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Rate-Limiting O-O Bond Formation Pathways for Water Oxidation on Hematite Photoanode
Zhang, Yuchao; Zhang, Hongna; Liu, Anan; Chen, Chuncheng; Song, Wenjing; Zhao, Jincai
MAR 7 2018
Source PublicationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume140Issue:9Pages:3264-3269
AbstractPhotoelectrochemical (PEC) water oxidation has attracted heightened interest in solar fuel production. It is well accepted that water oxidation on hematite is mediated by surface trapped holes, characterized to be the high valent -Fe=O species. However, the mechanism of the subsequent rate-limiting O-O bond formation step is still a missing piece. Herein we investigate the reaction order of interfacial hole transfer by rate law analysis based on electrochemical impedance spectroscopy (EIS) measurement and probe the reaction intermediates by operando Fourier-transform infrared (FTIR) spectroscopy. Distinct reaction orders of similar to 1 and similar to 2 were observed in near-neutral and highly alkaline environments, respectively. The unity rate law in near-neutral pH regions suggests a mechanism of water nucleophilic attack (WNA) to -Fe=O to form the O-O bond. Operando observation of a surface superoxide species that hydrogen bonded to the adjacent hydroxyl group by FT-IR further confirmed this pathway. In highly alkaline regions, coupling of adjacent surface trapped holes (I2M) becomes the dominant mechanism. While both are operable at intermediate pHs, mechanism switch from I2M to WNA induced by local pH decrease was observed at high photocurrent level. Our results highlight the significant impact of surface protonation on O-O bond formation pathways and oxygen evolution kinetics on hematite surfaces.
WOS IDWOS:000427203600019
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Cited Times:18[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/38718
Collection其它
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GB/T 7714
Zhang, Yuchao,Zhang, Hongna,Liu, Anan,et al. Rate-Limiting O-O Bond Formation Pathways for Water Oxidation on Hematite Photoanode[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,MAR ,140(9):3264-3269.
APA Zhang, Yuchao,Zhang, Hongna,Liu, Anan,Chen, Chuncheng,Song, Wenjing,&Zhao, Jincai.(MAR ).Rate-Limiting O-O Bond Formation Pathways for Water Oxidation on Hematite Photoanode.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,140(9),3264-3269.
MLA Zhang, Yuchao,et al."Rate-Limiting O-O Bond Formation Pathways for Water Oxidation on Hematite Photoanode".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 140.9(MAR ):3264-3269.
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