biodiesel production is complex process which need systematic design and optimization. However, no case study using the process system engineering (PSE) elements which are superstructure optimization of batch process, it involves complex problems and uses mixed-integer nonlinear programming (MINLP). The PSE offers a solution to complex engineering system by enabling the use of viable tools and techniques to better manage and comprehend the complexity of the system. This study is aimed to apply the PSE tools for the simulation of biodiesel process and optimization and to develop mathematical models for component of the plant for case A, B, C by using published kinetic data. Secondly, to determine economic analysis for biodiesel production, focusing on heterogeneous catalyst. Finally, the objective of this study is to develop the superstructure for biodiesel production by using heterogeneous catalyst. The mathematical models are developed by the superstructure and solving the resulting mixed integer non-linear model and estimation economic analysis by using MATLAB software. The results of the optimization process with the objective function of minimizing the annual production cost by batch process from case C is 23.2587 million USD. Overall, the implementation a study of process system engineering (PSE) has optimized the process of modelling, design and cost estimation. By optimizing the process, it results in solving the complex production and processing of biodiesel by batch.

Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

NASA Technical Reports Server (NTRS)

Meier, Anne J.; Shah, Malay; Petersen, Elspeth; Hintze, Paul; Muscatello, Tony

2017-01-01

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

Synthesis-Structure-Activity Relationships in Co3O4 Catalyzed CO Oxidation

NASA Astrophysics Data System (ADS)

Mingle, Kathleen; Lauterbach, Jochen

2018-05-01

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

Small-Scale Coal-Biomass to Liquids Production Using Highly Selective Fischer-Tropsch Synthesis

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

Gangwal, Santosh K.; McCabe, Kevin

2015-04-30

The research project advanced coal-to-liquids (CTL) and coal-biomass to liquids (CBTL) processes by testing and validating Chevron’s highly selective and active cobalt-zeolite hybrid Fischer-Tropsch (FT) catalyst to convert gasifier syngas predominantly to gasoline, jet fuel and diesel range hydrocarbon liquids, thereby eliminating expensive wax upgrading operations The National Carbon Capture Center (NCCC) operated by Southern Company (SC) at Wilsonville, Alabama served as the host site for the gasifier slip-stream testing/demonstration. Southern Research designed, installed and commissioned a bench scale skid mounted FT reactor system (SR-CBTL test rig) that was fully integrated with a slip stream from SC/NCCC’s transport integrated gasifiermore » (TRIG TM). The test-rig was designed to receive up to 5 lb/h raw syngas augmented with bottled syngas to adjust the H 2/CO molar ratio to 2, clean it to cobalt FT catalyst specifications, and produce liquid FT products at the design capacity of 2 to 4 L/day. It employed a 2-inch diameter boiling water jacketed fixed-bed heat-exchange FT reactor incorporating Chevron’s catalyst in Intramicron’s high thermal conductivity micro-fibrous entrapped catalyst (MFEC) packing to efficiently remove heat produced by the highly exothermic FT reaction.« less

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

Sequential-Optimization-Based Framework for Robust Modeling and Design of Heterogeneous Catalytic Systems

DOE PAGES

Rangarajan, Srinivas; Maravelias, Christos T.; Mavrikakis, Manos

2017-11-09

Here, we present a general optimization-based framework for (i) ab initio and experimental data driven mechanistic modeling and (ii) optimal catalyst design of heterogeneous catalytic systems. Both cases are formulated as a nonlinear optimization problem that is subject to a mean-field microkinetic model and thermodynamic consistency requirements as constraints, for which we seek sparse solutions through a ridge (L 2 regularization) penalty. The solution procedure involves an iterative sequence of forward simulation of the differential algebraic equations pertaining to the microkinetic model using a numerical tool capable of handling stiff systems, sensitivity calculations using linear algebra, and gradient-based nonlinear optimization.more » A multistart approach is used to explore the solution space, and a hierarchical clustering procedure is implemented for statistically classifying potentially competing solutions. An example of methanol synthesis through hydrogenation of CO and CO 2 on a Cu-based catalyst is used to illustrate the framework. The framework is fast, is robust, and can be used to comprehensively explore the model solution and design space of any heterogeneous catalytic system.« less

Sequential-Optimization-Based Framework for Robust Modeling and Design of Heterogeneous Catalytic Systems

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

Rangarajan, Srinivas; Maravelias, Christos T.; Mavrikakis, Manos

Here, we present a general optimization-based framework for (i) ab initio and experimental data driven mechanistic modeling and (ii) optimal catalyst design of heterogeneous catalytic systems. Both cases are formulated as a nonlinear optimization problem that is subject to a mean-field microkinetic model and thermodynamic consistency requirements as constraints, for which we seek sparse solutions through a ridge (L 2 regularization) penalty. The solution procedure involves an iterative sequence of forward simulation of the differential algebraic equations pertaining to the microkinetic model using a numerical tool capable of handling stiff systems, sensitivity calculations using linear algebra, and gradient-based nonlinear optimization.more » A multistart approach is used to explore the solution space, and a hierarchical clustering procedure is implemented for statistically classifying potentially competing solutions. An example of methanol synthesis through hydrogenation of CO and CO 2 on a Cu-based catalyst is used to illustrate the framework. The framework is fast, is robust, and can be used to comprehensively explore the model solution and design space of any heterogeneous catalytic system.« less

Mechanistic details for cobalt catalyzed photochemical hydrogen production in aqueous solution: Efficiencies of the photochemical and non-photochemical steps

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

Shan, Bing; Baine, Teera; Ma, Xuan Anh N.

2013-04-17

The use of sunlight to drive chemical reactions that lead to the reduction of water to produce hydrogen is a potential avenue of solar energy utilization. There are many individual steps that take place in this process. This paper reports the investigation of a particular system that involves light absorbing molecules, electron donating agents and a catalyst for water reduction to hydrogen. We evaluated the efficiency of the light induced formation of a strong electron donor, the use of this donor to reduce the catalyst and finally the efficiency of the catalyst to produce hydrogen from water. From this, themore » sources of loss of efficiency could be clearly identified and used in the design of better systems to produce hydrogen from water.« less

Development of Advanced ISS-WPA Catalysts for Organic Oxidation at Reduced Pressure/Temperature

NASA Technical Reports Server (NTRS)

Yu, Ping; Nalette, Tim; Kayatin, Matthew

2016-01-01

The Water Processor Assembly (WPA) at International Space Station (ISS) processes a waste stream via multi-filtration beds, where inorganic and non-volatile organic contaminants are removed, and a catalytic reactor, where low molecular weight organics not removed by the adsorption process are oxidized at elevated pressure in the presence of oxygen and elevated temperature above the normal water boiling point. Operation at an elevated pressure requires a more complex system design compared to a reactor that could operate at ambient pressure. However, catalysts currently available have insufficient activity to achieve complete oxidation of the organic load at a temperature less than the water boiling point and ambient pressure. Therefore, it is highly desirable to develop a more active and efficient catalyst at ambient pressure and a moderate temperature that is less than water boiling temperature. This paper describes our efforts in developing high efficiency water processing catalysts. Different catalyst support structures and coating metals were investigated in subscale reactors and results were compared against the flight WPA catalyst. Detailed improvements achieved on alternate metal catalysts at ambient pressure and 200 F will also be presented in the paper.

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.

Design and use of nanostructured single-site heterogeneous catalysts for the selective transformation of fine chemicals.

PubMed

Dal Santo, Vladimiro; Liguori, Francesca; Pirovano, Claudio; Guidotti, Matteo

2010-05-26

Nanostructured single-site heterogeneous catalysts possess the advantages of classical solid catalysts, in terms of easy recovery and recycling, together with a defined tailored chemical and steric environment around the catalytically active metal site. The use of inorganic oxide supports with selected shape and porosity at a nanometric level may have a relevant impact on the regio- and stereochemistry of the catalytic reaction. Analogously, by choosing the optimal preparation techniques to obtain spatially isolated and well-characterised active sites, it is possible to achieve performances that are comparable to (or, in the most favourable cases, better than) those obtained with homogeneous systems. Such catalysts are therefore particularly suitable for the transformation of highly-functionalised fine chemicals and some relevant examples where high chemo-, regio- and stereoselectivity are crucial will be described.

The chemical properties of bimetallic surfaces: Importance of ensemble and electronic effects in the adsorption of sulfur and SO 2

NASA Astrophysics Data System (ADS)

Rodriguez, José A.

The understanding of the interaction of sulfur with bimetallic surfaces is a critical issue for preventing the deactivation of hydrocarbon reforming catalysts and for the design of better hydrodesulfurization catalysts. The alloying or combination of two metals can lead to materials with special chemical properties due to an interplay of “ensemble” and “electronic” effects. In recent years, several new interesting phenomena have been discovered when studying the interaction of sulfur with bimetallic surfaces using the modern techniques of surface science. Very small amounts of sulfur are able to induce dramatic changes in the morphology of bimetallic surfaces that combine noble metals (Cu, Ag, Au) and transition metals. This phenomenon can lead to big modifications in the activity and selectivity of bimetallic catalysts used for hydrocarbon reforming. In many cases, bimetallic bonding produces a significant redistribution of charge around the bonded metals. The electronic perturbations associated with the formation of a heteronuclear metal-metal bond can affect the reactivity of the bonded metals toward sulfur. This can be a very important issue to consider when trying to minimize the negative effects of sulfur poisoning (Sn/Pt versus Ag/Pt and Cu/Pt catalysts) or when trying to improve the performance of desulfurization catalysts (Co/Mo and Ni/Mo systems). Clearly much more work is necessary in this area, but new concepts are emerging that can be useful for designing more efficient bimetallic catalysts.

Ceria-based model catalysts: fundamental studies on the importance of the metal–ceria interface in CO oxidation, the water–gas shift, CO 2 hydrogenation, and methane and alcohol reforming

DOE PAGES

Rodriguez, José A.; Grinter, David C.; Liu, Zongyuan; ...

2017-02-17

Model metal/ceria and ceria/metal catalysts have been shown to be excellent systems for studying fundamental phenomena linked to the operation of technical catalysts. In the last fifteen years, many combinations of well-defined systems involving different kinds of metals and ceria have been prepared and characterized using the modern techniques of surface science. So far most of the catalytic studies have been centered on a few reactions: CO oxidation, the hydrogenation of CO 2, and the production of hydrogen through the water–gas shift reaction and the reforming of methane or alcohols. By using model catalysts it is been possible to examinemore » in detail correlations between the structural, electronic and catalytic properties of ceria–metal interfaces. In situ techniques (X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, infrared spectroscopy, scanning tunneling microscopy) have been combined to study the morphological changes under reaction conditions and investigate the evolution of active phases involved in the cleavage of C–O, C–H and C–C bonds. Several studies with model ceria catalysts have shown the importance of strong metal–support interactions. Generally, a substantial body of knowledge has been acquired and concepts have been developed for a more rational approach to the design of novel technical catalysts containing ceria.« less

Catalyst displacement assay: a supramolecular approach for the design of smart latent catalysts for pollutant monitoring and removal† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc05584b Click here for additional data file.

PubMed Central

Ho, Pui-Yu; Lu, Yu-Jing; Tang, Qian

2017-01-01

Latent catalysts can be tuned to function smartly by assigning a sensing threshold using the displacement approach for targeted analytes. Three cyano-bridged bimetallic complexes were synthesized as “smart” latent catalysts through the supramolecular assembly of different metallic donors [FeII(CN)6]4–, [FeII(tBubpy)(CN)4]2–, and FeII(tBubpy)2(CN)2 with a metallic acceptor [CuII(dien)]2+. The investigation of both their thermodynamic and kinetic properties on binding with toxic pollutants provided insight into their smart off–on catalytic capabilities, enabling us to establish a threshold-controlled catalytic system for the degradation of pollutants such as cyanide and oxalate. With these smart latent catalysts, a new catalyst displacement assay (CDA) was demonstrated and applied in a real wastewater treatment process to degrade cyanide pollutants in both domestic (level I, untreated) and industrial wastewater samples collected in Hong Kong, China. The smart system was adjusted to be able to initiate the catalytic oxidation of cyanide at a threshold concentration of 20 μM (the World Health Organization’s suggested maximum allowable level for cyanide in wastewater) to the less harmful cyanate under ambient conditions. PMID:28580114

A computer program for the design of optimum catalytic monoliths for CO2 lasers

NASA Technical Reports Server (NTRS)

Guinn, K.; Goldblum, S.; Noskowski, E.; Herz, R.

1990-01-01

Pulsed CO2 lasers have many applications in aeronautics, space research, weather monitoring and other areas. Full exploitation of the potential of these lasers is hampered by the dissociation of CO2 that occurs during laser operation. The development of closed-cycle CO2 lasers requires active CO-O2 recombination (CO oxidation) catalysts and design methods for implementation of catalysts inside lasers. The performance criteria and constraints involved in the design of catalyst configurations for use in a closed-cycle laser are discussed, and several design studies performed with a computerized design program that was written are presented. Trade-offs between catalyst activity and dimensions, flow channel dimensions, pressure drop, O2 conversion and other variables are discussed.

Innovative PCDD/F-containing gas stream generating system applied in catalytic decomposition of gaseous dioxins over V2O5-WO3/TiO2-based catalysts.

PubMed

Yang, Chia Cheng; Chang, Shu Hao; Hong, Bao Zhen; Chi, Kai Hsien; Chang, Moo Been

2008-10-01

Development of effective PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran) control technologies is essential for environmental engineers and researchers. In this study, a PCDD/F-containing gas stream generating system was developed to investigate the efficiency and effectiveness of innovative PCDD/F control technologies. The system designed and constructed can stably generate the gas stream with the PCDD/F concentration ranging from 1.0 to 100ng TEQ Nm(-3) while reproducibility test indicates that the PCDD/F recovery efficiencies are between 93% and 112%. This new PCDD/F-containing gas stream generating device is first applied in the investigation of the catalytic PCDD/F control technology. The catalytic decomposition of PCDD/Fs was evaluated with two types of commercial V(2)O(5)-WO(3)/TiO(2)-based catalysts (catalyst A and catalyst B) at controlled temperature, water vapor content, and space velocity. 84% and 91% PCDD/F destruction efficiencies are achieved with catalysts A and B, respectively, at 280 degrees C with the space velocity of 5000h(-1). The results also indicate that the presence of water vapor inhibits PCDD/F decomposition due to its competition with PCDD/F molecules for adsorption on the active vanadia sites for both catalysts. In addition, this study combined integral reaction and Mars-Van Krevelen model to calculate the activation energies of OCDD and OCDF decomposition. The activation energies of OCDD and OCDF decomposition via catalysis are calculated as 24.8kJmol(-1) and 25.2kJmol(-1), respectively.

Process of activation of a palladium catalyst system

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-08-02

Improved processes for activating a catalyst system used for the reduction of nitrogen oxides are provided. In one embodiment, the catalyst system is activated by passing an activation gas stream having an amount of each of oxygen, water vapor, nitrogen oxides, and hydrogen over the catalyst system and increasing a temperature of the catalyst system to a temperature of at least 180.degree. C. at a heating rate of from 1-20.degree./min. Use of activation processes described herein leads to a catalyst system with superior NOx reduction capabilities.

Supported catalyst systems and method of making biodiesel products using such catalysts

DOEpatents

Kim, Manhoe; Yan, Shuli; Salley, Steven O.; Ng, K. Y. Simon

2015-10-20

A heterogeneous catalyst system, a method of preparing the catalyst system and a method of forming a biodiesel product via transesterification reactions using the catalyst system is disclosed. The catalyst system according to one aspect of the present disclosure represents a class of supported mixed metal oxides that include at least calcium oxide and another metal oxide deposited on a lanthanum oxide or cerium oxide support. Preferably, the catalysts include CaO--CeO.sub.2ZLa.sub.2O.sub.3 or CaO--La.sub.2O.sub.3/CeO.sub.2. Optionally, the catalyst may further include additional metal oxides, such as CaO--La.sub.2O.sub.3--GdOxZLa.sub.2O.sub.3.

Methods of producing epoxides from alkenes using a two-component catalyst system

DOEpatents

Kung, Mayfair C.; Kung, Harold H.; Jiang, Jian

2013-07-09

Methods for the epoxidation of alkenes are provided. The methods include the steps of exposing the alkene to a two-component catalyst system in an aqueous solution in the presence of carbon monoxide and molecular oxygen under conditions in which the alkene is epoxidized. The two-component catalyst system comprises a first catalyst that generates peroxides or peroxy intermediates during oxidation of CO with molecular oxygen and a second catalyst that catalyzes the epoxidation of the alkene using the peroxides or peroxy intermediates. A catalyst system composed of particles of suspended gold and titanium silicalite is one example of a suitable two-component catalyst system.

Computational Modeling of Cobalt-based Water Oxidation: Current Status and Future Challenges

NASA Astrophysics Data System (ADS)

Schilling, Mauro; Luber, Sandra

2018-04-01

A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysis. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability towards real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions.

40 CFR Appendix Viii to Part 86 - Aging Bench Equipment and Procedures

Code of Federal Regulations, 2010 CFR

2010-07-01

.... Exhaust System Installation a. The entire catalyst(s)-plus-oxygen-sensor(s) system, together with all... catalysts, the entire catalyst system including all catalysts, all oxygen sensors and the associated exhaust... first catalyst at its longitudinal axis). Alternatively, the feed gas temperature just before the...

40 CFR Appendix Viii to Part 86 - Aging Bench Equipment and Procedures

Code of Federal Regulations, 2011 CFR

2011-07-01

.... Exhaust System Installation a. The entire catalyst(s)-plus-oxygen-sensor(s) system, together with all... catalysts, the entire catalyst system including all catalysts, all oxygen sensors and the associated exhaust... first catalyst at its longitudinal axis). Alternatively, the feed gas temperature just before the...

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.

Emission Abatement System

DOEpatents

Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander

2003-05-13

Emission abatement system. The system includes a source of emissions and a catalyst for receiving the emissions. Suitable catalysts are absorber catalysts and selective catalytic reduction catalysts. A plasma fuel converter generates a reducing gas from a fuel source and is connected to deliver the reducing gas into contact with the absorber catalyst for regenerating the catalyst. A preferred reducing gas is a hydrogen rich gas and a preferred plasma fuel converter is a plasmatron. It is also preferred that the absorber catalyst be adapted for absorbing NO.sub.x.

Alkene metathesis: the search for better catalysts.

PubMed

Deshmukh, Prashant H; Blechert, Siegfried

2007-06-28

Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts.

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

PubMed

Li, Di; Li, Xinyu; Gong, Jinlong

2016-10-12

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

Catalytic Production of Ethanol from Biomass-Derived Synthesis Gas

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

Trewyn, Brian G.; Smith, Ryan G.

2016-06-01

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

ATOMIC-SCALE DESIGN OF IRON FISCHER-TROPSCH CATALYSTS: A COMBINED COMPUTATIONAL CHEMISTRY, EXPERIMENTAL, AND MICROKINETIC MODELING APPROACH

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

Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale

2005-03-22

Efforts during this first year focused on four areas: (1) searching/summarizing published FTS mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) construction of mass spectrometer-TPD and Berty CSTR reactor systems; (3) preparation and characterization of unsupported iron and alumina-supported iron catalysts at various iron loadings (4) Determination of thermochemical parameters such as binding energies of reactive intermediates, heat of FTS elementary reaction steps, and kinetic parameters such as activation energies, and frequency factors of FTS elementary reaction steps on a number of model surfaces. Literature describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts wasmore » compiled in a draft review. Construction of the mass spectrometer-TPD system is 90% complete and of a Berty CSTR reactor system 98% complete. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by nonaqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2}, thus ideal for kinetic and mechanistic studies. The alumina-supported iron catalysts will be used for kinetic and mechanistic studies. In the coming year, adsorption/desorption properties, rates of elementary steps, and global reaction rates will be measured for these catalysts, with and without promoters, providing a database for understanding effects of dispersion, metal loading, and support on elementary kinetic parameters and for validation of computational models that incorporate effects of surface structure and promoters. Furthermore, using state-of-the-art self-consistent Density Functional Theory (DFT) methods, we have extensively studied the thermochemistry and kinetics of various elementary steps on three different model surfaces: (1) Fe(110), (2) Fe(110) modified by subsurface C, and (3) Fe surface modified with Pt adatoms. These studies have yielded valuable insights into the reactivity of Fe surfaces for FTS, and provided accurate estimates for the effect of Fe modifiers such as subsurface C and surface Pt.« 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

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions

PubMed Central

Kalz, Kai F.; Kraehnert, Ralph; Dvoyashkin, Muslim; Dittmeyer, Roland; Gläser, Roger; Krewer, Ulrike; Reuter, Karsten

2016-01-01

Abstract In the future, (electro‐)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power‐to‐chemical processes require a shift from steady‐state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well‐known that the structure of catalysts is very dynamic. However, in‐depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time‐resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions. PMID:28239429

Effect of H2O2 injection patterns on catalyst bed characteristics

NASA Astrophysics Data System (ADS)

Kang, Hongjae; Lee, Dahae; Kang, Shinjae; Kwon, Sejin

2017-01-01

The decomposition process of hydrogen peroxide can be applied to a bipropellant thruster, as well as to monopropellant thruster. To provide a framework for the optimal design of the injector and catalyst bed depending on a type of thruster, this research scrutinizes the effect of injection patterns of the propellant on the performance of the catalyst bed. A showerhead injector and impinging jet injector were tested with a 50 N monopropellant thruster. Manganese oxide/γ-alumina catalyst and manganese oxide/lanthanum-doped alumina catalyst were prepared and tested. The showerhead injector provided a fast response time, suitable for pulse mode operation. The impinging jet injector mitigated the performance instability and catalyst attrition that is favorable for large scale bipropellant thrusters. The design of a dual catalyst bed was conceptually proposed based on the data obtained from firing tests.

Catalytic destruction of PCDD/Fs over vanadium oxide-based catalysts.

PubMed

Yu, Ming-Feng; Lin, Xiao-Qing; Li, Xiao-Dong; Yan, Mi; Prabowo, Bayu; Li, Wen-Wei; Chen, Tong; Yan, Jian-Hua

2016-08-01

Vanadium oxide-based catalysts were developed for the destruction of vapour phase PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans). A vapour phase PCDD/Fs generating system was designed to supply stable PCDD/Fs steam with initial concentration of 3.2 ng I-TEQ Nm(-3). Two kinds of titania (nano-TiO2 and conventional TiO2) and alumina were used as catalyst supports. For vanadium-based catalysts supported on nano-TiO2, catalyst activity is enhanced with operating temperature increasing from 160 to 300 °C and then reduces with temperature rising further to 350 °C. It is mainly due to the fact that high volatility of organic compounds at 350 °C suppresses adsorption of PCDD/Fs on catalysts surface and then further inhibits the reaction between catalyst and PCDD/Fs. The optimum loading of vanadium on nano-TiO2 support is 5 wt.% where vanadium oxide presents highly dispersed amorphous state according to the Raman spectra and XRD patterns. Excessive vanadium will block the pore space and form microcrystalline V2O5 on the support surface. At the vanadium loading of 5 wt.%, nano-TiO2-supported catalyst performs best on PCDD/Fs destruction compared to Al2O3 and conventional TiO2. Chemical states of vanadium in the fresh, used and reoxidized VOx(5 %)/TiO2 catalysts at different operating temperature are also analysed by XPS.

Electronic π-Delocalization Boosts Catalytic Water Oxidation by Cu(II) Molecular Catalysts Heterogenized on Graphene Sheets.

PubMed

Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Moonshiram, Dooshaye; Picón, Antonio; Monge, Pere; Batista, Victor S; Llobet, Antoni

2017-09-20

A molecular water oxidation catalyst based on the copper complex of general formula [(L py )Cu II ] 2- , 2 2- , (L py is 4-pyrenyl-1,2-phenylenebis(oxamidate) ligand) has been rationally designed and prepared to support a more extended π-conjugation through its structure in contrast with its homologue, the [(L)Cu II ] 2- water oxidation catalyst, 1 2- (L is o-phenylenebis(oxamidate)). The catalytic performance of both catalysts has been comparatively studied in homogeneous phase and in heterogeneous phase by π-stacking anchorage to graphene-based electrodes. In the homogeneous system, the electronic perturbation provided by the pyrene functionality translates into a 150 mV lower overpotential for 2 2- with respect to 1 2- and an impressive increase in the k cat from 6 to 128 s -1 . Upon anchorage, π-stacking interactions with the graphene sheets provide further π-delocalization that improves the catalytic performance of both catalysts. In this sense, 2 2- turned out to be the most active catalyst due to the double influence of both the pyrene and the graphene, displaying an overpotential of 538 mV, a k cat of 540 s -1 and producing more than 5300 TONs.

Catalyst and Process Design for the Continuous Manufacture of Rare Sugar Alcohols by Epimerization-Hydrogenation of Aldoses.

PubMed

Lari, Giacomo M; Gröninger, Olivier G; Li, Qiang; Mondelli, Cecilia; López, Núria; Pérez-Ramírez, Javier

2016-12-20

Sugar alcohols are applied in the food, pharmaceutical, polymer, and fuel industries and are commonly obtained by reduction of the corresponding saccharides. In view of the rarity of some sugar substrates, epimerization of a readily available monosaccharide has been proposed as a solution, but an efficient catalytic system has not yet been identified. Herein, a molybdenum heteropolyacid-based catalyst is developed to transform glucose, arabinose, and xylose into less-abundant mannose, ribose, and lyxose, respectively. Adsorption of molybdic acid onto activated carbon followed by ion exchange to the cesium form limits leaching of the active phase, which greatly improves the catalyst stability over 24 h on stream. The hydrogenation of mixtures of epimers is studied over ruthenium catalysts, and it is found that the precursor to the desired polyol is advantageously converted with faster kinetics. This is explained by density functional theory on the basis of its more favorable adsorption on the metal surface and the lower energy barrier for the addition of a hydrogen atom to the primary carbon atom. Finally, different designs for a continuous process for the conversion of glucose into mannitol are studied, and it is uncovered that two reactors in series with one containing the epimerization catalyst and the other containing a mixture of the epimerization and hydrogenation catalysts increases the mannitol/sorbitol ratio to 1.5 from 1 for a single mixed-bed reactor. This opens a prospective route to the efficient valorization of renewables to added-value chemicals. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Templating Routes to Supported Oxide Catalysts by Design

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

Notestein, Justin M.

2016-09-08

The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas.more » First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MO x-SiO 2 catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO 2-Al 2O 3 acid catalysts and to control reactant selectivity in Al 2O 3-TiO 2 photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported oxide catalysts for energy applications.« less

Emission abatement system utilizing particulate traps

DOEpatents

Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander

2004-04-13

Emission abatement system. The system includes a source of emissions and a catalyst for receiving the emissions. Suitable catalysts are absorber catalysts and selective catalytic reduction catalysts. A plasma fuel converter generates a reducing gas from a fuel source and is connected to deliver the reducing gas into contact with the absorber catalyst for regenerating the catalyst. A preferred reducing gas is a hydrogen rich gas and a preferred plasma fuel converter is a plasmatron. It is also preferred that the absorber catalyst be adapted for absorbing NO.sub.x.

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

DOEpatents

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

1998-01-01

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

de novo computational enzyme design.

PubMed

Zanghellini, Alexandre

2014-10-01

Recent advances in systems and synthetic biology as well as metabolic engineering are poised to transform industrial biotechnology by allowing us to design cell factories for the sustainable production of valuable fuels and chemicals. To deliver on their promises, such cell factories, as much as their brick-and-mortar counterparts, will require appropriate catalysts, especially for classes of reactions that are not known to be catalyzed by enzymes in natural organisms. A recently developed methodology, de novo computational enzyme design can be used to create enzymes catalyzing novel reactions. Here we review the different classes of chemical reactions for which active protein catalysts have been designed as well as the results of detailed biochemical and structural characterization studies. We also discuss how combining de novo computational enzyme design with more traditional protein engineering techniques can alleviate the shortcomings of state-of-the-art computational design techniques and create novel enzymes with catalytic proficiencies on par with natural enzymes. Copyright © 2014 Elsevier Ltd. All rights reserved.

A target-triggered strand displacement reaction cycle: the design and application in adenosine triphosphate sensing.

PubMed

Cheng, Sheng; Zheng, Bin; Wang, Mozhen; Lam, Michael Hon-Wah; Ge, Xuewu

2014-02-01

A strand displacement reaction (SDR) system that runs solely on oligonucleotides has been developed for the amplification detection of adenosine triphosphate (ATP). It involves a target-induced SDR and an entropy-driven catalytic cycle of two SDRs with five oligonucleotides, denoted as substrate, fuel, catalyst, C-1, and C-2. Catalyst, released from the ATP aptamer-catalyst duplex by ATP molecule, catalyzes the SDRs to finally form the substrate-fuel duplex. All of the intermediates in the catalytic SDR processes have been identified by polyacrylamide gel electrophoresis (PAGE) analysis. The introduction of ATP into the SDR system will induce the ATP aptamer to form G-quadruplex conformation so as to release catalyst and trigger the SDR cycle. When the substrate and C-2 oligonucleotides were labeled with a carboxyfluorescein (FAM) fluorophore and a 4-([4-(dimethylamino)phenyl]azo)benzoic acid (DABCYL) quencher, this SDR catalytic system exhibited a "turn-on" response for ATP. The condition for detecting ATP, such as Mg²⁺ concentration, has been optimized to afford a detection limit of 20 nM. This work provides an enzyme-free biosensing strategy and has potential application in aptamer-based biosensing. Copyright © 2013 Elsevier Inc. All rights reserved.

Towards the Rational Design of Nanoparticle Catalysts

NASA Astrophysics Data System (ADS)

Dash, Priyabrat

This research is focused on development of routes towards the rational design of nanoparticle catalysts. Primarily, it is focused on two main projects; (1) the use of imidazolium-based ionic liquids (ILs) as greener media for the design of quasi-homogeneous nanoparticle catalysts and (2) the rational design of heterogeneous-supported nanoparticle catalysts from structured nanoparticle precursors. Each project has different studies associated with the main objective of the design of nanoparticle catalysts. In the first project, imidazolium-based ionic liquids have been used for the synthesis of nanoparticle catalysts. In particular, studies on recyclability, reuse, mode-of-stability, and long-term stability of these ionic-liquid supported nanoparticle catalysts have been done; all of which are important factors in determining the overall "greenness" of such synthetic routes. Three papers have been published/submitted for this project. In the first publication, highly stable polymer-stabilized Au, Pd and bimetallic Au-Pd nanoparticle catalysts have been synthesized in imidazolium-based 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid (Journal of Molecular Catalysis A: Chemical, 2008, 286, 114). The resulting nanoparticles were found to be effective and selective quasi-homogeneous catalysts towards a wide-range of hydrogenation reactions and the catalyst solution was reused for further catalytic reactions with minimal loss in activity. The synthesis of very pure and clean ILs has allowed a platform to study the effects of impurities in the imidazolium ILs on nanoparticle stability. In a later study, a new mode of stabilization was postulated where the presence of low amounts of 1-methylimidazole has substantial effects on the resulting stability of Au and Pd-Au nanoparticles in these ILs (Chemical Communications, 2009, 812). In further continuation of this study, a comparative study involving four stabilization protocols for nanoparticle stabilization in BMIMPF6 IL is described, and have shown that nanoparticle stability and catalytic activity of nanoparticles is dependent on the overall stability of the nanoparticles towards aggregation (manuscript submitted). The second major project is focused on synthesizing structurally well-defined supported catalysts by incorporating the nanoparticle precursors (both alloy and core shell) into oxide frameworks (TiO2 and Al2O 3), and examining their structure-property relationships and catalytic activity. a full article has been published on this project (Journal of Physical Chemistry C, 2009, 113, 12719) in which a route to rationally design supported catalysts from structured nanoparticle precursors with precise control over size, composition, and internal structure of the nanoparticles has been shown. In a continuation of this methodology for the synthesis of heterogeneous catalysts, efforts were carried out to apply the same methodology in imidazolium-based ILs as a one-pot media for the synthesis of supported-nanoparticle heterogeneous catalysts via the trapping of pre-synthesized nanoparticles into porous inorganic oxide materials. Nanoparticle catalysts in highly porous titania supports were synthesized using this methodology (manuscript to be submitted).

CATALYTIC OXIDATION OF GROUNDWATER STRIPPING EMISSIONS

EPA Science Inventory

The paper reviews the applicability of catalytic oxidation to control ground-water air stripping gaseous effluents, with special attention to system designs and case histories. The variety of contaminants and catalyst poisons encountered in stripping operations are also reviewed....

A commitment to values. A system integrates core values with leadership development.

PubMed

Maxfield, M M

1991-01-01

The Values in Leadership program, a new leadership development program created by the Sisters of Charity Health Care Systems (SCHCS), is designed to empower effective leaders to live out personal values compatible with those of the organization. The program, designed for middle and senior managers, comprises seven educational modules- Living Our Values; Valuing Individual Differences; Leader as Servant; Leader as Visionary; Leader as Catalyst; Leader as Mentor; Formative Leadership; and Leader as Mentor; Motivational Coaching. Throughout the sessions, participants discuss the four roles of an effective leader-servant, visionary, catalyst, and mentor-which are grounded in SCHCS core values. Participants are also challenged to identify specific actions that can be integrated into their leadership styles. These actions, drawn from SCHCS leadership practices and core values, are reinforced when participants return to their jobs and write plans to incorporate these practices into their daily work.

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

PubMed

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

2018-02-16

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

Non-Transition-Metal Catalytic System for N 2 Reduction to NH 3: A Density Functional Theory Study of Al-Doped Graphene

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

Tian, Yong-Hui; Hu, Shuangli; Sheng, Xiaolan

The prevalent catalysts for natural and artificial N 2 fixation are known to hinge upon transition-metal (TM) elements. In this paper, we demonstrate by density functional theory that Al-doped graphene is a potential non-TM catalyst to convert N 2 to NH 3 in the presence of relatively mild proton/electron sources. In the integrated structure of the catalyst, the Al atom serves as a binding site and catalytic center while the graphene framework serves as an electron buffer during the successive proton/electron additions to N 2 and its various downstream N xH y intermediates. The initial hydrogenation of N 2 canmore » readily take place via an internal H-transfer process with the assistance of a Li + ion as an additive. Finally, in view of the recurrence of H transfer in the first step of N 2 reduction observed in biological nitrogenases and other synthetic catalysts, this finding highlights the significance of heteroatom-assisted H transfer in the design of synthetic catalysts for N 2 fixation.« less

Adsorptive removal of catalyst poisons from coal gas for methanol synthesis

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

Bhatt, B.L.; Golden, T.C.; Hsiung, T.H.

1991-12-01

As an integral part of the liquid-phase methanol (LPMEOH) process development program, the present study evaluated adsorptive schemes to remove traces of catalyst poisons such as iron carbonyl, carbonyl sulfide, and hydrogen sulfide from coal gas on a pilot scale. Tests were conducted with coal gas from the Cool Water gasification plant at Daggett, California. Iron carbonyl, carbonyl sulfide, and hydrogen sulfide were effectively removed from the coal gas. The adsorption capacities of Linde H-Y zeolite and Calgon BPL carbon for Fe(CO){sub 5} compared well with previous bench-scale results at similar CO{sub 2} partial pressure. Adsorption of COS by Calgonmore » FCA carbon appeared to be chemical and nonregenerable by thermal treatment in nitrogen. A Cu/Zn catalyst removed H{sub 2}S very effectively. With the adsorption system on-line, a methanol catalyst showed stable activity during 120 h operation, demonstrating the feasibility of adsorptive removal of trace catalyst poisons from the synthesis gas. Mass transfer coefficients were estimated for Fe(CO){sub 5} and COS removal which can be directly used for design and scale up.« less

Non-Transition-Metal Catalytic System for N 2 Reduction to NH 3: A Density Functional Theory Study of Al-Doped Graphene

DOE PAGES

Tian, Yong-Hui; Hu, Shuangli; Sheng, Xiaolan; ...

2018-01-16

The prevalent catalysts for natural and artificial N 2 fixation are known to hinge upon transition-metal (TM) elements. In this paper, we demonstrate by density functional theory that Al-doped graphene is a potential non-TM catalyst to convert N 2 to NH 3 in the presence of relatively mild proton/electron sources. In the integrated structure of the catalyst, the Al atom serves as a binding site and catalytic center while the graphene framework serves as an electron buffer during the successive proton/electron additions to N 2 and its various downstream N xH y intermediates. The initial hydrogenation of N 2 canmore » readily take place via an internal H-transfer process with the assistance of a Li + ion as an additive. Finally, in view of the recurrence of H transfer in the first step of N 2 reduction observed in biological nitrogenases and other synthetic catalysts, this finding highlights the significance of heteroatom-assisted H transfer in the design of synthetic catalysts for N 2 fixation.« less

Environmental Technology Verification: Test Report of Mobile Source Emission Control Devices--Johnson Matthey PCRT2 1000, Version 2, Filter + Diesel Oxidation Catalyst

EPA Science Inventory

The Johnson Matthey PCRT2 1000, v.2 system is a partial continuously regenerating technology (PCRT) system that consists of a flow-through partial filter combined with a DOC. The system is designed for low temperature exhaust resulting from intermittent loads from medium and heav...

Sol-gel based oxidation catalyst and coating system using same

NASA Technical Reports Server (NTRS)

Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Patry, JoAnne L. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor)

2010-01-01

An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

Stochastic pumping of non-equilibrium steady-states: how molecules adapt to a fluctuating environment.

PubMed

Astumian, R D

2018-01-11

In the absence of input energy, a chemical reaction in a closed system ineluctably relaxes toward an equilibrium state governed by a Boltzmann distribution. The addition of a catalyst to the system provides a way for more rapid equilibration toward this distribution, but the catalyst can never, in and of itself, drive the system away from equilibrium. In the presence of external fluctuations, however, a macromolecular catalyst (e.g., an enzyme) can absorb energy and drive the formation of a steady state between reactant and product that is not determined solely by their relative energies. Due to the ubiquity of non-equilibrium steady states in living systems, the development of a theory for the effects of external fluctuations on chemical systems has been a longstanding focus of non-equilibrium thermodynamics. The theory of stochastic pumping has provided insight into how a non-equilibrium steady-state can be formed and maintained in the presence of dissipation and kinetic asymmetry. This effort has been greatly enhanced by a confluence of experimental and theoretical work on synthetic molecular machines designed explicitly to harness external energy to drive non-equilibrium transport and self-assembly.

Coke Accumulation on Catalysts used in a Fluidized Bed Pyrolyzer

USDA-ARS?s Scientific Manuscript database

We have examined the impact of various solid catalysts on the product distribution resulting from the pyrolysis of biomass. Though catalysts do have a discernible impact, this impact is small. In our bench-top pyrolyzer designed as a catalyst screening tool, we measure bulk product distribution as...

40 CFR 63.2292 - What definitions apply to this subpart?

Code of Federal Regulations, 2010 CFR

2010-07-01

... designed and maintained to capture all emissions for discharge through a control device. Work practice..., and bagasse. Biofilter means an enclosed control system such as a tank or series of tanks with a fixed.... Catalytic oxidizer means a control system that combusts or oxidizes, in the presence of a catalyst, exhaust...

40 CFR 63.640 - Applicability and designation of affected source.

Code of Federal Regulations, 2014 CFR

2014-07-01

... reformer catalyst regeneration vents, and sulfur plant vents; and (5) Emission points routed to a fuel gas... required for refinery fuel gas systems or emission points routed to refinery fuel gas systems. (e) The... petroleum refining process unit that is subject to this subpart; (3) Units processing natural gas liquids...

40 CFR 63.640 - Applicability and designation of affected source.

Code of Federal Regulations, 2013 CFR

2013-07-01

... reformer catalyst regeneration vents, and sulfur plant vents; and (5) Emission points routed to a fuel gas... required for refinery fuel gas systems or emission points routed to refinery fuel gas systems. (e) The... petroleum refining process unit that is subject to this subpart; (3) Units processing natural gas liquids...

Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

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

Su, Hui

2001-01-01

Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, we introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties of suitablymore » designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, we demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm 2 for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection.« less

Chemical engineering design of CO oxidation catalysts

NASA Technical Reports Server (NTRS)

Herz, Richard K.

1987-01-01

How a chemical reaction engineer would approach the challenge of designing a CO oxidation catalyst for pulsed CO2 lasers is described. CO oxidation catalysts have a long history of application, of course, so it is instructive to first consider the special requirements of the laser application and then to compare them to the characteristics of existing processes which utilize CO oxidation catalysts. All CO2 laser applications require a CO oxidation catalyst with the following characteristics: (1) active at stoichiometric ratios of O2 and CO, (2) no inhibition by CO2 or other components of the laser environment, (3) releases no particulates during vibration or thermal cycling, and (4) long lifetime with a stable activity. In all applications, low consumption of power is desirable, a characteristic especially critical in aerospace applications and, thus, catalyst activity at low temperatures is highly desirable. High power lasers with high pulse repetition rates inherently require circulation of the gas mixture and this forced circulation is available for moving gas past the catalyst. Low repetition rate lasers, however, do not inherently require gas circulation, so a catalyst that did not require such circulation would be favorable from the standpoint of minimum power consumption. Lasers designed for atmospheric penetration of their infrared radiation utilize CO2 formed from rare isotopes of oxygen and this application has the additional constraint that normal abundance oxygen isotopes in the catalyst must not exchange with rare isotopes in the gas mixture.

