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Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid

Description: Single crystalline surface such as (100), (111), (110) has been studied as an idealized platform for electrocatalytic reactions since the atomic arrangement affects a catalytic property. The secondary metal deposition on these surfaces also alters the catalytic property often showing improvement such as poisoning decrease. On the other hand, electrocatalysts used for practical purpose usually have a size on the order of nanometers. Therefore, linking the knowledge from single crystalline studies to nanoparticle catalysts is of enormous importance. Recently, the Pt nanoparticles which surface structure was preferentially oriented was synthesized and used as electrocatalysts. Here, we demonstrate a rational design of a binary metallic nanocatalyst based on the single crystalline study.
Date: December 14, 2007
Creator: Lee, Hyunjoo; Habas, Susan; Somorjai, Gabor & Yang, Peidong
Partner: UNT Libraries Government Documents Department

Recent advances in the kinetics of oxygen reduction

Description: Oxygen reduction is considered an important electrocatalytic reaction; the most notable need remains improvement of the catalytic activity of existing metal electrocatalysts and development of new ones. A review is given of new advances in the understanding of reaction kinetics and improvements of the electrocatalytic properties of some surfaces, with focus on recent studies of relationship of the surface properties to its activity and reaction kinetics. The urgent need is to improve catalytic activity of Pt and synthesize new, possibly non- noble metal catalysts. New experimental techniques for obtaining new level of information include various {ital in situ} spectroscopies and scanning probes, some involving synchrotron radiation. 138 refs, 18 figs, 2 tabs.
Date: July 1, 1996
Creator: Adzic, R.
Partner: UNT Libraries Government Documents Department

Novel electrocatalytic sensors

Description: Basic principles employed for previously developed oxygen and SO{sub 2} sensors have been applied to other chemical sensor needs. Oxide electrodes used for oxygen sensors also possess novel catalytic properties that have been utilized for CO detection through the use of electrocatalysts on solid electrolyte membranes. These oxides offer the ability to catalyze reactions selectively for oxidation and/or reduction of analyte gas species. A combination of a catalytic and noncatalytic electrode deposited on a solid electrolyte was used to sense the reactive species by locally changing the oxygen concentration on the electrode surfaces. Multiple species can be sensed on a single substrate through the use of different electrocatalysts. A related concept is to control the catalytic properties of these materials by controlling the oxygen stoichiometry using an electrochemical pump. Presence of a gas species was sensed by changes in the electronic conductivity of the semiconducting electrode layer.
Date: November 1, 1996
Creator: Garzon, F. & Brosha, E.
Partner: UNT Libraries Government Documents Department

Florida Hydrogen Initiative

Description: The Florida Hydrogen Initiative (FHI) was a research, development and demonstration hydrogen and fuel cell program. The FHI program objectives were to develop Florida?s hydrogen and fuel cell infrastructure and to assist DOE in its hydrogen and fuel cell activities The FHI program funded 12 RD&D projects as follows: Hydrogen Refueling Infrastructure and Rental Car Strategies -- L. Lines, Rollins College This project analyzes strategies for Florida's early stage adaptation of hydrogen-powered public transportation. In particular, the report investigates urban and statewide network of refueling stations and the feasibility of establishing a hydrogen rental-car fleet based in Orlando. Methanol Fuel Cell Vehicle Charging Station at Florida Atlantic University ? M. Fuchs, EnerFuel, Inc. The project objectives were to design, and demonstrate a 10 kWnet proton exchange membrane fuel cell stationary power plant operating on methanol, to achieve an electrical energy efficiency of 32% and to demonstrate transient response time of less than 3 milliseconds. Assessment of Public Understanding of the Hydrogen Economy Through Science Center Exhibits, J. Newman, Orlando Science Center The project objective was to design and build an interactive Science Center exhibit called: ?H2Now: the Great Hydrogen Xchange?. On-site Reformation of Diesel Fuel for Hydrogen Fueling Station Applications ? A. Raissi, Florida Solar Energy Center This project developed an on-demand forecourt hydrogen production technology by catalytically converting high-sulfur hydrocarbon fuels to an essentially sulfur-free gas. The removal of sulfur from reformate is critical since most catalysts used for the steam reformation have limited sulfur tolerance. Chemochromic Hydrogen Leak Detectors for Safety Monitoring ? N. Mohajeri and N. Muradov, Florida Solar Energy Center This project developed and demonstrated a cost-effective and highly selective chemochromic (visual) hydrogen leak detector for safety monitoring at any facility engaged in transport, handling and use of hydrogen. Development of High Efficiency Low Cost Electrocatalysts ...
Date: June 30, 2013
Creator: Block, David L.
Partner: UNT Libraries Government Documents Department

