Nonstoichiometric Perovskite CaMnO3-δ for Oxygen Electrocatalysis with High Activity

被引:211
作者
Du, Jing [1 ]
Zhang, Tianran [1 ]
Cheng, Fangyi [1 ]
Chu, Wangsheng [2 ]
Wu, Ziyu [2 ]
Chen, Jun [1 ]
机构
[1] Nankai Univ, Key Lab Adv Energy Mat Chem, Collaborat Innovat Ctr Chem Sci & Engn Tianjin, Minist Educ,Coll Chem, Tianjin 300071, Peoples R China
[2] Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Peoples R China
关键词
MANGANESE OXIDE NANOPARTICLES; REDUCTION REACTION ORR; WATER OXIDATION; AIR BATTERIES; EVOLUTION; CATALYST; MNO2; NANOSTRUCTURES; VACANCIES; MECHANISM;
D O I
10.1021/ic501631h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Perovskite oxides offer efficient and cheap electrocatalysts for both oxygen reduction reactions and oxygen evolution reactions (ORR/OER) in diverse oxygen-based electrochemical technologies. In this study, we report a facile strategy to enhance the electrocatalytic activity of CaMnO3 by introducing oxygen defects. The nonstoichiometric CaMnO3-delta (0 < delta <= 0.5) was prepared through thermal reduction of pristine perovskite microspheres and nanoparticles, which were synthesized from thermal-decomposition of carbonate precursors and the Pechini route, respectively. The as-prepared samples were analyzed by chemical titration, structural refinement, thermogravimetric analysis, and energy spectrometry. In 0.1 M KOH aqueous solution, the nonstoichiometric CaMnO3-delta with delta near 0.25 and an average Mn valence close to 3.5 exhibited the highest ORR activity (36.7 A g(-1) at 0.70 V vs RHE, with onset potential of 0.96 V), which is comparable to that of benchmark Pt/C. Density functional theory (DFT) studies and electrical conductivity measurement revealed that the enhanced ORR kinetics is due to facilitated oxygen activation and improved electrical properties. Besides high activity, the nonstoichiometric perovskite oxides showed respectable catalytic stability. Furthermore, the moderate oxygen-defective CaMnO3-delta (delta approximate to 0.25) favored the OER because of the improved electrical conductivity. This study makes nonstoichiometric CaMnO3-delta a promising active, inexpensive bifunctional catalytic material for reversible ORR and OER.
引用
收藏
页码:9106 / 9114
页数:9
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