Highly active and efficient catalysts for alkoxycarbonylation of alkenes

PubMed Central

Dong, Kaiwu; Fang, Xianjie; Gülak, Samet; Franke, Robert; Spannenberg, Anke; Neumann, Helfried; Jackstell, Ralf; Beller, Matthias

2017-01-01

Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h−1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product. PMID:28120947

Advanced technology lightweight fuel cell program

NASA Technical Reports Server (NTRS)

Martin, R. E.

1981-01-01

The potential of the alkaline electrolyte fuel cell as the power source in a multi hundred kilowatt orbital energy storage system was studied. The total system weight of an electrolysis cell energy storage system was determined. The tests demonstrated: (1) the performance stability of a platinum on carbon anode catalyst configuration after 5000 hours of testing has no loss in performance; (2) capability of the alkaline fuel cell to operate to a cyclical load profile; (3) suitability of a lightweight graphite electrolyte reservoir plate for use in the alkaline fuel cell; (4) long life potential of a hybrid polysulfone cell edge frame construction; and (5) long term stability of a fiber reinforced potassium titanate matrix structure. The power section tested operates with passive water removal eliminating the requirement for a dynamic hydrogen pump water separator thereby allowing a powerplant design with reduced weight, lower parasite power, and a potential for high reliability and extended endurance. It is concluded that two perovskites are unsuitable for use as a catalyst or as a catalyst support at the cathode of an alkaline fuel cell.

Fe2P as a novel efficient catalyst promoter in Pd/C system for formic acid electro-oxidation in fuel cells reaction

NASA Astrophysics Data System (ADS)

Wang, Fulong; Xue, Huaiguo; Tian, Zhiqun; Xing, Wei; Feng, Ligang

2018-01-01

Developing catalyst promoter for Pd/C catalyst is significant for the catalytic ability improvement in energy transfer related electrochemical reactions. Herein, we demonstrate Fe2P as an efficient catalyst promoter in Pd/C catalyst system for formic acid electro-oxidation in fuel cells reactions. Adding Fe2P in the Pd/C catalyst system greatly increases the performances for formic acid oxidation by 3-4 times; the CO stripping technique displays two kinds of active sites formation in the Pd-Fe2P/C catalyst system coming from the interaction of Pd, Fe2P and Pd oxide species and both are more efficient for formic acid and CO-species electrooxidation. The smaller charge transfer resistance and Tafel slope for formic acid oxidation indicate the improvements in kinetics by Fe2P in the Pd-Fe2P/C system. The nanostructured hybrid units of Pd, Fe2P and carbon are evidently visible in the high resolution microscopy images and XPS technique confirmes the electronic effect in the catalyst system. The promotion effect of Fe2P in the catalyst system arising from the structure, composition and electronic effect changes is discussed with the help from multiple physical and electrochemical techniques. It is concluded that Fe2P as a significant catalyst promoter will have potential application in energy transfer related electrochemical reactions.

Laccases as palladium oxidases.

PubMed

Mekmouche, Yasmina; Schneider, Ludovic; Rousselot-Pailley, Pierre; Faure, Bruno; Simaan, A Jalila; Bochot, Constance; Réglier, Marius; Tron, Thierry

2015-02-01

The first example of a coupled catalytic system involving an enzyme and a palladium(ii) catalyst competent for the aerobic oxidation of alcohol in mild conditions is described. In the absence of dioxygen, the fungal laccase LAC3 is reduced by a palladium(0) species as evidenced by the UV/VIS and ESR spectra of the enzyme. During the oxidation of veratryl alcohol performed in water, at room temperature and atmospheric pressure, LAC3 regenerates the palladium catalyst, is reduced and catalyzes the four-electron reduction of dioxygen into water with no loss of enzyme activity. The association of a laccase with a water-soluble palladium complex results in a 7-fold increase in the catalytic efficiency of the complex. This is the first step in the design of a family of renewable palladium catalysts for aerobic oxidation.

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

Not Available

The objective of the contract is to consolidate the advances made during the previous contract in the conversion of syngas to motor fuels using Molecular Sieve-containing catalysts and to demonstrate the practical utility and economic value of the new catalyst/process systems with appropriate laboratory runs. Work on the program is divided into the following six tasks: (1) preparation of a detailed work plan covering the entire performance of the contract; (2) preliminary techno-economic assessment of the UCC catalyst/process system; (3) optimization of the most promising catalyst developed under prior contract; (4) optimization of the UCC catalyst system in a mannermore » that will give it the longest possible service life; (5) optimization of a UCC process/catalyst system based upon a tubular reactor with a recycle loop containing the most promising catalyst developed under Tasks 3 and 4 studies; and (6) economic evaluation of the optimal performance found under Task 5 for the UCC process/catalyst system. Progress reports are presented for tasks 2 through 5. 232 figs., 19 tabs.« less

Fuel processing for PEM fuel cells: transport and kinetic issues of system design

NASA Astrophysics Data System (ADS)

Zalc, J. M.; Löffler, D. G.

In light of the distribution and storage issues associated with hydrogen, efficient on-board fuel processing will be a significant factor in the implementation of PEM fuel cells for automotive applications. Here, we apply basic chemical engineering principles to gain insight into the factors that limit performance in each component of a fuel processor. A system consisting of a plate reactor steam reformer, water-gas shift unit, and preferential oxidation reactor is used as a case study. It is found that for a steam reformer based on catalyst-coated foils, mass transfer from the bulk gas to the catalyst surface is the limiting process. The water-gas shift reactor is expected to be the largest component of the fuel processor and is limited by intrinsic catalyst activity, while a successful preferential oxidation unit depends on strict temperature control in order to minimize parasitic hydrogen oxidation. This stepwise approach of sequentially eliminating rate-limiting processes can be used to identify possible means of performance enhancement in a broad range of applications.

Nickel nanoparticles-embedded N-doped carbon nanotubes as a biocompatible electrocatalyst in a water splitting-biosynthetic hybrid system for CO2 conversion.

PubMed

Li, Zhongjian; Li, Gang; Chen, Xinlu; Xia, Zheng; Yao, Jiani; Yang, Bin; Lei, Lecheng; Hou, Yang

2018-05-29

CO2 reduction has drawn increasing attention due to the concern of global warming. Water splitting-biosynthetic hybrid systems are novel and efficient approaches for CO2 conversion. Intimate coupling of electrocatalysts and biosynthesis requires the catalysts possess both high catalytic performance and excellent biocompatibility, which is a bottleneck of developing such catalysts. Here, a novel Ni nanoparticles-embedded N-doped carbon nanotubes (Ni@N-C) complex was synthesized as a hydrogen evolution reaction electrocatalyst and was coupled with a hydrogen-oxidizing autotroph, Cupriavidus necator H16, to convert CO2 to poly-β-hydroxybutyrate. In the Ni@N-C, the Ni nanoparticles were encapsulated in N-C nanotubes, which prevented bacteria from direct contact with Ni and inhibited Ni2+ leaching. As a result, Ni@N-C exhibited excellent biocompatibility and stability. This work demonstrates electrocatalysts and biosynthesis can be intimately coupled via rational catalyst design. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt nanoparticles encapsulated in nitrogen-rich carbon nanotubes as efficient catalysts for organic pollutants degradation via sulfite activation.

PubMed

Wu, Deming; Ye, Peng; Wang, Manye; Wei, Yi; Li, Xiaoxia; Xu, Aihua

2018-06-15

The activation of sulfite by heterogeneous catalysts displays a great potential in the development of new sulfate radials based technologies for wastewater treatment. Herein, cobalt nanoparticles embedded in N-doped carbon nanotubes (Co@NC) were prepared by a simple pyrolysis method. Due to the synergistic effects of the cobalt nanoparticles and N-doped carbon nanotubes, the Co@NC catalyst intrinsically shows an outstanding efficiency, excellent reusability and high stability in the catalytic oxidation of methyl orange (MO) in the presence of sulfite and dioxygen. The structure and efficiency of the catalyst was significantly affected by the content of cobalt and pyrolysis temperature. Several quenching experiments and electron paramagnetic resonance were carried out to investigate the catalytic mechanism. It is found that hydroxyl and sulfate radicals worked together to degrade MO in the system. The formation and decomposition of peroxymonosulfate may be an important route of these reactive radicals production. The effect of different anions, bicarbonate concentration, initial solution pH and dye types on the performance of the catalyst was also studied. This study can open a new approach for design and preparation of encapsulated cobalt in carbon materials as effective catalysts for pollutants degradation via sulfite activation. Copyright © 2018 Elsevier B.V. All rights reserved.

Semiconductor-Electrocatalyst Interfaces: Theory, Experiment, and Applications in Photoelectrochemical Water Splitting.

PubMed

Nellist, Michael R; Laskowski, Forrest A L; Lin, Fuding; Mills, Thomas J; Boettcher, Shannon W

2016-04-19

Light-absorbing semiconductor electrodes coated with electrocatalysts are key components of photoelectrochemical energy conversion and storage systems. Efforts to optimize these systems have been slowed by an inadequate understanding of the semiconductor-electrocatalyst (sem|cat) interface. The sem|cat interface is important because it separates and collects photoexcited charge carriers from the semiconductor. The photovoltage generated by the interface drives "uphill" photochemical reactions, such as water splitting to form hydrogen fuel. Here we describe efforts to understand the microscopic processes and materials parameters governing interfacial electron transfer between light-absorbing semiconductors, electrocatalysts, and solution. We highlight the properties of transition-metal oxyhydroxide electrocatalysts, such as Ni(Fe)OOH, because they are the fastest oxygen-evolution catalysts known in alkaline media and are (typically) permeable to electrolyte. We describe the physics that govern the charge-transfer kinetics for different interface types, and show how numerical simulations can explain the response of composite systems. Emphasis is placed on "limiting" behavior. Electrocatalysts that are permeable to electrolyte form "adaptive" junctions where the interface energetics change during operation as charge accumulates in the catalyst, but is screened locally by electrolyte ions. Electrocatalysts that are dense, and thus impermeable to electrolyte, form buried junctions where the interface physics are unchanged during operation. Experiments to directly measure the interface behavior and test the theory/simulations are challenging because conventional photoelectrochemical techniques do not measure the electrocatalyst potential during operation. We developed dual-working-electrode (DWE) photoelectrochemistry to address this limitation. A second electrode is attached to the catalyst layer to sense or control current/voltage independent from that of the semiconductor back ohmic contact. Consistent with simulations, electrolyte-permeable, redox-active catalysts such as Ni(Fe)OOH form "adaptive" junctions where the effective barrier height for electron exchange depends on the potential of the catalyst. This is in contrast to sem|cat interfaces with dense electrolyte-impermeable catalysts, such as nanocrystalline IrOx, that behave like solid-state buried (Schottky-like) junctions. These results elucidate a design principle for catalyzed photoelectrodes. The buried heterojunctions formed by dense catalysts are often limited by Fermi-level pinning and low photovoltages. Catalysts deposited by "soft" methods, such as electrodeposition, form adaptive junctions that tend to provide larger photovoltages and efficiencies. We also preview efforts to improve theory/simulations to account for the presence of surface states and discuss the prospect of carrier-selective catalyst contacts.

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.

Monolithic Hydrogen Peroxide Catalyst Bed Development

NASA Technical Reports Server (NTRS)

Ponzo, J. B.

2003-01-01

With recent increased industry and government interest in rocket grade hydrogen peroxide as a viable propellant, significant effort has been expended to improve on earlier developments. This effort has been predominately centered in improving heterogeneous. typically catalyst beds; and homogeneous catalysts, which are typically solutions of catalytic substances. Heterogeneous catalyst beds have traditionally consisted of compressed wire screens plated with a catalytic substance, usually silver, and were used m many RCS applications (X-1, Mercury, and Centaur for example). Aerojet has devised a heterogeneous catalyst design that is monolithic (single piece), extremely compact, and has pressure drops equal to or less than traditional screen beds. The design consists of a bonded stack of very thin, photoetched metal plates, silver coated. This design leads to a high surface area per unit volume and precise flow area, resulting in high, stable, and repeatable performance. Very high throughputs have been demonstrated with 90% hydrogen peroxide. (0.60 lbm/s/sq in at 1775-175 psia) with no flooding of the catalyst bed. Bed life of over 900 seconds has also been demonstrated at throughputs of 0.60 lbm/s/sq in across varying chamber pressures. The monolithic design also exhibits good starting performance, short break-in periods, and will easily scale to various sizes.

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

Not Available

The objective of the contract is to consolidate the advances made during the previous contract in the conversion of syngas to motor fuels using Molecular Sieve-containing catalysts and to demonstrate the practical utility and economic value of the new catalyst/process systems with appropriate laboratory runs. Work on the program is divided into the following six tasks: (1) preparation of a detailed work plan covering the entire performance of the contract; (2) preliminary techno-economic assessment of the UCC catalyst/process system; (3) optimization of the most promising catalysts developed under prior contract; (4) optimization of the UCC catalyst system in a mannermore » that will give it the longest possible service life; (5) optimization of a UCC process/catalyst system based upon a tubular reactor with a recycle loop; and (6) economic evaluation of the optimal performance found under Task 5 for the UCC process/catalyst system. Accomplishments are reported for Tasks 2 through 5.« less

ENVIRONMENTAL TECHNOLOGY VERIFICATION, TEST REPORT OF MOBILE SOURCE EMISSIONS CONTROL DEVICES/CLEAN DIESEL TECHNOLOGIES FUEL BORNE CATALYST WITH CLEANAIR SYSTEM'S DIESEL OXIDATION CATALYST

EPA Science Inventory

The Environmental Technology Verification report discusses the technology and performance of the Fuel-Borne Catalyst with CleanAir System's Diesel Oxidation Catalyst manufactured by Clean Diesel Technologies, Inc. The technology is a fuel-borne catalyst used in ultra low sulfur d...

Steam reforming of fuel to hydrogen in fuel cells

DOEpatents

Fraioli, Anthony V.; Young, John E.

1984-01-01

A fuel cell capable of utilizing a hydrocarbon such as methane as fuel and having an internal dual catalyst system within the anode zone, the dual catalyst system including an anode catalyst supporting and in heat conducting relationship with a reforming catalyst with heat for the reforming reaction being supplied by the reaction at the anode catalyst.

Making a Splash in Homogeneous CO₂ Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms.

PubMed

Wiedner, Eric; Linehan, John

2018-06-06

Molecular catalysts for hydrogenation of CO₂ are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO₂ hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO₂. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO₂. Additionally, the solvent can impact catalysis by converting CO₂ into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Steam reforming of fuel to hydrogen in fuel cell

DOEpatents

Young, J.E.; Fraioli, A.V.

1983-07-13

A fuel cell is described capable of utilizing a hydrocarbon such as methane as fuel and having an internal dual catalyst system within the anode zone, the dual catalyst system including an anode catalyst supporting and in heat conducting relationship with a reforming catalyst with heat for the reforming reaction being supplied by the reaction at the anode catalyst.

Bioinspired catalytic materials for energy-relevant conversions

NASA Astrophysics Data System (ADS)

Artero, Vincent

2017-09-01

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

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

DOEpatents

Reilly, Peter T. A.

2010-03-23

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

Multi-stage catalyst systems and uses thereof

DOEpatents

Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

2009-02-10

Catalyst systems and methods provide benefits in reducing the content of nitrogen oxides in a gaseous stream containing nitric oxide (NO), hydrocarbons, carbon monoxide (CO), and oxygen (O.sub.2). The catalyst system comprises an oxidation catalyst comprising a first metal supported on a first inorganic oxide for catalyzing the oxidation of NO to nitrogen dioxide (NO.sub.2), and a reduction catalyst comprising a second metal supported on a second inorganic oxide for catalyzing the reduction of NO.sub.2 to nitrogen (N.sub.2).

Designing Catalytic Monoliths For Closed-Cycle CO2 Lasers

NASA Technical Reports Server (NTRS)

Guinn, Keith; Herz, Richard K.; Goldblum, Seth; Noskowski, ED

1992-01-01

LASCAT (Design of Catalytic Monoliths for Closed-Cycle Carbon Dioxide Lasers) computer program aids in design of catalyst in monolith by simulating effects of design decisions on performance of laser. Provides opportunity for designer to explore tradeoffs among activity and dimensions of catalyst, dimensions of monolith, pressure drop caused by flow of gas through monolith, conversion of oxygen, and other variables. Written in FORTRAN 77.

Characteristics of back corona discharge in a honeycomb catalyst and its application for treatment of volatile organic compounds.

PubMed

Feng, Fada; Zheng, Yanyan; Shen, Xinjun; Zheng, Qinzhen; Dai, Shaolong; Zhang, Xuming; Huang, Yifan; Liu, Zhen; Yan, Keping

2015-06-02

The main technical challenges for the treatment of volatile organic compounds (VOCs) with plasma-assisted catalysis in industrial applications are large volume plasma generation under atmospheric pressure, byproduct control, and aerosol collection. To solve these problems, a back corona discharge (BCD) configuration has been designed to evenly generate nonthermal plasma in a honeycomb catalyst. Voltage-current curves, discharge images, and emission spectra have been used to characterize the plasma. Grade particle collection results and flow field visualization in the discharge zones show not only that the particles can be collected efficiently, but also that the pressure drop of the catalyst layer is relatively low. A three-stage plasma-assisted catalysis system, comprising a dielectric barrier discharge (DBD) stage, BCD stage, and catalyst stage, was built to evaluate toluene treatment performance by BCD. The ozone analysis results indicate that BCD enhances the ozone decomposition by collecting aerosols and protecting the Ag-Mn-O catalyst downstream from aerosol contamination. The GC and FTIR results show that BCD contributes to toluene removal, especially when the specific energy input is low, and the total removal efficiency reaches almost 100%. Furthermore, this removal results in the emission of fewer byproducts.

Dual Layer Monolith ATR of Pyrolysis Oil for Distributed Synthesis Gas Production

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

Lawal, Adeniyi

We have successfully demonstrated a novel reactor technology, based on BASF dual layer monolith catalyst, for miniaturizing the autothermal reforming of pyrolysis oil to syngas, the second and most critical of the three steps for thermochemically converting biomass waste to liquid transportation fuel. The technology was applied to aged as well as fresh samples of pyrolysis oil derived from five different biomass feedstocks, namely switch-grass, sawdust, hardwood/softwood, golden rod and maple. Optimization of process conditions in conjunction with innovative reactor system design enabled the minimization of carbon deposit and control of the H2/CO ratio of the product gas. A comprehensivemore » techno-economic analysis of the integrated process using in part, experimental data from the project, indicates (1) net energy recovery of 49% accounting for all losses and external energy input, (2) weight of diesel oil produced as a percent of the biomass to be ~14%, and (3) for a demonstration size biomass to Fischer-Tropsch liquid plant of ~ 2000 daily barrels of diesel, the price of the diesel produced is ~$3.30 per gallon, ex. tax. However, the extension of catalyst life is critical to the realization of the projected economics. Catalyst deactivation was observed and the modes of deactivation, both reversible and irreversible were identified. An effective catalyst regeneration strategy was successfully demonstrated for reversible catalyst deactivation while a catalyst preservation strategy was proposed for preventing irreversible catalyst deactivation. Future work should therefore be focused on extending the catalyst life, and a successful demonstration of an extended (> 500 on-stream hours) catalyst life would affirm the commercial viability of the process.« less

Photo-oxidation catalysts

DOEpatents

Pitts, J Roland [Lakewood, CO; Liu, Ping [Irvine, CA; Smith, R Davis [Golden, CO

2009-07-14

Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

Assembly of multiple components in a hybrid microcapsule: designing a magnetically separable Pd catalyst for selective hydrogenation.

PubMed

Amali, Arlin Jose; Sharma, Bikash; Rana, Rohit Kumar

2014-09-15

In analogy to the role of long-chain polyamines in biosilicification, poly-L-lysine facilitates the assembly of nanocomponents to design multifunctional microcapsule structures. The method is demonstrated by the fabrication of a magnetically separable catalyst that accommodates Pd nanoparticles (NPs) as active catalyst, Fe3O4 NPs as magnetic component for easy recovery of the catalyst, and silica NPs to impart stability and selectivity to the catalyst. In addition, polyamines embedded inside the microcapsule prevent the agglomeration of Pd NPs and thus result in efficient catalytic activity in hydrogenation reactions, and the hydrophilic silica surface results in selectivity in reactions depending on the polarity of substrates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Staged Catalytic Partial Oxidation (SCPO) System - The State of Art Integrated Short Contact Time Hydrogen Generator

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

Ke Liu; Jin Ki Hong; Wei Wei

Research and development on hydrogen and syngas production have great potential in addressing the following challenges in energy arena: (1) produce more clean fuels to meet the increasing demands for clean liquid and gaseous fuels for transportation and electricity generation, (2) increase the efficiency of energy utilization for fuels and electricity production, and (3) eliminate the pollutants and decouple the link between energy utilization and greenhouse gas emissions in end-use systems [Song, 2006, Liu, Song & Subramani 2009]. In this project, GE Global Research (GEGR) collaborated with Argonne National Laboratory (ANL) and the University of Minnesota (UoMn), developed and demonstratedmore » a low cost, compact staged catalytic partial oxidation (SCPO) technology for distributed hydrogen generation. GEGR analyzed different reforming system designs, and developed the SCPO reforming system which is a unique technology staging and integrating 3 different short contact time catalysts in a single, compact reactor: catalytic partial oxidation (CPO), steam methane reforming (SMR) and water-gas shift (WGS). This integration is demonstrated via the fabrication of a prototype scale unit of each key technology. Approaches for key technical challenges of the program includes: · Analyzed different system designs · Designed the SCPO hydrogen production system · Developed highly active and sulfur tolerant CPO catalysts · Designed and built different pilot-scale reactors to demonstrate each key technology · Evaluated different operating conditions · Quantified the efficiency and cost of the system · Developed process design package (PDP) for 1500 kg H2/day distributed H2 production unit. SCPO met the Department of Energy (DOE) and GE’s cost and efficiency targets for distributed hydrogen production.« less

Fuel cell system with sodium borohydride as hydrogen source for unmanned aerial vehicles

NASA Astrophysics Data System (ADS)

Kim, Kyunghwan; Kim, Taegyu; Lee, Kiseong; Kwon, Sejin

In this study, we design and fabricate a fuel cell system for application as a power source in unmanned aerial vehicles (UAVs). The fuel cell system consists of a fuel cell stack, hydrogen generator, and hybrid power management system. PEMFC stack with an output power of 100 W is prepared and tested to decide the efficient operating conditions; the stack must be operated in the dead-end mode with purge in order to ensure prolonged stack performance. A hydrogen generator is fabricated to supply gaseous hydrogen to the stack. Sodium borohydride (NaBH 4) is used as the hydrogen source in the present study. Co/Al 2O 3 catalyst is prepared for the hydrolysis of the alkaline NaBH 4 solution at room temperature. The fabricated Co catalyst is comparable to the Ru catalyst. The UAV consumes more power in the takeoff mode than in the cruising mode. A hybrid power management system using an auxiliary battery is developed and evaluated for efficient energy management. Hybrid power from both the fuel cell and battery powers takeoff and turning flight operations, while the fuel cell supplies steady power during the cruising flight. The capabilities of the fuel-cell UAVs for long endurance flights are validated by successful flight tests.

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

Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi

Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design.

PubMed

Greeley, Jeffrey

2016-06-07

Scaling relationships are theoretical constructs that relate the binding energies of a wide variety of catalytic intermediates across a range of catalyst surfaces. Such relationships are ultimately derived from bond order conservation principles that were first introduced several decades ago. Through the growing power of computational surface science and catalysis, these concepts and their applications have recently begun to have a major impact in studies of catalytic reactivity and heterogeneous catalyst design. In this review, the detailed theory behind scaling relationships is discussed, and the existence of these relationships for catalytic materials ranging from pure metal to oxide surfaces, for numerous classes of molecules, and for a variety of catalytic surface structures is described. The use of the relationships to understand and elucidate reactivity trends across wide classes of catalytic surfaces and, in some cases, to predict optimal catalysts for certain chemical reactions, is explored. Finally, the observation that, in spite of the tremendous power of scaling relationships, their very existence places limits on the maximum rates that may be obtained for the catalyst classes in question is discussed, and promising strategies are explored to overcome these limitations to usher in a new era of theory-driven catalyst design.

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.

Catalysts, systems and methods to reduce NOX in an exhaust gas stream

DOEpatents

Castellano, Christopher R.; Moini, Ahmad; Koermer, Gerald S.; Furbeck, Howard

2010-07-20

Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having an SCR catalyst comprising silver tungstate on an alumina support. The emissions treatment system may be used for the treatment of exhaust streams from diesel engines and lean burn gasoline engines. An emissions treatment system may further comprise an injection device operative to dispense a hydrocarbon reducing agent upstream of the catalyst.

Selective catalytic reduction system and process using a pre-sulfated zirconia binder

DOEpatents

Sobolevskiy, Anatoly; Rossin, Joseph A.

2010-06-29

A selective catalytic reduction (SCR) process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream with a catalyst system, the catalyst system comprising (ZrO.sub.2)SO.sub.4, palladium, and a pre-sulfated zirconia binder. The inclusion of a pre-sulfated zirconia binder substantially increases the durability of a Pd-based SCR catalyst system. A system for implementing the disclosed process is further provided.

Supported metal catalysts for alcohol/sugar alcohol steam reforming

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

Davidson, Stephen; Zhang, He; Sun, Junming

Despite extensive studies on hydrogen production via steam reforming of alcohols and sugar alcohols, catalysts typically suffer a variety of issues from poor hydrogen selectivity to rapid deactivation. Here, we summarize recent advances in fundamental understanding of functionality and structure of catalysts for alcohol/sugar alcohol steam reforming, and provide perspectives on further development required to design highly efficient steam reforming catalysts.

GREENING OF OXIDATION CATALYSIS THROUGH IMPROVED CATALYST AND PROCESS DESIGN

EPA Science Inventory

Greening of Oxidation Catalysis Through Improved Catalysts and Process Design
Michael A. Gonzalez*, Thomas Becker, and Raymond Smith

United State Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, 26 W...

Model systems in heterogeneous catalysis: towards the design and understanding of structure and electronic properties.

PubMed

Pan, Q; Li, L; Shaikhutdinov, S; Fujimori, Y; Hollerer, M; Sterrer, M; Freund, H-J

2018-05-29

We discuss in this paper two case studies related to nano-particle catalyst systems. One concerns a model system for the Cr/SiO2 Phillips catalyst for ethylene polymerization and here we present XPS data to complement the previously published TPD, IRAS and reactivity studies to elucidate the electronic structure of the system in some detail. The second case study provides additional information on Au nano-particles supported on ultrathin MgO(100)/Ag(100) films where we had observed a specific activity of the particle's rim at the metal-oxide interface with respect to CO2 activation and oxalate formation, obviously connected to electron transfer through the MgO film from the metal substrate underneath. Here we present XPS and Auger data, which allows detailed analysis of the observed chemical shifts. This analysis corroborates previous findings deduced via STM.

Development of a chemiluminescent and bioluminescent system for the detection of bacteria in wastewater effluent

NASA Technical Reports Server (NTRS)

Thomas, R. R.

1975-01-01

Automated chemiluminescent and bioluminescent sensors were developed for continuous monitoring of microbial levels in wastewater effluent. Development of the chemiluminescent system included optimization of reagent concentrations as well as two new techniques which will allow for increased sensitivity and specificity. The optimal reagent concentrations are 0.0025 M luminol and 0.0125 M sodium perborate in 0.75N sodium hydroxide before addition of sample. The methods developed to increase specificity include (1) extraction of porphyrins from bacteria collected in a filter using 0.1N NaOH - 50 percent Ethanol, and (2) use of the specific reaction rate characteristics for the different luminol catalysts. Since reaction times are different for each catalyst, the reaction can be made specific for bacteria by measuring only the light emission from the particular reaction time zone specific for bacteria. Developments of the bioluminescent firefly luciferase system were in the area of flow system design.

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.

High-throughput heterogeneous catalyst research

NASA Astrophysics Data System (ADS)

Turner, Howard W.; Volpe, Anthony F., Jr.; Weinberg, W. H.

2009-06-01

With the discovery of abundant and low cost crude oil in the early 1900's came the need to create efficient conversion processes to produce low cost fuels and basic chemicals. Enormous investment over the last century has led to the development of a set of highly efficient catalytic processes which define the modern oil refinery and which produce most of the raw materials and fuels used in modern society. Process evolution and development has led to a refining infrastructure that is both dominated and enabled by modern heterogeneous catalyst technologies. Refineries and chemical manufacturers are currently under intense pressure to improve efficiency, adapt to increasingly disadvantaged feedstocks including biomass, lower their environmental footprint, and continue to deliver their products at low cost. This pressure creates a demand for new and more robust catalyst systems and processes that can accommodate them. Traditional methods of catalyst synthesis and testing are slow and inefficient, particularly in heterogeneous systems where the structure of the active sites is typically complex and the reaction mechanism is at best ill-defined. While theoretical modeling and a growing understanding of fundamental surface science help guide the chemist in designing and synthesizing targets, even in the most well understood areas of catalysis, the parameter space that one needs to explore experimentally is vast. The result is that the chemist using traditional methods must navigate a complex and unpredictable diversity space with a limited data set to make discoveries or to optimize known systems. We describe here a mature set of synthesis and screening technologies that together form a workflow that breaks this traditional paradigm and allows for rapid and efficient heterogeneous catalyst discovery and optimization. We exemplify the power of these new technologies by describing their use in the development and commercialization of a novel catalyst for the hydrodesulfurization of gasoline distillates having 50% more selectivity and 30% more activity for sulfur removal than the state-of-the-art commercial reference.

Comparing kinetic profiles between bifunctional and binary type of Zn(salen)-based catalysts for organic carbonate formation

PubMed Central

Martín, Carmen

2014-01-01

Summary Zn(salen) complexes have been employed as active catalysts for the formation of cyclic carbonates from epoxides and CO2. A series of kinetic experiments was carried out to obtain information about the mechanism for this process catalyzed by these complexes and in particular about the order-dependence in catalyst. A comparative analysis was done between the binary catalyst system Zn(salphen)/NBu4I and a bifunctional system Zn(salpyr)·MeI with a built-in nucleophile. The latter system demonstrates an apparent second-order dependence on the bifunctional catalyst concentration and thus follows a different, bimetallic mechanism as opposed to the binary catalyst that is connected with a first-order dependence on the catalyst concentration and a monometallic mechanism. PMID:25161742

Dual reactor for in situ/operando fluorescent mode XAS studies of sample containing low-concentration 3d or 5d metal elements

NASA Astrophysics Data System (ADS)

Nguyen, Luan; Tang, Yu; Li, Yuting; Zhang, Xiaoyan; Wang, Ding; Tao, Franklin Feng

2018-05-01

Transition metal elements are the most important elements of heterogeneous catalysts used for chemical and energy transformations. Many of these catalysts are active at a temperature higher than 400 °C. For a catalyst containing a 3d or 5d metal element with a low concentration, typically their released fluorescence upon the K-edge or L-edge adsorption of X-rays is collected for the analysis of chemical and coordination environments of these elements. However, it is challenging to perform in situ/operando X-ray absorption spectroscopy (XAS) studies of elements of low-energy absorption edges at a low concentration in a catalyst during catalysis at a temperature higher than about 450 °C. Here a unique reaction system consisting two reactors, called a dual reactor system, was designed for performing in situ or operando XAS studies of these elements of low-energy absorption edges in a catalyst at a low concentration during catalysis at a temperature higher than 450 °C in a fluorescent mode. This dual-reactor system contains a quartz reactor for preforming high-temperature catalysis up to 950 °C and a Kapton reactor remaining at a temperature up to 450 °C for collecting data in the same gas of catalysis. With this dual reactor, chemical and coordination environments of low-concentration metal elements with low-energy absorption edges such as the K-edge of 3d metals including Ti, V, Cr, Mn, Fe, Co, Ni, and Cu and L edge of 5d metals including W, Re, Os, Ir, Pt, and Au can be examined through first performing catalysis at a temperature higher than 450 °C in the quartz reactor and then immediately flipping the catalyst in the same gas flow to the Kapton reactor remained up to 450 °C to collect data. The capability of this dual reactor was demonstrated by tracking the Mn K-edge of the MnOx/Na2WO4 catalyst during activation in the temperature range of 300-900 °C and catalysis at 850 °C.

Thermal protection system repair kit program

NASA Technical Reports Server (NTRS)

1979-01-01

The feasibility and conceptual design aspects of repair materials and procedures for in orbit repair of the space shuttle orbiter TPS tiles are investigated. Material studies to investigate cure in place materials are described including catalyst and cure studies, ablation tests and evaluations, and support mixing and applicator design. The feasibility of the repair procedures, the storage of the TPS, dispensing, and cure problems are addressed.

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

Arendt, Paul N.; DePaula, Ramond F.; Zhu, Yuntian T.

An array of carbon nanotubes is prepared by exposing a catalyst structure to a carbon nanotube precursor. Embodiment catalyst structures include one or more trenches, channels, or a combination of trenches and channels. A system for preparing the array includes a heated surface for heating the catalyst structure and a cooling portion that cools gas above the catalyst structure. The system heats the catalyst structure so that the interaction between the precursor and the catalyst structure results in the formation of an array of carbon nanotubes on the catalyst structure, and cools the gas near the catalyst structure and alsomore » cools any carbon nanotubes that form on the catalyst structure to prevent or at least minimize the formation of amorphous carbon. Arrays thus formed may be used for spinning fibers of carbon nanotubes.« less

From fundamental studies of reactivity on single crystals to the design of catalysts

NASA Astrophysics Data System (ADS)

H. Larsen, Jane; Chorkendorff, Ib

One of the prominent arguments for performing surface science studies have for many years been to improve and design new and better catalysts. Although surface science has provided the fundamental framework and tools for understanding heterogeneous catalysis until now there have been extremely few examples of actually designing new catalysts based solely on surface science studies. In this review, we shall demonstrate how a close collaboration between different fundamental disciplines like structural-, theoretical-and reactivity-studies of surfaces as well as a strong interaction with industry can have strong synergetic effects and how this was used to develop a new catalyst. As so often before the studies reviewed here were not initiated with the objective to solve a specific problem, but realizing that a new class of very stable two-dimensional alloys could be synthesized from otherwise immiscible metals made it possible to present a new solution to a specific problem in the industrial catalysis relating to methane activation in the steam reforming process. Methane is the main constituent of natural gas and it is an extremely important raw material for many large scale chemical processes such as production of hydrogen, ammonia, and methanol. In the steam reforming process methane and water are converted into a mixture of mainly hydrogen and carbon monoxide, the so-called synthesis gas. Industrially the steam reforming process usually takes place over a catalyst containing small nickel crystallites highly dispersed on a porous support material like aluminum/magnesium oxides in order to achieve a high active metal area. There is a general consensus that the rate limiting step of this process is the dissociative sticking of methane on the nickel surface. Driven by the desire to understand this step and hopefully be able to manipulate the reactivity, a large number of investigations of the methane/nickel interaction have been performed using nickel single crystals as model catalysts. The process has been investigated, both under thermal conditions and by using supersonic molecular beams elucidating the dynamical aspects of the interaction. The results obtained will be reviewed both with respect to the clean and modified nickel surfaces. Especially the two-dimensional gold-nickel alloy system will be considered since the fundamental results here have lead to the invention of a new nickel based catalyst, which is much more resistant to carbon formation than the conventional nickel catalysts. This may be one of the first examples of how fundamental research can lead to the invention of new catalysts. Other overlayer/alloy combinations, their stability, and reactivity are briefly discussed with respect to manipulation of the surface reactivity towards methane.

Tailor-made Molecular Cobalt Catalyst System for the Selective Transformation of Carbon Dioxide to Dialkoxymethane Ethers.

PubMed

Schieweck, Benjamin G; Klankermayer, Jürgen

2017-08-28

Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH 2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-Platinum Group Metal OER/ORR Catalysts for Alkaline Membrane Fuel Cells and Electrolyzers

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

Danilovic, Nemanja; Ayers, Katherine

Regenerative fuel cells (RFC) are energy storage devices that capture electrical energy in the form of hydrogen, with potential application for backup power and energy storage in remote locations, unmanned missions, and renewable energy capture. A unitized regenerative fuel cell (URFC) combines two separate electrochemical devices (fuel cell and electrolyzer) into one stack. The stack cost is driven by the platinum group metal (PGM) catalysts and the flow field components designed to withstand high potentials in acidic environments. Since the stack is the most expensive subcomponent of both the fuel cell and electrolyzer system, combining the two devices results inmore » substantial reduction in capital cost. However, in the past, combining the two stacks sacrificed device performance (operating cost) largely because the fuel cell had to operate with the thick electrolysis membranes in a URFC configuration, and due to water management issues in switching modes. Recent work in membrane-based electrolysis has resulted in more mechanically robust designs and materials that allow much thinner membranes, and work in flow cell design such as flow batteries has shown improved water transport through channel design and wet-proofing approaches. Therefore, the URFC concept is worth revisiting. At the same time, alkaline exchange membrane (AEM) devices are gathering attention due to the promise of PGM and valve metal elimination from the stack and a resulting strategic and capital cost benefit as compared with proton exchange membrane (PEM) systems. The result is a lower capital cost system that has half the precious metal group (PGM) catalysts, membrane and other stack component materials compared with discrete RFCs, although at the sacrifice of performance (operating cost). Proton has identified innovative AEM based RFC's to fulfill the role of low capital cost energy storage device owing to the use of non-precious metal containing electrodes, that enables certain markets where higher operating costs can be tolerated.« less

Chiral poly-rare earth metal complexes in asymmetric catalysis

PubMed Central

Shibasaki, Masakatsu

2006-01-01

Asymmetric catalysis is a powerful component of modern synthetic organic chemistry. To further broaden the scope and utility of asymmetric catalysis, new basic concepts for the design of asymmetric catalysts are crucial. Because most chemical reactions involve bond-formation between two substrates or moieties, high enantioselectivity and catalyst activity should be realized if an asymmetric catalyst can activate two reacting substrates simultaneously at defined positions. Thus, we proposed the concept of bifunctional asymmetric catalysis, which led us to the design of new asymmetric catalysts containing two functionalities (e.g. a Lewis acid and a Brønsted base or a Lewis acid and a Lewis base). These catalysts demonstrated broad reaction applicability with excellent substrate generality. Using our catalytic asymmetric reactions as keys steps, efficient total syntheses of pharmaceuticals and their biologically active lead natural products were achieved. PMID:25792774

Perovskites in catalysis and electrocatalysis.

PubMed

Hwang, Jonathan; Rao, Reshma R; Giordano, Livia; Katayama, Yu; Yu, Yang; Shao-Horn, Yang

2017-11-10

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. Copyright © 2017, American Association for the Advancement of Science.

The Information Ecology of Personal Health Record Systems: Secure Messaging as Catalyst and Its Evolving Impact on Use and Consequences

ERIC Educational Resources Information Center

Nazi, Kim M.

2012-01-01

Personal Health Records (PHRs) and PHR systems have been designed as consumer-oriented tools to empower patients and improve health care. Despite significant consumer interest and anticipated benefits, adoption remains low. Understanding the consumer perspective is necessary, but insufficient by itself. Consumer PHR use also has broad implications…

Contemporary Character Education

ERIC Educational Resources Information Center

Smith, Matthew R.

2006-01-01

When the National Commission on Excellence in Education published "A Nation at Risk" (1983) in response to the perception that the U.S. public education system was failing to help students succeed, it gave policymakers the catalyst to introduce legislative and regulatory reforms that were designed to increase student achievement. Through such…

System for reactivating catalysts

DOEpatents

Ginosar, Daniel M.; Thompson, David N.; Anderson, Raymond P.

2010-03-02

A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst is provided. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

Catalytic hydrodechlorination of trichloroethylene in a novel NaOH/2-propanol/methanol/water system on ceria-supported Pd and Rh catalysts.