Structure Effects on the Energetics of the Electrochemical Reduction of CO2 by Copper Surfaces

Description: Polycrystalline copper electrocatalysts have been experimentally shown to be capable of reducing CO{sub 2} into CH{sub 4} and C{sub 2}H{sub 4} with relatively high selectivity, and a mechanism has recently been proposed for this reduction on the fcc(211) surface of copper, which was assumed to be the most active facet. In the current work, we use computational methods to explore the effects of the nanostructure of the copper surface and compare the effects of the fcc(111), fcc(100) and fcc(211) facets of copper on the energetics of the electroreduction of CO{sub 2}. The calculations performed in this study generally show that the intermediates in CO{sub 2} reduction are most stabilized by the (211) facet, followed by the (100) facet, with the (111) surface binding the adsorbates most weakly. This leads to the prediction that the (211) facet is the most active surface among the three in producing CH{sub 4} from CO{sub 2}, as well as the by-products H{sub 2} and CO. HCOOH production may be mildly enhanced on the more close-packed surfaces ((111) and (100)) as compared to the (211) facet, due to a change in mechanism from a carboxyl intermediate to a formate intermediate. The results are compared to experimental data on these same surfaces; the predicted trends in voltage requirements are consistent between the experimental and computational data.
Date: August 19, 2011
Creator: Durand, William
Partner: UNT Libraries Government Documents Department

High Temperature Membrane & Advanced Cathode Catalyst Development

Description: Current project consisted of three main phases and eighteen milestones. Short description of each phase is given below. Table 1 lists program milestones. Phase 1--High Temperature Membrane and Advanced Catalyst Development. New polymers and advanced cathode catalysts were synthesized. The membranes and the catalysts were characterized and compared against specifications that are based on DOE program requirements. The best-in-class membranes and catalysts were downselected for phase 2. Phase 2--Catalyst Coated Membrane (CCM) Fabrication and Testing. Laboratory scale catalyst coated membranes (CCMs) were fabricated and tested using the down-selected membranes and catalysts. The catalysts and high temperature membrane CCMs were tested and optimized. Phase 3--Multi-cell stack fabrication. Full-size CCMs with the down-selected and optimized high temperature membrane and catalyst were fabricated. The catalyst membrane assemblies were tested in full size cells and multi-cell stack.
Date: April 20, 2006
Creator: Protsailo, Lesia
Partner: UNT Libraries Government Documents Department

Amperometric detection and electrochemical oxidation of aliphatic amines and ammonia on silver-lead oxide thin-film electrodes

Description: This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.
Date: January 8, 1996
Creator: Ge, Jisheng
Partner: UNT Libraries Government Documents Department

ELECTROCATALYSIS ON SURFACES MODIFIED BY METAL MONOLAYERS DEPOSITED AT UNDERPOTENTIALS.

Description: The remarkable catalytic properties of electrode surfaces modified by monolayer amounts of metal adatoms obtained by underpotential deposition (UPD) have been the subject of a large number of studies during the last couple of decades. This interest stems from the possibility of implementing strictly surface modifications of electrocatalysts in an elegant, well-controlled way, and these bi-metallic surfaces can serve as models for the design of new catalysts. In addition, some of these systems may have potential for practical applications. The UPD of metals, which in general involves the deposition of up to a monolayer of metal on a foreign substrate at potentials positive to the reversible thermodynamic potential, facilitates this type of surface modification, which can be performed repeatedly by potential control. Recent studies of these surfaces and their catalytic properties by new in situ surface structure sensitive techniques have greatly improved the understanding of these systems.
Date: December 2000
Creator: Adzic, R.
Partner: UNT Libraries Government Documents Department

ELECTROCATALYSIS ON SURFACES MODIFIED BY METAL MONOLAYERS DEPOSITED AT UNDERPOTENTIALS.

