Mn3O4 Supported on Glassy Carbon: An Active Non-Precious Metal Catalyst for the Oxygen Reduction Reaction

被引:196
作者
Gorlin, Yelena [1 ]
Chung, Chia-Jung [2 ]
Nordlund, Dennis [3 ]
Clemens, Bruce M. [2 ]
Jaramillo, Thomas F. [1 ]
机构
[1] Stanford Univ, Dept Chem Engn, Stanford, CA 94305 USA
[2] Stanford Univ, Dept Mat Sci & Engn, Stanford, CA 94305 USA
[3] SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
来源
ACS CATALYSIS | 2012年 / 2卷 / 12期
基金
美国国家卫生研究院;
关键词
oxygen reduction reaction; manganese oxide; glassy carbon; X-ray absorption spectroscopy; nanoparticles; RAY-ABSORPTION SPECTROSCOPY; MANGANESE OXIDES; ALKALINE MEDIA; ELECTROCATALYTIC ACTIVITY; ELECTROCHEMICAL-BEHAVIOR; DIOXYGEN REDUCTION; ELECTRON-TRANSFER; WATER OXIDATION; AIR BATTERIES; SURFACE;
D O I
10.1021/cs3004352
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
In this work, we explore the interplay between manganese oxide (MnOx) nanomaterials and a glassy carbon (GC) support in catalyzing the oxygen reduction reaction (ORR) in an alkaline environment. Initially, we characterize the ORR activity of bare GC electrodes as a function of heat treatments in air, and find that ORR activity increases with increasing temperature up to 500 degrees C. Modification of GC with size-selected 1 nm MnOx nanoparticles prior to the 500 degrees C heat treatment yields a highly porous GC (pGC) structure, devoid of MnOx. This pGC sample exhibits the highest ORR performance of the bare carbon electrodes reaching an onset potential of 0.75 V vs the reversible hydrogen electrode (RHE) and a complete 2-electron reduction of oxygen to peroxide. Having established ORR activity of bare GC electrodes, we deposit size-selected 14 nm MnO nanoparticles onto the GC and pGC electrodes and then incite phase changes in MnO through heat treatments in air. Electrochemical characterization of the resulting electrodes reveals that MnO nanoparticles offer no improvement in the ORR onset potential over bare GC or pGC and only slightly increase the number of electrons transferred. By contrast, thermal oxidation of MnO nanoparticles to Mn3O4 at 500 degrees C, confirmed by Mn L-edge X-ray absorption spectroscopy, results in an improved ORR onset potential of 0.80 V and a 4-electron reduction of oxygen. Thus at low overpotentials, where GC and pGC were inactive for the ORR, MnOx sites must contribute to all steps of the reaction. The catalyst's estimated specific activity of 3700 mu A.cm(cat)(-2), at 0.75 V compares favorably with specific activities of Pt/C as well as the best nonprecious metal catalysts. This establishes Mn3O4 as another MnOx phase with high activity for the ORR.
引用
收藏
页码:2687 / 2694
页数:8
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