PubMed

Cobo, Martha; Becerra, Jorge; Castelblanco, Miguel; Cifuentes, Bernay; Conesa, Juan A

2015-08-01

The catalytic hydrodechlorination (HDC) of high concentrations of trichloroethylene (TCE) (4.9 mol%, 11.6 vol%) was studied over 1%Pd, 1%Rh and 0.5%Pd-0.5%Rh catalysts supported on CeO2 under conditions of room temperature and pressure. For this, a one-phase system of NaOH/2-propanol/methanol/water was designed with molar percentages of 13.2/17.5/36.9/27.6, respectively. In this system, the alcohols delivered the hydrogen required for the reaction through in-situ dehydrogenation reactions. PdRh/CeO2 was the most active catalyst for the degradation of TCE among the evaluated materials, degrading 85% of the trichloroethylene, with alcohol dehydrogenation rates of 89% for 2-propanol and 83% for methanol after 1 h of reaction. Fresh and used catalysts were characterized by Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric analysis (TGA). These results showed important differences of the active phase in each catalyst sample. Rh/CeO2 had particle sizes smaller than 1 nm and the active metal was partially oxidized (Rh(0)/Rh(+δ) ratio of 0.43). This configuration showed to be suitable for alcohols dehydrogenation. On the contrary, Pd/CeO2 showed a Pd completed oxidized and with a mean particle size of 1.7 nm, which seemed to be unfavorable for both, alcohols dehydrogenation and TCE HDC. On PdRh/CeO2, active metals presented a mean particle size of 2.7 nm and more reduced metallic species, with ratios of Rh(0)/Rh(+δ) = 0.67 and Pd(0)/Pd(+δ) = 0.28, which showed to be suitable features for the TCE HDC. On the other hand, TGA results suggested some deposition of NaCl residues over the catalyst surfaces. Thus, the new reaction system using PdRh/CeO2 allowed for the degradation of high concentrations of the chlorinated compound by using in situ hydrogen liquid donors in a reaction at room temperature and pressure. Copyright © 2015 Elsevier Ltd. All rights reserved.

Catalyst system for the polymerization of alkenes to polyolefins

DOEpatents

Miller, Stephen A.; Bercaw, John E.

2002-01-01

The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M.sub.w)in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

Catalyst system for the polymerization of alkenes to polyolefins

DOEpatents

Miller, Stephen A.; Bercaw, John E.

2004-02-17

The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M.sub.W) in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

Electrostatic self-assembly of Fe3O4/GO nanocomposites and their application as an efficient Fenton-like catalyst for degradation of rhodamine B

NASA Astrophysics Data System (ADS)

Wang, Wenxia; He, Qi; Xiao, Kaijun; Zhu, Liang

2018-03-01

In the study, a two-major step involving a hydrothermal method and an electrostatic self-assembly method was adopted to synthesis Fe3O4/GO nanocomposites. The Fe3O4 nanoparticles were successfully modified with the 3-aminopropyltrimethoxy-silane and homogeneously deposited onto the surface of GO. They were used as Fenton-like catalyst to degrade Rhodamine B and displayed a higher activity compared with the pristine Fe3O4 nanoparticles, H2O2, Fe3O4/GO nanocomposite and Fe3O4/H2O2 system, demonstrating the synergistic effect between the superior adsorption properties of GO and the excellent catalytic activity of Fe3O4/H2O2 system. Besides, the possible catalytic mechanism and degradation pathway for RhB molecules by Fe3O4/GO nanocomposites and H2O2 was proposed based on the liquid chromatography-mass spectrometry (LC-MS) analysis. The result reveals that the •OH radicals should be the main actives species during catalytic degradation of RhB by the Fe3O4/GO/H2O2 system. In addition, the catalyst is reusable and shows efficiency up to 5 cycles. We believe the strategy in our work can provide insight into designing the novel catalysts for large-scale degradation of organic pollutants in the wastewater.

Laccases as palladium oxidases† †Electronic supplementary information (ESI) available: Experimental procedures, synthesis of catalysts molecules, enzyme activity assay, bleaching experiments, oxygraph traces, oxidation of veratryl alcohol assay, inhibition experiments, electrophoresis. See DOI: 10.1039/c4sc02564d Click here for additional data file.

PubMed Central

Schneider, Ludovic; Rousselot-Pailley, Pierre; Faure, Bruno; Simaan, A. Jalila; Bochot, Constance; Réglier, Marius

2015-01-01

The first example of a coupled catalytic system involving an enzyme and a palladium(ii) catalyst competent for the aerobic oxidation of alcohol in mild conditions is described. In the absence of dioxygen, the fungal laccase LAC3 is reduced by a palladium(0) species as evidenced by the UV/VIS and ESR spectra of the enzyme. During the oxidation of veratryl alcohol performed in water, at room temperature and atmospheric pressure, LAC3 regenerates the palladium catalyst, is reduced and catalyzes the four-electron reduction of dioxygen into water with no loss of enzyme activity. The association of a laccase with a water-soluble palladium complex results in a 7-fold increase in the catalytic efficiency of the complex. This is the first step in the design of a family of renewable palladium catalysts for aerobic oxidation. PMID:29560210

Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

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

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less

Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

2016-09-20

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less

Exhaust emission control and diagnostics

DOEpatents

Mazur, Christopher John; Upadhyay, Devesh

2006-11-14

A diesel engine emission control system uses an upstream oxidation catalyst and a downstream SCR catalyst to reduce NOx in a lean exhaust gas environment. The engine and upstream oxidation catalyst are configured to provide approximately a 1:1 ratio of NO to NO2 entering the downstream catalyst. In this way, the downstream catalyst is insensitive to sulfur contamination, and also has improved overall catalyst NOx conversion efficiency. Degradation of the system is determined when the ratio provided is no longer near the desired 1:1 ratio. This condition is detected using measurements of engine operating conditions such as from a NOx sensor located downstream of the catalysts. Finally, control action to adjust an injected amount of reductant in the exhaust gas based on the actual NO to NO2 ratio upstream of the SCR catalyst and downstream of the oxidation catalyst.

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2011 CFR

2011-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device...) and (d) of this section. (c) Any fluid catalytic cracking unit catalyst regenerator under paragraph (b...

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2012 CFR

2012-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device...) and (d) of this section. (c) Any fluid catalytic cracking unit catalyst regenerator under paragraph (b...

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2010 CFR

2010-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device...) and (d) of this section. (c) Any fluid catalytic cracking unit catalyst regenerator under paragraph (b...

Recent advances in secondary ion mass spectrometry of solid acid catalysts: large zeolite crystals under bombardment.

PubMed

Hofmann, Jan P; Rohnke, Marcus; Weckhuysen, Bert M

2014-03-28

This Perspective aims to inform the heterogeneous catalysis and materials science community about the recent advances in Time-of-Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) to characterize catalytic solids by taking large model H-ZSM-5 zeolite crystals as a showcase system. SIMS-based techniques have been explored in the 1980-1990's to study porous catalyst materials but, due to their limited spectral and spatiotemporal resolution, there was no real major breakthrough at that time. The technical advancements in SIMS instruments, namely improved ion gun design and new mass analyser concepts, nowadays allow for a much more detailed analysis of surface species relevant to catalytic action. Imaging with high mass and lateral resolution, determination of fragment ion patterns, novel sputter ion concepts as well as new mass analysers (e.g. ToF, FTICR) are just a few novelties, which will lead to new fundamental insight from SIMS analysis of heterogeneous catalysts. The Perspective article ends with an outlook on instrumental innovations and their potential use for catalytic systems other than zeolite crystals.

Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol

DOE PAGES

Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi; ...

2017-01-06

Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

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

Not Available

The objective of the contract is to consolidate the advances made during the previous contract in the conversion of syngas to motor fuels using Molecular Sieve-containing catalysts and to demonstrate the practical utility and economic value of the new catalyst/process systems with appropriate laboratory runs. Work on the program is divided into the following six tasks: (1) preparation of a detailed work plan covering the entire performance of the contract; (2) techno-economic studies that will supplement those that are presently being carried out by MITRE; (3) optimization of the most promising catalysts developed under prior contract; (4) optimization of themore » UCC catalyst system in a manner that will give it the longest possible service life; (5) optimization of a UCC process/catalyst system based upon a tubular reactor with a recycle loop containing the most promising catalyst developed under Tasks 3 and 4 studies; and (6) economic evaluation of the optimal performance found under Task 5 for the UCC process/catalyst system. Progress reports are presented for Tasks 1, 3, 4, and 5.« 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.

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

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

DOE PAGES

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.; ...

2017-01-23

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Water-gas-shift over metal-free nanocrystalline ceria: An experimental and theoretical study

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

Guild, Curtis J.; Vovchok, Dimitriy; Kriz, David A.

A tandem experimental and theoretical investigation of a mesoporous ceria catalyst reveals the properties of the metal oxide are conducive for activity typically ascribed to metals, suggesting reduced Ce 3+ and oxygen vacancies are responsible for the inherent bi-functionality of CO oxidation and dissociation of water required for facilitating the production of H 2. The degree of reduction of the ceria, specifically the (1 0 0) face, is found to significantly influence the binding of reagents, suggesting reduced surfaces harbor the necessary reactive sites. The metal-free catalysis of the reaction is significant for catalyst design considerations, and the suite ofmore » in situ analyses provides a comprehensive study of the dynamic nature of the high surface area catalyst system. Finally, this study postulates feasible improvements in catalytic activity may redirect the purpose of the water-gas shift reaction from CO purification to primary hydrogen production.« less

Multi-wavelength Raman spectroscopy study of supported vanadia catalysts: Structure identification and quantification

DOE PAGES

Wu, Zili

2014-10-20

Revealing the structure of supported metal oxide catalysts is a prerequisite for establishing the structure - catalysis relationship. Among a variety of characterization techniques, multi-wavelength Raman spectroscopy, combining resonance Raman and non-resonance Raman with different excitation wavelengths, has recently emerged as a particularly powerful tool in not only identifying but also quantifying the structure of supported metal oxide clusters. In our review, we make use of two supported vanadia systems, VO x/SiO 2 and VO x/CeO 2, as examples to showcase how one can employ this technique to investigate the heterogeneous structure of active oxide clusters and to understand themore » complex interaction between the oxide clusters and the support. Moreover, the qualitative and quantitative structural information gained from the multi-wavelength Raman spectroscopy can be utilized to provide fundamental insights for designing more efficient supported metal oxide catalysts.« less

Enhanced Oxidation Catalysts for Water Reclamation

NASA Technical Reports Server (NTRS)

Jolly, Clifford D.

1999-01-01

This effort seeks to develop and test high-performance, long operating life, physically stable catalysts for use in spacecraft water reclamation systems. The primary goals are to a) reduce the quantity of expendable water filters used to purify water aboard spacecraft, b) to extend the life of the oxidation catalysts used for eliminating organic contaminants in the water reclamation systems, and c) reduce the weight/volume of the catalytic oxidation systems (e.g. VRA) used. This effort is targeted toward later space station utilization and will consist of developing flight-qualifiable catalysts and long-term ground tests of the catalyst prior to their utilization in flight. Fixed -bed catalytic reactors containing 5% platinum on granular activated carbon have been subjected to long-term dynamic column tests to measure catalyst stability vs throughput. The data generated so far indicate that an order of magnitude improvement can be obtained with the treated catalysts vs the control catalyst, at only a minor loss (approx 10%) in the initial catalytic activity.

Integrated Biomass Gasification with Catalytic Partial Oxidation for Selective Tar Conversion

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

Zhang, Lingzhi; Wei, Wei; Manke, Jeff

Biomass gasification is a flexible and efficient way of utilizing widely available domestic renewable resources. Syngas from biomass has the potential for biofuels production, which will enhance energy security and environmental benefits. Additionally, with the successful development of low Btu fuel engines (e.g. GE Jenbacher engines), syngas from biomass can be efficiently used for power/heat co-generation. However, biomass gasification has not been widely commercialized because of a number of technical/economic issues related to gasifier design and syngas cleanup. Biomass gasification, due to its scale limitation, cannot afford to use pure oxygen as the gasification agent that used in coal gasification.more » Because, it uses air instead of oxygen, the biomass gasification temperature is much lower than well-understood coal gasification. The low temperature leads to a lot of tar formation and the tar can gum up the downstream equipment. Thus, the biomass gasification tar removal is a critical technology challenge for all types of biomass gasifiers. This USDA/DOE funded program (award number: DE-FG36-O8GO18085) aims to develop an advanced catalytic tar conversion system that can economically and efficiently convert tar into useful light gases (such as syngas) for downstream fuel synthesis or power generation. This program has been executed by GE Global Research in Irvine, CA, in collaboration with Professor Lanny Schmidt's group at the University of Minnesota (UoMn). Biomass gasification produces a raw syngas stream containing H2, CO, CO2, H2O, CH4 and other hydrocarbons, tars, char, and ash. Tars are defined as organic compounds that are condensable at room temperature and are assumed to be largely aromatic. Downstream units in biomass gasification such as gas engine, turbine or fuel synthesis reactors require stringent control in syngas quality, especially tar content to avoid plugging (gum) of downstream equipment. Tar- and ash-free syngas streams are a critical requirement for commercial deployment of biomass-based power/heat co-generation and biofuels production. There are several commonly used syngas clean-up technologies: (1) Syngas cooling and water scrubbing has been commercially proven but efficiency is low and it is only effective at small scales. This route is accompanied with troublesome wastewater treatment. (2) The tar filtration method requires frequent filter replacement and solid residue treatment, leading to high operation and capital costs. (3) Thermal destruction typically operates at temperatures higher than 1000oC. It has slow kinetics and potential soot formation issues. The system is expensive and materials are not reliable at high temperatures. (4) In-bed cracking catalysts show rapid deactivation, with durability to be demonstrated. (5) External catalytic cracking or steam reforming has low thermal efficiency and is faced with problematic catalyst coking. Under this program, catalytic partial oxidation (CPO) is being evaluated for syngas tar clean-up in biomass gasification. The CPO reaction is exothermic, implying that no external heat is needed and the system is of high thermal efficiency. CPO is capable of processing large gas volume, indicating a very compact catalyst bed and a low reactor cost. Instead of traditional physical removal of tar, the CPO concept converts tar into useful light gases (eg. CO, H2, CH4). This eliminates waste treatment and disposal requirements. All those advantages make the CPO catalytic tar conversion system a viable solution for biomass gasification downstream gas clean-up. This program was conducted from October 1 2008 to February 28 2011 and divided into five major tasks. - Task A: Perform conceptual design and conduct preliminary system and economic analysis (Q1 2009 ~ Q2 2009) - Task B: Biomass gasification tests, product characterization, and CPO tar conversion catalyst preparation. This task will be conducted after completing process design and system economics analysis. Major milestones include identification of syngas cleaning requirements for proposed system design, identification and selection of tar compounds and 2 mixtures for use in CPO tests, and preparation of CPO catalysts for validation. (Q3 2009 ~ Q4 2009) - Task C: Test CPO with biomass gasification product gas. Optimize CPO performance with selected tar compounds. Optimize CPO performance with multi-component mixtures. Milestones include optimizing CPO catalysts design, collecting CPO experimental data for next stage kinetic modeling and understanding the effect of relative reactivities on ultimate tar conversion and syngas yields. (Q1 2010 ~ Q3 2010) - Task D: Develop tar CPO kinetic model with CPO kinetic model and modeling results as deliverables. (Q3 2010 ~ Q2 2011) - Task E: Project management and reporting. Milestone: Quarterly reports and presentations, final report, work presented at national technical conferences (Q1 2009 ~ Q2 2011) At the beginning of the program, IP landscaping was conducted to understand the operation of various types of biomass gasifiers, their unique syngas/tar compositions and potential tar mitigation options using the catalytic partial oxidation technology. A process simulation model was developed to quantify the system performance and economics impact of CPO tar removal technology. Biomass gasification product compositions used for performance evaluation tests were identified after literature review and system modeling. A reaction system for tar conversion tests was designed, constructed, with each individual component shaken-down in 2009. In parallel, University of Minnesota built a lab-scale unit and evaluated the tar removal performance using catalytic reforming. Benzene was used as the surrogate compound. The biomass gasification raw syngas composition was provided by GE through system studies. In 2010, GE selected different tar compounds and evaluated the tar removal effectiveness of the CPO catalyst. The catalytic performance was evaluated under different operating conditions, including catalyst geometry, S/C ratio, O/C ratio, GHSV, and N2 dilution. An understanding of how to optimize catalytic tar removal efficiency by varying operating conditions has been developed. GE collaborated with UoMn in examining inorganic impurities effects. Catalysts were pre-impregnated with inorganic impurities commonly present in biomass gasification syngas, including Si, Ca, Mg, Na, K, P and S. UoMn performed catalyst characterization and has acquired fundamental understandings of impurities effect on catalytic tar removal. Based on experimental data and the proposed reaction pathway, GE constructed a model to predict kinetic performance for biomass gasification tar cleanup process. Experimental data (eg. tar conversion, reactor inlet and outlet temperatures, product distribution) at different operating conditions were used to validate the model. A good fit between model predictions and experimental data was found. This model will be a valuable tool in designing the tar removal reactor and identifying appropriate operating conditions. We attended the 2011 DOE Biomass Program Thermochemical Platform Review held in Denver, CO from February 16 to 18 and received very positive comments from the review panel. Further, syngas utility and biomass to power/fuel companies expressed strong interest in our tar removal technology.« less

Minimalist Design of Allosterically Regulated Protein Catalysts.

PubMed

Makhlynets, O V; Korendovych, I V

2016-01-01

Nature facilitates chemical transformations with exceptional selectivity and efficiency. Despite a tremendous progress in understanding and predicting protein function, the overall problem of designing a protein catalyst for a given chemical transformation is far from solved. Over the years, many design techniques with various degrees of complexity and rational input have been developed. Minimalist approach to protein design that focuses on the bare minimum requirements to achieve activity presents several important advantages. By focusing on basic physicochemical properties and strategic placing of only few highly active residues one can feasibly evaluate in silico a very large variety of possible catalysts. In more general terms minimalist approach looks for the mere possibility of catalysis, rather than trying to identify the most active catalyst possible. Even very basic designs that utilize a single residue introduced into nonenzymatic proteins or peptide bundles are surprisingly active. Because of the inherent simplicity of the minimalist approach computational tools greatly enhance its efficiency. No complex calculations need to be set up and even a beginner can master this technique in a very short time. Here, we present a step-by-step protocol for minimalist design of functional proteins using basic, easily available, and free computational tools. © 2016 Elsevier Inc. All rights reserved.

40 CFR 91.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2014 CFR

2014-07-01

... PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM MARINE SPARK-IGNITION ENGINES Gaseous Exhaust Test... efficiency. The thermal stress is imposed on the test catalyst by exposing it to quiescent heated air in an... that the catalyst being tested was not designed to reduce/oxidize. The engine manufacturer must specify...

40 CFR 91.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2011 CFR

2011-07-01

... PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM MARINE SPARK-IGNITION ENGINES Gaseous Exhaust Test... efficiency. The thermal stress is imposed on the test catalyst by exposing it to quiescent heated air in an... that the catalyst being tested was not designed to reduce/oxidize. The engine manufacturer must specify...

40 CFR 91.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2010 CFR

2010-07-01

... PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM MARINE SPARK-IGNITION ENGINES Gaseous Exhaust Test... efficiency. The thermal stress is imposed on the test catalyst by exposing it to quiescent heated air in an... that the catalyst being tested was not designed to reduce/oxidize. The engine manufacturer must specify...

40 CFR 91.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2013 CFR

2013-07-01

... PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM MARINE SPARK-IGNITION ENGINES Gaseous Exhaust Test... efficiency. The thermal stress is imposed on the test catalyst by exposing it to quiescent heated air in an... that the catalyst being tested was not designed to reduce/oxidize. The engine manufacturer must specify...

40 CFR 91.427 - Catalyst thermal stress resistance evaluation.

Code of Federal Regulations, 2012 CFR

2012-07-01

... PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM MARINE SPARK-IGNITION ENGINES Gaseous Exhaust Test... efficiency. The thermal stress is imposed on the test catalyst by exposing it to quiescent heated air in an... that the catalyst being tested was not designed to reduce/oxidize. The engine manufacturer must specify...

Catalysts for the decomposition of hydrazine, hydrazine derivatives and mixtures of both

NASA Technical Reports Server (NTRS)

Sasse, R.

1986-01-01

This invention concerns a catalyst designed for the decomposition of hydrazine, hydrazine derivatives and mixtures of the two. The objective is to develop a catalyst of the type described that is cheap and easy to produce and is also characterized by extremely short response times.

Hydroxylation of Benzene via C-H Activation Using Bimetallic CuAg@g-C3N4

EPA Science Inventory

A photoactive bimetallic CuAg@g-C3N4 catalyst system has been designed and synthesized by impregnating copper and silver nanoparticles over the graphitic carbon nitride surface. Its application has been demonstrated in the hydroxylation of benzene under visible light.

The Systems Autonomy Demonstration Project - Catalyst for Space Station advanced automation

NASA Technical Reports Server (NTRS)

Healey, Kathleen J.

1988-01-01

The Systems Autonomy Demonstration Project (SADP) was initiated by NASA to address the advanced automation needs for the Space Station program. The application of advanced automation to the Space Station's operations management system (OMS) is discussed. The SADP's future goals and objectives are discussed with respect to OMS functional requirements, design, and desired evolutionary capabilities. Major technical challenges facing the designers, developers, and users of the OMS are identified in order to guide the definition of objectives, plans, and scenarios for future SADP demonstrations, and to focus the efforts on the supporting research.

A Synthetic Single-Site Fe Nitrogenase: High Turnover, Freeze-Quench (57)Fe Mössbauer Data, and a Hydride Resting State.

PubMed

Del Castillo, Trevor J; Thompson, Niklas B; Peters, Jonas C

2016-04-27

The mechanisms of the few known molecular nitrogen-fixing systems, including nitrogenase enzymes, are of much interest but are not fully understood. We recently reported that Fe-N2 complexes of tetradentate P3(E) ligands (E = B, C) generate catalytic yields of NH3 under an atmosphere of N2 with acid and reductant at low temperatures. Here we show that these Fe catalysts are unexpectedly robust and retain activity after multiple reloadings. Nearly an order of magnitude improvement in yield of NH3 for each Fe catalyst has been realized (up to 64 equiv of NH3 produced per Fe for P3(B) and up to 47 equiv for P3(C)) by increasing acid/reductant loading with highly purified acid. Cyclic voltammetry shows the apparent onset of catalysis at the P3(B)Fe-N2/P3(B)Fe-N2(-) couple and controlled-potential electrolysis of P3(B)Fe(+) at -45 °C demonstrates that electrolytic N2 reduction to NH3 is feasible. Kinetic studies reveal first-order rate dependence on Fe catalyst concentration (P3(B)), consistent with a single-site catalyst model. An isostructural system (P3(Si)) is shown to be appreciably more selective for hydrogen evolution. In situ freeze-quench Mössbauer spectroscopy during turnover reveals an iron-borohydrido-hydride complex as a likely resting state of the P3(B)Fe catalyst system. We postulate that hydrogen-evolving reaction activity may prevent iron hydride formation from poisoning the P3(B)Fe system. This idea may be important to consider in the design of synthetic nitrogenases and may also have broader significance given that intermediate metal hydrides and hydrogen evolution may play a key role in biological nitrogen fixation.

PEROXIDE DESTRUCTION TESTING FOR THE 200 AREA EFFLUENT TREATMENT FACILITY

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

HALGREN DL

2010-03-12

The hydrogen peroxide decomposer columns at the 200 Area Effluent Treatment Facility (ETF) have been taken out of service due to ongoing problems with particulate fines and poor destruction performance from the granular activated carbon (GAC) used in the columns. An alternative search was initiated and led to bench scale testing and then pilot scale testing. Based on the bench scale testing three manganese dioxide based catalysts were evaluated in the peroxide destruction pilot column installed at the 300 Area Treated Effluent Disposal Facility. The ten inch diameter, nine foot tall, clear polyvinyl chloride (PVC) column allowed for the samemore » six foot catalyst bed depth as is in the existing ETF system. The flow rate to the column was controlled to evaluate the performance at the same superficial velocity (gpm/ft{sup 2}) as the full scale design flow and normal process flow. Each catalyst was evaluated on peroxide destruction performance and particulate fines capacity and carryover. Peroxide destruction was measured by hydrogen peroxide concentration analysis of samples taken before and after the column. The presence of fines in the column headspace and the discharge from carryover was generally assessed by visual observation. All three catalysts met the peroxide destruction criteria by achieving hydrogen peroxide discharge concentrations of less than 0.5 mg/L at the design flow with inlet peroxide concentrations greater than 100 mg/L. The Sud-Chemie T-2525 catalyst was markedly better in the minimization of fines and particle carryover. It is anticipated the T-2525 can be installed as a direct replacement for the GAC in the peroxide decomposer columns. Based on the results of the peroxide method development work the recommendation is to purchase the T-2525 catalyst and initially load one of the ETF decomposer columns for full scale testing.« less

Reduction of low temperature engine pollutants by understanding the exhaust species interactions in a diesel oxidation catalyst.

PubMed

Lefort, I; Herreros, J M; Tsolakis, A

2014-02-18

The interactions between exhaust gas species and their effect (promotion or inhibition) on the light-off and activity of a diesel oxidation catalyst (DOC) for the removal of pollutants are studied, using actual engine exhaust gases from the combustion of diesel, alternative fuels (rapeseed methyl ester and gas-to-liquid fuel) and diesel/propane dual fuel combustion. The activity of the catalyst was recorded during a heating temperature ramp where carbon monoxide (CO) and hydrocarbon (HC) light-off curves were obtained. From the catalyst activity tests, it was found that the presence of species including CO, medium-heavy HC, alkenes, alkanes, and NOx and their concentration influence the catalyst ability to reduce CO and total HC emissions before release to the atmosphere. CO could inhibit itself and other species oxidation (e.g., light and medium-heavy hydrocarbons) while suffering from competitive adsorption with NO. Hydrocarbon species were also found to inhibit their own oxidation as well as CO through adsorption competition. On the other hand, NO2 was found to promote low temperature HC oxidation through its partial reduction, forming NO. The understanding of these exhaust species interactions within the DOC could aid the design of an efficient aftertreatment system for the removal of diesel exhaust pollutants.

Computationally Guided Catalyst Design in the Type I Dynamic Kinetic Asymmetric Pauson-Khand Reaction of Allenyl Acetates.

PubMed

Burrows, Lauren C; Jesikiewicz, Luke T; Lu, Gang; Geib, Steven J; Liu, Peng; Brummond, Kay M

2017-10-25

The Rh(I)-catalyzed allenic Pauson-Khand reaction (APKR) is an efficient, redox-neutral method of synthesizing α-acyloxy cyclopentenones. An enantioselective APKR could provide access to chiral, nonracemic α-acyloxy and α-hydroxy cyclopentenones and their corresponding redox derivatives, such as thapsigargin, a cytotoxic natural product with potent antitumor activity. Rapid scrambling of axial chirality of allenyl acetates in the presence of Rh(I) catalysts enables the conversion of racemic allene to enantiopure cyclopentenone product in a dynamic kinetic asymmetric transformation (DyKAT). A combined experimental and computational approach was taken to develop an effective catalytic system to achieve the asymmetric transformation. The optimization of the denticity, and steric and electronic properties of the ancillary ligand (initially (S)-MonoPhos, 58:42 er), afforded a hemilabile bidentate (S)-MonoPhos-alkene-Rh(I) catalyst that provided α-acyloxy cyclopentenone product in up to 14:86 er. Enantioselectivity of the Rh(I)-(S)-MonoPhos-alkene catalyst was rationalized using ligand-substrate steric interactions and distortion energies in the computed transition states. This asymmetric APKR of allenyl acetates is a rare example of a Type I DyKAT reaction of an allene, the first example of DyKAT in a cyclocarbonylation reaction, and the first catalyst-controlled enantioselective APKR.

Reducing fischer-tropsch catalyst attrition losses in high agitation reaction systems

DOEpatents

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

2001-01-01

A method for reducing catalyst attrition losses in hydrocarbon synthesis processes conducted in high agitation reaction systems; a method of producing an attrition-resistant catalyst; a catalyst produced by such method; a method of producing an attrition-resistant catalyst support; and a catalyst support produced by such method. The inventive method of reducing catalyst attrition losses comprises the step of reacting a synthesis gas in a high agitation reaction system in the presence of a catalyst. In one aspect, the catalyst preferably comprises a .gamma.-alumina support including an amount of titanium effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support which has been treated, after calcination, with an acidic, aqueous solution. The acidic aqueous solution preferably has a pH of not more than about 5. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support wherein the cobalt has been applied to the .gamma.-alumina support by totally aqueous, incipient wetness-type impregnation. In another aspect, the catalyst preferably comprises cobalt on a .gamma.-alumina support with an amount of a lanthana promoter effective for increasing the attrition resistance of the catalyst. In another aspect, the catalyst preferably comprises a .gamma.-alumina support produced from boehmite having a crystallite size, in the 021 plane, in the range of from about 30 to about 55 .ANG.ngstrons. In another aspect, the inventive method of producing an attrition-resistant catalyst comprises the step of treating a .gamma.-alumina support, after calcination of and before adding catalytic material to the support, with an acidic solution effective for increasing the attrition resistance of the catalyst. In another aspect, the inventive method of producing an attrition-resistant catalyst support comprises the step of treating calcined .gamma.-alumina with an acidic, aqueous solution effective for increasing the attrition resistance of the .gamma.-alumina.

Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2

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

Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.

2013-08-14

Our central premise is that catalytic scientists can learn by studying how these important metabolic processes occur in nature. Complementarily, biochemists can learn by studying how catalytic scientists view these same chemical transformations promoted by synthetic catalysts. From these studies, hypotheses can be developed and tested through manipulation of enzyme structure and by synthesizing simple molecular catalysts to incorporate different structural features of the enzymes. It is hoped that these studies will lead to new and useful concepts in catalyst design for fuel production and utilization. This paper describes the results of a workshop held to explore these concepts inmore » regard to the development of new and more efficient catalytic processes for the conversion of CO2 to a variety of carbon-based fuels. The organization of this overview/review is as follows: 1) The first section briefly explores how interactions between the catalysis and biological communities have been fruitful in developing new catalysts for the reduction of protons to hydrogen, the simplest fuel generation reaction. 2) The second section assesses the state of the art in both biological and chemical reduction of CO2 by two electrons to form either carbon monoxide (CO) or formate (HCOO-). It also attempts to identify common principles between biological and synthetic catalysts and productive areas for future research. 3) The third section explores both biological and chemical processes that result in the reduction of CO2 beyond the level of CO and formate, again seeking to identify common principles and productive areas of future research. 4) The fourth section explores the formation of carbon-carbon bonds in biological and chemical systems in the same vein as the other sections. 5) A fifth section addresses the role of non-redox reactions of CO2 in biological systems and their role in carbon metabolism, with a parallel discussion of chemical systems. 6) In section 6, the topics of electrode modification, photochemical systems, and tandem catalysis are briefly discussed. These areas may be important for developing practical systems for CO2 reduction, and they share the common theme of coupling chemical reactions. 7) Section 7 describes some of the crosscutting activities that are critical for advancing the science underpinning catalyst development. 8) The last section attempts to summarize common issues in biological and chemical catalysis and to identify challenges that must be addressed to achieve practical catalysts that are suitable for the reduction of CO2 to fuels.« less

Identification of optimal solar fuel electrocatalysts via high throughput in situ optical measurements

DOE PAGES

Shinde, Aniketa; Guevarra, Dan; Haber, Joel A.; ...

2014-10-21

For many solar fuel generator designs involve illumination of a photoabsorber stack coated with a catalyst for the oxygen evolution reaction (OER). In this design, impinging light must pass through the catalyst layer before reaching the photoabsorber(s), and thus optical transmission is an important function of the OER catalyst layer. Many oxide catalysts, such as those containing elements Ni and Co, form oxide or oxyhydroxide phases in alkaline solution at operational potentials that differ from the phases observed in ambient conditions. To characterize the transparency of such catalysts during OER operation, 1031 unique compositions containing the elements Ni, Co, Ce,more » La, and Fe were prepared by a high throughput inkjet printing technique. Moreover, the catalytic current of each composition was recorded at an OER overpotential of 0.33 V with simultaneous measurement of the spectral transmission. By combining the optical and catalytic properties, the combined catalyst efficiency was calculated to identify the optimal catalysts for solar fuel applications within the material library. Our measurements required development of a new high throughput instrument with integrated electrochemistry and spectroscopy measurements, which enables various spectroelectrochemistry experiments.« less

Engineered Sulfur‐Resistant Catalyst System with an Assisted Regeneration Strategy for Lean‐Burn Methane Combustion

PubMed Central

Kallinen, Kauko; Maunula, Teuvo; Suvanto, Mika

2018-01-01

Abstract Catalytic combustion of methane, the main component of natural gas, is a challenge under lean‐burn conditions and at low temperatures owing to sulfur poisoning of the Pd‐rich catalyst. This paper introduces a more sulfur‐resistant catalyst system that can be regenerated during operation. The developed catalyst system lowers the barrier that has restrained the use of liquefied natural gas as a fuel in energy production. PMID:29780434

DEFE0023863 Final Report, Technology for GHG Emission Reduction and CostCompetitive MilSpec Jet Fuel Production using CTL

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

Hartvigsen, Joseph J; Dimick, Paul; Laumb, Jason D

Ceramatec Inc, in collaboration with IntraMicron (IM), the Energy & Environmental Research Center (EERC) and Sustainable Energy Solutions, LLC (SES), have completed a three-year research project integrating their respective proprietary technologies in key areas to demonstrate production of a jet fuel from coal and biomass sources. The project goals and objectives were to demonstrate technology capable of producing a “commercially-viable quantity” of jet fuel and make significant progress toward compliance with Section 526 of the Energy Independence and Security Act of 2007 (EISA 2007 §526) lifecycle greenhouse gas (GHG) emissions requirements. The Ceramatec led team completed the demonstration of nominalmore » 2 bbl/day Fischer-Tropsch (FT) synthesis pilot plant design, capable of producing a nominal 1 bbl/day in the Jet-A/JP-8 fraction. This production rate would have a capacity of 1,000 gallons of jet fuel per month and provide the design basis of a 100 bbl/day module producing over 2,000 gallons of jet fuel per day. Co-gasification of coal-biomass blends enables a reduction of lifecycle greenhouse gas emissions from equivalent conventional petroleum derived fuel basis. Due to limits of biomass availability within an economic transportation range, implementation of a significant biomass feed fraction will require smaller plants than current world scale CTL and GTL FT plants. Hence a down-scaleable design is essential. The pilot plant design leverages Intramicron’s MicroFiber Entrapped Catalyst (MFEC) support which increases the catalyst bed thermal conductivity two orders of magnitude, allowing thermal management of the FT reaction exotherm in much larger reactor tubes. In this project, single tube reactors having 4.5 inch outer diameter and multi-tube reactors having 4 inch outer diameters were operated, with productivities as high as 1.5 gallons per day per linear foot of reactor tube. A significant reduction in tube count results from the use of large diameter reactor tubes, with an associated reduction in reactor cost. The pilot plant was designed with provisions for product collection capable of operating with conventional wax producing FT catalysts but was operated with a Chevron hybrid wax-free FT catalyst. Process simplification enabled by elimination of the wax hydrocracking process unit provides economic advantages in scaling to biomass capable plant sizes. Intramicron also provided a sulfur capture system based on their Oxidative Sulfur Removal (OSR) catalyst process. The integrated sulfur removal and FT systems were operated with syngas produced by the Transport Reactor Development Unit (TRDU) gasifier at the University of North Dakota EERC. SES performed modeling of their cryogenic carbon capture process on the energy, cost and CO2 emissions impact of the Coal-biomass synthetic fuel process.« less

Combined UHV/high-pressure catalysis setup for depth-resolved near-surface spectroscopic characterization and catalytic testing of model catalysts

NASA Astrophysics Data System (ADS)

Mayr, Lukas; Rameshan, Raffael; Klötzer, Bernhard; Penner, Simon; Rameshan, Christoph

2014-05-01

An ultra-high vacuum (UHV) setup for "real" and "inverse" model catalyst preparation, depth-resolved near-surface spectroscopic characterization, and quantification of catalytic activity and selectivity under technologically relevant conditions is described. Due to the all-quartz reactor attached directly to the UHV-chamber, transfer of the catalyst for in situ testing without intermediate contact to the ambient is possible. The design of the UHV-compatible re-circulating batch reactor setup allows the study of reaction kinetics under close to technically relevant catalytic conditions up to 1273 K without contact to metallic surfaces except those of the catalyst itself. With the attached differentially pumped exchangeable evaporators and the quartz-microbalance thickness monitoring equipment, a reproducible, versatile, and standardised sample preparation is possible. For three-dimensional near-surface sample characterization, the system is equipped with a hemispherical analyser for X-ray photoelectron spectroscopy (XPS), electron-beam or X-ray-excited Auger-electron spectroscopy, and low-energy ion scattering measurements. Due the dedicated geometry of the X-ray gun (54.7°, "magic angle") and the rotatable sample holder, depth analysis by angle-resolved XPS measurements can be performed. Thus, by the combination of characterisation methods with different information depths, a detailed three-dimensional picture of the electronic and geometric structure of the model catalyst can be obtained. To demonstrate the capability of the described system, comparative results for depth-resolved sample characterization and catalytic testing in methanol steam reforming on PdGa and PdZn near-surface intermetallic phases are shown.

Alcohol synthesis in a high-temperature slurry reactor

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

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

1995-12-31

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

Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

PubMed

Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

2017-09-27

A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

Evaluation and characterization of the methane-carbon dioxide decomposition reaction

NASA Technical Reports Server (NTRS)

Davenport, R. J.; Schubert, F. H.; Shumar, J. W.; Steenson, T. S.

1975-01-01

A program was conducted to evaluate and characterize the carbon dioxide-methane (CO2-CH4) decomposition reaction, i.e., CO2 + CH4 = 2C + 2H2O. The primary objective was to determine the feasibility of applying this reaction at low temperatures as a technique for recovering the oxygen (O2) remaining in the CO2 which exits mixed with CH4 from a Sabatier CO2 reduction subsystem (as part of an air revitalization system of a manned spacecraft). A test unit was designed, fabricated, and assembled for characterizing the performance of various catalysts for the reaction and ultraviolet activation of the CH4 and CO2. The reactor included in the test unit was designed to have sufficient capacity to evaluate catalyst charges of up to 76 g (0.17 lb). The test stand contained the necessary instrumentation and controls to obtain the data required to characterize the performance of the catalysts and sensitizers tested: flow control and measurement, temperature control and measurement, product and inlet gas analysis, and pressure measurement. A product assurance program was performed implementing the concepts of quality control and safety into the program effort.

On the suitability of different representations of solid catalysts for combinatorial library design by genetic algorithms.

PubMed

Gobin, Oliver C; Schüth, Ferdi

2008-01-01

Genetic algorithms are widely used to solve and optimize combinatorial problems and are more often applied for library design in combinatorial chemistry. Because of their flexibility, however, their implementation can be challenging. In this study, the influence of the representation of solid catalysts on the performance of genetic algorithms was systematically investigated on the basis of a new, constrained, multiobjective, combinatorial test problem with properties common to problems in combinatorial materials science. Constraints were satisfied by penalty functions, repair algorithms, or special representations. The tests were performed using three state-of-the-art evolutionary multiobjective algorithms by performing 100 optimization runs for each algorithm and test case. Experimental data obtained during the optimization of a noble metal-free solid catalyst system active in the selective catalytic reduction of nitric oxide with propene was used to build up a predictive model to validate the results of the theoretical test problem. A significant influence of the representation on the optimization performance was observed. Binary encodings were found to be the preferred encoding in most of the cases, and depending on the experimental test unit, repair algorithms or penalty functions performed best.

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

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

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

Highly chemoselective intermolecular cross-benzoin reactions using an ad hoc designed novel N-heterocyclic carbene catalyst.

PubMed

Delany, Eoghan G; Connon, Stephen J

2018-01-31

The design of a novel N-heterocyclic carbene catalyst incorporating a bulky yet highly electron-deficient N-aryl substituent has allowed the development of an efficient protocol for the first highly chemoselective intermolecular benzoin condensations between two non-identical aromatic aldehydes.

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

EPA Science Inventory

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

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...

Evaluation of Commercial Off-the-Shelf Sorbents and Catalysts for Control of Ammonia and Carbon Monoxide

NASA Technical Reports Server (NTRS)

Luna, Bernadette; Somi, George; Winchester, J. Parker; Grose, Jeffrey; Mulloth, Lila; Perry, Jay L.

2010-01-01

Designers of future space vehicles envision simplifying the Atmosphere Revitalization (AR) system by combining the functions of trace contaminant (TC) control and carbon dioxide removal into one swing-bed system. Flow rates and bed sizes of the TC and CO2 systems have historically been very different. There is uncertainty about the ability of trace contaminant sorbents to adsorb adequately in high-flow or short bed length configurations, and to desorb adequately during short vacuum exposures. There is also concern about ambient ammonia levels in the absence of a condensing heat exchanger. In addition, new materials and formulations have become commercially available, formulations never evaluated by NASA for purposes of trace contaminant control. The optimal air revitalization system for future missions may incorporate a swing-bed system for carbon dioxide (CO2) and partial trace contaminant control, with a reduced-size, low-power, targeted trace contaminant system supplying the remaining contaminant removal capability. This paper describes the results of a comparative experimental investigation into materials for trace contaminant control that might be part of such a system. Ammonia sorbents and low temperature carbon monoxide (CO) oxidation catalysts are the foci. The data will be useful to designers of AR systems for future flexible path missions. This is a continuation of work presented in a prior year, with extended test results.

