Rate-Limiting O-O Bond Formation Pathways for Water Oxidation on Hematite Photoanode
文献类型：期刊论文
| 作者 | Zhang, Yuchao; Zhang, Hongna; Liu, Anan; Chen, Chuncheng; Song, Wenjing; Zhao, Jincai |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | MAR 7 2018 |
| 卷号 | 140期号:9页码:3264-3269 |
| 英文摘要 | Photoelectrochemical (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记录号 | WOS:000427203600019 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/38718]  |
| 专题 | 化学研究所_其它 |
| 推荐引用方式 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. |
入库方式： OAI收割
来源：化学研究所
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