Crystal orientation dependent charge transfer dynamics and interfacial water configuration boosting photoelectrocatalytic water oxidation to H2O2

IF 10.3 4区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Yan Zhao , Zhenming Tian , Qisen Jia , Ting Yao , Jiashu Li , Yanan Wang , Xuejing Cui , Jing Liu , Xin Chen , Luhua Jiang
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Abstract

Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H2O2 is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO3 photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm−2 at 1.76 VRHE) and high selectivity to H2O2 (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO3-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO3-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO3-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H+, lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H2O2 is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO3-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.

Abstract Image

晶体取向依赖的电荷转移动力学和界面水结构促进光电催化水氧化成H2O2
光电化学水氧化反应(PEC-WOR)作为一种可持续的生产H2O2的途径是有吸引力的,但由于光生电荷效率有限和热力学不利,其活性低,产物选择性差。在这里,通过晶体取向工程,WO3光阳极暴露(200)面获得了优异的WOR活性(15.4 mA cm−2,1.76 VRHE)和对H2O2的高选择性(~ 70%)。综合实验和理论研究发现,WO3-(200)具有较高的PEC-WOR活性是由于在WO3-(200)面体和界面处光生电荷的快速分离/转移,从而降低了电荷转移阻力。这与operando PEC傅里叶变换红外光谱证明的WO3-(200)/电解质界面处独特的缺陷氢键网络相结合,促进了wor产生的H+向外转移,降低了PEC- wor的总体反应势垒。PEC-WOR对H2O2具有优异的选择性,这是由于其独特的缺陷氢键网络减轻了WO3-(200)面对∗OH的吸附,与4电子途径相比,这特别降低了2电子途径的能垒。本研究探讨了晶体取向工程对光电催化活性和选择性的重要作用,并通过了解光照下的水吸附行为揭示了光电催化的潜在机制。所获得的知识有望扩展到其他光电化学反应。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
结构化学
结构化学 化学-晶体学
CiteScore
4.70
自引率
22.70%
发文量
5334
审稿时长
13 days
期刊介绍: Chinese Journal of Structural Chemistry “JIEGOU HUAXUE ”, an academic journal consisting of reviews, articles, communications and notes, provides a forum for the reporting and discussion of current novel research achievements in the fields of structural chemistry, crystallography, spectroscopy, quantum chemistry, pharmaceutical chemistry, biochemistry, material science, etc. Structural Chemistry has been indexed by SCI, CA, and some other prestigious publications.
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