Evaluation of Commercial Off-the-Shelf Sorbents and Catalysts for Control of Ammonia and Carbon Monoxide

NASA Technical Reports Server (NTRS)

Luna, Bernadette; Somi, George; Winchester, J. Parker; Grose, Jeffrey; Mulloth, Lila; Perry, Jay L.

2013-01-01

Designers of future space vehicles envision simplifying the Atmosphere Revitalization (AR) system by combining the functions of trace contaminant (TC) control and carbon dioxide removal into one swing-bed system. Flow rates and bed sizes of the TC and CO2 systems have historically been very different. There is uncertainty about the ability of trace contaminant sorbents to adsorb adequately in high-flow or short bed length configurations, and to desorb adequately during short vacuum exposures. There is also concern about ambient ammonia levels in the absence of a condensing heat exchanger. In addition, new materials and formulations have become commercially available, formulations never evaluated by NASA for purposes of trace contaminant control. The optimal air revitalization system for future missions may incorporate a swing-bed system for carbon dioxide (CO2) and partial trace contaminant control, with a reduced-size, low-power, targeted trace contaminant system supplying the remaining contaminant removal capability. This paper describes the results of a comparative experimental investigation into materials for trace contaminant control that might be part of such a system. Ammonia sorbents and low temperature carbon monoxide (CO) oxidation catalysts are the foci. The data will be useful to designers of AR systems for future flexible path missions. This is a continuation of work presented in a prior year, with extended test results.

Development of biologically modified anodes for energy harvesting using microbial fuel cells

NASA Astrophysics Data System (ADS)

Sumner, James J.; Ganguli, Rahul; Chmelka, Brad

2012-06-01

Biological fuel cells hold promise as an alternative energy source to batteries for unattended ground sensor applications due to the fact that they can be extremely long lived. This lifetime can be extended over batteries by scavenging fuel from the deployed environment. Microbial fuel cells (MFC) are one class of such sources that produce usable energy from small organic compounds (i.e. sugars, alcohols, organic acids, and biopolymers) which can be easily containerized or scavenged from the environment. The use of microorganisms as the anodic catalysts is what makes these systems unique from other biofuel cell designs. One of the main drawbacks of engineering a sensor system powered by an MFC is that power densities and current flux are extremely low in currently reported systems. The power density is limited by the mass transfer of the fuel source to the catalyst, the metabolism of the microbial catalysts and the electron transfer from the organism to the anode. This presentation will focus on the development of a new style of microbially-modified anodes which will increase power density to a level where a practical power source can be engineered. This is being achieved by developing a three dimensional matrix as an artificial, conductive biofilm. These artificial biofilms will allow the capture of a consortium of microbes designed for efficient metabolism of the available fuel source. Also it will keep the microbes close to the electrode allowing ready access by fuel and providing a low resistance passage of the liberated electrons from fuel oxidation.

Evolving Maturation of the Series-Bosch System

NASA Technical Reports Server (NTRS)

Stanley, Christine; Abney, Morgan B.; Barnett, Bill

2017-01-01

Human exploration missions to Mars and other destinations beyond low Earth orbit require highly robust, reliable, and maintainable life support systems that maximize recycling of water and oxygen. In order to meet this requirement, NASA has continued the development of a Series-Bosch System, a two stage reactor process that reduces carbon dioxide (CO2) with hydrogen (H2) to produce water and solid carbon. Theoretically, the Bosch process can recover 100% of the oxygen (O2) from CO2 in the form of water, making it an attractive option for long duration missions. The Series Bosch system includes a reverse water gas shift (RWGS) reactor, a carbon formation reactor (CFR), an H2 extraction membrane, and a CO2 extraction membrane. In 2016, the results of integrated testing of the Series Bosch system showed great promise and resulted in design modifications to the CFR to further improve performance. This year, integrated testing was conducted with the modified reactor to evaluate its performance and compare it with the performance of the previous configuration. Additionally, a CFR with the capability to load new catalyst and remove spent catalyst in-situ was built. Flow demonstrations were performed to evaluate both the catalyst loading and removal process and the hardware performance. The results of the integrated testing with the modified CFR as well as the flow demonstrations are discussed in this paper.

High-temperature catalyst for catalytic combustion and decomposition

NASA Technical Reports Server (NTRS)

Mays, Jeffrey A. (Inventor); Lohner, Kevin A. (Inventor); Sevener, Kathleen M. (Inventor); Jensen, Jeff J. (Inventor)

2005-01-01

A robust, high temperature mixed metal oxide catalyst for propellant composition, including high concentration hydrogen peroxide, and catalytic combustion, including methane air mixtures. The uses include target, space, and on-orbit propulsion systems and low-emission terrestrial power and gas generation. The catalyst system requires no special preheat apparatus or special sequencing to meet start-up requirements, enabling a fast overall response time. Start-up transients of less than 1 second have been demonstrated with catalyst bed and propellant temperatures as low as 50 degrees Fahrenheit. The catalyst system has consistently demonstrated high decomposition effeciency, extremely low decomposition roughness, and long operating life on multiple test particles.

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

NASA Technical Reports Server (NTRS)

Kaufman, A.

1981-01-01

An integrated 5 kW power system based upon methanol fuel and a phosphoric acid fuel cell operating at about 473 K is described. Description includes test results of advanced fuel cell catalysts, a semiautomatic acid replenishment system and a completed 5 kW methanol/system reformer. The results of a preliminary system test on a reformer/stack/inverter combination are reported. An initial design for a 25 kW stack is presented. Experimental plans are outlined for data acquisition necessary for design of a 50 kW methanol/steam reformer. Activities related to complete mathematical modelling of the integrated power system, including wasteheat utilization, are described.

Insights into the Mechanism of a Covalently Linked Organic Dye–Cobaloxime Catalyst System for Dye‐Sensitized Solar Fuel Devices

PubMed Central

Pati, Palas Baran; Zhang, Lei; Philippe, Bertrand; Fernández‐Terán, Ricardo; Ahmadi, Sareh; Tian, Lei; Rensmo, Håkan; Hammarström, Leif

2017-01-01

Abstract A covalently linked organic dye–cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye‐sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time‐resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye–catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye–catalyst system on the photocathode is proposed on the basis of this study. PMID:28338295

Improving the hydrocarbon production via co-pyrolysis of bagasse with bio-plastic and dual-catalysts layout.

PubMed

Zhang, Huiyan; Likun, Peter Keliona Wani; Xiao, Rui

2018-03-15

Catalytic fast pyrolysis (CFP) of bagasse and bio-plastic (chicken feather keratin) and their mixtures were conducted to produce aromatic hydrocarbons over a HZSM-5, USY, and dual-catalysts layout. The effects of temperature, co-feeding ratios, feed-to-catalyst ratios and dual catalysts on hydrocarbon yields and selectivities were investigated. The results show a general improvement in the aromatic hydrocarbons yields in all cases compared to non-catalytic and pure biomass pyrolysis. The aromatic hydrocarbons increased by 10 fold with the increase of temperature from 400°C to 700°C. The aromatic yields increased 1.5 times at co-feeding, 2.0 greater at feed/HZSM-5 ratio of 1:6, 1.2 times at feed/USY ratio of 1:16, and 2.66 times at USY/HZSM-5 scenario. The selectivities towards benzene increased, at higher co-feeding ratios, while that of toluene shows an opposite trend. Xylenes selectivities were less sensitive to the changes of co-feeding ratios. In contrast, the USY catalyst only produced little amount of toluene and xylenes. The dual catalyst design (USY/HZSM-5) resulted in the highest aromatic yields, than other catalyst design scenarios. The pyrolysis temperature is a significant parameter for hydrocarbon production. Co-feeding bagasse and bio-plastic enhanced biomass conversion to aromatic compounds. For any type of zeolite catalyst, there was an optimum feed-to-catalyst ratio that generated maximum hydrocarbons. Dual catalyst layout shows a new opportunity for efficient conversion of biomass materials into hydrocarbons. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

PubMed

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal-support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

The Catalytic Asymmetric Intramolecular Stetter Reaction

PubMed Central

de Alaniz, Javier Read; Rovis, Tomislav

2010-01-01

This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows. PMID:20585467

Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

PubMed

Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng

2018-04-13

Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

PubMed Central

Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

2016-01-01

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

Plasmatron-catalyst system

DOEpatents

Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander; Alexeev, Nikolai

2004-09-21

A plasmatron-catalyst system. The system generates hydrogen-rich gas and comprises a plasmatron and at least one catalyst for receiving an output from the plasmatron to produce hydrogen-rich gas. In a preferred embodiment, the plasmatron receives as an input air, fuel and water/steam for use in the reforming process. The system increases the hydrogen yield and decreases the amount of carbon monoxide.

Plasmatron-catalyst system

DOEpatents

Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander; Alexeev, Nikolai

2007-10-09

A plasmatron-catalyst system. The system generates hydrogen-rich gas and comprises a plasmatron and at least one catalyst for receiving an output from the plasmatron to produce hydrogen-rich gas. In a preferred embodiment, the plasmatron receives as an input air, fuel and water/steam for use in the reforming process. The system increases the hydrogen yield and decreases the amount of carbon monoxide.

Direct evidence of atomic-scale structural fluctuations in catalyst nanoparticles.

PubMed

Lin, Pin Ann; Gomez-Ballesteros, Jose L; Burgos, Juan C; Balbuena, Perla B; Natarajan, Bharath; Sharma, Renu

2017-05-01

Rational catalyst design requires an atomic scale mechanistic understanding of the chemical pathways involved in the catalytic process. A heterogeneous catalyst typically works by adsorbing reactants onto its surface, where the energies for specific bonds to dissociate and/or combine with other species (to form desired intermediate or final products) are lower. Here, using the catalytic growth of single-walled carbon nanotubes (SWCNTs) as a prototype reaction, we show that the chemical pathway may in-fact involve the entire catalyst particle, and can proceed via the fluctuations in the formation and decomposition of metastable phases in the particle interior. We record in situ and at atomic resolution, the dynamic phase transformations occurring in a Cobalt catalyst nanoparticle during SWCNT growth, using a state-of-the-art environmental transmission electron microscope (ETEM). The fluctuations in catalyst carbon content are quantified by the automated, atomic-scale structural analysis of the time-resolved ETEM images and correlated with the SWCNT growth rate. We find the fluctuations in the carbon concentration in the catalyst nanoparticle and the fluctuations in nanotube growth rates to be of complementary character. These findings are successfully explained by reactive molecular dynamics (RMD) simulations that track the spatial and temporal evolution of the distribution of carbon atoms within and on the surface of the catalyst particle. We anticipate that our approach combining real-time, atomic-resolution image analysis and molecular dynamics simulations will facilitate catalyst design, improving reaction efficiencies and selectivity towards the growth of desired structure.

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.

Advances in microreaction technology for portable fuel cell applications: Wall coating of thin catalytic films in microreactors

NASA Astrophysics Data System (ADS)

Bravo Bersano, Jaime Cristian

This research has focused on the need to coat microreactor systems composed of channels in the micron size range of 100 to 1000 mum. The experimental procedures and learning are outlined in terms of slurry and surface preparation requirements which are detailed in the experimental section. This system is motivated and applied to micro methanol steam reformers. Thus, a detailed discussion on the driving motivation is given in the introduction. The low temperatures required for steam-reforming of methanol ˜ 493°K (220°C) make it possible to utilize the reformate as a feed to the fuel cell anode. The group of catalysts that shows the highest activity for methanol steam reforming (SR) at low temperature has composition of CuO/ZnO/Al 2O3, which is also the catalyst used for methanol synthesis. Steam reforming of methanol is a highly endothermic process. Conventional reactor configurations, such as a packed bed reactor, operate in a heat transfer limited mode for this reaction. Using catalyst in packed bed form for portable devices is also not convenient due to high pressure drop and possible channeling of gases in addition to poor heat transfer. A wall-coated catalyst represents a superior geometry since it provides lower pressure drop and ease of manufacturing. Due to their small size, microreactors are especially suited for endothermic reactions whose reactivity depends on the rate of heat input. A brief review on microreaction technology is given with a comprehensive survey for catalyst integration into microreactors for catalytic heterogeneous gas phase reactions. The strength of this research is the model that was developed to coat the interior of micron sized capillaries with coats of CuO/ZnO/Al2O 3 slurries as thick as 25 mum in the dry state. The details of the model are given in terms Taylor's theory and Rayleigh's theory. A model is presented that can predict the coat thickness based on experimental conditions The model combines Taylor's experimental work with Lord Rayleigh's instability theory for annular coatings. The model presented serves as a design tool for microreactor design. The model can also estimate the maximum coat thickness possible for a given system. The results are presented in graphical format in the Microchannel Coating Model chapter.

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.

General entanglement-assisted transformation for bipartite pure quantum states

NASA Astrophysics Data System (ADS)

Song, Wei; Huang, Yan; Nai-LeLiu; Chen, Zeng-Bing

2007-01-01

We introduce the general catalysts for pure entanglement transformations under local operations and classical communications in such a way that we disregard the profit and loss of entanglement of the catalysts per se. As such, the possibilities of pure entanglement transformations are greatly expanded. We also design an efficient algorithm to detect whether a k × k general catalyst exists for a given entanglement transformation. This algorithm can also be exploited to witness the existence of standard catalysts.

Instruments for Characterizing Carbon and Sulfur-Resistant Core-Shell Redox Catalysts for Combined Hydrocarbon Reforming and Water-Splitting

DTIC Science & Technology

2015-11-22

SECURITY CLASSIFICATION OF: This project aims to investigate a novel core-shell redox catalyst for combined methane partial oxidation and water...Properly designed redox catalyst are shown to be highly effective for syngas production (from methane ) and water-splitting. The resulting syngas has a...27709-2211 redox catalyst, methane partial oxidation, water-splitting REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR

Rational Design of N- S- Fe- Doped Nanoporous Carbon Catalysts from Covalent Triazine Framework for High Efficient ORR.

PubMed

Zhu, Yuanzhi; Chen, Xifan; Liu, Jing; Zhang, Junfeng; Xu, Danyun; Peng, Wenchao; Li, Yang; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

2018-05-15

Porous organic polymers (POFs) are promising precursors for developing high performance transition metal-nitrogen-carbon (M-N/C) catalysts towards ORR. But the rational design of POFs precursors remain a great challenge, because of the elusive structural association between the sacrificial POFs and the final M-N/C catalysts. Based on covalent triazine frameworks (CTFs), we developed a series of sulfur-doped Fe-N/C catalysts by selecting six different aromatic nitriles as building blocks. A new mixed solvent of molten FeCl3 and S was used for CTF polymerization, which benefit the formation of Fe-Nx site and make the subsequent pyrolysis process more convenient. Comprehensive study on these CTF-derived catalysts shows their ORR activities are not directly dependent on the theoretical N/C ratio of the building block, but closely correlated to the ratios of the nitrile group to benzene ring (Nnitrile/Nbenzene) and geometries of the building blocks. The high ratios of the Nnitrile/Nbenzene are crucial for ORR activity of the final catalysts due to the formation of more N-doped microporous and Fe-Nx sites in pyrolysis possess. The optimized catalyst shows high ORR performances in acid and superior ORR activity to the Pt/C catalysts under alkaline conditions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Production of alpha-hydroxy carboxylic acids and esters from higher sugars using tandem catalyst systems

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

Orazov, Marat; Davis, Mark E.

The present disclosure is directed to methods and composition used in the preparation of alpha-hydroxy carboxylic acids and esters from higher sugars using a tandem catalyst system comprising retro-aldol catalysts and Lewis acid catalysts. In some embodiments, these alpha-hydroxy carboxylic acids may be prepared from pentoses and hexoses. The retro-aldol and Lewis catalysts may be characterized by their respective ability to catalyze a 1,2-carbon shift reaction and a 1,2-hydride shift reaction on an aldose or ketose substrate.

Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G; Liu, Shetian

2014-12-09

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality gasoline components, aromatic compounds, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel molybdenum-zeolite catalyst in high pressure hydrogen for conversion, as well as a novel rhenium-zeolite catalyst in place of the molybdenum-zeolite catalyst, and provides for use of the novel catalysts in the process and system of the invention.

Attrition of precipitated iron Fischer-Tropsch catalysts

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

Datye, A.K.; Reardon, J.; Hanprasopwattana, A.

1996-12-31

Precipitated Iron catalysts used in slurry phase bubble column reactors are known to undergo attrition during use. The attrition reduces the lifetime of the catalyst as well as causing problems in separating the product liquids from the catalyst. In this study, the authors have investigated the underlying mechanisms that lead to attrition in precipitated iron catalysts. They have discovered that attrition takes place on two length scales. On the macro scale, attrition is caused by the break-up of the weak agglomerates that constitute this catalyst into individual crystallites. Addition of binders such as kaolin does not help significantly in strengtheningmore » the catalyst particles. In addition, there is a second process leading to nanoscale attrition that is caused by the break-up of individual iron oxide crystallites into nano particles of iron carbide as the catalyst is activated for reaction. Design of attrition resistant F-T catalysts must consider these two modes of catalyst attrition. Preliminary work in the laboratory directed at improving the attrition resistance of precipitated iron catalysts will also be described in this paper.« less

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

Raugei, Simone; DuBois, Daniel L.; Rousseau, Roger J.

Rational design of molecular catalysts requires a systematic approach to designing ligands with specific functionality and precisely tailored electronic and steric properties. It then becomes possible to devise computer protocols to predict accurately the required properties and ultimately to design catalysts by computer. In this account we first review how thermodynamic properties such as oxidation-reduction potentials (E0), acidities (pKa), and hydride donor abilities (ΔGH-) form the basis for a systematic design of molecular catalysts for reactions that are critical for a secure energy future (hydrogen evolution and oxidation, oxygen and nitrogen reduction, and carbon dioxide reduction). We highlight how densitymore » functional theory allows us to determine and predict these properties within “chemical” accuracy (~ 0.06 eV for redox potentials, ~ 1 pKa unit for pKa values, and ~ 1.5 kcal/mol for hydricities). These quantities determine free energy maps and profiles associated with catalytic cycles, i.e. the relative energies of intermediates, and help us distinguish between desirable and high-energy pathways and mechanisms. Good catalysts have flat profiles that avoid high activation barriers due to low and high energy intermediates. We illustrate how the criterion of a flat energy profile lends itself to the prediction of design points by computer for optimum catalysts. This research was carried out in the Center for Molecular Electro-catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated for the DOE by Battelle.« less

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

NASA Astrophysics Data System (ADS)

Tsubogo, Tetsu; Oyamada, Hidekazu; Kobayashi, Shū

2015-04-01

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

Hydroxylation of Benzene via CH Activation Using Bimetallic ...

EPA Pesticide Factsheets

A photoactive bimetallic CuAg@g-C3N4 catalyst system has been designed and synthesized by impregnating copper and silver nanoparticles over the graphitic carbon nitride surface. Its application has been demonstrated in the hydroxylation of benzene under visible light. Prepared for submission to American Chemical Society (ACS) journal, ACS Sustainable Chemistry & Engineering.

Development and Comparison of the Substrate Scope of Pd-Catalysts for the Aerobic Oxidation of Alcohols

PubMed Central

Schultz, Mitchell J.; Hamilton, Steven S.; Jensen, David R.; Sigman, Matthew S.

2009-01-01

Three catalysts for aerobic oxidation of alcohols are discussed and the effectiveness of each is evaluated for allylic, benzylic, aliphatic, and functionalized alcohols. Additionally, chiral nonracemic substrates as well as chemoselective and diastereoselective oxidations are investigated. In this study, the most convenient system for the Pd-catalyzed aerobic oxidation of alcohols is Pd(OAc)2 in combination with triethylamine. This system functions effectively for the majority of alcohols tested and uses mild conditions (3 to 5 mol % of catalyst, room temperature). Pd(IiPr)(OAc)2(H2O) (1) also successfully oxidizes the majority of alcohols evaluated. This system has the advantage of significantly lowering catalyst loadings but requires higher temperatures (0.1 to 1 mol % of catalyst, 60 °C). A new catalyst is also disclosed, Pd(IiPr)(OPiv)2 (2). This catalyst operates under very mild conditions (1 mol %, room temperature, and air as the O2 source) but with a more limited substrate scope. PMID:15844968

Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

DOEpatents

Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

2001-01-01

An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

Catalyst systems and uses thereof

DOEpatents

Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

2012-07-24

A method of carbon monoxide (CO) removal comprises providing an oxidation catalyst comprising cobalt supported on an inorganic oxide. The method further comprises feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to the catalyst system, and removing CO from the gaseous stream by oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of the oxidation catalyst at a temperature between about 20 to about 200.degree. C.

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

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

None

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

The Bosch Process-Performance of a Developmental Reactor and Experimental Evaluation of Alternative Catalysts

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Mansell, J. Matthew

2010-01-01

Bosch-based reactors have been in development at NASA since the 1960's. Traditional operation involves the reduction of carbon dioxide with hydrogen over a steel wool catalyst to produce water and solid carbon. While the system is capable of completely closing the loop on oxygen and hydrogen for Atmosphere Revitalization, steel wool requires a reaction temperature of 650C or higher for optimum performance. The single pass efficiency of the reaction over steel wool has been shown to be less than 10% resulting in a high recycle stream. Finally, the formation of solid carbon on steel wool ultimately fouls the catalyst necessitating catalyst resupply. These factors result in high mass, volume and power demands for a Bosch system. Interplanetary transportation and surface exploration missions of the moon, Mars, and near-earth objects will require higher levels of loop closure than current technology cannot provide. A Bosch system can provide the level of loop closure necessary for these long-term missions if mass, volume, and power can be kept low. The keys to improving the Bosch system lie in reactor and catalyst development. In 2009, the National Aeronautics and Space Administration refurbished a circa 1980's developmental Bosch reactor and built a sub-scale Bosch Catalyst Test Stand for the purpose of reactor and catalyst development. This paper describes the baseline performance of two commercially available steel wool catalysts as compared to performance reported in the 1960's and 80's. Additionally, the results of sub-scale testing of alternative Bosch catalysts, including nickel- and cobalt-based catalysts, are discussed.

Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C–H bond activation† †Electronic supplementary information (ESI) available: Experimental details, material characterization data, catalytic measurement details. See DOI: 10.1039/c7sc00713b Click here for additional data file.

PubMed Central

Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu

2017-01-01

Heterogeneous metal complex catalysts for direct C–H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2′-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)]2 (Cp* = η5-pentamethylcyclopentadienyl) and [Ir(cod)(OMe)]2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C–H oxidation of heterocycles and cycloalkanes as well as C–H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations. PMID:28970878

Inverse Catalysts for CO Oxidation: Enhanced Oxide–Metal Interactions in MgO/Au(111), CeO 2/Au(111), and TiO 2/Au(111)

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

Palomino, Robert M.; Gutiérrez, Ramón A.; Liu, Zongyuan

Au(111) does not bind CO and O 2 well. The deposition of small nanoparticles of MgO, CeO 2, and TiO 2 on Au(111) produces excellent catalysts for CO oxidation at room temperature. In an inverse oxide/metal configuration there is a strong enhancement of the oxide–metal interactions, and the inverse catalysts are more active than conventional Au/MgO(001), Au/CeO 2(111), and Au/TiO 2(110) catalysts. An identical trend was seen after comparing the CO oxidation activity of TiO2/Au and Au/TiO 2 powder catalysts. In the model systems, the activity increased following the sequence: MgO/Au(111) < CeO 2/Au(111) < TiO 2/Au(111). Ambient pressure X-raymore » photoelectron spectroscopy (AP-XPS) was used to elucidate the role of the titania–gold interface in inverse TiO 2/Au(111) model catalysts during CO oxidation. Stable surface intermediates such as CO(ads), CO 3 2–(ads), and OH(ads) were identified under reaction conditions. CO 3 2–(ads) and OH(ads) behaved as spectators. The concentration of CO(ad) initially increased and then decreased with increasing TiO 2 coverage, demonstrating a clear role of the Ti–Au interface and the size of the TiO 2 nanostructures in the catalytic process. Overall, our results show an enhancement in the strength of the oxide–metal interactions when working with inverse oxide/metal configurations, a phenomenon that can be utilized for the design of efficient catalysts useful for green and sustainable chemistry.« less

Inverse Catalysts for CO Oxidation: Enhanced Oxide–Metal Interactions in MgO/Au(111), CeO 2/Au(111), and TiO 2/Au(111)

DOE PAGES

Palomino, Robert M.; Gutiérrez, Ramón A.; Liu, Zongyuan; ...

2017-09-26

Au(111) does not bind CO and O 2 well. The deposition of small nanoparticles of MgO, CeO 2, and TiO 2 on Au(111) produces excellent catalysts for CO oxidation at room temperature. In an inverse oxide/metal configuration there is a strong enhancement of the oxide–metal interactions, and the inverse catalysts are more active than conventional Au/MgO(001), Au/CeO 2(111), and Au/TiO 2(110) catalysts. An identical trend was seen after comparing the CO oxidation activity of TiO2/Au and Au/TiO 2 powder catalysts. In the model systems, the activity increased following the sequence: MgO/Au(111) < CeO 2/Au(111) < TiO 2/Au(111). Ambient pressure X-raymore » photoelectron spectroscopy (AP-XPS) was used to elucidate the role of the titania–gold interface in inverse TiO 2/Au(111) model catalysts during CO oxidation. Stable surface intermediates such as CO(ads), CO 3 2–(ads), and OH(ads) were identified under reaction conditions. CO 3 2–(ads) and OH(ads) behaved as spectators. The concentration of CO(ad) initially increased and then decreased with increasing TiO 2 coverage, demonstrating a clear role of the Ti–Au interface and the size of the TiO 2 nanostructures in the catalytic process. Overall, our results show an enhancement in the strength of the oxide–metal interactions when working with inverse oxide/metal configurations, a phenomenon that can be utilized for the design of efficient catalysts useful for green and sustainable chemistry.« less

Laser-Induced Fluorescence Detection in High-Throughput Screening of Heterogeneous Catalysts and Single Cells Analysis

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

Su, Hui

2001-01-01

Laser-induced fluorescence detection is one of the most sensitive detection techniques and it has found enormous applications in various areas. The purpose of this research was to develop detection approaches based on laser-induced fluorescence detection in two different areas, heterogeneous catalysts screening and single cell study. First, the author introduced laser-induced imaging (LIFI) as a high-throughput screening technique for heterogeneous catalysts to explore the use of this high-throughput screening technique in discovery and study of various heterogeneous catalyst systems. This scheme is based on the fact that the creation or the destruction of chemical bonds alters the fluorescence properties ofmore » suitably designed molecules. By irradiating the region immediately above the catalytic surface with a laser, the fluorescence intensity of a selected product or reactant can be imaged by a charge-coupled device (CCD) camera to follow the catalytic activity as a function of time and space. By screening the catalytic activity of vanadium pentoxide catalysts in oxidation of naphthalene, they demonstrated LIFI has good detection performance and the spatial and temporal resolution needed for high-throughput screening of heterogeneous catalysts. The sample packing density can reach up to 250 x 250 subunits/cm 2 for 40-μm wells. This experimental set-up also can screen solid catalysts via near infrared thermography detection. In the second part of this dissertation, the author used laser-induced native fluorescence coupled with capillary electrophoresis (LINF-CE) and microscope imaging to study the single cell degranulation. On the basis of good temporal correlation with events observed through an optical microscope, they have identified individual peaks in the fluorescence electropherograms as serotonin released from the granular core on contact with the surrounding fluid.« less

Technology development for iron Fischer-Tropsch catalysts. Technical progress report No. 8, July 1, 1992--September 30, 1992

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

Frame, R.R.; Gala, H.B.

1992-12-31

The objectives of this contract are to develop a technology for the production of active and stable iron Fischer-Tropsch catalysts for use in slurry-phase synthesis reactors and to develop a scaleup procedure for large-scale synthesis of such catalysts for process development and long-term testing in slurry bubble-column reactors. With a feed containing hydrogen and carbon monoxide in the molar ratio of 0.5 to 1.0 to the slurry bubble-column reactor, the catalyst performance target is 88% CO + H{sub 2} conversion at a minimum space velocity of 2.4 NL/hr/gFe. The desired sum of methane and ethane selectivities is no more thanmore » 4%, and the conversion loss per week is not to exceed 1%. Contract Tasks are as follows: 1.0--Catalyst development, 1.1--Technology assessment, 1.2--Precipitated catalyst preparation method development, 1.3--Novel catalyst preparation methods investigation, 1.4--Catalyst pretreatment, 1.5--Catalyst characterization, 2.0--Catalyst testing, 3.0--Catalyst aging studies, and 4.0--Preliminary design and cost estimate of a catalyst synthesis facility. This paper reports progress made on Task 1.« less

Insights into the Mechanism of a Covalently Linked Organic Dye-Cobaloxime Catalyst System for Dye-Sensitized Solar Fuel Devices.

PubMed

Pati, Palas Baran; Zhang, Lei; Philippe, Bertrand; Fernández-Terán, Ricardo; Ahmadi, Sareh; Tian, Lei; Rensmo, Håkan; Hammarström, Leif; Tian, Haining

2017-06-09

A covalently linked organic dye-cobaloxime catalyst system based on mesoporous NiO is synthesized by a facile click reaction for mechanistic studies and application in a dye-sensitized solar fuel device. The system is systematically investigated by photoelectrochemical measurements, density functional theory, time-resolved fluorescence, transient absorption spectroscopy, and photoelectron spectroscopy. The results show that irradiation of the dye-catalyst on NiO leads to ultrafast hole injection into NiO from the excited dye, followed by a fast electron transfer process to reduce the catalyst. Moreover, the dye adopts different structures with different excited state energies, and excitation energy transfer occurs between neighboring molecules on the semiconductor surface. The photoelectrochemical experiments also show hydrogen production by this system. The axial chloride ligands of the catalyst are released during photocatalysis to create the active sites for proton reduction. A working mechanism of the dye-catalyst system on the photocathode is proposed on the basis of this study. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

NASA Technical Reports Server (NTRS)

Fisher, John W.; Abraham, Martin

1993-01-01

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

Improvements in the gaseous hydrogen-water equilibration technique for hydrogen isotope ratio analysis

USGS Publications Warehouse

Coplen, T.B.; Wildman, J.D.; Chen, J.

1991-01-01

Improved precision in the H2-H2O equilibration method for ??D analysis has been achieved in an automated system. Reduction in 1-?? standard deviation of a single mass-spectrometer analysis to 1.3??? is achieved by (1) bonding catalyst to glass rods and assigning use to specific equilibration chambers to monitor performance of catalyst, (2) improving the apparatus design, and (3) reducing the H3+ contribution of the mass-spectrometer ion source. For replicate analysis of a water sample, the standard deviation improved to 0.8???. H2S-bearing samples and samples as small as 0.1 mL can be analyzed routinely with this method.

Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen.

PubMed

Oughli, Alaa A; Ruff, Adrian; Boralugodage, Nilusha Priyadarshani; Rodríguez-Maciá, Patricia; Plumeré, Nicolas; Lubitz, Wolfgang; Shaw, Wendy J; Schuhmann, Wolfgang; Rüdiger, Olaf

2018-02-28

The Ni(P 2 N 2 ) 2 catalysts are among the most efficient non-noble-metal based molecular catalysts for H 2 cycling. However, these catalysts are O 2 sensitive and lack long term stability under operating conditions. Here, we show that in a redox silent polymer matrix the catalyst is dispersed into two functionally different reaction layers. Close to the electrode surface is the "active" layer where the catalyst oxidizes H 2 and exchanges electrons with the electrode generating a current. At the outer film boundary, insulation of the catalyst from the electrode forms a "protection" layer in which H 2 is used by the catalyst to convert O 2 to H 2 O, thereby providing the "active" layer with a barrier against O 2 . This simple but efficient polymer-based electrode design solves one of the biggest limitations of these otherwise very efficient catalysts enhancing its stability for catalytic H 2 oxidation as well as O 2 tolerance.

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.

Ultraviolet-Visible (UV-Vis) Microspectroscopic System Designed for the In Situ Characterization of the Dehydrogenation Reaction Over Platinum Supported Catalytic Microchannel Reactor.

PubMed

Suarnaba, Emee Grace Tabares; Lee, Yi Fuan; Yamada, Hiroshi; Tagawa, Tomohiko

2016-11-01

An ultraviolet visible (UV-Vis) microspectroscopic system was designed for the in situ characterization of the activity of the silica supported platinum (Pt) catalyst toward the dehydrogenation of 1-methyl-1,4-cyclohexadiene carried out in a custom-designed catalytic microreactor cell. The in situ catalytic microreactor cell (ICMC) with inlet/outlet ports was prepared using quartz cover as the optical window to facilitate UV-Vis observation. A fabricated thermometric stage was adapted to the UV-Vis microspectrophotometer to control the reaction temperature inside the ICMC. The spectra were collected by focusing the UV-Vis beam on a 30 × 30 µm area at the center of ICMC. At 393 K, the sequential measurement of the spectra recorded during the reaction exhibited a broad absorption peak with maximum absorbance at 260 nm that is characteristic for gaseous toluene. This result indicates that the silica supported Pt catalyst is active towards the dehydrogenation of 1-methyl-1,4-cyclohexadiene at the given experimental conditions. The onset of coke formation was also detected based on the appearance of absorption bands at 300 nm. The UV-Vis microspectroscopic system developed can be used further in studying the mechanism of the dehydrogenation reaction. © The Author(s) 2016.

Catalytic Tar Reduction for Assistance in Thermal Conversion of Space Waste for Energy Production

NASA Technical Reports Server (NTRS)

Caraccio, Anne Joan; Devor, Robert William; Hintze, Paul E.; Muscatello, Anthony C.; Nur, Mononita

2014-01-01

The Trash to Gas (TtG) project investigates technologies for converting waste generated during spaceflight into various resources. One of these technologies was gasification, which employed a downdraft reactor designed and manufactured at NASA's Kennedy Space Center (KSC) for the conversion of simulated space trash to carbon dioxide. The carbon dioxide would then be converted to methane for propulsion and water for life support systems. A minor byproduct of gasification includes large hydrocarbons, also known as tars. Tars are unwanted byproducts that add contamination to the product stream, clog the reactor and cause complications in analysis instrumentation. The objective of this research was to perform reduction studies of a mock tar using select catalysts and choose the most effective for primary treatment within the KSC downdraft gasification reactor. Because the KSC reactor is operated at temperatures below typical gasification reactors, this study evaluates catalyst performance below recommended catalytic operating temperatures. The tar reduction experimentation was observed by passing a model tar vapor stream over the catalysts at similar conditions to that of the KSC reactor. Reduction in tar was determined using gas chromatography. Tar reduction efficiency and catalyst performances were evaluated at different temperatures.

Bottom-up meets top-down: tailored raspberry-like Fe3O4-Pt nanocrystal superlattices.

PubMed

Qiu, Fen; Vervuurt, René H J; Verheijen, Marcel A; Zaia, Edmond W; Creel, Erin B; Kim, Youngsang; Urban, Jeffrey J; Bol, Ageeth A

2018-03-29

Supported catalysts are widely used in industry and can be optimized by tuning the composition, chemical structure, and interface of the nanoparticle catalyst and oxide support. Here we firstly combine a bottom up colloidal synthesis method with a top down atomic layer deposition (ALD) process to achieve a raspberry-like Pt-decorated Fe3O4 (Fe3O4-Pt) nanoparticle superlattices. This nanocomposite ensures the precision of the catalyst/support interface, improving the catalytic efficiency of the Fe3O4-Pt nanocomposite system. The morphology of the hybrid nanocomposites resulting from different cycles of ALD was monitored by scanning transmission electron microscopy, giving insight into the nucleation and growth mechanism of the ALD process. X-ray photoelectron spectroscopy studies confirm the anticipated electron transfer from Fe3O4 to Pt through the nanocomposite interface. Photocurrent measurement further suggests that Fe3O4 superlattices with controlled decoration of Pt have substantial promise for energy-efficient photoelectrocatalytic oxygen evolution reaction. This work opens a new avenue for designing supported catalyst architectures via precisely controlled decoration of single component superlattices with noble metals.

Catalysts to reduce NO.sub.x in an exhaust gas stream and methods of preparation

DOEpatents

Koermer, Gerald S [Basking Ridge, NJ; Moini, Ahmad [Princeton, NJ; Furbeck, Howard [Hamilton, NJ; Castellano, Christopher R [Ringoes, NJ

2012-05-08

Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having a catalyst comprising silver on a particulate alumina support, the silver having a diameter of less than about 20 nm. Methods of manufacturing catalysts are described in which ionic silver is impregnated on particulate hydroxylated alumina particles.

Process for producing ethanol from syngas

DOEpatents

Krause, Theodore R; Rathke, Jerome W; Chen, Michael J

2013-05-14

The invention provides a method for producing ethanol, the method comprising establishing an atmosphere containing methanol forming catalyst and ethanol forming catalyst; injecting syngas into the atmosphere at a temperature and for a time sufficient to produce methanol; and contacting the produced methanol with additional syngas at a temperature and for a time sufficient to produce ethanol. The invention also provides an integrated system for producing methanol and ethanol from syngas, the system comprising an atmosphere isolated from the ambient environment; a first catalyst to produce methanol from syngas wherein the first catalyst resides in the atmosphere; a second catalyst to product ethanol from methanol and syngas, wherein the second catalyst resides in the atmosphere; a conduit for introducing syngas to the atmosphere; and a device for removing ethanol from the atmosphere. The exothermicity of the method and system obviates the need for input of additional heat from outside the atmosphere.

Exhaust gas purification system for lean burn engine

DOEpatents

Haines, Leland Milburn

2002-02-19

An exhaust gas purification system for a lean burn engine includes a thermal mass unit and a NO.sub.x conversion catalyst unit downstream of the thermal mass unit. The NO.sub.x conversion catalyst unit includes at least one catalyst section. Each catalyst section includes a catalytic layer for converting NO.sub.x coupled to a heat exchanger. The heat exchanger portion of the catalyst section acts to maintain the catalytic layer substantially at a desired temperature and cools the exhaust gas flowing from the catalytic layer into the next catalytic section in the series. In a further aspect of the invention, the exhaust gas purification system includes a dual length exhaust pipe upstream of the NO.sub.x conversion catalyst unit. The dual length exhaust pipe includes a second heat exchanger which functions to maintain the temperature of the exhaust gas flowing into the thermal mass downstream near a desired average temperature.

Dual-catalyst system to broaden the window of operability in the reduction of NO/sub chi/ with ammonia

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

Medros, F.G.; Eldridge, J.W.; Kittrell, J.R.

1989-08-01

The objective of the research discussed in this paper was to determine if a dual-catalyst system for NO reduction with NH/sub 3/ can achieve a given percent NO reduction over a wider range of temperatures and space velocities than either catalyst used alone in the same total reactor volume. Hydrogen mordenite (20/32 mesh) and copper-ion-exchanged hydrogen mordenite (2.2% Cu) were used in series at temperatures from 200 to 600 {sup 0}C and space velocities from 1000000 to 450000 h/sup -1/ (STP). The superiority of the dual-catalyst system was demonstrated experimentally, and a model was developed which predicted its performance verymore » well from data on the individual catalysts. A technique was then developed for predicting quantitatively the dual-catalyst enhancement of the space velocity versus temperature window for achieving a given percent NO conversion.« less

Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils

DOEpatents

Yan, Shuli [Detroit, MI; Salley, Steven O [Grosse Pointe Park, MI; Ng, K Y. Simon [West Bloomfield, MI

2012-04-24

A method of forming a biodiesel product and a heterogeneous catalyst system used to form said product that has a high tolerance for the presence of water and free fatty acids (FFA) in the oil feedstock is disclosed. This catalyst system may simultaneously catalyze both the esterification of FAA and the transesterification of triglycerides present in the oil feedstock. The catalyst system according to one aspect of the present disclosure represents a class of zinc and lanthanum oxide heterogeneous catalysts that include different ratios of zinc oxide to lanthanum oxides (Zn:La ratio) ranging from about 10:0 to 0:10. The Zn:La ratio in the catalyst is believed to have an effect on the number and reactivity of Lewis acid and base sites, as well as the transesterification of glycerides, the esterification of fatty acids, and the hydrolysis of glycerides and biodiesel.

Study of removal of ammonia from urine vapor by dual catalyst

NASA Technical Reports Server (NTRS)

Budininkas, P.

1976-01-01

The feasibility of ammonia removal from urine vapor by a low temperature dual-catalyst system was investigated. The process is based on the initial catalytic oxidation of ammonia present in urine vapor to nitrogen and nitrous oxide, followed by a catalytic decomposition of the nitrous oxide formed into its elements. The most active catalysts for the oxidation of ammonia and for the decomposition of N2O, identified in screening tests, were then combined into dual catalyst systems and tested to establish their overall efficiencies for the removal of ammonia from artificial gas mixtures. Dual catalyst systems capable of ammonia removal from the artificial gas mixtures were then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual catalyst bed arrangement was found that achieved the removal of ammonia and organic carbon, and recovered water of good quality from urine vapor.

