Nonstoichiometric perovskite CaMnO3-δ for oxygen electrocatalysis with high activity

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Title:	Nonstoichiometric perovskite CaMnO3-δ for oxygen electrocatalysis with high activity
Authors:	鄭芳怡;Du, Jing;Zhang, Tianran;Cheng, Fangyi;Chu, Wangsheng;Wu, Ziyu;Chen, Jun
Contributors:	地球科學學院大氣科學學系
Date:	2014-09-02
Issue Date:	2026-04-21 13:57:29 (UTC+8)
Publisher:	American Chemical Society
Abstract:	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−δ (0 < δ ≤ 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−δ with δ 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−δ (δ ≈ 0.25) favored the OER because of the improved electrical conductivity. This study makes nonstoichiometric CaMnO3−δ a promising active, inexpensive bifunctional catalytic material for reversible ORR and OER. 其他題名： Inorg. Chem 出版者： American Chemical Society 出版日期： 2014-09-02 出處： Inorganic chemistry, 2014-09, Vol.53 (17), p.9106-9114 資源來源： American Chemical Society Journals 版權： Copyright © 2014 American Chemical Society 識別號： ISSN: 0020-1669 識別號： EISSN: 1520-510X 識別號： DOI: 10.1021/ic501631h
Appears in Collections:	[Department of Atmospheric Sciences] journal & Dissertation

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