{"title":"The role of titanium at the interface of hematite photoanode in multisite mechanism: Reactive site or cocatalyst site?","authors":"","doi":"10.1016/S1872-2067(24)60093-8","DOIUrl":null,"url":null,"abstract":"<div><p>Hematite (α-Fe<sub>2</sub>O<sub>3</sub>) constitutes one of the most promising photoanode materials for oxygen evolution reaction (OER). Recent research on Fe<sub>2</sub>O<sub>3</sub> have found a fast OER rate dependence on surface hole density, suggesting a multisite reaction pathway. However, the effect of heteroatom in Fe<sub>2</sub>O<sub>3</sub> on the multisite mechanism is still poorly understood. Herein we synthesized Fe<sub>2</sub>O<sub>3</sub> on Ti substrates (Fe<sub>2</sub>O<sub>3</sub>/Ti) to study the oxygen intermediates of OER by light-dark electrochemical scans. We identified the Fe-OH species disappeared and Ti-OH intermediates appeared on Fe<sub>2</sub>O<sub>3</sub>/Ti when pH = 11−14, which significantly improved the OER performance of Fe<sub>2</sub>O<sub>3</sub>/Ti. Combined with the density functional theory calculations, we propose that Ti atom acts as cocatalyst site and captures proton from neighboring Fe-OH species under highly alkaline condition, thereby promoting the coupling of Fe=O and reducing the energy barrier of the non-electrochemical step. Our work provides a new insight into the role of heteroatom in OER multisite mechanism based on clarifying the reaction intermediates.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":15.7000,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1872206724600938","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
Abstract
Hematite (α-Fe2O3) constitutes one of the most promising photoanode materials for oxygen evolution reaction (OER). Recent research on Fe2O3 have found a fast OER rate dependence on surface hole density, suggesting a multisite reaction pathway. However, the effect of heteroatom in Fe2O3 on the multisite mechanism is still poorly understood. Herein we synthesized Fe2O3 on Ti substrates (Fe2O3/Ti) to study the oxygen intermediates of OER by light-dark electrochemical scans. We identified the Fe-OH species disappeared and Ti-OH intermediates appeared on Fe2O3/Ti when pH = 11−14, which significantly improved the OER performance of Fe2O3/Ti. Combined with the density functional theory calculations, we propose that Ti atom acts as cocatalyst site and captures proton from neighboring Fe-OH species under highly alkaline condition, thereby promoting the coupling of Fe=O and reducing the energy barrier of the non-electrochemical step. Our work provides a new insight into the role of heteroatom in OER multisite mechanism based on clarifying the reaction intermediates.
期刊介绍:
The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.