Description: The remarkable catalytic properties of electrode surfaces modified by monolayer amounts of metal adatoms obtained by underpotential deposition (UPD) have been the subject of a large number of studies during the last couple of decades. This interest stems from the possibility of implementing strictly surface modifications of electrocatalysts in an elegant, well-controlled way, and these bi-metallic surfaces can serve as models for the design of new catalysts. In addition, some of these systems may have potential for practical applications. The UPD of metals, which in general involves the deposition of up to a monolayer of metal on a foreign substrate at potentials positive to the reversible thermodynamic potential, facilitates this type of surface modification, which can be performed repeatedly by potential control. Recent studies of these surfaces and their catalytic properties by new in situ surface structure sensitive techniques have greatly improved the understanding of these systems.
Date: December 2000
Creator: Adzic, R.
Partner: UNT Libraries Government Documents Department

Cornell Fuel Cell Institute: Materials Discovery to Enable Fuel Cell Technologies

Description: The discovery and understanding of new, improved materials to advance fuel cell technology are the objectives of the Cornell Fuel Cell Institute (CFCI) research program. CFCI was initially formed in 2003. This report highlights the accomplishments from 2006-2009. Many of the grand challenges in energy science and technology are based on the need for materials with greatly improved or even revolutionary properties and performance. This is certainly true for fuel cells, which have the promise of being highly efficient in the conversion of chemical energy to electrical energy. Fuel cells offer the possibility of efficiencies perhaps up to 90 % based on the free energy of reaction. Here, the challenges are clearly in the materials used to construct the heart of the fuel cell: the membrane electrode assembly (MEA). The MEA consists of two electrodes separated by an ionically conducting membrane. Each electrode is a nanocomposite of electronically conducting catalyst support, ionic conductor and open porosity, that together form three percolation networks that must connect to each catalyst nanoparticle; otherwise the catalyst is inactive. This report highlights the findings of the three years completing the CFCI funding, and incudes developments in materials for electrocatalyts, catalyst supports, materials with structured and functional porosity for electrodes, and novel electrolyte membranes. The report also discusses developments at understanding electrocatalytic mechanisms, especially on novel catalyst surfaces, plus in situ characterization techniques and contributions from theory. Much of the research of the CFCI continues within the Energy Materials Center at Cornell (emc2), a DOE funded, Office of Science Energy Frontier Research Center (EFRC).
Date: June 29, 2012
Creator: Abruna, H.D. & DiSalvo, Francis J.
Partner: UNT Libraries Government Documents Department

Recent Advances in Developing Platinum Monolayer Electrocatalysts for the O2 Reduction Reaction

Description: For Pt, the best single-element catalyst for many reactions, the question of content and loading is exceedingly important because of its price and availability. Using platinum as a fuel-cell catalyst in automotive applications will cause an unquantifiable increase in the demand for this metal. This big obstacle for using fuel cells in electric cars must be solved by decreasing the content of Pt, which is a great challenge of electrocatalysis Over the last several years we inaugurated a new class of electrocatalysts for the oxygen reduction reaction (ORR) based on a monolayer of Pt deposited on metal or alloy carbon-supported nanoparticles. The possibility of decreasing the Pt content in the ORR catalysts down to a monolayer level has a considerable importance because this reaction requires high loadings due to its slow kinetics. The Pt-monolayer approach has several unique features and some of them are: high Pt utilization, enhanced (or decreased) activity, enhanced stability, and direct activity correlations. The synthesis of Pt monolayer (ML) electrocatalysts was facilitated by our new synthesis method which allowed us to deposit a monolayer of Pt on various metals, or alloy nanoparticles [1, 2] for the cathode electrocatalyst. In this synthesis approach Pt is laid down by the galvanically displacing a Cu monolayer, which was deposited at underpotentials in a monolayer-limited reaction on appropriate metal substrate, with Pt after immersing the electrode in a K{sub 2}PtCl{sub 4} solution.
Date: September 15, 2008
Creator: Vukmirovic,M.B.; Sasaki, K.; Zhou, W.-P.; Li, M.; Liu, P.; Wang, J.X. et al.
Partner: UNT Libraries Government Documents Department

PHOTOCHEMICAL CO2 REDUCTION BY RHENUIM AND RUTHENIUM COMPLEXES.

