Structural and Electronic Effects of Carbon-Supported PtxPd1-x Nanoparticles on the Electrocatalytic Activity of the Oxygen-Reduction Reaction and on Methanol Tolerance

被引:37
作者
Chang, Shih-Hong [1 ]
Su, Wei-Nien [1 ]
Yeh, Min-Hsin [1 ]
Pan, Chun-Jern [1 ]
Yu, Kuan-Li [2 ]
Liu, Din-Goa [2 ]
Lee, Jyh-Fu [2 ]
Hwang, Bing-Joe [1 ,2 ]
机构
[1] Natl Taiwan Univ Sci & Technol, Dept Chem Engn, Taipei 10607, Taiwan
[2] Natl Synchrotron Radiat Res Ctr, Hsinchu 30076, Taiwan
关键词
fuel cells; nanoparticles; oxygen reduction reaction; palladium; platinum; PLATINUM-MONOLAYER ELECTROCATALYSTS; PARTICLE-SIZE; CATALYTIC-ACTIVITY; O-2; REDUCTION; FUEL-CELLS; D-BAND; RAY; PALLADIUM; ELECTROREDUCTION; ORIGIN;
D O I
10.1002/chem.201000458
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report a systematic investigation on the structural and electronic effects of carbon-supported PtxPd1-x bimetallic nanoparticles on the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in acid electrolyte. PtxPd1-x/C nanocatalysts with various Pt/Pd atomic ratios (x = 0.25, 0.5, and 0.75) were synthesized by using a borohydride-reduction method. Rotating-disk electrode measurements revealed that the Pt3Pd1/C nanocatalyst has a synergistic effect on the ORR, showing 50% enhancement, and an antagonistic effect on the MOR, showing 90% reduction, relative to JM 20 Pt/C on a mass basis. The extent of alloying and Pt d-band vacancies of the PtxPd1-x/C nanocatalysts were explored by extended X-ray absorption fine-structure spectroscopy (EXAFS) and X-ray absorption near-edge structure spectroscopy (XANES). The structure activity relationship indicates that ORR activity and methanol tolerance of the nanocatalysts strongly depend on their extent of alloying and d-band vacancies. The optimal composition for enhanced ORR activity is Pt3Pd1/C, with high extent of alloying and low Pt d-band vacancies, owing to favorable O-O scission and inhibited formation of oxygenated intermediates. MOR activity also shows structure dependence. For example, Pt1Pd3/C with Ptrich-corePdrich-shell structure process lower MOR activity than the Pt3Pd1/C nanocatalyst with random alloy structure. Herein, extent of alloying and d-band vacancies reveal new insights into the synergistic and antagonistic effects of the Pt(x)d(1-x)/C nanocatalysts on surface reactivity.
引用
收藏
页码:11064 / 11071
页数:8
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