Indirect Liquefaction of Coal-Biomass Mixture for Production of Jet Fuel with High Productivity and Selectivity

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

Gangwal, Santosh K; McCabe, Kevin

Coal to liquids (CTL) and coal-biomass to liquids (CBTL) processes were advanced by testing and demonstrating Southern Research’s sulfur tolerant nickel-based reforming catalyst and Chevron’s highly selective and active cobalt-zeolite hybrid Fischer-Tropsch (FT) catalyst to clean, upgrade and convert syngas predominantly to jet fuel range hydrocarbon liquids, thereby minimizing expensive cleanup and wax upgrading operations. The National Carbon Capture Center (NCCC) operated by Southern Company (SC) at Wilsonville, Alabama served as the host site for the gasifier slip-stream and simulated syngas testing/demonstration. Reformer testing was performed to (1) reform tar and light hydrocarbons, (2) decompose ammonia in the presence H2S,more » and (3) deliver the required H2 to CO ratio for FT synthesis. FT Testing was performed to produce a product primarily containing C5-C20 liquid hydrocarbons and no C21+ waxy hydrocarbons with productivity greater than 0.7 gC5+/g catalyst/h, and at least 70% diesel and jet fuel range (C8-C20) hydrocarbon selectivity in the liquid product. A novel heat-exchange reactor system was employed to enable the use of the highly active FT catalyst and larger diameter reactors that results in cost reduction for commercial systems. Following laboratory development and testing, SR’s laboratory reformer was modified to operate in a Class 1 Div. 2 environment, installed at NCCC, and successfully tested for 125 hours using raw syngas. The catalyst demonstrated near equilibrium reforming (~90%) of methane and complete reforming/decomposition of tar and ammonia in the presence of up to 380 ppm H2S. For FT synthesis, SR modified and utilized a bench scale skid mounted FT reactor system (SR-CBTL test rig) that was fully integrated with a slip stream from SC/NCCC’s transport gasifier (TRIG). The test-rig developed in a previous project (DE-FE0010231) was modified to receive up to 7.5 lb/h raw syngas augmented with bottled syngas to adjust the H2/CO molar ratio to 2, clean it to cobalt FT catalyst specifications, and produce liquid FT products at the design capacity of up to 6 L/day. Promising Chevron catalyst candidates in the size range from 70-200 μm were loaded onto SR’s 2-inch ID and 4-inch ID bench-scale reactors utilizing IntraMicron’s micro-fiber entrapped catalyst (MFEC) heat exchange reactor technology. During 2 test campaigns, the FT reactors were successfully demonstrated at NCCC using syngas for ~420 hours. The catalyst did not experience deactivation during the tests. SR’s thermo-syphon heat removal system maintained reactor operating temperature along the axis to within ±4 °C. The experiments gave a steady catalyst productivity of 0.7-0.8 g/g catalyst/h, liquid hydrocarbon selectivity of ~75%, and diesel and jet fuel range hydrocarbon selectivity in the liquid product as high as 85% depending on process conditions. A preliminary techno-economic evaluation showed that the SR technology-based 50,000 bpd plant had a 10 % lower total plant cost compared to a conventional slurry reactor based plant. Furthermore, because of the modular nature of the SR technology, it was shown that the total plant cost advantage increases to >35 % as the plant is scaled down to 1000 bpd.« less

Catalytic asymmetric dihydroxylation of olefins with reusable OsO(4)(2-) on ion-exchangers: the scope and reactivity using various cooxidants.

PubMed

Choudary, Boyapati M; Chowdari, Naidu S; Jyothi, Karangula; Kantam, Mannepalli L

2002-05-15

Exchanger-OsO(4) catalysts are prepared by an ion-exchange technique using layered double hydroxides and quaternary ammonium salts covalently bound to resin and silica as ion-exchangers. The ion-exchangers with different characteristics and opposite ion selectivities are specially chosen to produce the best heterogeneous catalyst that can operate using the various cooxidants in the asymmetric dihydroxylation reaction. LDH-OsO(4) catalysts composed of different compositions are evaluated for the asymmetric dihydroxylation of trans-stilbene. Resin-OsO(4) and SiO(2)-OsO(4) designed to overcome the problems associated with LDH-OsO(4) indeed show consistent activity and enantioselectivity in asymmetric dihydroxylation of olefins using K(3)Fe(CN)(6) and molecular oxygen as cooxidants. Compared to the Kobayashi heterogeneous systems, resin-OsO(4) is a very efficient catalyst for the dihydroxylation of a wide variety of aromatic, aliphatic, acyclic, cyclic, mono-, di-, and trisubstituted olefins to afford chiral vicinal diols with high yields and enantioselectivities irrespective of the cooxidant used. Resin-OsO(4) is recovered quantitatively by a simple filtration and reused for a number of cycles with consistent activity. The high binding ability of the heterogeneous osmium catalyst enables the use of an equimolar ratio of ligand to osmium to give excellent enantioselectives in asymmetric dihydroxylation in contrast to the homogeneous osmium system in which excess molar quantities of the expensive chiral ligand to osmium are invariably used. The complexation of the chiral ligand (DHQD)(2)PHAL, having very large dimension, a prerequisite to obtain higher ee, is possible only with the OsO(4)(2-) located on the surface of the supports.

Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al2O 3 catalyst.

PubMed

Chen, Chunmao; Yoza, Brandon A; Wang, Yandan; Wang, Ping; Li, Qing X; Guo, Shaohui; Yan, Guangxu

2015-04-01

There is of great interest to develop an economic and high-efficient catalytic ozonation system (COS) for the treatment of biologically refractory wastewaters. Applications of COS require options of commercially feasible catalysts. Experiments in the present study were designed to prepare and investigate a novel manganese-iron-copper oxide-supported alumina-assisted COS (Mn-Fe-Cu/Al2O3-COS) for the pretreatment of petroleum refinery wastewater. The highly dispersed composite metal oxides on the catalyst surface greatly promoted the performance of catalytic ozonation. Hydroxyl radical mediated oxidation is a dominant reaction in Mn-Fe-Cu/Al2O3-COS. Mn-Fe-Cu/Al2O3-COS enhanced COD removal by 32.7% compared with a single ozonation system and by 8-16% compared with Mn-Fe/Al2O3-COS, Mn-Cu/Al2O3-COS, and Fe-Cu/Al2O3-COS. The O/C and H/C ratios of oxygen-containing polar compounds significantly increased after catalytic ozonation, and the biodegradability of petroleum refinery wastewater was significantly improved. This study illustrates potential applications of Mn-Fe-Cu/Al2O3-COS for pretreatment of biologically refractory wastewaters.

Defining a Materials Database for the Design of Copper Binary Alloy Catalysts for Electrochemical CO2 Conversion.

PubMed

Lee, Chan Woo; Yang, Ki Dong; Nam, Dae-Hyun; Jang, Jun Ho; Cho, Nam Heon; Im, Sang Won; Nam, Ki Tae

2018-01-24

While Cu electrodes are a versatile material in the electrochemical production of desired hydrocarbon fuels, Cu binary alloy electrodes are recently proposed to further tune reaction directionality and, more importantly, overcome the intrinsic limitation of scaling relations. Despite encouraging empirical demonstrations of various Cu-based metal alloy systems, the underlying principles of their outstanding performance are not fully addressed. In particular, possible phase segregation with concurrent composition changes, which is widely observed in the field of metallurgy, is not at all considered. Moreover, surface-exposed metals can easily form oxide species, which is another pivotal factor that determines overall catalytic properties. Here, the understanding of Cu binary alloy catalysts for CO 2 reduction and recent progress in this field are discussed. From the viewpoint of the thermodynamic stability of the alloy system and elemental mixing, possible microstructures and naturally generated surface oxide species are proposed. These basic principles of material science can help to predict and understand metal alloy structure and, moreover, act as an inspiration for the development of new binary alloy catalysts to further improve CO 2 conversion and, ultimately, achieve a carbon-neutral cycle. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

PubMed

Duan, Lele; Wang, Lei; Li, Fusheng; Li, Fei; Sun, Licheng

2015-07-21

The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven-coordinate Ru(IV) species was isolated as a reaction intermediate, shedding light on the reaction mechanisms of Ru-catalyzed water oxidation chemistry. Auxiliary ligands have dramatic effects on the water oxidation catalysis in terms of the reactivity and the reaction mechanism. For instance, Ru-bda (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts catalyze Ce(IV)-driven water oxidation extremely fast via the radical coupling of two Ru(V)═O species, while Ru-pda (H2pda = 1,10-phenanthroline-2,9-dicarboxylic acid) water oxidation catalysts catalyze the same reaction slowly via water nucleophilic attack on a Ru(V)═O species. With a number of active Ru catalysts in hands, light driven water oxidation was accomplished using catalysts with low catalytic onset potentials. The structures of molecular catalysts could be readily tailored to introduce additional functional groups, which favors the fabrication of state-of-the-art Ru-based water oxidation devices, such as electrochemical water oxidation anodes and photo-electrochemical anodes. The development of efficient water oxidation catalysts has led to a step forward in the sustainable energy system.

Heterogeneous Catalysis: Understanding for Designing, and Designing for Applications.

PubMed

Corma, Avelino

2016-05-17

"… Despite the introduction of high-throughput and combinatorial methods that certainly can be useful in the process of catalysts optimization, it is recognized that the generation of fundamental knowledge at the molecular level is key for the development of new concepts and for reaching the final objective of solid catalysts by design …" Read more in the Editorial by Avelino Corma. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on Endurance and Performance of Impregnated Ruthenium Catalyst for Thruster System.

PubMed

Kim, Jincheol; Kim, Taegyu

2018-02-01

Performance and endurance of the Ru catalyst were studied for nitrous oxide monopropellant thruster system. The thermal decomposition of N2O requires a considerably high temperature, which make it difficult to be utilized as a thruster propellant, while the propellant decomposition temperature can be reduced by using the catalyst through the decomposition reaction with the propellant. However, the catalyst used for the thruster was frequently exposed to high temperature and high-pressure environment. Therefore, the state change of the catalyst according to the thruster operation was analyzed. Characterization of catalyst used in the operation condition of the thruster was performed using FE-SEM and EDS. As a result, performance degradation was occurred due to the volatilization of Ru catalyst and reduction of the specific surface area according to the phase change of Al2O3.

Rapid total volatile organic carbon quantification from microbial fermentation using a platinum catalyst and proton transfer reaction-mass spectrometry.

PubMed

Schoen, Heidi R; Peyton, Brent M; Knighton, W Berk

2016-12-01

A novel analytical system was developed to rapidly and accurately quantify total volatile organic compound (VOC) production from microbial reactor systems using a platinum catalyst and a sensitive CO 2 detector. This system allows nearly instantaneous determination of total VOC production by utilizing a platinum catalyst to completely and quantitatively oxidize headspace VOCs to CO 2 in coordination with a CO 2 detector. Measurement of respiratory CO 2 by bypassing the catalyst allowed the total VOC content to be determined from the difference in the two signals. To the best of our knowledge, this is the first instance of a platinum catalyst and CO 2 detector being used to quantify the total VOCs produced by a complex bioreactor system. Continuous recording of these CO 2 data provided a record of respiration and total VOC production throughout the experiments. Proton transfer reaction-mass spectrometry (PTR-MS) was used to identify and quantify major VOCs. The sum of the individual compounds measured by PTR-MS can be compared to the total VOCs quantified by the platinum catalyst to identify potential differences in detection, identification and calibration. PTR-MS measurements accounted on average for 94 % of the total VOC carbon detected by the platinum catalyst and CO 2 detector. In a model system, a VOC producing endophytic fungus Nodulisporium isolate TI-13 was grown in a solid state reactor utilizing the agricultural byproduct beet pulp as a substrate. Temporal changes in production of major volatile compounds (ethanol, methanol, acetaldehyde, terpenes, and terpenoids) were quantified by PTR-MS and compared to the total VOC measurements taken with the platinum catalyst and CO 2 detector. This analytical system provided fast, consistent data for evaluating VOC production in the nonhomogeneous solid state reactor system.

Biphasic catalysis in water/carbon dioxide micellar systems

DOEpatents

Jacobson, Gunilla B.; Tumas, William; Johnston, Keith P.

2002-01-01

A process is provided for catalyzing an organic reaction to form a reaction product by placing reactants and a catalyst for the organic reaction, the catalyst of a metal complex and at least one ligand soluble within one of the phases of said aqueous biphasic system, within an aqueous biphasic system including a water phase, a dense phase fluid, and a surfactant adapted for forming an emulsion or microemulsion within the aqueous biphasic system, the reactants soluble within one of the phases of the aqueous biphasic system and convertible in the presence of the catalyst to a product having low solubility in the phase in which the catalyst is soluble; and, maintaining the aqueous biphasic system under pressures, at temperatures, and for a period of time sufficient for the organic reaction to occur and form the reaction product and to maintain sufficient density on the dense phase fluid, the reaction product characterized as having low solubility in the phase in which the catalyst is soluble.

Cooling by Para-to-Ortho-Hydrogen Conversion

NASA Technical Reports Server (NTRS)

Sherman, A.; Nast, T.

1983-01-01

Catalyst speeds conversion, increasing capacity of solid hydrogen cooling system. In radial-flow catalytic converter, para-hydrogen is converted to equilibrium mixture of para-hydrogen and ortho-hydrogen as it passes through porous cylinder of catalyst. Addition of catalyst increases capacity of hydrogen sublimation cooling systems for radiation detectors.

Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

PubMed

Hu, Pingping; Huang, Zhiwei; Gu, Xiao; Xu, Fei; Gao, Jiayi; Wang, Yue; Chen, Yaxin; Tang, Xingfu

2015-06-02

A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.

Design of a genetic algorithm for the simulated evolution of a library of asymmetric transfer hydrogenation catalysts.

PubMed

Vriamont, Nicolas; Govaerts, Bernadette; Grenouillet, Pierre; de Bellefon, Claude; Riant, Olivier

2009-06-15

A library of catalysts was designed for asymmetric-hydrogen transfer to acetophenone. At first, the whole library was submitted to evaluation using high-throughput experiments (HTE). The catalysts were listed in ascending order, with respect to their performance, and best catalysts were identified. In the second step, various simulated evolution experiments, based on a genetic algorithm, were applied to this library. A small part of the library, called the mother generation (G0), thus evolved from generation to generation. The goal was to use our collection of HTE data to adjust the parameters of the genetic algorithm, in order to obtain a maximum of the best catalysts within a minimal number of generations. It was namely found that simulated evolution's results depended on the selection of G0 and that a random G0 should be preferred. We also demonstrated that it was possible to get 5 to 6 of the ten best catalysts while investigating only 10 % of the library. Moreover, we developed a double algorithm making this result still achievable if the evolution started with one of the worst G0.

Rational Catalyst Design of Titanium-Silica Materials Aided by Site-Specific Titration Tools

NASA Astrophysics Data System (ADS)

Eaton, Todd Robert

Silica-supported titanium materials are widely used for thermocatalytic applications such as hydroxylation of alkanes and aromatics, oxidation of alcohols and ethers, ammoximation of carbonyls, and sulfoxidations, while Ti-based materials are widely studied for photocatalytic applications such as photo-oxidation of organic substrates and photo-reduction of CO 2. However, the underlying phenomena of how to synthesize, identify, and control the active structures in these materials is not well understood because of the narrow scope of previous work. Studies of titanium-based catalysts typically focus on materials where the metal is present as either highly-dispersed Ti cations or in bulk crystalline TiO2 form, neglecting the numerous and potentially useful intermediate structures. Furthermore, these works typically focus on a single synthesis technique and rely upon bulk characterization techniques to understand the materials. Here rigorous titanium-silica synthesis-structure-function relationships are established by examining several different synthetic method and utilizing characterization techniques that enable an atomic-level understanding of the materials. The materials studied span the range from isolated Ti cations to clustered TiOx domains, polymeric TiO x domains, anatase-like 2D TiO2 domains, and 3D crystalline TiO2. Tools to quantify accessible TiO x and tetrahedral Ti sites are developed, utilizing the selective titration of titanium with phenylphosphonic acid (PPA). Catalytic properties are probed with the photocatalytic oxidation of benzyl alcohol and the thermocatalytic epoxidation of cis-cyclooctene with H2O2 . PPA titration data indicate that the rate of benzyl alcohol photo-oxidation is independent of titanium coordination, while the rate of alkene epoxidation with H2O2 is proportional to the number of tetrahedral titanium sites on the catalyst. PPA titration data also enables the estimation of TiO2 particle size and reveals an important distinction between particle and crystal size, as obtained from XRD. In the course of establishing these relationships we've gained the knowledge of how to control TiO x structure, which enables the design of new and better catalysts. Understanding the synthesis-structure-function relationships allow for the design of a tandem photo/thermocatalytic reaction system for producing and consuming H2O2. By partially overcoating a TiO 2 photocatalyst with a ˜2 nm silica layer we observe a 56-fold rate improvement compared to bare-TiO2 for H2O2 synthesis from the proton-assisted reduction of O2. Addition of metal-SiO2 thermocatalysts (metal=Ti, Nb, or Ta) with sites needed for H2O2 activation creates a tandem system wherein the H2O2 produced in situ is utilized for alkene epoxidation. Compared to a thermocatalytic-only system, the tandem system accelerates epoxidation for cis-cyclooctene(11x faster), styrene(20x) and 1-octene(30x). This approach demonstrates a means for epoxidation with O2 that avoids H2O2 purification and transport, simplifies the total process, provides new opportunities for control by independent H2O2 production and consumption in the same reactor, and enhances rates relative to thermocatalytic-only epoxidation by intimately coupling H2O2 generation and consumption. Critically, establishment of titanium-silica synthesis-structure-function relationships enables the design of new catalysts and systems that are less energy- and material-intensive, leading towards more sustainable chemistry.

Multi-Phase Field Models and Microstructural Evolution with Applications in Fuel Cell Technology

NASA Astrophysics Data System (ADS)

Davis, Ryan Scott

The solid oxide fuel cell (SOFC) has shown tremendous potential as an efficient energy conversion device that may be instrumental in the transition to renewable resources. However, commercialization is hindered by many degradation mechanisms that plague long term stability. In this dissertation, computation methods are used to explore the relationship between the microstructure of the fuel cell anode and performance critical metrics. The phase field method and standard modeling procedures are introduced using a classic model of spinodal decomposition. This is further developed into a complete, multi-phase modeling framework designed for the complex microstructural evolution of SOFC anode systems. High-temperature coarsening of the metallic phase in the state-of-the-art SOFC cermet anode is investigated using our phase field model. A systematic study into the effects of interface properties on microstructural evolution is accomplished by altering the contact angle between constituent phases. It is found that metrics of catalytic activity and conductivity display undesirable minima near the contact angle of conventional SOFC materials. These results suggest that tailoring the interface properties of the constituent phases could lead to a significant increase in the performance and lifetime of SOFCs. Supported-metal catalyst systems are investigated in the first detailed study of their long-term stability and application to SOFC anode design. Porous support structures are numerically sintered to mimic specific fabrication techniques, and these structures are then infiltrated with a nanoscale catalyst phase ranging from 2% to 21% loading. Initially, these systems exhibit enhanced potential for catalytic activity relative to conventional cells. However, extended evolution results in severe degradation, and we show that Ostwald ripening and particle migration are key kinetic processes. Strong geometric heterogeneity in the support structure via a novel approach to nanopore formation is proposed as a potential solution for catalyst stabilization.

Mediator- and co-catalyst-free direct Z-scheme composites of Bi2WO6-Cu3P for solar-water splitting.

PubMed

Rauf, Ali; Ma, Ming; Kim, Sungsoon; Sher Shah, Md Selim Arif; Chung, Chan-Hwa; Park, Jong Hyeok; Yoo, Pil J

2018-02-08

Exploring new single, active photocatalysts for solar-water splitting is highly desirable to expedite current research on solar-chemical energy conversion. In particular, Z-scheme-based composites (ZBCs) have attracted extensive attention due to their unique charge transfer pathway, broader redox range, and stronger redox power compared to conventional heterostructures. In the present report, we have for the first time explored Cu 3 P, a new, single photocatalyst for solar-water splitting applications. Moreover, a novel ZBC system composed of Bi 2 WO 6 -Cu 3 P was designed employing a simple method of ball-milling complexation. The synthesized materials were examined and further investigated through various microscopic, spectroscopic, and surface area characterization methods, which have confirmed the successful hybridization between Bi 2 WO 6 and Cu 3 P and the formation of a ZBC system that shows the ideal position of energy levels for solar-water splitting. Notably, the ZBC composed of Bi 2 WO 6 -Cu 3 P is a mediator- and co-catalyst-free photocatalyst system. The improved photocatalytic efficiency obtained with this system compared to other ZBC systems assisted by mediators and co-catalysts establishes the critical importance of interfacial solid-solid contact and the well-balanced position of energy levels for solar-water splitting. The promising solar-water splitting under optimum composition conditions highlighted the relationship between effective charge separation and composition.

Catalysts and process for liquid hydrocarbon fuel production

DOEpatents

White, Mark G.; Ranaweera, Samantha A.; Henry, William P.

2016-08-02

The present invention provides a novel process and system in which a mixture of carbon monoxide and hydrogen synthesis gas, or syngas, is converted into hydrocarbon mixtures composed of high quality distillates, gasoline components, and lower molecular weight gaseous olefins in one reactor or step. The invention utilizes a novel supported bimetallic ion complex catalyst for conversion, and provides methods of preparing such novel catalysts and use of the novel catalysts in the process and system of the invention.

Hydrocarbon-Seeded Ignition System for Small Spacecraft Thrusters Using Ionic Liquid Propellants

NASA Technical Reports Server (NTRS)

Whitmore, Stephen A.; Merkley, Daniel P.; Eilers, Shannon D.; Taylor, Terry L.

2013-01-01

"Green" propellants based on Ionic-liquids (ILs) like Ammonium DiNitramide and Hydroxyl Ammonium Nitrate have recently been developed as reduced-hazard replacements for hydrazine. Compared to hydrazine, ILs offer up to a 50% improvement in available density-specific impulse. These materials present minimal vapor hazard at room temperature, and this property makes IL's potentially advantageous for "ride-share" launch opportunities where hazards introduced by hydrazine servicing are cost-prohibitive. Even though ILs present a reduced hazard compared to hydrazine, in crystalline form they are potentially explosive and are mixed in aqueous solutions to buffer against explosion. Unfortunately, the high water content makes IL-propellants difficult to ignite and currently a reliable "coldstart" capability does not exist. For reliable ignition, IL-propellants catalyst beds must be pre-heated to greater than 350 C before firing. The required preheat power source is substantial and presents a significant disadvantage for SmallSats where power budgets are extremely limited. Design and development of a "micro-hybrid" igniter designed to act as a "drop-in" replacement for existing IL catalyst beds is presented. The design requires significantly lower input energy and offers a smaller overall form factor. Unlike single-use "squib" pyrotechnic igniters, the system allows the gas generation cycle to be terminated and reinitiated on demand.

Hindered diffusion of coal liquids. Quarterly report No. 12, June 18, 1995--September 17, 1995

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

Tsotsis, T.T.; Sahimi, M.; Webster, I.A.

1995-12-31

The design of industrial catalysts requires that the diffusivity of the reacting species within the catalyst be accurately known. Nowhere is this more important than in the area of coal liquefaction and upgrading of coal liquids. In this area one is faced with the task of processing a number of heavy oils, containing metals and other contaminants, in a variety of process dependent solvents. It is important, therefore, on the basis of predicting catalyst activity, selectivity, and optimizing reactor performance, that the diffusivities of these oil species be accurately known. It is the purpose of the project described here tomore » provide such a correct concept of coal asphaltenes by careful and detailed investigations of asphaltene transport through porous systems under realistic process temperature and pressure conditions. The experimental studies will be coupled with detailed, in-depth statistical and molecular dynamics models intended to provide a fundamental understanding of the overall transport mechanisms.« less

Artificial photosynthesis: understanding water splitting in nature

PubMed Central

Cox, Nicholas; Pantazis, Dimitrios A.; Neese, Frank; Lubitz, Wolfgang

2015-01-01

In the context of a global artificial photosynthesis (GAP) project, we review our current work on nature's water splitting catalyst. In a recent report (Cox et al. 2014 Science 345, 804–808 (doi:10.1126/science.1254910)), we showed that the catalyst—a Mn4O5Ca cofactor—converts into an ‘activated’ form immediately prior to the O–O bond formation step. This activated state, which represents an all MnIV complex, is similar to the structure observed by X-ray crystallography but requires the coordination of an additional water molecule. Such a structure locates two oxygens, both derived from water, in close proximity, which probably come together to form the product O2 molecule. We speculate that formation of the activated catalyst state requires inherent structural flexibility. These features represent new design criteria for the development of biomimetic and bioinspired model systems for water splitting catalysts using first-row transition metals with the aim of delivering globally deployable artificial photosynthesis technologies. PMID:26052426

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

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. Here in this perspective article, we describe the current status of AEMFCs as having reached beginningmore » of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. Finally, these perspectives may provide useful insights for the development of next-generation of AEMFCs.« less

Biodiesel synthesis by direct transesterification of microalga Botryococcus braunii with continuous methanol reflux.

PubMed

Hidalgo, Pamela; Ciudad, Gustavo; Schober, Sigurd; Mittelbach, Martin; Navia, Rodrigo

2015-04-01

Direct transesterification of Botryococcus braunii with continuous acyl acceptor reflux was evaluated. This method combines in one step lipid extraction and esterification/transesterification. Fatty acid methyl esters (FAME) synthesis by direct conversion of microalgal biomass was carried out using sulfuric acid as catalyst and methanol as acyl acceptor. In this system, once lipids are extracted, they are contacted with the catalyst and methanol reaching 82%wt of FAME yield. To optimize the reaction conditions, a factorial design using surface response methodology was applied. The effects of catalyst concentration and co-solvent concentration were studied. Hexane was used as co-solvent for increasing lipid extraction performance. The incorporation of hexane in the reaction provoked an increase in FAME yield from 82% (pure methanol) to 95% when a 47%v/v of hexane was incorporated in the reaction. However, the selectivity towards non-saponifiable lipids such as sterols was increased, negatively affecting biodiesel quality. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts.

PubMed

Taylor, Martin J; Jiang, Li; Reichert, Joachim; Papageorgiou, Anthoula C; Beaumont, Simon K; Wilson, Karen; Lee, Adam F; Barth, Johannes V; Kyriakou, Georgios

2017-04-20

Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation.

Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts

PubMed Central

2017-01-01

Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction conditions, in particular, surface crowding and associated changes in the adsorption geometry: furfural adopts a planar geometry on clean Pt(111) at low coverage, tilting at higher coverage to form a densely packed furfural adlayer. This switch in adsorption geometry strongly influences product selectivity. STM reveals the formation of hydrogen-bonded networks for planar furfural, which favor decarbonylation on clean Pt(111) and hydrogenolysis in the presence of coadsorbed hydrogen. Preadsorbed hydrogen promotes furfural hydrogenation to furfuryl alcohol and its subsequent hydrogenolysis to methyl furan, while suppressing residual surface carbon. Furfural chemistry over Pt is markedly different from that over Pd, with weaker adsorption over the former affording a simpler product distribution than the latter; Pd catalyzes a wider range of chemistry, including ring-opening to form propene. Insight into the role of molecular orientation in controlling product selectivity will guide the design and operation of more selective and stable Pt catalysts for furfural hydrogenation. PMID:29225721

Enhancing H2 evolution performance of an immobilised cobalt catalyst by rational ligand design† †Electronic supplementary information (ESI) available: Additional figures and tables, synthetic procedures, experimental details for NMR and UV-vis spectroscopy, electrochemistry and photocatalytic experiments. See DOI: 10.1039/c4sc03946g

PubMed Central

Willkomm, Janina; Muresan, Nicoleta M.

2015-01-01

The catalyst [CoIIIBr((DO)(DOH)(4-BnPO3H2)(2-CH2py)pn)]Br, CoP3, has been synthesised to improve the stability and activity of cobalt catalysts immobilised on metal oxide surfaces. The CoP3 catalyst contains an equatorial diimine–dioxime ligand, (DOH)2pn = N2,N2′-propanediyl-bis(2,3-butanedione-2-imine-3-oxime), with a benzylphosphonic acid (4-BnPO3H2) group and a methylpyridine (2-CH2py) ligand covalently linked to the bridgehead of the pseudo-macrocyclic diimine–dioxime ligand. The phosphonic acid functionality provides a robust anchoring group for immobilisation on metal oxides, whereas the pyridine is coordinated to the Co ion to enhance the catalytic activity of the catalyst. Electrochemical investigations in solution confirm that CoP3 shows electrocatalytic activity for the reduction of aqueous protons between pH 3 and 7. The metal oxide anchor provides the catalyst with a high affinity for mesostructured Sn-doped In2O3 electrodes (mesoITO; loading of approximately 22 nmol cm–2) and the electrostability of the attached CoP3 was confirmed by cyclic voltammetry. Finally, immobilisation of the catalyst on ruthenium-dye sensitised TiO2 nanoparticles in aqueous solutions in the presence of a hole scavenger establishes the activity of the catalyst in this photocatalytic scheme. The advantages of the elaborate catalyst design in CoP3 in terms of stability and catalytic activity are shown by direct comparison with previously reported phosphonated Co catalysts. We therefore demonstrate that rational ligand design is a viable route for improving the performance of immobilised molecular catalysts. PMID:29142677

Exquisite Enzyme-Fenton Biomimetic Catalysts for Hydroxyl Radical Production by Mimicking an Enzyme Cascade.

PubMed

Zhang, Qi; Chen, Shuo; Wang, Hua; Yu, Hongtao

2018-03-14

Hydrogen peroxide (H 2 O 2 ) is a key reactant in the Fenton process. As a byproduct of enzymatic reaction, H 2 O 2 can be obtained via catalytical oxidation of glucose using glucose oxidase in the presence of O 2 . Another oxidation product (gluconic acid) can suitably adjust the microenvironmental pH contributing to the Fe 3+ /Fe 2+ cycle in the Fenton reaction. Enzymes are extremely efficient at catalyzing a variety of reactions with high catalytic activity, substrate specificity, and yields in living organisms. Inspired by the multiple functions of natural multienzyme systems, an exquisite nanozyme-modified α-FeOOH/porous carbon (PC) biomimetic catalyst constructed by in situ growth of glucose oxidase-mimicking Au nanoparticles and crystallization of adsorbed ferric ions within carboxyl into hierarchically PC is developed as an efficient enzyme-Fenton catalyst. The products (H 2 O 2 , ∼4.07 mmol·L -1 ) of the first enzymatic reaction are immediately used as substrates for the second Fenton-like reaction to generate the valuable • OH (∼96.84 μmol·L -1 ), thus mimicking an enzyme cascade pathway. α-FeOOH nanocrystals, attached by C-O-Fe bondings, are encapsulated into the mesoporous PC frameworks, facilitating the electron transfer between α-FeOOH and the PC support and greatly suppressing iron leaching. This study paves a new avenue for designing biomimetic enzyme-based Fenton catalysts mimicking a natural system for • OH production.

Linking Past to Present to Create an Image of the Child

ERIC Educational Resources Information Center

Hughes, Eileen

2007-01-01

Principles of the Reggio Emilia approach are a catalyst for thinking about practices in early childhood education. Teachers in the child care system of Reggio Emilia encourage us to think about our image of childhood and the ways we interact with children, plan curriculum, and design environments. This article examines experiences in a rural…

New insights into non-precious metal catalyst layer designs for proton exchange membrane fuel cells: Improving performance and stability

NASA Astrophysics Data System (ADS)

Banham, Dustin; Kishimoto, Takeaki; Sato, Tetsutaro; Kobayashi, Yoshikazu; Narizuka, Kumi; Ozaki, Jun-ichi; Zhou, Yingjie; Marquez, Emil; Bai, Kyoung; Ye, Siyu

2017-03-01

The activity of non-precious metal catalysts (NPMCs) has now reached a stage at which they can be considered as possible alternatives to Pt for some proton exchange membrane fuel cell (PEMFC) applications. However, despite significant efforts over the past 50 years on catalyst development, only limited studies have been performed on NPMC-based cathode catalyst layer (CCL) designs. In this work, an extensive ionomer study is performed to investigate the impact of ionomer equivalent weight on performance, which has uncovered two crucial findings. Firstly, it is demonstrated that beyond a critical CCL conductance, no further improvement in performance is observed. The procedure used to determine this critical conductance can be used by other researchers in this field to aid in their design of high performing NPMC-based CCLs. Secondly, it is shown that the stability of NPMC-based CCLs can be improved through the use of low equivalent weight ionomers. This represents a completely unexplored pathway for further stability improvements, and also provides new insights into the possible degradation mechanisms occurring in NPMC-based CCLs. These findings have broad implications on all future NPMC-based CCL designs.

Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

DOEpatents

Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

2013-07-16

The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

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.

Performance enhancement of iron-chromium redox flow batteries by employing interdigitated flow fields

NASA Astrophysics Data System (ADS)

Zeng, Y. K.; Zhou, X. L.; Zeng, L.; Yan, X. H.; Zhao, T. S.

2016-09-01

The catalyst for the negative electrode of iron-chromium redox flow batteries (ICRFBs) is commonly prepared by adding a small amount of Bi3+ ions in the electrolyte and synchronously electrodepositing metallic particles onto the electrode surface at the beginning of charge process. Achieving a uniform catalyst distribution in the porous electrode, which is closely related to the flow field design, is critically important to improve the ICRFB performance. In this work, the effects of flow field designs on catalyst electrodeposition and battery performance are investigated. It is found that compared to the serpentine flow field (SFF) design, the interdigitated flow field (IFF) forces the electrolyte through the porous electrode between the neighboring channels and enhances species transport during the processes of both the catalyst electrodeposition and iron/chromium redox reactions, thus enabling a more uniform catalyst distribution and higher mass transport limitation. It is further demonstrated that the energy efficiency of the ICRFB with the IFF reaches 80.7% at a high current density (320 mA cm-2), which is 8.2% higher than that of the ICRFB with the SFF. With such a high performance and intrinsically low-cost active materials, the ICRFB with the IFF offers a great promise for large-scale energy storage.

The potential for increasing the use of catalytic carbons in commercial applications

USGS Publications Warehouse

Kruse, C.W.

1996-01-01

A carbon catalyst, prepared either by oxidizing activated carbon with air at 500-700??C or by oxidizing activated carbon with boiling nitric acid followed by heating it to 500-700??C, is the subject of this paper. This catalyst, designated OAC500-700, catalyzes the removal of hydrogen chloride from alkyl halides. Because OAC500-700 retains adsorptive properties of an activated carbon it can be used both to adsorb pollutants from liquid or gaseous streams and to convert them to recyclable products. A highly-developed micropore structure is not required for all uses of activated carbon or a catalyst produced from it. A comparatively inexpensive ($325/ton projected) low surface area (<300 m2/g) carbon has been developed at the Illinois State Geological Survey (ISGS) for cleaning incinerator flue gas. This grade of activated carbon is widely used in Europe for flue gas cleaning and for other applications. Activated carbon adsorbers of some type are required by recently passed U.S. Environmental Protection Agency (EPA) regulations for municipal waste combustors to control emission of cadmium, mercury, lead, dioxins, furans and acid gases (U.S. EPA, 1995). Similar regulations are expected for hospital and hazardous waste incinerators. The marketing of less costly activated carbons of the type used widely in Europe is expected in the United States. Low cost OAC500-700 made from less expensive grades of activated carbon may become available for large scale adsorbent/catalyst systems designed to both remove and decompose toxic pollutants found in liquid and gaseous streams, chlorinated organic compounds in particular.

A review of engineering development of aqueous phase solar photocatalytic detoxification and disinfection processes

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

Goswami, D.Y.

1997-05-01

Scientific research on photocatalytic oxidation of hazardous chemicals has been conducted extensively over the last three decades. Use of solar radiation in photocatalytic detoxification and disinfection has only been explored in the last decade. Developments of engineering scale systems, design methodologies, and commercial and industrial applications have occurred even more recently. A number of reactor concepts and designs including concentrating and nonconcentrating types and methods of catalyst deployment have been developed. Some commercial and industrial field tests of solar detoxification systems have been conducted. This paper reviews the engineering developments of the solar photocatalytic detoxification and disinfection processes, including systemmore » design methodologies.« less

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1985-01-01

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

Enhanced catalyst for conversion of syngas to liquid motor fuels

DOEpatents

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

1985-12-03

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

Iron catalyzed coal liquefaction process

DOEpatents

Garg, Diwakar; Givens, Edwin N.

1983-01-01

A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

Process and catalyst for carbonylating olefins

DOEpatents

Zoeller, Joseph Robert

1998-06-02

Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

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

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

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

Singleton, A.H.

1995-06-28

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

Lagrangian Approach to Study Catalytic Fluidized Bed Reactors

NASA Astrophysics Data System (ADS)

Madi, Hossein; Hossein Madi Team; Marcelo Kaufman Rechulski Collaboration; Christian Ludwig Collaboration; Tilman Schildhauer Collaboration

2013-03-01

Lagrangian approach of fluidized bed reactors is a method, which simulates the movement of catalyst particles (caused by the fluidization) by changing the gas composition around them. Application of such an investigation is in the analysis of the state of catalysts and surface reactions under quasi-operando conditions. The hydrodynamics of catalyst particles within a fluidized bed reactor was studied to improve a Lagrangian approach. A fluidized bed methanation employed in the production of Synthetic Natural Gas from wood was chosen as the case study. The Lagrangian perspective was modified and improved to include different particle circulation patterns, which were investigated through this study. Experiments were designed to evaluate the concepts of the model. The results indicate that the setup is able to perform the designed experiments and a good agreement between the simulation and the experimental results were observed. It has been shown that fluidized bed reactors, as opposed to fixed beds, can be used to avoid the deactivation of the methanation catalyst due to carbon deposits. Carbon deposition on the catalysts tested with the Lagrangian approach was investigated by temperature programmed oxidation (TPO) analysis of ex-situ catalyst samples. This investigation was done to identify the effects of particles velocity and their circulation patterns on the amount and type of deposited carbon on the catalyst surface. Ecole Polytechnique Federale de Lausanne(EPFL), Paul Scherrer Institute (PSI)

Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

PubMed

Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

2016-08-24

A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

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

PubMed Central

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

2010-01-01

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

Experimental research of technology activating catalysts for SCR DeNOx in boiler

NASA Astrophysics Data System (ADS)

Zeng, Xi; Yang, Zhengde; Li, Yan; Chen, Donglin

2018-01-01

In order to improve activity of the catalysts used in SCR DeNOx system of flue gas, a series of catalysts activated by different activating liquids under varied conditions in boiler directly were conducted. Then these catalysts were characterized by SEM, FT-IR and BET technology. And NO conversions of the activated catalysts were studied and compared with that of inactivated catalyst. The above experiment shows that NO conversion of the activated catalyst can be up to 99%, which 30% higher than that of inactivated catalyst, so activity of catalysts were improved greatly. Furthermore, optimal activating liquid labeled L2 and effective technology parameters were gained in the experiment.

The synergistic effect in the Fe-Co bimetallic catalyst system for the growth of carbon nanotube forests

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

Hardeman, D.; Esconjauregui, S., E-mail: cse28@cam.ac.uk; Cartwright, R.

2015-01-28

We report the growth of multi-walled carbon nanotube forests employing an active-active bimetallic Fe-Co catalyst. Using this catalyst system, we observe a synergistic effect by which—in comparison to pure Fe or Co—the height of the forests increases significantly. The homogeneity in the as-grown nanotubes is also improved. By both energy dispersive spectroscopy and in-situ x-ray photoelectron spectroscopy, we show that the catalyst particles consist of Fe and Co, and this dramatically increases the growth rate of the tubes. Bimetallic catalysts are thus potentially useful for synthesising nanotube forests more efficiently.

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.

Catalysts to reduce NO.sub.x in an exhaust gas stream and methods of preparation

DOEpatents

Castellano, Christopher R [Ringoes, NJ; Moini, Ahmad [Princeton, NJ; Koermer, Gerald S [Basking Ridge, NJ; Furbeck, Howard [Hamilton, NJ; Schmieg, Steven J [Troy, MI; Blint, Richard J [Shelby Township, MI

2011-05-17

Catalysts, systems and methods are described to reduce NO.sub.x emissions of an internal combustion engine. In one embodiment, an emissions treatment system for an exhaust stream is provided having a catalyst comprising silver and a platinum group metal on a particulate alumina support, the atomic fraction of the platinum group metal being less than or equal to about 0.25. Methods of manufacturing catalysts are described in which silver is impregnated on alumina particles.

Investigation of internal elements impaction on particles circulation in a fluidized bed reactor

NASA Astrophysics Data System (ADS)

Solovev, S. A.; Soloveva, O. V.; Antipin, A. V.; Shamsutdinov, E. V.