Description: Photochemical conversion of CO{sub 2} to fuels or useful chemicals using renewable solar energy is an attractive solution to both the world's need for fuels and the reduction of greenhouse gases. Rhenium(I) and ruthenium(II) diimine complexes have been shown to act as photocatalysts and/or electrocatalysts for CO{sub 2} reduction to CO. We have studied these photochemical systems focusing on the identification of intermediates and the bond formation/cleavage reactions between the metal center and CO{sub 2}. For example, we have produced the one-electron-reduced monomer (i.e. Re(dmb)(CO){sub 3}S where dmb = 4,4'-dimethy-2,2'-bipyridine and S = solvent) either by reductive quenching of the excited states of fac-[Re(dmb)(CO){sub 3}(CH{sub 3}CN)]PF{sub 6} or by photo-induced homolysis of [Re(dmb)(CO){sub 3}]{sub 2}. We previously found that: (1) the remarkably slow dimerization of Re(dmb)(CO){sub 3}S is due to the absence of a vacant coordination site for Re-Re bond formation, and the extra electron is located on the dmb ligand; (2) the reaction of Re(dmb)(CO){sub 3}S with CO{sub 2} forms a CO{sub 2}-bridged binuclear species (CO){sub 3}(dmb)Re-CO(O)-Re(dmb)(CO){sub 3} as an intermediate in CO formation; and (3) the kinetics and mechanism of reactions are consistent with the interaction of the CO{sub 2}-bridged binuclear species with CO{sub 2} to form CO and CO{sub 3}{sup 2-}.
Date: November 30, 2007
Creator: FUJITA,E.; MUCKERMAN, J.T. & TANAKA, K.
Partner: UNT Libraries Government Documents Department

Lattice-Strain Control of Exceptional Activity in Dealloyed Core-Shell Fuel Cell Catalysts

Description: We present a combined experimental and theoretical approach to demonstrate how lattice strain can be used to continuously tune the catalytic activity of the oxygen reduction reaction (ORR) on bimetallic nanoparticles that have been dealloyed. The sluggish kinetics of the ORR is a key barrier to the adaptation of fuel cells and currently limits their widespread use. Dealloyed Pt-Cu bimetallic nanoparticles, however, have been shown to exhibit uniquely high reactivity for this reaction. We first present evidence for the formation of a core-shell structure during dealloying, which involves removal of Cu from the surface and subsurface of the precursor nanoparticles. We then show that the resulting Pt-rich surface shell exhibits compressive strain that depends on the composition of the precursor alloy. We next demonstrate the existence of a downward shift of the Pt d-band, resulting in weakening of the bond strength of intermediate oxygenated species due to strain. Finally, we combine synthesis, strain, and catalytic reactivity in an experimental/theoretical reactivity-strain relationship which provides guidelines for the rational design of strained oxygen reduction electrocatalysts. The stoichiometry of the precursor, together with the dealloying conditions, provides experimental control over the resulting surface strain and thereby allows continuous tuning of the surface electrocatalytic reactivity - a concept that can be generalized to other catalytic reactions.
Date: August 19, 2011
Creator: Strasser, Peter
Partner: UNT Libraries Government Documents Department

Synthesis and Characterization of CO- and H2S-Tolerant Electrocatalysts for PEM Fuel Cell

Description: The present state-of-art Proton Exchange Membrane Fuel Cell (PEMFC) technology is based on platinum (Pt) as a catalyst for both the fuel (anode) and air (cathode) electrodes. This catalyst is highly active but susceptible to poisoning by CO, which may be present in the H{sub 2}-fuel used or may be introduced during the fuel processing. Presence of trace amount of CO and H{sub 2}S in the H{sub 2}-fuel poisons the anode irreversibly and decreases the performance of the PEMFCs. In an effort to reduce the Pt-loading and improve the PEMFC performance, we propose to synthesize a number of Pt-based binary, ternary, and quaternary electrocatalysts using Ru, Mo, Ir, Ni, and Co as a substitute for Pt. By fine-tuning the metal loadings and compositions of candidate electrocatalysts, we plan to minimize the cost and optimize the catalyst activity and performance in PEMFC. The feasibility of the novel electrocatalysts will be demonstrated in the proposed effort with gas phase CO and H{sub 2}S concentrations typical of those found in reformed fuel gas with coal/natural gas/methanol feedstocks. In this work binary, ternary, and quaternary platinum-based electrocatalysts were synthesized for the purpose of lowering the cost and increasing the CO tolerance of the membrane electrode assembly (MEA) in the fuel cell. The metals Ru, Mo, W, Ir, Co and Se were alloyed with platinum on a carbon support using a modified reduction method. These catalysts were fabricated into MEAs and evaluated for electrical performance and CO tolerance with polarization experiments. The quaternary system Pt/Ru/Mo/Ir system is the most CO tolerant in the PEMFC and has a low total metal loading of 0.4 mg/cm{sup 2} in the electrode of the cell.
Date: September 30, 2006
Creator: Ilias, Shamsuddin
Partner: UNT Libraries Government Documents Department

