The impact of geometric and surface electronic properties of Pt-catalysts on the particle size effect in electocatalysis

被引:582
作者
Mayrhofer, KJJ [1 ]
Blizanac, BB [1 ]
Arenz, M [1 ]
Stamenkovic, VR [1 ]
Ross, PN [1 ]
Markovic, NM [1 ]
机构
[1] Lawrence Berkeley Lab, Div Mat Sci, Berkeley, CA 94720 USA
关键词
D O I
10.1021/jp051735z
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The particle size effect on the formation of OH adlayer, the CO bulk oxidation, and the oxygen reduction reaction (ORR) have been studied on Pt nanoparticles in perchloric acid electrolyte. From measurements of the CO displacement charge at controlled potential, the corresponding surface charge density versus potential curves yielded the potentials of total zero charge (pztc), which shifts approximately 35 mV negative by decreasing the particle size from 30 nm down to 1 nm. As a consequence, the energy of adsorption of OH is more enhanced, that is, at the same potential the surface coverage with OH increases by decreasing the particle size, which in turn affects the catalytic reactions thereon. The impact of the electronically induced potential shift in the OH adsorption is demonstrated at the CO bulk oxidation, in which adsorbed OH is an educt species and promotes the reaction, and the ORR, where it can act as a surface site blocking species and inhibits the reaction.
引用
收藏
页码:14433 / 14440
页数:8
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