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At least 19 records

In Situ/Operando Probing of Dynamic Phase Structures of Alumina‐Supported Ultrasmall Copper‐Gold Alloy Nanoparticles Under Reaction Conditions

Abstract The ability to control phase structures and surface sites of ultrasmall alloy nanoparticles under reaction conditions is essential for preparing catalysts by design. This is, however, challenging due to limited understanding of the atomic‐scale phases and their correlation with the ensemble‐averaged structures and activities of catalysts during catalytic reactions. We reveal here a dynamic structural stability of alumina‐supported ultrasmall and equiatomic copper‐gold alloy nanoparticles under reaction conditions as a model system in the in situ/operando study. In situ atomic‐scale morphological tracking under oxygen reveals temperature‐dependent dynamic crystalline‐amorphous dual‐phase structures, showing dynamic stability over an elevated temperature range. This atomic‐scale dynamic phase stability coincides with a “conversion plateau” observed for carbon monoxide oxidation on the catalyst. It is substantiated by the stable lattice ordering/disordering structures and surface sites with oscillatory characteristics shown by operando ensemble‐average structural tracking of the catalyst during the oxidation reaction. The understanding of the atomic‐scale dynamic phase structures in correlation with the ensemble‐average dynamic ordering/disordering phase structures and surface sites provides fresh insights into the unique synergy of the supported alloy nanoparticles. This understanding has implications for the design and structural tuning of active and stable ultrasmall alloy catalysts under elevated temperatures.

Chemistry

Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

Miller, R. O.

Development of gold alloy catalyst cathode for alkaline electrolyte fuel cells

A program for the development of improved catalyst and Teflon-bonded electrode structures using this improved catalyst is described, for use in fuel cell cathodes. It was found that Au-Pt was superior to the traditional platinum black as a catalyst. The impetus to the program was provided by the discovery that a life-limiting mechanism on the old catalyst was the gradual dissolution of platinum from the cathode and subsequent redeposition in the electrolyte-containing matrix.

Freed, M. S.

Polishing gold and gold-alloy crystals

Sawed cross-section samples are rough polished at minimum pressure with 14 micron grit. After saw marks are polished away, polishing grit is changed to 0.05 micron. When smooth appearance is attained, surface is then chemically polished by hand in dust free room.

Doty, J. P.

Measurements of thermoelectric power in annealed and quenched gold-platinum alloys

Report gives measurements of absolute thermoelectric powers of dilute gold-platinum alloys and influence of quenched-in lattice vacancies on their thermoelectric powers. It investigates phonon-drag component of thermoelectric power as a function of platinum concentration, and change in phonon-drag thermoelectric power by lattice vacancies.

Baarle, C. V.

Low gravity containerless processing of immiscible gold rhodium alloys

Under normal one-g conditions immiscible alloys segregate extensively during solidification due to sedementation of the more dense of the immiscible liquid phases. However, under low-g conditions it should be possible to form a dispersion of the two immiscible liquids and maintain this dispersed structure during solidification. Immiscible (hypermonotectic) gold-rhodium alloys were processed in the Marshall Space Flight Center 105 meter drop tube in order to investigate the influence of low gravity, containerless solidification on their microstructure. Hypermonotectic alloys composed of 65 atomic % rhodium exhibited a tendency for the gold rich liquid to wet the outer surface of the containerless processed samples. This tendency led to extensive segregation in several cases. However, well dispersed microstructures consisting of 2 to 3 micron diameter rhodium-rich spheres in a gold-rich matrix were produced in 23.4 atomic % rhodium alloys. This is one of the best dispersions obtained in research on immiscible alloy-systems to data.

Andrews, J. Barry

Alkaline fuel cell performance investigation

An exploratory experimental fuel cell test program was conducted to investigate the performance characteristics of alkaline laboratory research electrodes. The objective of this work was to establish the effect of temperature, pressure, and concentration upon performance and evaluate candidate cathode configurations having the potential for improved performance. The performance characterization tests provided data to empirically establish the effect of temperature, pressure, and concentration upon performance for cell temperatures up to 300 F and reactant pressures up to 200 psia. Evaluation of five gold alloy cathode catalysts revealed that three doped gold alloys had more that two times the surface areas of reference cathodes and therefore offered the best potential for improved performance.

Martin, R. E.

Alkaline fuel cell performance investigation

An exploratory experimental fuel cell test program was conducted to investigate the performance characteristics of alkaline laboratory research electrodes. The objective of this work was to establish the effect of temperature, pressure, and concentration upon performance and evaluate candidate cathode configurations having the potential for improved performance. The performance characterization tests provided data to empirically establish the effect of temperature, pressure, and concentration upon performance for cell temperatures up to 300 F and reactant pressures up to 200 psia. Evaluation of five gold alloy cathode catalysts revealed that three doped gold alloys had more than two times the surface areas of reference cathodes and therefore offered the best potential for improved performance.

Martin, R. E.

A reversible solvent segregation transition at grain boundaries in gold-platinum alloys

Solute segregation to grain boundaries in polycrystalline metals and ceramics is a well-known phenomenon that reduces the total energy of the material. In this letter, the segregation of the solvent (Au) to grain boundaries in a binary Au 1-x Pt x (x = 0.15 to 0.18) alloy is demonstrated. After heating in the range of 500 °C to 600 °C and quenching to room temperature, grain boundaries in the alloy are enriched in Au at a mean level of ∼ 4 atoms/nm 2 . When the alloy is annealed at 300 °C and quenched, the mean grain boundary composition is closer to the bulk composition. When the alloy is reheated to 500 °C, the segregation is reestablished, demonstrating that the transformation from the strongly segregated complexion to the weakly segregated complexion is reversible. The driving force for the solvent segregation is likely the lower grain boundary energy of Au in comparison to Pt.

36 MATERIALS SCIENCE