2018-01-01

A numerical study of the fluidized bed apparatus in the presence of various internal elements is carried out. A chemical reaction for temperature-dependent processes with heat absorption is considered. The task of incoming heated catalyst granules to the reactor is investigated. The main emphasis is focused on the circulation flows of the catalyst particles, heating of the reactor, and the efficiency of the chemical reaction. The analysis of the impact of various design elements on the efficiency of the reactor is carried out. The influence of feeding heated catalyst device design on the effectiveness of whole reactor heating is educed. The influence of the presence of fine particles on the efficiency of the reaction for different reactor design features is also educed.

Ultraefficient homogeneous catalyst for the CO2-to-CO electrochemical conversion.

PubMed

Costentin, Cyrille; Passard, Guillaume; Robert, Marc; Savéant, Jean-Michel

2014-10-21

A very efficient electrogenerated Fe(0) porphyrin catalyst was obtained by substituting in tetraphenylporphyrin two of the opposite phenyl rings by ortho-, ortho'-phenol groups while the other two are perfluorinated. It proves to be an excellent catalyst of the CO2-to-CO conversion as to selectivity (the CO faradaic yield is nearly quantitative), overpotential, and turnover frequency. Benchmarking with other catalysts, through catalytic Tafel plots, shows that it is the most efficient, to the best of our knowledge, homogeneous molecular catalyst of the CO2-to-CO conversion at present. Comparison with another Fe(0) tetraphenylporphyrin bearing eight ortho-, ortho'-phenol functionalities launches a general strategy where changes in substituents will be designed so as to optimize the operational combination of all catalyst elements of merit.

Evaluation of Bosch-Based Systems Using Non-Traditional Catalysts at Reduced Temperatures

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Mansell, J. Matthew

2011-01-01

Oxygen and water resupply make open loop atmosphere revitalization (AR) systems unfavorable for long-term missions beyond low Earth orbit. Crucial to closing the AR loop are carbon dioxide reduction systems with low mass and volume, minimal power requirements, and minimal consumables. For this purpose, NASA is exploring using Bosch-based systems. The Bosch process is favorable over state-of-the-art Sabatier-based processes due to complete loop closure. However, traditional operation of the Bosch required high reaction temperatures, high recycle rates, and significant consumables in the form of catalyst resupply due to carbon fouling. A number of configurations have been proposed for next-generation Bosch systems. First, alternative catalysts (catalysts other than steel wool) can be used in a traditional single-stage Bosch reactor to improve reaction kinetics and increase carbon packing density. Second, the Bosch reactor may be split into separate stages wherein the first reactor stage is dedicated to carbon monoxide and water formation via the reverse water-gas shift reaction and the second reactor stage is dedicated to carbon formation. A series system will enable maximum efficiency of both steps of the Bosch reaction, resulting in optimized operation and maximum carbon formation rate. This paper details the results of testing of both single-stage and two-stage Bosch systems with alternative catalysts at reduced temperatures. These results are compared to a traditional Bosch system operated with a steel wool catalyst.

The Experimental Measurement of Local and Bulk Oxygen Transport Resistances in the Catalyst Layer of Proton Exchange Membrane Fuel Cells.

PubMed

Wang, Chao; Cheng, Xiaojing; Lu, Jiabin; Shen, Shuiyun; Yan, Xiaohui; Yin, Jiewei; Wei, Guanghua; Zhang, Junliang

2017-12-07

Remarkable progress has been made in reducing the cathodic Pt loading of PEMFCs; however, a huge performance loss appears at high current densities, indicating the existence of a large oxygen transport resistance associated with the ultralow Pt loading catalyst layer. To reduce the Pt loading without sacrificing cell performance, it is essential to illuminate the oxygen transport mechanism in the catalyst layer. Toward this goal, an experimental approach to measure the oxygen transport resistance in catalyst layers is proposed and realized for the first time in this study. The measuring approach involves a dual-layer catalyst layer design, which consists of a dummy catalyst layer and a practical catalyst layer, followed by changing the thickness of dummy layer to respectively quantify the local and bulk resistances via limiting current measurements combined with linear extrapolation. The experimental results clearly reveal that the local resistance dominates the total resistance in the catalyst layer.

Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability

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

Davidson, Stephen D.; Spies, Kurt A.; Mei, Donghai

We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, andmore » activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from acetic acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.« less

Pt skin on AuCu intermetallic substrate: a strategy to maximize Pt utilization for fuel cells.

PubMed

Wang, Gongwei; Huang, Bing; Xiao, Li; Ren, Zhandong; Chen, Hao; Wang, Deli; Abruña, Héctor D; Lu, Juntao; Zhuang, Lin

2014-07-09

The dependence on Pt catalysts has been a major issue of proton-exchange membrane (PEM) fuel cells. Strategies to maximize the Pt utilization in catalysts include two main approaches: to put Pt atoms only at the catalyst surface and to further enhance the surface-specific catalytic activity (SA) of Pt. Thus far there has been no practical design that combines these two features into one single catalyst. Here we report a combined computational and experimental study on the design and implementation of Pt-skin catalysts with significantly improved SA toward the oxygen reduction reaction (ORR). Through screening, using density functional theory (DFT) calculations, a Pt-skin structure on AuCu(111) substrate, consisting of 1.5 monolayers of Pt, is found to have an appropriately weakened oxygen affinity, in comparison to that on Pt(111), which would be ideal for ORR catalysis. Such a structure is then realized by substituting the Cu atoms in three surface layers of AuCu intermetallic nanoparticles (AuCu iNPs) with Pt. The resulting Pt-skinned catalyst (denoted as Pt(S)AuCu iNPs) has been characterized in depth using synchrotron XRD, XPS, HRTEM, and HAADF-STEM/EDX, such that the Pt-skin structure is unambiguously identified. The thickness of the Pt skin was determined to be less than two atomic layers. Finally the catalytic activity of Pt(S)AuCu iNPs toward the ORR was measured via rotating disk electrode (RDE) voltammetry through which it was established that the SA was more than 2 times that of a commercial Pt/C catalyst. Taking into account the ultralow Pt loading in Pt(S)AuCu iNPs, the mass-specific catalytic activity (MA) was determined to be 0.56 A/mg(Pt)@0.9 V, a value that is well beyond the DOE 2017 target for ORR catalysts (0.44 A/mg(Pt)@0.9 V). These findings provide a strategic design and a realizable approach to high-performance and Pt-efficient catalysts for fuel cells.

Design and cost analysis for an ammonia-based solar thermochemical cavity absorber

NASA Astrophysics Data System (ADS)

Williams, O. M.

1980-01-01

A design and cost analysis is introduced for a solar thermochemical cavity absorber operated at the focus of a tracking paraboloidal concentrator and based on the ammonia dissociation reaction. The absorber design consists of a catalyst-filled nickel alloy tube wound into a spiral forming the inner cavity wall and shaped to match the incident power density profile to the reactor heat requirements. The reactor tube is welded to a coaxial counterflow heat exchanger. The relationships among the power density profile, the reaction thermodynamics and kinetics, and the heat transfer characteristics are examined in detail and it is shown that an installed cost goal of typically 10 U.S. dollars per square meter of solar collector area can be achieved through use of high activity ammonia dissociation catalyst. The optimum absorber size for a given paraboloidal dish area is calculated for a system pressure of 20 MPa and it is shown that a cost effective absorber suitable for 100,000-hr operation would operate at 90% efficiency at 750 C wall temperature.

Design Guidelines for High-Performance Particle-Based Photoanodes for Water Splitting: Lanthanum Titanium Oxynitride as a Model.

PubMed

Landsmann, Steve; Maegli, Alexandra E; Trottmann, Matthias; Battaglia, Corsin; Weidenkaff, Anke; Pokrant, Simone

2015-10-26

Semiconductor powders are perfectly suited for the scalable fabrication of particle-based photoelectrodes, which can be used to split water using the sun as a renewable energy source. This systematic study is focused on variation of the electrode design using LaTiO2 N as a model system. We present the influence of particle morphology on charge separation and transport properties combined with post-treatment procedures, such as necking and size-dependent co-catalyst loading. Five rules are proposed to guide the design of high-performance particle-based photoanodes by adding or varying several process steps. We also specify how much efficiency improvement can be achieved using each of the steps. For example, implementation of a connectivity network and surface area enhancement leads to thirty times improvement in efficiency and co-catalyst loading achieves an improvement in efficiency by a factor of seven. Some of these guidelines can be adapted to non-particle-based photoelectrodes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance of an ablator for Space Shuttle inorbit repair in an arc-plasma airstream

NASA Technical Reports Server (NTRS)

Stewart, D. A.; Cuellar, M.; Flowers, O.

1983-01-01

An ablator patch material performed well in an arc plasma environment simulating nominal Earth entry conditions for the Space Shuttle. Ablation tests using vacuum molded cones provided data to optimize the formulation of a two part polymer system for application under space conditions. The blunt cones were made using a Teflon mold and a state of the art caulking gun. Char stability of formulations with various amounts of catalyst and diluent were investigated. The char was found to be unstable in formulations with low amounts of catalyst and high amounts of diluent. The best polymer system determined by these tests was evaluated using a half tile patch in a multiple High Temperature Reusable surface Insulation tile model. It was demonstrated that this ablator could be applied in a space environment using a state of the art caulking gun, would maintain the outer mold line of the thermal protection system during entry, and would keep the bond line temperature at the aluminum tile interface below the design limit.

Impact of Fuel Metal Impurities on the Durability of a Light-Duty Diesel Aftertreatment System

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

Williams, A.; Burton, J.; McCormick, R. L.

2013-04-01

Alkali and alkaline earth metal impurities found in diesel fuels are potential poisons for diesel exhaust catalysts. A set of diesel engine production exhaust systems was aged to 150,000 miles. These exhaust systems included a diesel oxidation catalyst, selective catalytic reduction (SCR) catalyst, and diesel particulate filter (DPF). Four separate exhaust systems were aged, each with a different fuel: ultralow sulfur diesel containing no measureable metals, B20 (a common biodiesel blend) containing sodium, B20 containing potassium, and B20 containing calcium, which were selected to simulate the maximum allowable levels in B100 according to ASTM D6751. Analysis included Federal Test Proceduremore » emissions testing, bench-flow reactor testing of catalyst cores, electron probe microanalysis (EPMA), and measurement of thermo-mechanical properties of the DPFs. EPMA imaging found that the sodium and potassium penetrated into the washcoat, while calcium remained on the surface. Bench-flow reactor experiments were used to measure the standard nitrogen oxide (NOx) conversion, ammonia storage, and ammonia oxidation for each of the aged SCR catalysts. Vehicle emissions tests were conducted with each of the aged catalyst systems using a chassis dynamometer. The vehicle successfully passed the 0.2 gram/mile NOx emission standard with each of the four aged exhaust systems.« less

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

PubMed

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-10-23

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

Precision is essential for efficient catalysis in an evolved Kemp eliminase.

PubMed

Blomberg, Rebecca; Kries, Hajo; Pinkas, Daniel M; Mittl, Peer R E; Grütter, Markus G; Privett, Heidi K; Mayo, Stephen L; Hilvert, Donald

2013-11-21

Linus Pauling established the conceptual framework for understanding and mimicking enzymes more than six decades ago. The notion that enzymes selectively stabilize the rate-limiting transition state of the catalysed reaction relative to the bound ground state reduces the problem of design to one of molecular recognition. Nevertheless, past attempts to capitalize on this idea, for example by using transition state analogues to elicit antibodies with catalytic activities, have generally failed to deliver true enzymatic rates. The advent of computational design approaches, combined with directed evolution, has provided an opportunity to revisit this problem. Starting from a computationally designed catalyst for the Kemp elimination--a well-studied model system for proton transfer from carbon--we show that an artificial enzyme can be evolved that accelerates an elementary chemical reaction 6 × 10(8)-fold, approaching the exceptional efficiency of highly optimized natural enzymes such as triosephosphate isomerase. A 1.09 Å resolution crystal structure of the evolved enzyme indicates that familiar catalytic strategies such as shape complementarity and precisely placed catalytic groups can be successfully harnessed to afford such high rate accelerations, making us optimistic about the prospects of designing more sophisticated catalysts.

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.

Genetically programmed chiral organoborane synthesis

NASA Astrophysics Data System (ADS)

Kan, S. B. Jennifer; Huang, Xiongyi; Gumulya, Yosephine; Chen, Kai; Arnold, Frances H.

2017-12-01

Recent advances in enzyme engineering and design have expanded nature’s catalytic repertoire to functions that are new to biology. However, only a subset of these engineered enzymes can function in living systems. Finding enzymatic pathways that form chemical bonds that are not found in biology is particularly difficult in the cellular environment, as this depends on the discovery not only of new enzyme activities, but also of reagents that are both sufficiently reactive for the desired transformation and stable in vivo. Here we report the discovery, evolution and generalization of a fully genetically encoded platform for producing chiral organoboranes in bacteria. Escherichia coli cells harbouring wild-type cytochrome c from Rhodothermus marinus (Rma cyt c) were found to form carbon-boron bonds in the presence of borane-Lewis base complexes, through carbene insertion into boron-hydrogen bonds. Directed evolution of Rma cyt c in the bacterial catalyst provided access to 16 novel chiral organoboranes. The catalyst is suitable for gram-scale biosynthesis, providing up to 15,300 turnovers, a turnover frequency of 6,100 h-1, a 99:1 enantiomeric ratio and 100% chemoselectivity. The enantiopreference of the biocatalyst could also be tuned to provide either enantiomer of the organoborane products. Evolved in the context of whole-cell catalysts, the proteins were more active in the whole-cell system than in purified forms. This study establishes a DNA-encoded and readily engineered bacterial platform for borylation; engineering can be accomplished at a pace that rivals the development of chemical synthetic methods, with the ability to achieve turnovers that are two orders of magnitude (over 400-fold) greater than those of known chiral catalysts for the same class of transformation. This tunable method for manipulating boron in cells could expand the scope of boron chemistry in living systems.

A feasible process for furfural production from the pre-hydrolysis liquor of corncob via biochar catalysts in a new biphasic system.

PubMed

Deng, Aojie; Lin, Qixuan; Yan, Yuhuan; Li, Huiling; Ren, Junli; Liu, Chuanfu; Sun, Runcang

2016-09-01

A feasible approach was developed to produce furfural from the pre-hydrolysis liquor of corncob via biochar catalysts as the solid acid catalyst in a new biphasic system with dichloromethane (DCM) as the organic phase and the concentrated pre-hydrolysis liquor (CPHL) containing NaCl as the aqueous phase. The biochar catalyst possessing many acidity groups (SO3H, COOH and phenolic OH groups) was prepared by the carbonization and sulfonation process of the corncob hydrolyzed residue. The influence of the catalytic condition on furfural yield and selectivity was comparatively studied. It was found that 81.14% furfural yield and 83.0% furfural selectivity were obtained from CPHL containing 5wt% xylose using this biochar catalyst in the CPHL-NaCl/DCM biphasic system at 170°C for 60min. In addition, with the regeneration process, this catalyst displayed the high performance and excellent recyclability. Copyright © 2016 Elsevier Ltd. All rights reserved.

Toward Catalyst Design from Theoretical Calculations (464th Brookhaven Lecture)

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

Liu, Ping

2010-12-15

Catalysts have been used to speed up chemical reactions as long as yeast has been used to make bread rise. Today, catalysts are used everywhere from home kitchens to industrial chemical factories. In the near future, new catalysts being developed at Brookhaven Lab may be used to speed us along our roads and highways as they play a major role in solving the world’s energy challenges. During the lecture, Liu will discuss how theorists and experimentalists at BNL are working together to formulate and test new catalysts that could be used in real-life applications, such as hydrogen-fuel cells that maymore » one day power our cars and trucks.« less

CuAAC-Based Click Chemistry in Self-Healing Polymers.

PubMed

Döhler, Diana; Michael, Philipp; Binder, Wolfgang H

2017-10-17

Click chemistry has emerged as a significant tool for materials science, organic chemistry, and bioscience. Based on the initial concept of Barry Sharpless in 2001, the copper(I)-catalyzed azide/alkyne cycloaddition (CuAAC) reaction has triggered a plethora of chemical concepts for linking molecules and building blocks under ambient conditions, forming the basis for applications in autonomous cross-linking materials. Self-healing systems on the other hand are often based on mild cross-linking chemistries that are able to react either autonomously or upon an external trigger. In the ideal case, self-healing takes place efficiently at low temperatures, independent of the substrate(s) used, by forming strong and stable networks, binding to the newly generated (cracked) interfaces to restore the original material properties. The use of the CuAAC in self-healing systems, most of all the careful design of copper-based catalysts linked to additives as well as the chemical diversity of substrates, has led to an enormous potential of applications of this singular reaction. The implementation of click-based strategies in self-healing systems therefore is highly attractive, as here chemical (and physical) concepts of molecular reactivity, molecular design, and even metal catalysis are connected to aspects of materials science. In this Account, we will show how CuAAC reactions of multivalent components can be used as a tool for self-healing materials, achieving cross-linking at low temperatures (exploiting concepts of autocatalysis or internal chelation within the bulk CuAAC and systematic optimization of the efficiency of the used Cu(I) catalysts). Encapsulation strategies to separate the click components by micro- and nanoencapsulation are required in this context. Consequently, the examples reported here describe chemical concepts to realize more efficient and faster click reactions in self-healing polymeric materials. Thus, enhanced chain diffusion in (hyper)branched polymers, autocatalysis, or internal chelation concepts enable efficient click cross-linking already at 5 °C with a simultaneously reduced amount of Cu(I) catalyst and increased reaction rates, culminating in the first reported self-healing system based on click cycloaddition reactions. Via tailor-made nanocarbon/Cu(I) catalysts we can further improve the click cross-linking reaction in view of efficiency and kinetics, leading to the generation of self-healing graphene-based epoxy nanocomposites. Additionally, we have designed special CuAAC click methods for chemical reporting and visualization systems based on the detection of ruptured capsules via a fluorogenic click reaction, which can be combined with CuAAC cross-linking reactions to obtain simultaneous stress detection and self-healing within polymeric materials. In a similar concept, we have prepared polymeric Cu(I)-biscarbene complexes to detect (mechanical) stress within self-healing polymeric materials via a triggered fluorogenic reaction, thus using a destructive force for a constructive chemical response.

Heterolytic Activation of Hydrogen Promoted by Ruthenium Nanoparticles immobilized on Basic Supports and Hydrogenation of Aromatic Compounds

NASA Astrophysics Data System (ADS)

Fang, Minfeng

Despite the aggressive development and deployment of new renewable and nuclear technologies, petroleum-derived transportation fuels---gasoline, diesel and jet fuels---will continue to dominate the markets for decades. Environmental legislation imposes severe limits on the tolerable proportion of aromatics, sulfur and nitrogen contents in transportation fuels, which is difficult to achieve with current refining technologies. Catalytic hydrogenation plays an important role in the production of cleaner fuels, both as a direct means to reduce the aromatics and as a key step in the hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) processes. However, conventional catalysts require drastic conditions and/or are easily poisoned by S or N aromatics. Therefore, there is still a need for new efficient catalysts for hydrogenation reactions relevant to the production of cleaner fossil fuels. Our catalyst design involves metallic nanoparticles intimately associated with a basic support, with the aim of creating a nanostructure capable of promoting the heterolytic activation of hydrogen and ionic hydrogenation mechanisms, as a strategy to avoid catalyst poisoning and enhance catalytic activity. We have designed and prepared a new nanostructured catalytic material composed of RuNPs immobilized on the basic polymer P4VPy. We have demonstrated that the Ru/P4VPy catalyst can promote heterolytic hydrogen activation and a unique surface ionic hydrogenation mechanism for the efficient hydrogenation of N-aromatics. This is the first time these ionic hydrogenation pathways have been demonstrated on solid surfaces. For the RuNPs surfaces without basic sites in close proximity, the conventional homolytic H2 splitting is otherwise involved. Using the mechanistic concepts from Ru/P4VPy, we have designed and prepared the Ru/MgO catalyst, with the aim to improve the catalytic efficiency for the hydrogenation of heteroatom aromatics operating by the ionic hydrogenation mechanism. The Ru/MgO catalyst significantly improves the catalytic efficiency for hydrogenation of a variety of N-/S-heteroaromatics and mono-/polycyclic aromatic hydrocarbons representative of components of petroleum-derived fuels. The catalyst is superior to the few other known supported noble metal catalysts for these reactions. Mechanistic studies also point to the ionic hydrogenation mechanism on the Ru/MgO surfaces. In addition, the Ru/MgO catalyst is highly recyclable and long-lived.

Electrochemical performance and durability of carbon supported Pt catalyst in contact with aqueous and polymeric proton conductors.

PubMed

Andersen, Shuang Ma; Skou, Eivind

2014-10-08

Significant differences in catalyst performance and durability are often observed between the use of a liquid electrolyte (e.g., sulfuric acid), and a solid polymer electrolyte (e.g., Nafion). To understand this phenomenon, we studied the electrochemical behavior of a commercially available carbon supported platinum catalyst in four different electrode structures: catalyst powder (CP), catalyst ionomer electrode (CIE), half membrane electrode assembly (HMEA), and full membrane electrode assembly (FMEA) in both ex situ and in situ experiments under a simulated start/stop cycle. We found that the catalyst performance and stability are very much influenced by the presence of the Nafion ionomers. The proton conducting phase provided by the ionomer and the self-assembled electrode structure render the catalysts a higher utilization and better stability. This is probably due to an enhanced dispersion, an improved proton-catalyst interface, the restriction of catalyst particle aggregation, and the improved stability of the ionomer phase especially after the lamination. Therefore, an innovative electrode HMEA design for ex-situ catalyst characterization is proposed. The electrode structure is identical to the one used in a real fuel cell, where the protons transport takes place solely through solid state proton conducting phase.

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

Recent developments in biocatalysis in multiphasic ionic liquid reaction systems.

PubMed

Meyer, Lars-Erik; von Langermann, Jan; Kragl, Udo

2018-06-01

Ionic liquids are well known and frequently used 'designer solvents' for biocatalytic reactions. This review highlights recent achievements in the field of multiphasic ionic liquid-based reaction concepts. It covers classical biphasic systems including supported ionic liquid phases, thermo-regulated multi-component solvent systems (TMS) and polymerized ionic liquids. These powerful concepts combine unique reaction conditions with a high potential for future applications on a laboratory and industrial scale. The presence of a multiphasic system simplifies downstream processing due to the distribution of the catalyst and reactants in different phases.

Production of aromatics from di- and polyoxygenates

DOEpatents

Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy

2016-08-02

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline alumina support.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Production of aromatics from di- and polyoxygenates

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

Beck, Taylor; Blank, Brian; Jones, Casey

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline aluminamore » support.« less

Production of aromatics from di- and polyoxygenates

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

Beck, Taylor; Blank, Brian; Jones, Casey

Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Group VIII metal and a crystallinemore » alumina support.« less

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.

A Tandem Catalyst with Multiple Metal Oxide Interfaces Produced by Atomic Layer Deposition.

PubMed

Ge, Huibin; Zhang, Bin; Gu, Xiaomin; Liang, Haojie; Yang, Huimin; Gao, Zhe; Wang, Jianguo; Qin, Yong

2016-06-13

Ideal heterogeneous tandem catalysts necessitate the rational design and integration of collaborative active sites. Herein, we report on the synthesis of a new tandem catalyst with multiple metal-oxide interfaces based on a tube-in-tube nanostructure using template-assisted atomic layer deposition, in which Ni nanoparticles are supported on the outer surface of the inner Al2 O3 nanotube (Ni/Al2 O3 interface) and Pt nanoparticles are attached to the inner surface of the outer TiO2 nanotube (Pt/TiO2 interface). The tandem catalyst shows remarkably high catalytic efficiency in nitrobenzene hydrogenation over Pt/TiO2 interface with hydrogen formed in situ by the decomposition of hydrazine hydrate over Ni/Al2 O3 interface. This can be ascribed to the synergy effect of the two interfaces and the confined nanospace favoring the instant transfer of intermediates. The tube-in-tube tandem catalyst with multiple metal-oxide interfaces represents a new concept for the design of highly efficient and multifunctional nanocatalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase structuring in metal alloys: Ultrasound-assisted top-down approach to engineering of nanostructured catalytic materials.

PubMed

Cherepanov, Pavel V; Andreeva, Daria V

2017-03-01

High intensity ultrasound (HIUS) is a novel and efficient tool for top-down nanostructuring of multi-phase metal systems. Ultrasound-assisted structuring of the phase in metal alloys relies on two main mechanisms including interfacial red/ox reactions and temperature driven solid state phase transformations which affect surface composition and morphology of metals. Physical and chemical properties of sonication medium strongly affects the structuring pathways as well as morphology and composition of catalysts. HIUS can serve as a simple, fast, and effective approach for the tuning of structure and surface properties of metal particles, opening the new perspectives in design of robust and efficient catalysts. Copyright © 2016 Elsevier B.V. All rights reserved.

In use performance of catalytic converters on properly maintained high mileage vehicles

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

Sabourin, M.A.; Larson, R.E.; Donahue, K.S.

1986-01-01

A test program to evaluate the performance of catalytic converters from fifty-six 1981 and 1982 model year high mileage properly maintained in-use vehicles (from 21 engine families) was performed by the Certification Division of the Office of Mobile Sources (EPA). The program is called the Catalyst Change Program. All program vehicles were screened for proper maintenance and for mileages that ranged from 35,000 to 60,000 miles. Among vehicles belonging to 21 high sales volume and high technology engine and emission control system designs tested, poor catalyst performance was determined to be a significant contributor to emissions failure of properly-maintained vehiclesmore » at or near their warranted useful life mileage.« less

The effects of aniline impurities on monopropellant hydrazine thruster performance

NASA Technical Reports Server (NTRS)

Holcomb, L.; Mattson, L.; Oshiro, R.

1976-01-01

Both a 0.45-N and a 0.9-N thruster representative of the designs being flown on 3-axis stabilized spacecraft were used in testing various grades of hydrazine for the phenomenon of monopropellant hydrazine thruster catalyst bed poisoning. Both designs employed Shell 405 ABSG spontaneous catalyst. It is found that pulse shape distortion can be minimized, if not eliminated, by using aniline-free hydrazine. The mechanisms for both steady-state and pulse-mode performance loss are associated with the formation of a catalyst coke similar to the polycyclic aromatic poisons encountered in the petroleum industry. These poisoning mechanisms are reversible, with high-temperature operation being required to drive off the aniline coke deposits. It is recommended that a purified-grade hydrazine be considered for any mission that imposes operational conditions on a thruster which can result in aniline-induced poisoning of the catalyst bed.

Systems and methods for rebalancing redox flow battery electrolytes

DOEpatents

Pham, Ai Quoc; Chang, On Kok

2015-03-17

Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

Three-Dimensional Networks of S-Doped Fe/N/C with Hierarchical Porosity for Efficient Oxygen Reduction in Polymer Electrolyte Membrane Fuel Cells.

PubMed

Wu, Yi-Jin; Wang, Yu-Cheng; Wang, Rui-Xiang; Zhang, Peng-Fang; Yang, Xiao-Dong; Yang, Hui-Juan; Li, Jun-Tao; Zhou, Yao; Zhou, Zhi-You; Sun, Shi-Gang

2018-05-02

Reasonable design and synthesis of Fe/N/C-based catalysts is one of the most promising way for developing precious metal-free oxygen reduction reaction (ORR) catalysts in acidic mediums. Herein, we developed a highly active metal-organic framework-derived S-doped Fe/N/C catalyst [S-Fe/Z8/2-aminothiazole (2-AT)] prepared by thermal treatment. The S-Fe/Z8/2-AT catalyst with uniform S-doping possesses a three-dimensional macro-meso-micro hierarchically porous structure. Moreover, the chemical composition and structural features have been well-optimized and characterized for such S-Fe/Z8/2-AT catalysts; and their formation mechanism was also revealed. Significantly, applying the optimal S-Fe/Z8/2-AT catalysts into electrocatalytic test exhibits remarkable ORR catalytic activity with a half-wave potential of 0.82 V (vs reversible hydrogen electrode) and a mass activity of 18.3 A g -1 at 0.8 V in 0.1 M H 2 SO 4 solution; the polymer electrolyte membrane fuel cell test also confirmed their excellent catalytic activity, which gives a maximal power density as high as 800 mW cm -2 at 1 bar. A series of designed experiments disclosed that the favorable structural merits and desirable chemical compositions of S-Fe/Z8/2-AT catalysts are critical factors for efficient electrocatalytic performance. The work provides a new approach to open an avenue for accurately controlling the composition and structure of Fe/N/C catalysts with highly activity for ORR.

Chemical Insights into the Design and Development of Face-Centered Cubic Ruthenium Catalysts for Fischer-Tropsch Synthesis.

PubMed

Li, Wei-Zhen; Liu, Jin-Xun; Gu, Jun; Zhou, Wu; Yao, Si-Yu; Si, Rui; Guo, Yu; Su, Hai-Yan; Yan, Chun-Hua; Li, Wei-Xue; Zhang, Ya-Wen; Ma, Ding

2017-02-15

Ruthenium is a promising low-temperature catalyst for Fischer-Tropsch synthesis (FTS). However, its scarcity and modest specific activity limit its widespread industrialization. We demonstrate here a strategy for tuning the crystal phase of catalysts to expose denser and active sites for a higher mass-specific activity. Density functional theory calculations show that upon CO dissociation there are a number of open facets with modest barrier available on the face-centered cubic (fcc) Ru but only a few step edges with a lower barrier on conventional hexagonal-closest packed (hcp) Ru. Guided by theoretical calculations, water-dispersible fcc Ru catalysts containing abundant open facets were synthesized and showed an unprecedented mass-specific activity in the aqueous-phase FTS, 37.8 mol CO ·mol Ru -1 ·h -1 at 433 K. The mass-specific activity of the fcc Ru catalysts with an average size of 6.8 nm is about three times larger than the previous best hcp catalyst with a smaller size of 1.9 nm and a higher specific surface area. The origin of the higher mass-specific activity of the fcc Ru catalysts is identified experimentally from the 2 orders of magnitude higher density of the active sites, despite its slightly higher apparent barrier. Experimental results are in excellent agreement with prediction of theory. The great influence of the crystal phases on site distribution and their intrinsic activities revealed here provides a rationale design of catalysts for higher mass-specific activity without decrease of the particle size.

Immobilization of molecular catalysts in supported ionic liquid phases.

PubMed

Van Doorslaer, Charlie; Wahlen, Joos; Mertens, Pascal; Binnemans, Koen; De Vos, Dirk

2010-09-28

In a supported ionic liquid phase (SILP) catalyst system, an ionic liquid (IL) film is immobilized on a high-surface area porous solid and a homogeneous catalyst is dissolved in this supported IL layer, thereby combining the attractive features of homogeneous catalysts with the benefits of heterogeneous catalysts. In this review reliable strategies for the immobilization of molecular catalysts in SILPs are surveyed. In the first part, general aspects concerning the application of SILP catalysts are presented, focusing on the type of catalyst, support, ionic liquid and reaction conditions. Secondly, organic reactions in which SILP technology is applied to improve the performance of homogeneous transition-metal catalysts are presented: hydroformylation, metathesis reactions, carbonylation, hydrogenation, hydroamination, coupling reactions and asymmetric reactions.

Energy level shifts at the silica/Ru(0001) heterojunction driven by surface and interface dipoles

DOE PAGES

Wang, Mengen; Zhong, Jian -Qiang; Kestell, John; ...

2016-09-12

Charge redistribution at heterogeneous interfaces is a fundamental aspect of surface chemistry. Manipulating the amount of charges and the magnitude of dipole moments at the interface in a controlled way has attracted tremendous attention for its potential to modify the activity of heterogeneous catalysts in catalyst design. Two-dimensional ultrathin silica films with well-defined atomic structures have been recently synthesized and proposed as model systems for heterogeneous catalysts studies. R. Wlodarczyk et al. (Phys. Rev. B, 85, 085403 (2012)) have demonstrated that the electronic structure of silica/Ru(0001) can be reversibly tuned by changing the amount of interfacial chemisorbed oxygen. Here wemore » carried out systematic investigations to understand the underlying mechanism through which the electronic structure at the silica/Ru(0001) interface can be tuned. As corroborated by both in situ X-ray photoelectron spectroscopy and density functional theory calculations, the observed interface energy level alignments strongly depend on the surface and interfacial charge transfer induced dipoles at the silica/Ru(0001) heterojunction. These observations may help to understand variations in catalytic performance of the model system from the viewpoint of the electronic properties at the confined space between the silica bilayer and the Ru(0001) surface. As a result, the same behavior is observed for the aluminosilicate bilayer, which has been previously proposed as a model system for zeolites.« less

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

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.

Catalysts for low-energy aldehyde processes

NASA Technical Reports Server (NTRS)

Gupta, A.; Rembaum, A.; Frazier, C.; Gray, H. B.

1977-01-01

Photochemical reaction of dicobalt octacarbonyl with polymeric support systems results in formation of polymer bonded metal catalyst. Catalyst is used in hydroformylation (addition of carbon dioxide and hydrogen) of olefins to yield aldehydes.

Preparation of a magnetic N-Fe/AC catalyst for aqueous pharmaceutical treatment in heterogeneous sonication system.

PubMed

Zhang, Nan; Zhao, He; Zhang, Guangming; Chong, Shan; Liu, Yucan; Sun, Liyan; Chang, Huazhen; Huang, Ting

2017-02-01

High efficiency and facile separation are desirable for catalysts used in water treatment. In this study, a magnetic catalyst (nitrogen doped iron/activated carbon) was prepared and used for pharmaceutical wastewater treatment. The catalyst was characterized using BET, SEM, XRD, VSM and XPS. Results showed that iron and nitrogen were successfully loaded and doped, magnetic Fe 2 N was formed, large amount of active surface oxygen and Fe(II) were detected, and the catalyst could be easily separated from water. Diclofenac was then degraded using the catalyst in ultrasound system. The catalyst showed high catalytic activity with 95% diclofenac removal. Analysis showed that ·OH attack of diclofenac was a main pathway, and then ·OH generation mechanism was clarified. The effects of catalyst dosage, sonication time, ultrasonic density, initial pH, and inorganic anions on diclofenac degradation were studied. Sulfate anion enhanced the degradation of diclofenac. Mechanism in the catalytic ultrasonic process was analyzed and reactions were clarified. Large quantity of oxidants was generated on the catalyst surface, including ·OH, O 2 - , O - and HO 2 ·, which degraded diclofenac efficiently. In the solution and interior of cavitation bubbles, ·OH and "hot spot" effects contributed to the degradation of diclofenac. Reuse of the catalyst was further investigated to enhance its economy, and the catalyst maintained activity after seven uses. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

NASA Technical Reports Server (NTRS)

Abraham, Martin; Fisher, John W.

1995-01-01

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

A self-improved water-oxidation catalyst: is one site really enough?

PubMed

López, Isidoro; Ertem, Mehmed Z; Maji, Somnath; Benet-Buchholz, Jordi; Keidel, Anke; Kuhlmann, Uwe; Hildebrandt, Peter; Cramer, Christopher J; Batista, Victor S; Llobet, Antoni

2014-01-03

The homogeneous catalysis of water oxidation by transition-metal complexes has experienced spectacular development over the last five years. Practical energy-conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water-oxidation catalyst that is generated by self-assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water-oxidation catalyst that does not decompose over extended periods of time. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reticulation of Aqueous Polyurethane Systems Controlled by DSC Method

PubMed Central

Cakic, Suzana; Lacnjevac, Caslav; Rajkovic, Milos B.; Raskovic, Ljiljana; Stamenkovic, Jakov

2006-01-01

The DSC method has been employed to monitor the kinetics of reticulation of aqueous polyurethane systems without catalysts, and with the commercial catalyst of zirconium (CAT®XC-6212) and the highly selective manganese catalyst, the complex Mn(III)-diacetylacetonemaleinate (MAM). Among the polyol components, the acrylic emulsions were used for reticulation in this research, and as suitable reticulation agents the water emulsible aliphatic polyisocyanates based on hexamethylendoisocyanate with the different contents of NCO-groups were employed. On the basis of DSC analysis, applying the methods of Kissinger, Freeman-Carroll and Crane-Ellerstein the pseudo kinetic parameters of the reticulation reaction of aqueous systems were determined. The temperature of the examination ranged from 50°C to 450°C with the heat rate of 0.5°C/min. The reduction of the activation energy and the increase of the standard deviation indicate the catalytic action of the selective catalysts of zirconium and manganese. The impact of the catalysts on the reduction of the activation energy is the strongest when using the catalysts of manganese and applying all the three afore-said methods. The least aberrations among the stated methods in defining the kinetic parameters were obtained by using the manganese catalyst.

Flexible 3D Fe@VO2 core-shell mesh: A highly efficient and easy-recycling catalyst for the removal of organic dyes.

PubMed

Li, Jing; Wang, Ruoqi; Su, Zhen; Zhang, Dandan; Li, Heping; Yan, Youwei

2018-10-01

Nowadays, it is extremely urgent to search for efficient and effective catalysts for water purification due to the severe worldwide water-contamination crises. Here, 3D Fe@VO 2 core-shell mesh, a highly efficient catalyst toward removal of organic dyes with excellent recycling ability in the dark is designed and developed for the first time. This novel core-shell structure is actually 304 stainless steel mesh coated by VO 2 , fabricated by an electrophoretic deposition method. In such a core-shell structure, Fe as the core allows much easier separation from the water, endowing the catalyst with a flexible property for easy recycling, while VO 2 as the shell is highly efficient in degradation of organic dyes with the addition of H 2 O 2 . More intriguingly, the 3D Fe@VO 2 core-shell mesh exhibits favorable performance across a wide pH range. The 3D Fe@VO 2 core-shell mesh can decompose organic dyes both in a light-free condition and under visible irradiation. The possible catalytic oxidation mechanism of Fe@VO 2 /H 2 O 2 system is also proposed in this work. Considering its facile fabrication, remarkable catalytic efficiency across a wide pH range, and easy recycling characteristic, the 3D Fe@VO 2 core-shell mesh is a newly developed high-performance catalyst for addressing the universal water crises. Copyright © 2018 Elsevier B.V. All rights reserved.

Electric field tuned MoS2/metal interface for hydrogen evolution catalyst from first-principles investigations

NASA Astrophysics Data System (ADS)

Ling, F. L.; Zhou, T. W.; Liu, X. Q.; Kang, W.; Zeng, W.; Zhang, Y. X.; Fang, L.; Lu, Y.; Zhou, M.

2018-01-01

Understanding the interfacial properties of catalyst/substrate is crucial for the design of high-performance catalyst for important chemical reactions. Recent years have witnessed a surge of research in utilizing MoS2 as a promising electro-catalyst for hydrogen production, and field effect has been employed to enhance the activity (Wang et al 2017 Adv. Mater. 29, 1604464; Yan et al 2017 Nano Lett. 17, 4109-15). However, the underlying atomic mechanism remains unclear. In this paper, by using the prototype MoS2/Au system as a probe, we investigate effects of external electric field on the interfacial electronic structures via density functional theory (DFT) based first-principles calculations. Our results reveal that although there is no covalent interaction between MoS2 overlayer and Au substrate, an applied electric field efficiently adjusts the charge transfer between MoS2 and Au, leading to tunable Schottky barrier type (n-type to p-type) and decrease of barrier height to facilitate charge injection. Furthermore, we predict that the adsorption energy of atomic hydrogen on MoS2/Au to be readily controlled by electric field to a broad range within a modest magnitude of field, which may benefit the performance enhancement of hydrogen evolution reaction. Our DFT results provide valuable insight into the experimental observations and pave the way for future understanding and control of catalysts in practice, such as those with vacancies, defects, edge states or synthesized nanostructures.

Aldehyde-functionalized porous nanocellulose for effective removal of heavy metal ions from aqueous solutions

Treesearch

C. Yao; F. Wang; Z. Cai; X. Wang

2016-01-01

Nanoscale sorption is a promising strategy for catalyst and purification system design. In this paper, cellulose nanofibrils (CNFs) were densely attached with aldehyde functional groups on the surface via a mild periodate oxidation process, and then applied as mesoporous sorbents to remove Cu(II) and Pb(II) from aqueous solutions. In the studied concentration range (0....

Photocatalytic Conversion of CO2 to CO by a Copper(II) Quaterpyridine Complex.

PubMed

Guo, Zhenguo; Yu, Fei; Yang, Ying; Leung, Chi-Fai; Ng, Siu-Mui; Ko, Chi-Chiu; Cometto, Claudio; Lau, Tai-Chu; Robert, Marc

2017-10-23

The invention of efficient systems for the photocatalytic reduction of CO 2 comprising earth-abundant metal catalysts is a promising approach for the production of solar fuels. One bottleneck is to design highly selective and robust molecular complexes that are able to transform the CO 2 gas. The Cu II quaterpyridine complex [Cu(qpy)] 2+ (1) is found to be a highly efficient and selective catalyst for visible-light driven CO 2 reduction in CH 3 CN using [Ru(bpy) 3 ] 2+ (bpy: bipyridine) as photosensitizer and BIH/TEOA (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole/triethanolamine) as sacrificial reductant. The photocatalytic reaction is greatly enhanced by the presence of H 2 O (1-4 % v/v), and a turnover number of >12 400 for CO production can be achieved with 97 % selectivity, which is among the highest of molecular 3d CO 2 reduction catalysts. Results from Hg poisoning and dynamic light scattering experiments suggest that this photocatalyst is homogenous. To the best of our knowledge, 1 is the first example of molecular Cu-based catalyst for the photoreduction of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective Transformation of Various Nitrogen-Containing Exhaust Gases toward N2 over Zeolite Catalysts.

