Electrocatalytic Property of Facet-controlled Platinum Alloy Fuel Cell Catalysts PDF Download

Author: Jianbo Wu
Publisher:
ISBN:
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Languages : en
Pages : 217

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Book Description
"With rapid depletion of fossil fuel and the increasing concern over CO2 release, there is an urgent need to develop a new technology using alternative energy sources. Polymer electrolyte membrane fuel cell (PEMFC) is considered one of the promising technologies due to their high energy efficiency, and environmental friendliness. Platinum has been widely used as electrocatalyst in PEMFCs because of its ability to absorb and dissociate important chemical species, such as hydrogen and oxygen. The high cost of platinum used in the electrocatalysts however hinders the real world applications of PEMFCs. It is critical that consumption of platinum be reduced without sacrificing catalytic performance. Highly active and durable electrocatalysts with low Pt content need to be developed in order to advance the fuel cell technology. Studies have demonstrated that both d-band electron and surface geometric structure can greatly affect the activity of catalysts and be optimized by tailoring their composition and surface. In this thesis I present the synthesis, characterization and electrochemical property of facet-controlled platinum bimetallic alloy nanoparticles. A series of Pt-M (M= Co, Cu, Fe, Ni and Pd) bimetallic alloys with various shapes bounded with {111} or {100} facets have been prepared and their electrocatalytic properties have been tested. The surface-defined Pt3Ni nanocrystals have exhibited enhanced activity in oxygen reduction reaction (ORR), which is proportional to the surface ratio of {111} over {100} facets, when the shape of Pt3Ni nanocrystals changes gradually from cube to truncated octahedron, and to octahedron. Beyond the shape-controlled synthetic approach assisted by commonly used capping agents and reducing agents to produce bimetallic alloy nanocrystals with different compositions. CO, a gaseous reducing agent, was introduced to control the morphology of platinum alloys. Electrochemical stripping and Fourier transform infrared spectroscopy (FTIR) were used to show the strong facet-sensitive adsorption and oxidation play the key roles for the shape-controlled synthesis. This facet-preferential adsorption and oxidation property was also applied to address the issue on CO poisoning in methanol oxidation reaction (MOR). The size-dependent ORR catalytic properties of {111} surface-dominated octahedral Pt3Ni nanocrystals were examined in order to narrow the gap in ORR activity shown between the nanocrystal catalysts and extended single crystal surface of Pt3Ni alloys. The area-specific ORR activities of Pt3Ni catalysts at 0.9 V were 0.85 mA/cm2 Pt for the nanocubes, and 1.26 mA/cm2 Pt for the nanooctahedra. The ORR mass activity of the octahedral Pt3Ni catalyst reached 0.44 A/mg Pt. Pt-M (M = Au, Ni, Pd) alloy icosahedral nanocrystals was obtained based on CO assisted reduction methods. The area specific activity of icosahedral Pt3Ni catalysts (1.82 mA/cm2Pt) was about 50% higher than that of the octahedral (1.26 mA/cm2Pt), even though both shapes are bounded by {111} facets. Density functional theory (DFT) calculation and molecular dynamic simulation results showed that this improvement may come from strain-induced electronic effects. A quantitative surface segregation model on durability of bimetallic alloy ORR catalysts was established by studying the anisotropic diffusion coefficient, diffusion length and atomic size of non-platinum metals"--Pages v-vi.