CATALYST EVALUATION FOR A SULFUR DIOXIDE-DEPOLARIZED ELECTROLYZER

Description: Thermochemical processes are being developed to provide global-scale quantities of hydrogen. A variant on sulfur-based thermochemical cycles is the Hybrid Sulfur (HyS) Process which uses a sulfur dioxide depolarized electrolyzer (SDE) to produce the hydrogen. Testing examined the activity and stability of platinum and palladium as the electrocatalyst for the SDE in sulfuric acid solutions. Cyclic and linear sweep voltammetry revealed that platinum provided better catalytic activity with much lower potentials and higher currents than palladium. Testing also showed that the catalyst activity is strongly influenced by the concentration of the sulfuric acid electrolyte.
Date: January 31, 2007
Creator: Hobbs, D & Hector Colon-Mercado, H
Partner: UNT Libraries Government Documents Department

New technology for America`s electric power industry. Electrocatalytic gas sensor employing cermet materials, AI analysis, and control methods

Description: Argonne National Laboratory`s cermat sensors use cyclic voltammetry techniques with solid electrolyte sensors to generate unique electrical signatures of gases or gas mixtures `on demand`. Intelligent (neural network) signal-processing algorithms match these signals to a gas library.
Date: March 1, 1995
Partner: UNT Libraries Government Documents Department

Micro fuel cell

Description: An ambient temperature, liquid feed, direct methanol fuel cell device is under development. A metal barrier layer was used to block methanol crossover from the anode to the cathode side while still allowing for the transport of protons from the anode to the cathode. A direct methanol fuel cell (DMFC) is an electrochemical engine that converts chemical energy into clean electrical power by the direct oxidation of methanol at the fuel cell anode. This direct use of a liquid fuel eliminates the need for a reformer to convert the fuel to hydrogen before it is fed into the fuel cell.
Date: December 31, 1998
Creator: Zook, L.A.; Vanderborgh, N.E. & Hockaday, R.
Partner: UNT Libraries Government Documents Department

Direct methanol fuel cells: Developments for portable power and for potential transportation applications

Description: The authors describe here results of recent efforts at Los Alamos National Laboratory (LANL), devoted to potential application of Direct Methanol Fuel Cells (DMFCs) as (1) portable power sources at the 50 W level, and (2) primary power sources for electric vehicles. In general, DMFC R and D efforts focus on further improvements in anode catalytic activity, fuel utilization (as related to methanol crossover) and air cathode performance in the presence of the presence of the significant flux of aqueous methanol from anode to cathode. There are significant differences between technical parameters and targets for the two different DMFC applications, which the authors have addressed. They include the lower cell temperature (about 60 C) preferred in portable power vs. operation around 100 C as target temperature for transportation applications, and the much stronger concern for cost of catalyst and any other stack materials in DMFCs developed for potential transportation applications. Most, if not all, recent DMFC work for either portable power or potential transportation applications has strongly focused on cells with polymeric (primarily PFSA) membrane electrolytes. In work at LANL, thin film catalysts bonded to the membrane, e.g., by the decal method, provided best results in terms of catalyst utilization and overall cell performance. In most tests, the single DMFC hardware consisted of uncatalyzed carbon-cloth gas-diffusion backings and graphite blocks with machined serpentine flow channels--quite similar to hardware employed in work with hydrogen/air PEFCs. However, the machined graphite hardware has recently been replaced by alternative, non-machined flow-field/bipolar plates, which enables effective air and aqueous methanol solution distribution along an active area of 50 cm{sup 2}, at a pitch per cell of 2 mm.
Date: December 31, 1998
Creator: Ren, X.; Thomas, S.C.; Zelenay, P. & Gottesfeld, S.
Partner: UNT Libraries Government Documents Department