PubMed

Zhang, Runduo; Liu, Ning; Lei, Zhigang; Chen, Biaohua

2016-03-23

In this review we focus on the catalytic removal of a series of N-containing exhaust gases with various valences, including nitriles (HCN, CH3CN, and C2H3CN), ammonia (NH3), nitrous oxide (N2O), and nitric oxides (NO(x)), which can cause some serious environmental problems, such as acid rain, haze weather, global warming, and even death. The zeolite catalysts with high internal surface areas, uniform pore systems, considerable ion-exchange capabilities, and satisfactory thermal stabilities are herein addressed for the corresponding depollution processes. The sources and toxicities of these pollutants are introduced. The important physicochemical properties of zeolite catalysts, including shape selectivity, surface area, acidity, and redox ability, are described in detail. The catalytic combustion of nitriles and ammonia, the direct catalytic decomposition of N2O, and the selective catalytic reduction and direct catalytic decomposition of NO are systematically discussed, involving the catalytic behaviors as well as mechanism studies based on spectroscopic and kinetic approaches and molecular simulations. Finally, concluding remarks and perspectives are given. In the present work, emphasis is placed on the structure-performance relationship with an aim to design an ideal zeolite-based catalyst for the effective elimination of harmful N-containing compounds.

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Coutts, Janelle; Hintze, Paul E.; Muscatello, Anthony C.; Gibson, Tracy L.; Captain, James G.; Lunn, Griffin M.; Devor, Robert W.; Bauer, Brint; Parks, Steve

2016-01-01

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50 because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Hintze, Paul E.; Muscatello, Anthony C.; Meier, Anne J.; Gibson, Tracy L.; Captain, James G.; Lunn, Griffin M.; Devor, Robert W.

2016-01-01

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Hintze, Paul E.; Muscatello, Anthony C.; Gibson, Tracy L.; Captain, James G.; Lunn, Griffin M.; Devor, Robert W.; Bauer, Brint; Parks, Steve

2016-01-01

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon, is capable of recovering all the oxygen from carbon dioxide, and it is a promising alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon, and the resulting carbon buildup eventually fouls the catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

In situ characterization of catalysts and membranes in a microchannel under high-temperature water gas shift reaction conditions

NASA Astrophysics Data System (ADS)

Cavusoglu, G.; Dallmann, F.; Lichtenberg, H.; Goldbach, A.; Dittmeyer, R.; Grunwaldt, J.-D.

2016-05-01

Microreactor technology with high heat transfer in combination with stable catalysts is a very attractive approach for reactions involving major heat effects such as methane steam reforming and to some extent, also the high temperature water gas shift (WGS) reaction. For this study Rh/ceria catalysts and an ultrathin hydrogen selective membrane were characterized in situ in a microreactor specially designed for x-ray absorption spectroscopic measurements under WGS conditions. The results of these experiments can serve as a basis for further development of the catalysts and membranes.

Monolith catalysts for closed-cycle carbon dioxide lasers

NASA Technical Reports Server (NTRS)

Herz, Richard K.

1994-01-01

The general subject area of the project involved the development of solid catalysts that have high activity at low temperature for the oxidation of gases such as CO. The original application considered was CO oxidation in closed-cycle CO2 lasers. The scope of the project was subsequently extended to include oxidation of gases in addition to CO and applications such as air purification and exhaust gas emission control. The primary objective of the final phase grant was to develop design criteria for the formulation of new low-temperature oxidation catalysts utilizing Monte Carlo simulations of reaction over NASA-developed catalysts.

Environmentally benign Friedel-Crafts benzylation over nano-TiO2/SO4 2-

NASA Astrophysics Data System (ADS)

Devi, Kalathiparambil RPS; Sreeja, Puthenveetil B.; Sugunan, Sankaran

2013-05-01

During the past decade, much attention has been paid to the replacement of homogeneous catalysts by solid acid catalysts. Friedel-Crafts benzylation of toluene with benzyl chloride (BC) in liquid phase was carried out over highly active, nano-crystalline sulfated titania systems. These catalysts were prepared using the sol gel method. Modification was done by loading 3% of transition metal oxides over sulfated titania. Reaction parameters such as catalyst mass, molar ratio, temperature, and time have been studied. More than 80% conversion of benzyl chloride and 100% selectivity are shown by all the catalysts under optimum conditions. Catalytic activity is correlated with Lewis acidity obtained from perylene adsorption studies. The reaction appears to proceed by an electrophile, which involves the reaction of BC with the acidic titania catalyst. The catalyst was regenerated and reused up to four reaction cycles with equal efficiency as in the first run. The prepared systems are environmentally friendly and are easy to handle.

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.

Enhanced conversion of syngas to liquid motor fuels

DOEpatents

Coughlin, Peter K.; Rabo, Jule A.

1986-01-01

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

Tethered catalysts for the hydration of carbon dioxide

DOEpatents

Valdez, Carlos A; Satcher, Jr., Joe H; Aines, Roger D; Wong, Sergio E; Baker, Sarah E; Lightstone, Felice C; Stolaroff, Joshuah K

2014-11-04

A system is provided that substantially increases the efficiency of CO.sub.2 capture and removal by positioning a catalyst within an optimal distance from the air-liquid interface. The catalyst is positioned within the layer determined to be the highest concentration of carbon dioxide. A hydrophobic tether is attached to the catalyst and the hydrophobic tether modulates the position of the catalyst within the liquid layer containing the highest concentration of carbon dioxide.

Vertically-oriented graphenes supported Mn3O4 as advanced catalysts in post plasma-catalysis for toluene decomposition

NASA Astrophysics Data System (ADS)

Bo, Zheng; Hao, Han; Yang, Shiling; Zhu, Jinhui; Yan, Jianhua; Cen, Kefa

2018-04-01

This work reports the catalytic performance of vertically-oriented graphenes (VGs) supported manganese oxide catalysts toward toluene decomposition in post plasma-catalysis (PPC) system. Dense networks of VGs were synthesized on carbon paper (CP) via a microwave plasma-enhanced chemical vapor deposition (PECVD) method. A constant current approach was applied in a conventional three-electrode electrochemical system for the electrodeposition of Mn3O4 catalysts on VGs. The as-obtained catalysts were characterized and investigated for ozone conversion and toluene decomposition in a PPC system. Experimental results show that the Mn3O4 catalyst loading mass on VG-coated CP was significantly higher than that on pristine CP (almost 1.8 times for an electrodeposition current of 10 mA). Moreover, the decoration of VGs led to both enhanced catalytic activity for ozone conversion and increased toluene decomposition, exhibiting a great promise in PPC system for the effective decomposition of volatile organic compounds.

Locus-specific microemulsion catalysts for sulfur mustard (HD) chemical warfare agent decontamination.

PubMed

Fallis, Ian A; Griffiths, Peter C; Cosgrove, Terence; Dreiss, Cecile A; Govan, Norman; Heenan, Richard K; Holden, Ian; Jenkins, Robert L; Mitchell, Stephen J; Notman, Stuart; Platts, Jamie A; Riches, James; Tatchell, Thomas

2009-07-22

The rates of catalytic oxidative decontamination of the chemical warfare agent (CWA) sulfur mustard (HD, bis(2-chlororethyl) sulfide) and a range (chloroethyl) sulfide simulants of variable lipophilicity have been examined using a hydrogen peroxide-based microemulsion system. SANS (small-angle neutron scattering), SAXS (small-angle X-ray scattering), PGSE-NMR (pulsed-gradient spin-echo NMR), fluorescence quenching, and electrospray mass spectroscopy (ESI-MS) were implemented to examine the distribution of HD, its simulants, and their oxidation/hydrolysis products in a model oil-in-water microemulsion. These measurements not only present a means of interpreting decontamination rates but also a rationale for the design of oxidation catalysts for these toxic materials. Here we show that by localizing manganese-Schiff base catalysts at the oil droplet-water interface or within the droplet core, a range of (chloroethyl) sulfides, including HD, spanning some 7 orders of octanol-water partition coefficient (K(ow)), may be oxidized with equal efficacy using dilute (5 wt. % of aqueous phase) hydrogen peroxide as a noncorrosive, environmentally benign oxidant (e.g., t(1/2) (HD) approximately 18 s, (2-chloroethyl phenyl sulfide, C(6)H(5)SCH(2)CH(2)Cl) approximately 15 s, (thiodiglycol, S(CH(2)CH(2)OH)(2)) approximately 19 s {20 degrees C}). Our observations demonstrate that by programming catalyst lipophilicity to colocalize catalyst and substrate, the inherent compartmentalization of the microemulsion can be exploited to achieve enhanced rates of reaction or to exert control over product selectivity. A combination of SANS, ESI-MS and fluorescence quenching measurements indicate that the enhanced catalytic activity is due to the locus of the catalyst and not a result of partial hydrolysis of the substrate.

Method for reactivating catalysts and a method for recycling supercritical fluids used to reactivate the catalysts

DOEpatents

Ginosar, Daniel M.; Thompson, David N.; Anderson, Raymond P.

2008-08-05

A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

DOE PAGES

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.; ...

2017-05-02

Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for the imminentmore » commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo - TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. Furthermore, the ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

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

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.

Abstract Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for themore » imminent commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo—TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. The ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

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

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.

Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for the imminentmore » commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo - TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. Furthermore, the ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Technology development for iron Fischer-Tropsch catalysts

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

O`Brien, R.J.; Raje, A.; Keogh, R.A.

1995-12-31

The objective of this research project is to develop the technology for the production of physically robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry phase synthesis reactor development. The catalysts that are developed shall be suitable for testing in the Advanced Fuels Development Facility at LaPorte, Texas, to produce either low-or high-alpha product distributions. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the {open_quotes}standard-catalyst{close_quotes} developed by German workers for slurry phase synthesis. In parallel, work will be conducted to design a high-alphamore » iron catalyst this is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.« less

Highly recoverable pyridinium-tagged Hoveyda-Grubbs pre-catalyst for olefin metathesis. Design of the boomerang ligand toward the optimal compromise between activity and reusability.

PubMed

Rix, Diane; Caïjo, Fréderic; Laurent, Isabelle; Gulajski, Lukasz; Grela, Karol; Mauduit, Marc

2007-09-28

Whereas the boomerang ligand of Hoveyda-Grubbs pre-catalysts can be modified by attachment of a pyridinium tag to its benzylidene moiety, a precise adjustment of the length of the spacer allows the optimum balance to be reached between the activity of the catalyst and its recoverability, exceeding 98% after 6 catalytic runs in the best case.

Catalytic cracking of model compounds of bio-oil over HZSM-5 and the catalyst deactivation.

PubMed

Chen, Guanyi; Zhang, Ruixue; Ma, Wenchao; Liu, Bin; Li, Xiangping; Yan, Beibei; Cheng, Zhanjun; Wang, Tiejun

2018-08-01

The catalytic cracking upgrading reactions over HZSM-5 of different model compounds of bio-oil have been studied with a self-designed fluid catalytic cracking (FCC) equipment. Typical bio-oil model compounds, such as acetic acid, guaiacol, n-heptane, acetol and ethyl acetate, were chosen to study the products distribution, reaction pathway and deactivation of catalysts. The results showed: C 6 -C 8 aromatic hydrocarbons, C 2 -C 4 olefins, C 1 -C 5 alkanes, CO and CO 2 were the main products, and the selectivity of olefins was: ethylene>propylene>butylene. Catalyst characterization methods, such as FI-IR, TG-TPO and Raman, were used to study the deactivation mechanism of catalysts. According to the catalyst characterization results, a catalyst deactivation mechanism was proposed as follows: Firstly, the precursor which consisted of a large number of long chain saturated aliphatic hydrocarbons and a small amount CC of aromatics formed on the catalyst surface. Then the active sites of catalysts had been covered, the coke type changed from thermal coke to catalytic coke and gradually blocked the channels of the molecular sieve, which accelerated the deactivation of catalyst. Copyright © 2018 Elsevier B.V. All rights reserved.

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device

PubMed Central

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-01-01

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H2S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions. PMID:26512669

"Catalysis in a tea bag": synthesis, catalytic performance and recycling of dendrimer-immobilised bis- and trisoxazoline copper catalysts.

PubMed

Gaab, Manuela; Bellemin-Laponnaz, Stéphane; Gade, Lutz H

2009-01-01

Bis- and trisoxazolines (BOX and trisox), containing a linker unit in the ligand backbone that allows their covalent attachment to carbosilane dendrimers, have been employed as polyfunctional ligands for recyclable Cu(II) Lewis acid catalysts that were immobilised in a membrane bag. The oxazolines contained an alkynyl unit attached to their backbone that was deprotonated with LDA or BuLi and then reacted with the chlorosilyl termini of zeroth-, first- and second-generation carbosilane dendrimers in the presence of TlPF(6). The functionalised dendritic systems were subsequently separated from excess ligand by way of dialysis. The general catalytic potential of these systems was assessed by studying two benchmark reactions, the alpha-hydrazination of a beta-keto ester as well as the Henry reaction of 2-nitrobenzaldehyde with nitromethane. For both reactions the bisoxazoline-based catalysts displayed superior selectivity and, in particular, catalyst activity. The latter was interpreted as being due to the hindered decoordination of the third oxazoline unit, the key step in the generation of the active catalyst, in the immobilised trisox-copper complexes. Solutions of the second-generation dendrimer catalysts were placed in membrane bags, fabricated from commercially available dialysis membranes, with the purpose of catalyst recycling based on dialysis. Overall, the supported BOX catalyst gave good and highly reproducible results throughout the study, whereas the performance of the trisox dendrimer system decreased monotonically. The reason for the different behaviour is the markedly lower activity of trisox-based catalysts relative to those based on the BOX ligand. This necessitated an increased reaction time for each cycle of the trisox derivatives, resulting in higher levels of catalyst leaching, which was attributed to a modification of the structure of the membrane by its exposure to the solvent trifluoroethanol at 40 degrees C.

Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen

DOE PAGES

Oughli, Alaa A.; Ruff, Adrian; Boralugodage, Nilusha Priyadarshani; ...

2018-02-28

A bio-inspired O 2 sensitive nickel catalyst dispersed in a hydrophobic and redox-silent polymer matrix shows enhanced stability for catalytic H 2 oxidation as well as O 2 tolerance. A simple but efficient electrode design separates the catalyst into two different reaction layers to promote different reactivity on the catalyst. (1) close to the electrode surface, the catalyst can directly exchange electrons with the electrode and generate current from H 2 oxidation; and (2) at the outer film boundary, the electrolyte exposed layer is electrically isolated from the electrode, which enables the H 2 reduced Ni-complex to convert O 2more » to H 2O and thus provides protection to the O 2-sensitive inner reaction layer. This strategy solves one of the biggest limitations of these otherwise outstanding catalysts and could be used to protect other similar catalysts whose wider application is currently limited by sensitivity towards oxygen.« less

Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen

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

Oughli, Alaa A.; Ruff, Adrian; Boralugodage, Nilusha Priyadarshani

A bio-inspired O 2 sensitive nickel catalyst dispersed in a hydrophobic and redox-silent polymer matrix shows enhanced stability for catalytic H 2 oxidation as well as O 2 tolerance. A simple but efficient electrode design separates the catalyst into two different reaction layers to promote different reactivity on the catalyst. (1) close to the electrode surface, the catalyst can directly exchange electrons with the electrode and generate current from H 2 oxidation; and (2) at the outer film boundary, the electrolyte exposed layer is electrically isolated from the electrode, which enables the H 2 reduced Ni-complex to convert O 2more » to H 2O and thus provides protection to the O 2-sensitive inner reaction layer. This strategy solves one of the biggest limitations of these otherwise outstanding catalysts and could be used to protect other similar catalysts whose wider application is currently limited by sensitivity towards oxygen.« less

Selective catalytic reduction system and process for treating NOx emissions using a zinc or titanium promoted palladium-zirconium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-08-02

A process and system (18) for reducing NO.sub.x in a gas using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream (29) with a catalyst system (38) comprising sulfated zirconia washcoat particles (41), palladium, a pre-sulfated zirconia binder (44), and a promoter (45) comprising at least one of titanium, zinc, or a mixture thereof. The presence of zinc or titanium increases the resistance of the catalyst system to a sulfur and water-containing gas stream.

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

Snowden-Swan, Lesley J.; Spies, Kurt A.; Lee, Guo-Shuh J.

Bio-oil from fast pyrolysis of biomass requires multi-stage catalytic hydroprocessing to produce hydrocarbon drop-in fuels. The current proposed process design involves fixed beds of ruthenium-based catalyst and conventional petroleum hydrotreating catalyst. Similar to petroleum processing, the catalyst is spent as a result of coking and other deactivation mechanisms, and must be changed out periodically. Biofuel life cycle greenhouse gas (GHG) assessments typically ignore the impact of catalyst consumed during fuel conversion as a result of limited lifetime, representing a data gap in the analyses. To help fill this data gap, life cycle GHGs were estimated for two representative examples ofmore » fast pyrolysis bio-oil hydrotreating catalyst, NiMo/Al2O3 and Ru/C, and integrated into the conversion-stage GHG analysis. Life cycle GHGs for the NiMo/Al2O3 and Ru/C catalysts are estimated at 5.5 and 81 kg CO2-e/kg catalyst, respectively. Contribution of catalyst consumption to total conversion-stage GHGs is 0.5% for NiMo/Al2O3 and 5% for Ru/C. This analysis does not consider secondary sourcing of metals for catalyst manufacture and therefore these are likely to be conservative estimates compared to applications where a spent catalyst recycler can be used.« less

Synthesis, characterization and catalytic activity of nanosized Ni complexed aminoclay

NASA Astrophysics Data System (ADS)

Ranchani, A. Amala Jeya; Parthasarathy, V.; Devi, A. Anitha; Meenarathi, B.; Anbarasan, R.

2017-11-01

A novel Ni complexed aminoclay (AC) catalyst was prepared by complexation method followed by reduction reaction. Various analytical techniques such as FTIR spectroscopy, UV-visible spectroscopy, DSC, TGA, SEM, HRTEM, EDX, XPS and WCA measurement are used to characterize the synthesized material. The AC-Ni catalyst system exhibited improved thermal stability and fiber-like morphology. The XPS results declared the formation of Ni nanoparticles. Thus, synthesized catalyst was tested towards the Schiff base formation reaction between various bio-medical polymers and aniline under air atmosphere at 85 °C for 24 h. The catalytic activity of the catalyst was studied by varying the % weight loading of the AC-Ni system towards the Schiff base formation. The Schiff base formation was quantitatively calculated by the 1H-NMR spectroscopy. While increasing the % weight loading of the AC-Ni catalyst, the % yield of Schiff base was also increased. The k app and Ti values were determined for the reduction of indole and α-terpineol in the presence of AC-Ni catalyst system. The experimental results were compared with the literature report.

Synthesis, characterization and evaluation of CO-oxidation catalysts for high repetition rate CO2 TEA lasers

NASA Technical Reports Server (NTRS)

Moser, Thomas P.

1990-01-01

An extremely active class of noble metal catalysts supported on titania was developed and fabricated at Hughes for the recombination of oxygen (O2) and carbon monoxide (CO) in closed-cycle CO2 TEA lasers. The incipient wetness technique was used to impregnate titania and alumina pellets with precious metals including platinum and palladium. In particular, the addition of cerium (used as an oxygen storage promoter) produced an extremely active Pt/Ce/TiO2 catalyst. By comparison, the complementary Pt/Ce/ gamma-Al2O3 catalyst was considerably less active. In general, chloride-free catalyst precursors proved critical in obtaining an active catalyst while also providing uniform metal distributions throughout the support structure. Detailed characterization of the Pt/Ce/TiO2 catalyst demonstrated uniform dendritic crystal growth of the metals throughout the support. Electron spectroscopy for Chemical Analysis (ESCA) analysis was used to characterize the oxidation states of Pt, Ce and Ti. The performance of the catalysts was evaluated with an integral flow reactor system incorporating real time analysis of O2 and CO. With this system, the transient and steady-state behavior of the catalysts were evaluated. The kinetic evaluation was complemented by tests in a compact, closed-cycle Hughes CO2 TEA laser operating at a pulse repetition rate of 100 Hz with a catalyst temperature of 75 to 95 C. The Pt/Ce/TiO2 catalyst was compatible with a C(13)O(16)2 gas fill.

SU-E-T-350: Verification of Gating Performance of a New Elekta Gating Solution: Response Kit and Catalyst System

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

Xie, X; Cao, D; Housley, D

2014-06-01

Purpose: In this work, we have tested the performance of new respiratory gating solutions for Elekta linacs. These solutions include the Response gating and the C-RAD Catalyst surface mapping system.Verification measurements have been performed for a series of clinical cases. We also examined the beam on latency of the system and its impact on delivery efficiency. Methods: To verify the benefits of tighter gating windows, a Quasar Respiratory Motion Platform was used. Its vertical-motion plate acted as a respiration surrogate and was tracked by the Catalyst system to generate gating signals. A MatriXX ion-chamber array was mounted on its longitudinal-movingmore » platform. Clinical plans are delivered to a stationary and moving Matrix array at 100%, 50% and 30% gating windows and gamma scores were calculated comparing moving delivery results to the stationary result. It is important to note that as one moves to tighter gating windows, the delivery efficiency will be impacted by the linac's beam-on latency. Using a specialized software package, we generated beam-on signals of lengths of 1000ms, 600ms, 450ms, 400ms, 350ms and 300ms. As the gating windows get tighter, one can expect to reach a point where the dose rate will fall to nearly zero, indicating that the gating window is close to beam-on latency. A clinically useful gating window needs to be significantly longer than the latency for the linac. Results: As expected, the use of tighter gating windows improved delivery accuracy. However, a lower limit of the gating window, largely defined by linac beam-on latency, exists at around 300ms. Conclusion: The Response gating kit, combined with the C-RAD Catalyst, provides an effective solution for respiratorygated treatment delivery. Careful patient selection, gating window design, even visual/audio coaching may be necessary to ensure both delivery quality and efficiency. This research project is funded by Elekta.« less

Influence of lanthanum on the surface structure and CO hydrogenation activity of supported cobalt catalysts

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

Ledford, J.S.; Houalla, M.; Proctor, A.

1989-09-07

X-ray photoelectron spectroscopy (ESCA or XPS), X-ray diffraction (XRD), Raman spectroscopy, H{sub 2} chemisorption, and gravimetric analysis have been used to characterize three series of La/Al{sub 3}O{sub 3} and CoLa/Al{sub 2}O{sub 3} catalysts. CoLa/Al{sub 2}O{sub 3} catalysts were prepared by two methods: impregnation of La first followed by Co (designated CoLay) and impregnation of Co first followed by La (designated LayCo). The information obtained from surface and bulk characterization has been compared with CO hydrogenation activity and selectivity of the supported Co/Al{sub 2}O{sub 3} catalysts. For CoLay catalysts with low La loadings (La/Al atomic ratio {le} 0.026), the presence ofmore » La had little effect on the structure or CO hydrogenation activity. However, the selectivity to higher hydrocarbons and olefinic products increased with increasing La content. For CoLay catalysts with higher La loadings, Co{sub 3}O{sub 4} is suppressed in favor of an amorphous dispersed La-Co mixed oxide. ESCA and H{sub 2} chemisorption indicated higher dispersion of the metallic cobalt phase for high La loadings. The turnover frequency (TOF) for CO hydrogenation decreased dramatically for high La loadings. This has been correlated to the decrease in the amount of Co{sub 3}O{sub 4} present in the La-rich catalysts. Catalysts prepared by reverse impregnation (LayCo) showed little evidence of La-Co interaction. No significant variation in reducibility or cobalt metal dispersion was observed. Lanthanum addition had little effect on the TOF for CO hydrogenation or the selectivity to olefinic products and higher hydrocarbons.« 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.

Nitrogen-doped Carbon Derived from ZIF-8 as a High-performance Metal-free Catalyst for Acetylene Hydrochlorination

NASA Astrophysics Data System (ADS)

Chao, Songlin; Zou, Fang; Wan, Fanfan; Dong, Xiaobin; Wang, Yanlin; Wang, Yuxuan; Guan, Qingxin; Wang, Guichang; Li, Wei

2017-01-01

Acetylene hydrochlorination is a major industrial technology for manufacturing vinyl chloride monomer in regions with abundant coal resources; however, it is plagued by the use of mercury(II) chloride catalyst. The development of a nonmercury catalyst has been extensively explored. Herein, we report a N-doped carbon catalyst derived from ZIF-8 with both high activity and quite good stability. The acetylene conversion reached 92% and decreased slightly during a 200 h test at 220 °C and atmospheric pressure. Experimental studies and theoretical calculations indicate that C atoms adjacent to the pyridinic N are the active sites, and coke deposition covering pyridinic N is the main reason for catalyst deactivation. The performance of those N-doped carbons makes it possible for practical applications with further effort. Furthermore, the result also provides guidance for designing metal-free catalysts for similar reactions.

Nano-structured noble metal catalysts based on hexametallate architecture for the reforming of hydrocarbon fuels

DOEpatents

Gardner, Todd H.

2015-09-15

Nano-structured noble metal catalysts based on hexametallate lattices, of a spinel block type, and which are resistant to carbon deposition and metal sulfide formation are provided. The catalysts are designed for the reforming of hydrocarbon fuels to synthesis gas. The hexametallate lattices are doped with noble metals (Au, Pt, Rh, Ru) which are atomically dispersed as isolated sites throughout the lattice and take the place of hexametallate metal ions such as Cr, Ga, In, and/or Nb. Mirror cations in the crystal lattice are selected from alkali metals, alkaline earth metals, and the lanthanide metals, so as to reduce the acidity of the catalyst crystal lattice and enhance the desorption of carbon deposit forming moieties such as aromatics. The catalysts can be used at temperatures as high as 1000.degree. C. and pressures up to 30 atmospheres. A method for producing these catalysts and applications of their use also is provided.

Aromatics and phenols from catalytic pyrolysis of Douglas fir pellets in microwave with ZSM-5 as a catalyst

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

Wang, Lu; Lei, Hanwu; Ren, Shoujie

Microwave assisted catalytic pyrolysis was investigated to convert Douglas fir pellets to bio-oils by a ZSM-5 Zeolite catalyst. A central composite experimental design (CCD) was used to optimize the catalytic pyrolysis process. The effects of reaction time, temperature and catalyst to biomass ratio on the bio-oil, syngas, and biochar yields were determined. GC/MS analysis results showed that the bio-oil contained a series of important and useful chemical compounds. Phenols, guaiacols, and aromatic hydrocarbons were the most abundant compounds which were about 50-82 % in bio-oil depending on the pyrolysis conditions. Comparison between the bio-oils from microwave pyrolysis with and withoutmore » catalyst showed that the catalyst increased the content of aromatic hydrocarbons and phenols. A reaction pathway was proposed for microwave assisted catalyst pyrolysis of Douglas fir pellets.« less

Iron-catalyzed hydrogenation of bicarbonates and carbon dioxide to formates.

PubMed

Zhu, Fengxiang; Zhu-Ge, Ling; Yang, Guangfu; Zhou, Shaolin

2015-02-01

The catalytic hydrogenation of carbon dioxide and bicarbonate to formate has been explored extensively. The vast majority of the known active catalyst systems are based on precious metals. Herein, we describe an effective, phosphine-free, air- and moisture-tolerant catalyst system based on Knölker's iron complex for the hydrogenation of bicarbonate and carbon dioxide to formate. The catalyst system can hydrogenate bicarbonate at remarkably low hydrogen pressures (1-5 bar). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid

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

Jia, Qingying; Ramaswamy, Nagappan; Tylus, Urszula

Developing efficient and inexpensive catalysts for the sluggish oxygen reduction reaction (ORR) constitutes one of the grand challenges in the fabrication of commercially viable fuel cell devices and metal–air batteries for future energy applications. Despite recent achievements in designing advanced Pt-based and Pt-free catalysts, current progress primarily involves an empirical approach of trial-and-error combination of precursors and synthesis conditions, which limits further progress. Rational design of catalyst materials requires proper understanding of the mechanistic origin of the ORR and the underlying surface properties under operating conditions that govern catalytic activity. Herein, several different groups of iron-based catalysts synthesized via differentmore » methods and/or precursors were systematically studied by combining multiple spectroscopic techniques under ex situ and in situ conditions in an effort to obtain a comprehensive understanding of the synthesis-products correlations, nature of active sites, and the reaction mechanisms. These catalysts include original macrocycles, macrocycle-pyrolyzed catalysts, and Fe-N–C catalysts synthesized from individual Fe, N, and C precursors including polymer-based catalysts, metal organic framework (MOF)-based catalysts, and sacrificial support method (SSM)-based catalysts. The latter group of catalysts is most promising as not only they exhibit exceptional ORR activity and/or durability, but also the final products are controllable. We show that the high activity observed for most pyrolyzed Fe-based catalysts can mainly be attributed to a single active site: non-planar Fe–N 4 moiety embedded in distorted carbon matrix characterized by a high potential for the Fe 2+/3+ redox transition in acidic electrolyte/environment. The high intrinsic ORR activity, or turnover frequency (TOF), of this site is shown to be accounted for by redox catalysis mechanism that highlights the dominant role of the site-blocking effect. Moreover, a highly active MOF-based catalyst without Fe–N moieties was developed, and the active sites were identified as nitrogen-doped carbon fibers with embedded iron particles that are not directly involved in the oxygen reduction pathway. The high ORR activity and durability of catalysts involving this second site, as demonstrated in fuel cell, are attributed to the high density of active sites and the elimination or reduction of Fenton-type processes. The latter are initiated by hydrogen peroxide but are known to be accelerated by iron ions exposed to the surface, resulting in the formation of damaging free-radicals.« less

System and method for controlling an engine based on ammonia storage in multiple selective catalytic reduction catalysts

DOEpatents

Sun, MIn; Perry, Kevin L.

2015-11-20

A system according to the principles of the present disclosure includes a storage estimation module and an air/fuel ratio control module. The storage estimation module estimates a first amount of ammonia stored in a first selective catalytic reduction (SCR) catalyst and estimates a second amount of ammonia stored in a second SCR catalyst. The air/fuel ratio control module controls an air/fuel ratio of an engine based on the first amount, the second amount, and a temperature of a substrate disposed in the second SCR catalyst.

Mechanism of Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation

PubMed Central

Hoover, Jessica M.; Ryland, Bradford L.; Stahl, Shannon S.

2013-01-01

Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)CuI/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV–visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) “catalyst oxidation” in which CuI and TEMPO–H are oxidized by O2 via a binuclear Cu2O2 intermediate and (2) “substrate oxidation” mediated by CuII and the nitroxyl radical of TEMPO via a CuII-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O2 is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols. PMID:23317450

Investigation of the Interaction between Nafion Ionomer and Surface Functionalized Carbon Black Using Both Ultrasmall Angle X-ray Scattering and Cryo-TEM

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

Yang, Fan; Xin, Le; Uzunoglu, Aytekin

In making a catalyst ink, the interaction between Nafion ionomer and catalyst support are the key factors that directly affect both ionic conductivity and electronic conductivity of the catalyst layer in a membrane electrode assembly (MEA). One of the major aims of this investigation is to understand the behavior of the catalyst support, Vulcan XC-72 (XC-72) aggregates, in the existence of the Nafion ionomer in a catalyst ink to fill the knowledge gap of the interaction of these components. The dispersion of catalyst ink not only depends on the solvent, but also depends on the interaction of Nafion and carbonmore » particles in the ink. The interaction of Nafion ionomer particles and XC-72 catalyst aggregates in liquid media was studied using ultra small angle x-ray scattering (USAXS) and cryogenic TEM techniques. Carbon black XC-72) and functionalized carbon black systems were introduced to study the interaction behaviors. A multiple curve fitting was used to extract the particle size and size distribution from scattering data. The results suggest that the particle size and size distribution of each system changed significantly in Nafion + XC-72 system, Nafion + NH2-XC72 system, and Nafion + SO3H-XC-72 system, which indicates that an interaction among these components (i.e. ionomer particles and XC-72 aggregates) exists. The cryogenic TEM, which allows for the observation the size of particles in a liquid, was used to validate the scattering results and shows excellent agreement.« less

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

Hoffman, A. S.; Debefve, L. M.; Gates, B. C., E-mail: bcgates@ucdavis.edu

X-ray absorption spectroscopy is an element-specific technique for probing the local atomic-scale environment around an absorber atom. It is widely used to investigate the structures of liquids and solids, being especially valuable for characterization of solid-supported catalysts. Reported cell designs are limited in capabilities—to fluorescence or transmission and to static or flowing atmospheres, or to vacuum. Our goal was to design a robust and widely applicable cell for catalyst characterizations under all these conditions—to allow tracking of changes during genesis and during operation, both under vacuum and in reactive atmospheres. Herein, we report the design of such a cell andmore » a demonstration of its operation both with a sample under dynamic vacuum and in the presence of gases flowing at temperatures up to 300 °C, showing data obtained with both fluorescence and transmission detection. The cell allows more flexibility in catalyst characterization than any reported.« less

Infrastructure sensing.

PubMed

Soga, Kenichi; Schooling, Jennifer

2016-08-06

Design, construction, maintenance and upgrading of civil engineering infrastructure requires fresh thinking to minimize use of materials, energy and labour. This can only be achieved by understanding the performance of the infrastructure, both during its construction and throughout its design life, through innovative monitoring. Advances in sensor systems offer intriguing possibilities to radically alter methods of condition assessment and monitoring of infrastructure. In this paper, it is hypothesized that the future of infrastructure relies on smarter information; the rich information obtained from embedded sensors within infrastructure will act as a catalyst for new design, construction, operation and maintenance processes for integrated infrastructure systems linked directly with user behaviour patterns. Some examples of emerging sensor technologies for infrastructure sensing are given. They include distributed fibre-optics sensors, computer vision, wireless sensor networks, low-power micro-electromechanical systems, energy harvesting and citizens as sensors.

Infrastructure sensing

PubMed Central

Soga, Kenichi; Schooling, Jennifer

2016-01-01

Design, construction, maintenance and upgrading of civil engineering infrastructure requires fresh thinking to minimize use of materials, energy and labour. This can only be achieved by understanding the performance of the infrastructure, both during its construction and throughout its design life, through innovative monitoring. Advances in sensor systems offer intriguing possibilities to radically alter methods of condition assessment and monitoring of infrastructure. In this paper, it is hypothesized that the future of infrastructure relies on smarter information; the rich information obtained from embedded sensors within infrastructure will act as a catalyst for new design, construction, operation and maintenance processes for integrated infrastructure systems linked directly with user behaviour patterns. Some examples of emerging sensor technologies for infrastructure sensing are given. They include distributed fibre-optics sensors, computer vision, wireless sensor networks, low-power micro-electromechanical systems, energy harvesting and citizens as sensors. PMID:27499845

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

PubMed

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

2017-12-13

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

The role of uranium-arene bonding in H2O reduction catalysis

NASA Astrophysics Data System (ADS)

Halter, Dominik P.; Heinemann, Frank W.; Maron, Laurent; Meyer, Karsten

2018-03-01

The reactivity of uranium compounds towards small molecules typically occurs through stoichiometric rather than catalytic processes. Examples of uranium catalysts reacting with water are particularly scarce, because stable uranyl groups form that preclude the recovery of the uranium compound. Recently, however, an arene-anchored, electron-rich uranium complex has been shown to facilitate the electrocatalytic formation of H2 from H2O. Here, we present the precise role of uranium-arene δ bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O to the trivalent uranium catalyst. Both aspects were explored by synthesizing mid- and high-valent uranium-oxo intermediates and by performing comparative studies with a structurally related complex that cannot engage in δ bonding. The redox activity of the arene anchor and a covalent δ-bonding interaction with the uranium ion during H2 formation were supported by density functional theory analysis. Detailed insight into this catalytic system may inspire the design of ligands for new uranium catalysts.

Anion exchange membrane fuel cells: Current status and remaining challenges

NASA Astrophysics Data System (ADS)

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; Bae, Chulsung; Yan, Yushan; Zelenay, Piotr; Kim, Yu Seung

2018-01-01

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. In this perspective article, we describe the current status of AEMFCs as having reached beginning of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. These perspectives may provide useful insights for the development of next-generation of AEMFCs.

Anion exchange membrane fuel cells: Current status and remaining challenges

DOE PAGES

Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; ...

2017-09-01

The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. Here in this perspective article, we describe the current status of AEMFCs as having reached beginningmore » of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. Finally, these perspectives may provide useful insights for the development of next-generation of AEMFCs.« less

Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil

NASA Astrophysics Data System (ADS)

Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

2013-10-01

Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2-rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr0.8Ru0.2O3, LaCr0.8Ru0.1Ni0.1O3, and LaCr0.8Ni0.2O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ~50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds.

Hollow fibers networked with perovskite nanoparticles for H2 production from heavy oil.

PubMed

Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

2013-10-09

Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2-rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr(0.8)Ru(0.2)O3, LaCr(0.8)Ru(0.1)Ni(0.1)O3, and LaCr(0.8)Ni(0.2)O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ≈50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds.

Liquid phase fluid dynamic (methanol) run in the LaPorte alternative fuels development unit

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

Bharat L. Bhatt

1997-05-01

A fluid dynamic study was successfully completed in a bubble column at DOE's Alternative Fuels Development Unit (AFDU) in LaPorte, Texas. Significant fluid dynamic information was gathered at pilot scale during three weeks of Liquid Phase Methanol (LPMEOJP) operations in June 1995. In addition to the usual nuclear density and temperature measurements, unique differential pressure data were collected using Sandia's high-speed data acquisition system to gain insight on flow regime characteristics and bubble size distribution. Statistical analysis of the fluctuations in the pressure data suggests that the column was being operated in the churn turbulent regime at most of themore » velocities considered. Dynamic gas disengagement experiments showed a different behavior than seen in low-pressure, cold-flow work. Operation with a superficial gas velocity of 1.2 ft/sec was achieved during this run, with stable fluid dynamics and catalyst performance. Improvements included for catalyst activation in the design of the Clean Coal III LPMEOH{trademark} plant at Kingsport, Tennessee, were also confirmed. In addition, an alternate catalyst was demonstrated for LPMEOH{trademark}.« less

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.

Fluidized Bed Sputtering for Particle and Powder Metallization

DTIC Science & Technology

2013-04-01

Introduction Small particles are often added to material systems to modify mechanical, dielectric, optical, or other properties . However, the particle...the poor mechanical properties of the wax degrade the bulk mechanical properties of the composite material . Thin metal coatings on the catalyst...to create precisely tailored optical properties . Alternating layers of ceramic and metal thin films can be designed to create optical filters that

Catalytic systems used for polymerization, biomass conversion, and enhancing diffusion

NASA Astrophysics Data System (ADS)

Pong, Frances

A significant amount of research has been dedicated towards the study and improvement of catalysts. A better understanding of how catalysts work can lead to developing more cost-efficient catalytic systems for a variety of applications. My research is focuses on catalytic systems used in three different fields, which are (i) organometallic polymerization catalysts, (ii) molecular motors and (iii) biomass conversion. Researchers have long studied and modified organometallic catalysts for use in the direct co- and homopolymerization of monomers with polar functional groups. The ability to add polar moieties to polymers, which can potentially yield materials with a wider range of physical properties, is highly desirable. In this study (i), a series of naphthoxyimine palladium(II) catalysts -- in which the naphthyl backbone had been functionalized with different moieties -- were synthesized and systematically studied to determine the ligand structure's impact on catalytic activity. The study showed that slight modifications of the naphthyl backbone led to significant changes in the polymer's molecular weight and polydispersity index. The catalysts were also displayed some ability to co-polymerize ethylene and functionalized norbornene. These positive results suggest that further exploration of naphthoxyimine palladium (II) catalysts may be fundamentally interesting. The effect of active, motile particles at the nanoscale has been vigorously researched during the past decade. By understanding how such active suspensions behave, researchers can gain new insights which can potentially provide new applications in many fields. Here (ii) the momentum transfer of active catalysts (Grubbs' 2nd generation catalyst with a hydrodynamic radius of 6A) to their immediate surroundings is observed in an organic suspension. This phenomenon, which has been coined "enhanced diffusion," has not been well studied at the angstrom scale until now. Diffusion-NMR spectroscopy surprisingly revealed that these angstrom sized catalysts nearly double the speed of diffusion of passive molecular tracers in their immediate surroundings. This result is particularly intriguing because in this size regime, the viscosity of the surroundings is expected to completely overcome the inertial forces of these catalysts. This study has prompted further diffusion-NMR studies of molecular catalysts and enzymes as molecular motors. Catalytic systems play a crucial role in the conversion of renewable biomasses into energy and useful materials. This field of research has become increasingly important and lucrative as fossil fuel sources continue to decline/destabilize in the face of increased worldwide demand for more resources. In this work (iii), the efficacy of a hydrogen-pressurized, biphasic catalytic system to convert linear sugar polyols to iodoalkanes was examined. These iodoalkanes can easily be converted to 1-alkenes which can then be used for the synthesis of low density polyethylene. The results indicated that the system products were relatively pure and that the catalytic layer had a degree of recyclability, hinting that such a system may be viable for industrial use.

Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

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

Klier, Kamil; Herman, Richard G

2005-11-30

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

Modeling Geometric Arrangements of TiO2-Based Catalyst Substrates and Isotropic Light Sources to Enhance the Efficiency of a Photocatalystic Oxidation (PCO) Reactor

NASA Technical Reports Server (NTRS)

Richards, Jeffrey T.; Levine, Lanfang H.; Husk, Geoffrey K.

2011-01-01

The closed confined environments of the ISS, as well as in future spacecraft for exploration beyond LEO, provide many challenges to crew health. One such challenge is the availability of a robust, energy efficient, and re-generable air revitalization system that controls trace volatile organic contaminants (VOCs) to levels below a specified spacecraft maximum allowable concentration (SMAC). Photocatalytic oxidation (PCO), which is capable of mineralizing VOCs at room temperature and of accommodating a high volumetric flow, is being evaluated as an alternative trace contaminant control technology. In an architecture of a combined air and water management system, placing a PCO unit before a condensing heat exchanger for humidity control will greatly reduce the organic load into the humidity condensate loop ofthe water processing assembly (WPA) thereby enhancing the life cycle economics ofthe WPA. This targeted application dictates a single pass efficiency of greater than 90% for polar VOCs. Although this target was met in laboratory bench-scaled reactors, no commercial or SBIR-developed prototype PCO units examined to date have achieved this goal. Furthermore, the formation of partial oxidation products (e.g., acetaldehyde) was not eliminated. It is known that single pass efficiency and partial oxidation are strongly dependent upon the contact time and catalyst illumination, hence the requirement for an efficient reactor design. The objective of this study is to maximize the apparent contact time and illuminated catalyst surface area at a given reactor volume and volumetric flow. In this study, a Ti02-based photocatalyst is assumed to be immobilized on porous substrate panels and illumination derived from linear isotropic light sources. Mathematical modeling using computational fluid dynamics (CFD) analyses were performed to investigate the effect of: 1) the geometry and configuration of catalyst-coated substrate panels, 2) porosity of the supporting substrate, and 3) varying the light source and spacing on contact time and illuminated catalyst area.

Development of HAN-based Liquid Propellant Thruster

NASA Astrophysics Data System (ADS)

Hisatsune, K.; Izumi, J.; Tsutaya, H.; Furukawa, K.

2004-10-01

Many of propellants that are applied to the conventional spacecraft propulsion system are toxic propellants. Because of its toxicity, considering the environmental pollution or safety on handling, it will be necessary to apply the "green" propellant to the spacecraft propulsion system. The purpose of this study is to apply HAN based liquid propellant (LP1846) to mono propellant thruster. Compared to the hydrazine that is used in conventional mono propellant thruster, HAN based propellant is not only lower toxic but also can obtain higher specific impulse. Moreover, HAN based propellant can be decomposed by the catalyst. It means there are the possibility of applying to the mono propellant thruster that can leads to the high reliability of the propulsion system.[1],[2] However, there are two technical subjects, to apply HAN based propellant to the mono propellant thruster. One is the high combustion temperature. The catalyst will be damaged under high temperature condition. The other is the low catalytic activity. It is the serious problem on application of HAN based propellant to the mono propellant thruster that is used for attitude control of spacecraft. To improve the catalytic activity of HAN based propellant, it is necessary to screen the best catalyst for HAN based propellant. The adsorption analysis is conducted by Monte Carlo Simulation to screen the catalyst metal for HAN and TEAN. The result of analysis shows the Iridium is the best catalyst metal for HAN and TEAN. Iridium is the catalyst metal that is used at conventional mono propellant thruster catalyst Shell405. Then, to confirm the result of analysis, the reaction test about catalyst is conducted. The result of this test is the same as the result of adsorption analysis. That means the adsorption analysis is effective in screening the catalyst metal. At the evaluating test, the various types of carrier of catalyst are also compared to Shell 405 to improve catalytic activity. The test result shows the inorganic porous media is superior to Shell405 in catalytic activity. Next, the catalyst life with HAN based propellant (LP1846) is evaluated. The Shell405 and inorganic porous media catalyst are compared at the life test. The test result shows the inorganic porous media catalyst is superior to Shell405 in catalyst life. In this paper, the detail of the result of adsorption analysis and evaluating test are reported.

Twenty kW fuel cell units of compact design. Part 4: Accompanying research and development

NASA Astrophysics Data System (ADS)

Mund, K.

1980-10-01

Models describing the electrochemical kinetics at porous H2 and O2 electrodes using Raney nickel and silver catalysts were developed and their parameters determined by means of stationary and impedance measurements. A correct description of the hydrogen electrode with a Raney nickel catalyst is shown to encompass proper consideration of both diffusion in the pore electrolyte and surface diffusion. Impedance measurements yield a surface diffusion coefficient of 10 sub-8 cm2 S sub-1. The addition of titanium to the catalyst results in decreased electrode polarization and higher stability. Highly active doped silver catalysts are shown to allow high current densities and diaphragm resistances as low as 3 ohm cm at the oxygen electrode. Service tests show adequate stability of the catalysts.

Solar Reforming of Carbon Dioxide to Produce Diesel Fuel

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

Dennis Schuetzle; Robert Schuetzle

2010-12-31

This project focused on the demonstration of an innovative technology, referred to as the Sunexus CO2 Solar Reformer, which utilizes waste CO2 as a feedstock for the efficient and economical production of synthetic diesel fuel using solar thermal energy as the primary energy input. The Sunexus technology employs a two stage process for the conversion of CO2 to diesel fuel. A solar reforming system, including a specially designed reactor and proprietary CO2 reforming catalyst, was developed and used to convert captured CO2 rich gas streams into syngas (primarily hydrogen and carbon monoxide) using concentrated solar energy at high conversion efficiencies.more » The second stage of the system (which has been demonstrated under other funding) involves the direct conversion of the syngas into synthetic diesel fuel using a proprietary catalyst (Terra) previously developed and validated by Pacific Renewable Fuels and Chemicals (PRFC). The overall system energy efficiency for conversion of CO2 to diesel fuel is 74%, due to the use of solar energy. The results herein describe modeling, design, construction, and testing of the Sunexus CO2 Solar Reformer. Extensive parametric testing of the solar reformer and candidate catalysts was conducted and chemical kinetic models were developed. Laboratory testing of the Solar Reformer was successfully completed using various gas mixtures, temperatures, and gas flow rates/space velocities to establish performance metrics which can be employed for the design of commercial plants. A variety of laboratory tests were conducted including dry reforming (CO2 and CH{sub 4}), combination dry/steam reforming (CO2, CH{sub 4} & H{sub 2}O), and tri-reforming (CO2, CH{sub 4}, H{sub 2}O & O{sub 2}). CH{sub 4} and CO2 conversions averaged 95-100% and 50-90% per reformer cycle, respectively, depending upon the temperatures and gas space velocities. No formation of carbon deposits (coking) on the catalyst was observed in any of these tests. A 16 ft. diameter, concentrating solar dish was modified to accommodate the Sunexus CO2 Solar Reformer and the integrated system was installed at the Pacific Renewable Fuels and Chemicals test site at McClellan, CA. Several test runs were conducted without catalyst during which the ceramic heat exchanger in the Sunexus Solar Reformer reached temperatures between 1,050 F (566 C) and 2,200 F (1,204 C) during the test period. A dry reforming mixture of CO2/CH{sub 4} (2.0/1.0 molar ratio) was chosen for all of the tests on the integrated solar dish/catalytic reformer during December 2010. Initial tests were carried out to determine heat transfer from the collimated solar beam to the catalytic reactor. The catalyst was operated successfully at a steady-state temperature of 1,125 F (607 C), which was sufficient to convert 35% of the 2/1 CO2/CH{sub 4} mixture to syngas. This conversion efficiency confirmed the results from laboratory testing of this catalyst which provided comparable syngas production efficiencies (40% at 1,200 F [650 C]) with a resulting syngas composition of 20% CO, 16% H{sub 2}, 39% CO2 and 25% CH{sub 4}. As based upon the laboratory results, it is predicted that 90% of the CO2 will be converted to syngas in the solar reformer at 1,440 F (782 C) resulting in a syngas composition of 50% CO: 43% H{sub 2}: 7% CO2: 0% CH{sub 4}. Laboratory tests show that the higher catalyst operating temperature of 1,440 F (782 C) for efficient conversion of CO2 can certainly be achieved by optimizing solar reactor heat transfer, which would result in the projected 90% CO2-to-syngas conversion efficiencies. Further testing will be carried out during 2011, through other funding support, to further optimize the solar dish CO2 reformer. Additional studies carried out in support of this project and described in this report include: (1) An Assessment of Potential Contaminants in Captured CO2 from Various Industrial Processes and Their Possible Effect on Sunexus CO2 Reforming Catalysts; (2) Recommended Measurement Methods for Assessing Contaminant Levels in Captured CO2 Streams; (3) An Assessment of Current Commercial Scale Fisher-Tropsch (F-T) Technologies for the Conversion of Syngas to Fuels; (4) An Overview of CO2 Capture Technologies from Various Industrial Sources; and (5) Lifecycle Analysis for the Capture and Conversion of CO2 to Synthetic Diesel Fuel. Commercial scale Sunexus CO2 Solar Reformer plant designs, proposed in this report, should be able to utilize waste CO2 from a wide variety of industrial sources to produce a directly usable synthetic diesel fuel that replaces petroleum derived fuel, thus improving the United States energy security while also sequestering CO2. Our material balance model shows that every 5.0 lbs of CO2 is transformed using solar energy into 6.26 lbs (1.0 U.S. gallon) of diesel fuel and into by-products, which includes water. Details are provided in the mass and energy model in this report.« less

Sustainable Applications of Magnetic Nano-catalysts and Graphitic Carbon Nitrides (presentation)

EPA Science Inventory

Homogeneous catalysts, known for chemo-, regio- and enantioselectivity, have better contact with the reactants but the catalyst separation creates barriers. Heterogeneous systems enable better separation although at the cost of reduction in the availability of active sites. Becau...

Cyclic alkyl amino carbene (CAAC) ruthenium complexes as remarkably active catalysts for ethenolysis

DOE PAGES

Marx, Vanessa M.; Sullivan, Alexandra H.; Melaimi, Mohand; ...

2014-12-17

In this paper, an expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100,000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340 000, at a catalyst loading of only 1 ppm. Finally, this is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, withmore » activities sufficient to render ethenolysis applicable to the industrial-scale production of linear α-olefins (LAOs) and other terminal-olefin products.« less

Catalyst, 2000-01.

ERIC Educational Resources Information Center

Ryan, Barbara E., Ed.

2001-01-01

"Catalyst" is a publication designed to assist higher education in developing alcohol and other drug prevention polices and programs that will foster students' academic and social development and promote campus and community safety. Issue 1 of volume 6 introduces a series of "Presidential Profiles" in which university presidents describe their…

The surface sulfur doping induced enhanced performance of cobalt catalysts in oxygen evolution reactions.

PubMed

Al-Mamun, Mohammad; Zhu, Zhengju; Yin, Huajie; Su, Xintai; Zhang, Haimin; Liu, Porun; Yang, Huagui; Wang, Dan; Tang, Zhiyong; Wang, Yun; Zhao, Huijun

2016-08-04

A novel surface sulfur (S) doped cobalt (Co) catalyst for the oxygen evolution reaction (OER) is theoretically designed through the optimisation of the electronic structure of highly reactive surface atoms which is also validated by electrocatalytic OER experiments.

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2013 CFR

2013-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device... regenerator under paragraph (b) of this section which commences construction, reconstruction, or modification...

40 CFR 60.100 - Applicability, designation of affected facility, and reconstruction.

Code of Federal Regulations, 2014 CFR

2014-07-01

... petroleum refineries: fluid catalytic cracking unit catalyst regenerators, fuel gas combustion devices, and... petroleum refinery. (b) Any fluid catalytic cracking unit catalyst regenerator or fuel gas combustion device... regenerator under paragraph (b) of this section which commences construction, reconstruction, or modification...

Asymmetric catalytic hydrogenation. Design of new Ru catalysts and chiral ligands: from laboratory to industrial applications.

PubMed

Genet, Jean-Pierre

2003-12-01

This Account covers the design of Ru catalysts and ligands. Two classes of chiral phosphine ligands are prepared: the electron-rich trans-2,4-substituted phosphetanes, readily available from optically pure 1,3-diol cyclic sulfates, and atropoisomeric ligands (SYNPHOS, MeO-NAPhePHOS, bearing heterotopic biaryl moieties, and a chiral water-soluble diguanidinium binaphthyl diphosphine, Digm-BINAP). Applications of these ligands to rhodium- and ruthenium-mediated hydrogenation of ketones and olefins have been reported with high enantioselectivities. The recognition abilities of Ru-SYNPHOS for a wide range of ketones is superior to those observed with BINAP, MeO-NAPhePHOS, and MeO-BIPHEP. Several biologically active compounds have been prepared through dynamic kinetic resolution. This work gives access to a number of highly active catalysts of the type [Ru(biphosphane)(H)(eta(6)-cot)]BF(4). These catalysts have demonstrated their utility in the enantioselective hydrogenation of the tetrasubstituted cyclopentenone "dehydrodione", which leads to the commercially important perfume component Paradisone (Firmenich).

Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit

DOE PAGES

Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; ...

2015-10-09

Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One definite approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum–copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C–C bond scission that leads to loss of selectivity and catalyst deactivation.more » γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

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

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

PubMed Central

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; Li, Jinyang; Schwab, Mark J.; Brudvig, Gary W.; Taylor, André D.

2016-01-01

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme's oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage. PMID:27759005

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

DOE PAGES

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; ...

2016-10-19

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Uniformity index measurement technology using thermocouples to improve performance in urea-selective catalytic reduction systems

NASA Astrophysics Data System (ADS)

Park, Sangki; Oh, Jungmo

2018-05-01

The current commonly used nitrogen oxides (NOx) emission reduction techniques employ hydrocarbons (HCs), urea solutions, and exhaust gas emissions as the reductants. Two of the primary denitrification NOx (DeNOx) catalyst systems are the HC-lean NOx trap (HC-LNT) catalyst and urea-selective catalytic reduction (urea-SCR) catalyst. The secondary injection method depends on the type of injector, injection pressure, atomization, and spraying technique. In addition, the catalyst reaction efficiency is directly affected by the distribution of injectors; hence, the uniformity index (UI) of the reductant is very important and is the basis for system optimization. The UI of the reductant is an indicator of the NOx conversion efficiency (NCE), and good UI values can reduce the need for a catalyst. Therefore, improving the UI can reduce the cost of producing a catalytic converter, which are expensive due to the high prices of the precious metals contained therein. Accordingly, measurement of the UI is an important process in the development of catalytic systems. Two of the commonly used methods for measuring the reductant UI are (i) measuring the exhaust emissions at many points located upstream/downstream of the catalytic converter and (ii) acquisition of a reductant distribution image on a section of the exhaust pipe upstream of the catalytic converter. The purpose of this study is to develop a system and measurement algorithms to measure the exothermic response distribution in the exhaust gas as the reductant passes through the catalytic converter of the SCR catalyst system using a set of thermocouples downstream of the SCR catalyst. The system is used to measure the reductant UI, which is applied in real-time to the actual SCR system, and the results are compared for various types of mixtures for various engine operating conditions and mixer types in terms of NCE.

Rapid Catalyst Screening by a Continuous-Flow Microreactor Interfaced with Ultra High Pressure Liquid Chromatography

PubMed Central

Fang, Hui; Xiao, Qing; Wu, Fanghui; Floreancig, Paul E.; Weber, Stephen G.

2010-01-01

A high-throughput screening system for homogeneous catalyst discovery has been developed by integrating a continuous-flow capillary-based microreactor with ultra-high pressure liquid chromatography (UHPLC) for fast online analysis. Reactions are conducted in distinct and stable zones in a flow stream that allows for time and temperature regulation. UHPLC detection at high temperature allows high throughput online determination of substrate, product, and byproduct concentrations. We evaluated the efficacies of a series of soluble acid catalysts for an intramolecular Friedel-Crafts addition into an acyliminium ion intermediate within one day and with minimal material investment. The effects of catalyst loading, reaction time, and reaction temperature were also screened. This system exhibited high reproducibility for high-throughput catalyst screening and allowed several acid catalysts for the reaction to be identified. Major side products from the reactions were determined through off-line mass spectrometric detection. Er(OTf)3, the catalyst that showed optimal efficiency in the screening, was shown to be effective at promoting the cyclization reaction on a preparative scale. PMID:20666502

Catalyst activity maintenance study for the liquid phase dimethyl ether process

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

Peng, X.D.; Toseland, B.A.; Underwood, R.P.

1995-12-31

The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizesmore » a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.« less

Catalyst Development for Hydrogen Peroxide Rocket Engines

NASA Technical Reports Server (NTRS)

Morlan, P. W.; Wu, P.-K.; Ruttle, D. W.; Fuller, R. P.; Nejad, A. S.; Anderson, W. E.

1999-01-01

The development of various catalysts of hydrogen peroxide was conducted for the applications of liquid rocket engines. The catalyst development includes silver screen technology, solid catalyst technology, and homogeneous catalyst technology. The silver screen technology development was performed with 85% (by weight) hydrogen peroxide. The results of this investigation were used as the basis for the catalyst design of a pressure-fed liquid-fueled upper stage engine. Both silver-plated nickel 200 screens and pure silver screens were used as the active metal catalyst during the investigation, The data indicate that a high decomposition efficiency (greater than 90%) of 85% hydrogen peroxide can be achieved at a bed loading of 0.5 lbm/sq in/sec with both pure silver and silver plated screens. Samarium oxide coating, however, was found to retard the decomposition process and the catalyst bed was flooded at lower bed loading. A throughput of 200 lbm of hydrogen peroxide (1000 second run time) was tested to evaluate the catalyst aging issue and performance degradation was observed starting at approximately 400 seconds. Catalyst beds of 3.5 inch in diameter was fabricated using the same configuration for a 1,000-lbf rocket engine. High decomposition efficiency was obtained with a low pressure drop across the bed. Solid catalyst using precious metal was also developed for the decomposition of hydrogen peroxide from 85% to 98% by weight. Preliminary results show that the catalyst has a strong reactivity even after 15 minutes of peroxide decomposition. The development effort also includes the homogeneous catalyst technology. Various non-toxic catalysts were evaluated with 98% peroxide and hydrocarbon fuels. The results of open cup drop tests indicate an ignition delay around 11 ms.

Visible light-driven water oxidation promoted by host-guest interaction between photosensitizer and catalyst with a high quantum efficiency.

PubMed

Li, Hua; Li, Fei; Zhang, Biaobiao; Zhou, Xu; Yu, Fengshou; Sun, Licheng

2015-04-08

A highly active supramolecular system for visible light-driven water oxidation was developed with cyclodextrin-modified ruthenium complex as the photosensitizer, phenyl-modified ruthenium complexes as the catalysts, and sodium persulfate as the sacrificial electron acceptor. The catalysts were found to form 1:1 host-guest adducts with the photosensitizer. Stopped-flow measurement revealed the host-guest interaction is essential to facilitate the electron transfer from catalyst to sensitizer. As a result, a remarkable quantum efficiency of 84% was determined under visible light irradiation in neutral aqueous phosphate buffer. This value is nearly 1 order of magnitude higher than that of noninteraction system, indicating that the noncovalent incorporation of sensitizer and catalyst is an appealing approach for efficient conversion of solar energy into fuels.

PCDD/F adsorption and destruction in the flue gas streams of MWI and MSP via Cu and Fe catalysts supported on carbon.

PubMed

Chang, Shu Hao; Yeh, Jhy Wei; Chein, Hung Min; Hsu, Li Yeh; Chi, Kai Hsien; Chang, Moo Been

2008-08-01

Catalytic destruction has been applied to control polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) emissions from different facilities. The cost of carbon-based catalysts is considerably lower than that of the metal oxide or zeolite-based catalysts used in the selective catalytic reduction (SCR) system. In this study, destruction and adsorption efficiencies of PCDD/Fs achieved with Cu/C and Fe/C catalysts from flue gas streams of a metal smelting plant (MSP) and a large-scale municipal waste incinerator (MWI), respectively, are evaluated via the pilot-scale catalytic reactor system (PCRS). The results indicate that Cu and Fe catalysts supported on carbon surface are capable of decomposing and adsorbing PCDD/ Fs from gas streams. In the testing sources of MSP and MWI, the PCDD/F removal efficiencies achieved with Cu/C catalyst at 250 degrees C reach 96%, however, the destruction efficiencies are negative (-1,390% and -112%, respectively) due to significant PCDD/F formation on catalyst promoted by copper. In addition, Fe/C catalyst is of higher removal and destruction efficiencies compared with Cu/C catalyst in both testing sources. The removal efficiencies of PCDD/Fs achieved with Fe/C catalyst are 97 and 94% for MSP and MWI, respectively, whereas the destruction efficiencies are both higher than 70%. Decrease of PCDD/F destruction efficiency and increase of adsorption efficiency with increasing chlorination of dioxin congeners is also observed in the test via three-layer Fe/C catalyst. Furthermore, the mass of 2,3,7,8-PCDD/Fs retained on catalyst decreases on the order of first to third layer of catalyst. Each gram Fe/C catalyst in first layer adsorbs 10.9, 6.91, and 3.04 ng 2,3,7,8-PCDD/Fs in 100 min testing duration as the operating temperature is controlled at 150, 200, and 250 degrees C, respectively.

Comparison of designed and randomly generated catalysts for simple chemical reactions.

PubMed

Kipnis, Yakov; Baker, David

2012-09-01

There has been recent success in designing enzymes for simple chemical reactions using a two-step protocol. In the first step, a geometric matching algorithm is used to identify naturally occurring protein scaffolds at which predefined idealized active sites can be realized. In the second step, the residues surrounding the transition state model are optimized to increase transition state binding affinity and to bolster the primary catalytic side chains. To improve the design methodology, we investigated how the set of solutions identified by the design calculations relate to the overall set of solutions for two different chemical reactions. Using a TIM barrel scaffold in which catalytically active Kemp eliminase and retroaldolase designs were obtained previously, we carried out activity screens of random libraries made to be compositionally similar to active designs. A small number of active catalysts were found in screens of 10³ variants for each of the two reactions, which differ from the computational designs in that they reuse charged residues already present in the native scaffold. The results suggest that computational design considerably increases the frequency of catalyst generation for active sites involving newly introduced catalytic residues, highlighting the importance of interaction cooperativity in enzyme active sites. Copyright © 2012 The Protein Society.

Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction

PubMed Central

Siegel, Justin B.; Zanghellini, Alexandre; Lovick, Helena M.; Kiss, Gert; Lambert, Abigail R.; St.Clair, Jennifer L.; Gallaher, Jasmine L.; Hilvert, Donald; Gelb, Michael H.; Stoddard, Barry L.; Houk, Kendall N.; Michael, Forrest E.; Baker, David

2011-01-01

The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond forming reactions should be broadly useful in synthetic chemistry. PMID:20647463

Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction.

PubMed

Siegel, Justin B; Zanghellini, Alexandre; Lovick, Helena M; Kiss, Gert; Lambert, Abigail R; St Clair, Jennifer L; Gallaher, Jasmine L; Hilvert, Donald; Gelb, Michael H; Stoddard, Barry L; Houk, Kendall N; Michael, Forrest E; Baker, David

2010-07-16

The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond-forming reactions should be broadly useful in synthetic chemistry.

Steady state and transient simulation of anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Dekel, Dario R.; Rasin, Igal G.; Page, Miles; Brandon, Simon

2018-01-01

We present a new model for anion exchange membrane fuel cells. Validation against experimental polarization curve data is obtained for current densities ranging from zero to above 2 A cm-2. Experimental transient data is also successfully reproduced. The model is very flexible and can be used to explore the system's sensitivity to a wide range of material properties, cell design specifications, and operating parameters. We demonstrate the impact of gas inlet relative humidity (RH), operating current density, ionomer loading and ionomer ion exchange capacity (IEC) values on cell performance. In agreement with the literature, high air RH levels are shown to improve cell performance. At high current densities (>1 A cm-2) this effect is observed to be especially significant. Simulated hydration number distributions across the cell reveal the related critical dependence of cathode hydration on air RH and current density values. When exploring catalyst layer design, optimal intermediate ionomer loading values are demonstrated. The benefits of asymmetric (cathode versus anode) electrode design are revealed, showing enhanced performance using higher cathode IEC levels. Finally, electrochemical reaction profiles across the electrodes uncover inhomogeneous catalyst utilization. Specifically, at high current densities the cathodic reaction is confined to a narrow region near the membrane.

Process Upsets Involving Trace Contaminant Control Systems

NASA Technical Reports Server (NTRS)

Graf, John C.; Perry, Jay; Wright, John; Bahr, Jim

2000-01-01

Paradoxically, trace contaminant control systems that suffer unexpected upsets and malfunctions can release hazardous gaseous contaminants into a spacecraft cabin atmosphere causing potentially serious toxicological problems. Trace contaminant control systems designed for spaceflight typically employ a combination of adsorption beds and catalytic oxidation reactors to remove organic and inorganic trace contaminants from the cabin atmosphere. Interestingly, the same design features and attributes which make these systems so effective for purifying a spacecraft's atmosphere can also make them susceptible to system upsets. Cabin conditions can be contributing causes of phenomena such as adsorbent "rollover" and catalyst poisoning can alter a systems performance and in some in stances release contamination into the cabin. Evidence of these phenomena has been observed both in flight and during ground-based tests. The following discussion describes specific instances of system upsets found in trace contaminant control systems, groups these specific upsets into general hazard classifications, and recommends ways to minimize these hazards.

Formic acid decomposition on Pt1/Cu (111) single platinum atom catalyst: Insights from DFT calculations and energetic span model analysis

NASA Astrophysics Data System (ADS)

Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang

2018-04-01

Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.

Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

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

El-Sawy, Abdelhamid M.; Mosa, Islam M.; Su, Dong

Controlling active sites of metal-free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). We made many attempts have been made to develop metal-free catalysts, but the lack of understanding of active-sites at the atomic-level has slowed the design of highly active and stable metal-free catalysts. We also developed a sequential two-step strategy to dope sulfur into carbon nanotube–graphene nanolobes. This bidoping strategy introduces stable sulfur–carbon active-sites. Fluorescence emission of the sulfur K-edge by X-ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) mapping and spectra confirm thatmore » increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm -2, but also retains 100% of stability after 75 h. Furthermore, the bidoped sulfur carbon nanotube–graphene nanolobes behave like the state-of-the-art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm -2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light-weight bidoped sulfur carbon nanotubes are potential candidates for next-generation metal-free regenerative fuel cells.« less

Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

DOE PAGES

El-Sawy, Abdelhamid M.; Mosa, Islam M.; Su, Dong; ...

2015-12-03

Controlling active sites of metal-free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). We made many attempts have been made to develop metal-free catalysts, but the lack of understanding of active-sites at the atomic-level has slowed the design of highly active and stable metal-free catalysts. We also developed a sequential two-step strategy to dope sulfur into carbon nanotube–graphene nanolobes. This bidoping strategy introduces stable sulfur–carbon active-sites. Fluorescence emission of the sulfur K-edge by X-ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) mapping and spectra confirm thatmore » increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm -2, but also retains 100% of stability after 75 h. Furthermore, the bidoped sulfur carbon nanotube–graphene nanolobes behave like the state-of-the-art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm -2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light-weight bidoped sulfur carbon nanotubes are potential candidates for next-generation metal-free regenerative fuel cells.« less

Experimental investigation of the catalytic decomposition and combustion characteristics of a non-toxic ammonium dinitramide (ADN)-based monopropellant thruster

NASA Astrophysics Data System (ADS)

Chen, Jun; Li, Guoxiu; Zhang, Tao; Wang, Meng; Yu, Yusong

2016-12-01

Low toxicity ammonium dinitramide (ADN)-based aerospace propulsion systems currently show promise with regard to applications such as controlling satellite attitude. In the present work, the decomposition and combustion processes of an ADN-based monopropellant thruster were systematically studied, using a thermally stable catalyst to promote the decomposition reaction. The performance of the ADN propulsion system was investigated using a ground test system under vacuum, and the physical properties of the ADN-based propellant were also examined. Using this system, the effects of the preheating temperature and feed pressure on the combustion characteristics and thruster performance during steady state operation were observed. The results indicate that the propellant and catalyst employed during this work, as well as the design and manufacture of the thruster, met performance requirements. Moreover, the 1 N ADN thruster generated a specific impulse of 223 s, demonstrating the efficacy of the new catalyst. The thruster operational parameters (specifically, the preheating temperature and feed pressure) were found to have a significant effect on the decomposition and combustion processes within the thruster, and the performance of the thruster was demonstrated to improve at higher feed pressures and elevated preheating temperatures. A lower temperature of 140 °C was determined to activate the catalytic decomposition and combustion processes more effectively compared with the results obtained using other conditions. The data obtained in this study should be beneficial to future systematic and in-depth investigations of the combustion mechanism and characteristics within an ADN thruster.

Development of Augmented Spark Impinging Igniter System for Methane Engines

NASA Technical Reports Server (NTRS)

Marshall, William M.; Osborne, Robin J.; Greene, Sandra E.

2017-01-01

The Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) program is establishing multiple no-funds-exchanged Space Act Agreement (SAA) partnerships with U.S. private sector entities. The purpose of this program is to encourage the development of robotic lunar landers that can be integrated with U.S. commercial launch capabilities to deliver payloads to the lunar surface. NASA can share technology and expertise under the SAA for the benefit of the CATALYST partners. MSFC seeking to vacuum test Augmented Spark Impinging (ASI) igniter with methane and new exciter units to support CATALYST partners and NASA programs. ASI has previously been used/tested successfully at sea-level, with both O2/CH4 and O2/H2 propellants. Conventional ignition exciter systems historically experienced corona discharge issues in vacuum. Often utilized purging or atmospheric sealing on high voltage lead to remedy. Compact systems developed since PCAD could eliminate the high-voltage lead and directly couple the exciter to the spark igniter. MSFC developed Augmented Spark Impinging (ASI) igniter. Successfully used in several sea-level test programs. Plasma-assisted design. Portion of ox flow is used to generate hot plasma. Impinging flows downstream of plasma. Additional fuel flow down torch tube sleeve for cooling near stoichiometric torch flame. Testing done at NASA GRC Altitude Combustion Stand (ACS) facility 2000-lbf class facility with altitude simulation up to around 100,000 ft. (0.2 psia [10 Torr]) via nitrogen driven ejectors. Propellant conditioning systems can provide temperature control of LOX/CH4 up to test article.

Design and development of the Waukesha Custom Engine Control Air/Fuel Module

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

Moss, D.W.

1996-12-31

The Waukesha Custom Engine Control Air/Fuel Module (AFM) is designed to control the air-fuel ratio for all Waukesha carbureted, gaseous fueled, industrial engine. The AFM is programmed with a personal computer to run in one of four control modes: catalyst, best power, best economy, or lean-burn. One system can control naturally aspirated, turbocharged, in-line or vee engines. The basic system consists of an oxygen sensing system, intake manifold pressure transducer, electronic control module, actuator and exhaust thermocouple. The system permits correct operation of Waukesha engines in spite of changes in fuel pressure or temperature, engine load or speed, and fuelmore » composition. The system utilizes closed loop control and is centered about oxygen sensing technology. An innovative approach to applying oxygen sensors to industrial engines provides very good performance, greatly prolongs sensor life, and maintains sensor accuracy. Design considerations and operating results are given for application of the system to stationary, industrial engines operating on fuel gases of greatly varying composition.« less

Nanoscale Catalysts for NMR Signal Enhancement by Reversible Exchange

PubMed Central

2015-01-01

Two types of nanoscale catalysts were created to explore NMR signal enhancement via reversible exchange (SABRE) at the interface between heterogeneous and homogeneous conditions. Nanoparticle and polymer comb variants were synthesized by covalently tethering Ir-based organometallic catalysts to support materials composed of TiO2/PMAA (poly(methacrylic acid)) and PVP (polyvinylpyridine), respectively, and characterized by AAS, NMR, and DLS. Following parahydrogen (pH2) gas delivery to mixtures containing one type of “nano-SABRE” catalyst particle, a target substrate, and ethanol, up to ∼(−)40-fold and ∼(−)7-fold 1H NMR signal enhancements were observed for pyridine substrates using the nanoparticle and polymer comb catalysts, respectively, following transfer to high field (9.4 T). These enhancements appear to result from intact particles and not from any catalyst molecules leaching from their supports; unlike the case with homogeneous SABRE catalysts, high-field (in situ) SABRE effects were generally not observed with the nanoscale catalysts. The potential for separation and reuse of such catalyst particles is also demonstrated. Taken together, these results support the potential utility of rational design at molecular, mesoscopic, and macroscopic/engineering levels for improving SABRE and HET-SABRE (heterogeneous-SABRE) for applications varying from fundamental studies of catalysis to biomedical imaging. PMID:26185545

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.

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

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

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

Andersen, T.; Jensen, R.; Christensen, M. K.

2012-07-15

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/{Delta}m > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detectionmore » by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH{sub 3}.« less

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

NASA Astrophysics Data System (ADS)

Andersen, T.; Jensen, R.; Christensen, M. K.; Pedersen, T.; Hansen, O.; Chorkendorff, I.

2012-07-01

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/Δm > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detection by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH3.

Rhodium-Coordinated Poly(arylene-ethynylene)-alt-Poly(arylene-vinylene) Copolymer Acting as Photocatalyst for Visible-Light-Powered NAD+/NADH Reduction

PubMed Central

2014-01-01

A 2,2′-bipyridyl-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) polymer, acting as a light-harvesting ligand system, was synthesized and coupled to an organometallic rhodium complex designed for photocatalytic NAD+/NADH reduction. The material, which absorbs over a wide spectral range, was characterized by using various analytical techniques, confirming its chemical structure and properties. The dielectric function of the material was determined from spectroscopic ellipsometry measurements. Photocatalytic reduction of nucleotide redox cofactors under visible light irradiation (390–650 nm) was performed and is discussed in detail. The new metal-containing polymer can be used to cover large surface areas (e.g. glass beads) and, due to this immobilization step, can be easily separated from the reaction solution after photolysis. Because of its high stability, the polymer-based catalyst system can be repeatedly used under different reaction conditions for (photo)chemical reduction of NAD+. With this concept, enzymatic, photo-biocatalytic systems for solar energy conversion can be facilitated, and the precious metal catalyst can be recycled. PMID:25130570

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors.

PubMed

Andersen, T; Jensen, R; Christensen, M K; Pedersen, T; Hansen, O; Chorkendorff, I

2012-07-01

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m/Δm > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detection by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH(3).

Highly efficient temperature-induced visible light photocatalytic hydrogen production

NASA Astrophysics Data System (ADS)

Han, Bing

Photocatalysis is the acceleration of photoreaction in presence of a photocatalyst. Semiconductor photocatalysis has obtained much attention as a potential solution to the worldwide energy storage due to its promising ability to directly convert solar energy into chemical fuels. This dissertation research mainly employ three approaches to enhance photocatalytic activities, which includes (I) Modifying semiconductor nanomaterials for visible and near-IR light absorption; (II) Synthesis of light-diffuse-reflection-surface of SiO2 substrate to utilize scattered light; and (III) design of a hybrid system that combines light and heat to enhance visible light photocatalytic activity. Those approaches were applied to two systems: (1) hydrogen production from water; (2) carbon dioxide reforming of methane. The activity of noble metals such as platinum were investigated as co-catalysts and cheap earth abundant catalysts as alternatives to reduce cost were also developed. Stability, selectivity, mechanism were investigated. Great enhancement of visible light activity over a series of semiconductors/heterostructures were observed. Such extraordinary performance of artificial photosynthetic hydrogen production system would provide a novel approach for the utilization of solar energy for chemical fuel production.

Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

NASA Astrophysics Data System (ADS)

Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

2018-01-01

A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.

New insides in the characterization of HDS industrial catalysts by HAADF-STEM

NASA Astrophysics Data System (ADS)

Del Angel, Paz; Ponce, Arturo; Arellano, Josefina; Yacaman, Miguel J.; Hernandez-Pichardo, Martha; Montoya, J. Ascencion; Escobar, Jose

2015-03-01

Hydrodesulfurization (HDS) catalysts are of great importance in the petroleum industry. Transition metal sulphides catalysts of Ni(Co)Mo(W)/Al2O3 are widely used for hydrotreating reactions, like hydrodenitrogenation and HDS. One of the main issue in these catalysts is to understand the mechanism of the reaction, where MoS2 plays the most important role in the catalytic activity. We studied an industrial NiMo/Alumina sulfide catalyst highly active by using aberration-corrected HAADF-STEM techniques. The used catalysts was a state-of- the art commercial nickel-molybdenum alumina-supported formulation, including organic agent modifier. This type of material belongs to a novel family of catalysts specially designed for ultra-low sulfur production from straight-run gas oil (SRGO), cycle oil, coker gas oil, or their combinations at operating conditions of commercial interest in hydrotreating units at industrial scale. Aberration corrected HAADF-STEM allowed to observe the nanostructure and location of MoS2 and his interaction with the alumina. The results indicate that the MoS2 is highly dispersed on the alumina, however the location of Ni is one of the task of this kind of catalyst.

Interface dynamics and crystal phase switching in GaAs nanowires

NASA Astrophysics Data System (ADS)

Jacobsson, Daniel; Panciera, Federico; Tersoff, Jerry; Reuter, Mark C.; Lehmann, Sebastian; Hofmann, Stephan; Dick, Kimberly A.; Ross, Frances M.

2016-03-01

Controlled formation of non-equilibrium crystal structures is one of the most important challenges in crystal growth. Catalytically grown nanowires are ideal systems for studying the fundamental physics of phase selection, and could lead to new electronic applications based on the engineering of crystal phases. Here we image gallium arsenide (GaAs) nanowires during growth as they switch between phases as a result of varying growth conditions. We find clear differences between the growth dynamics of the phases, including differences in interface morphology, step flow and catalyst geometry. We explain these differences, and the phase selection, using a model that relates the catalyst volume, the contact angle at the trijunction (the point at which solid, liquid and vapour meet) and the nucleation site of each new layer of GaAs. This model allows us to predict the conditions under which each phase should be observed, and use these predictions to design GaAs heterostructures. These results could apply to phase selection in other nanowire systems.

Interface dynamics and crystal phase switching in GaAs nanowires.

PubMed

Jacobsson, Daniel; Panciera, Federico; Tersoff, Jerry; Reuter, Mark C; Lehmann, Sebastian; Hofmann, Stephan; Dick, Kimberly A; Ross, Frances M

2016-03-17

Controlled formation of non-equilibrium crystal structures is one of the most important challenges in crystal growth. Catalytically grown nanowires are ideal systems for studying the fundamental physics of phase selection, and could lead to new electronic applications based on the engineering of crystal phases. Here we image gallium arsenide (GaAs) nanowires during growth as they switch between phases as a result of varying growth conditions. We find clear differences between the growth dynamics of the phases, including differences in interface morphology, step flow and catalyst geometry. We explain these differences, and the phase selection, using a model that relates the catalyst volume, the contact angle at the trijunction (the point at which solid, liquid and vapour meet) and the nucleation site of each new layer of GaAs. This model allows us to predict the conditions under which each phase should be observed, and use these predictions to design GaAs heterostructures. These results could apply to phase selection in other nanowire systems.

Nano-sized layered Mn oxides as promising and biomimetic water oxidizing catalysts for water splitting in artificial photosynthetic systems.

PubMed

Najafpour, Mohammad Mahdi; Heidari, Sima; Amini, Emad; Khatamian, Masoumeh; Carpentier, Robert; Allakhverdiev, Suleyman I

2014-04-05

One challenge in artificial photosynthetic systems is the development of artificial model compounds to oxidize water. The water-oxidizing complex of Photosystem II which is responsible for biological water oxidation contains a cluster of four Mn ions bridged by five oxygen atoms. Layered Mn oxides as efficient, stable, low cost, environmentally friendly and easy to use, synthesize, and manufacture compounds could be considered as functional and structural models for the site. Because of the related structure of these Mn oxides and the catalytic centre of the active site of the water oxidizing complex of Photosystem II, the study of layered Mn oxides may also help to understand more about the mechanism of water oxidation by the natural site. This review provides an overview of the current status of layered Mn oxides in artificial photosynthesis and discuss the sophisticated design strategies for Mn oxides as water oxidizing catalysts. Copyright © 2014 Elsevier B.V. All rights reserved.