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

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 36期

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

页码：11064 / 11071

页数：8

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