{"title":"Dual Effect of Oxygen Vacancy-Enriched TiO2 Interlayer in Si Photocathode for Enhanced Photoelectrochemical CO2 Reduction to HCOOH","authors":"Jinqi Xing, Junxia Shen, Zhihe Wei, Zhangyi Zheng, Ying Cao, Cong Chen, Pierre-Yves Olu, Wen Dong, Yang Peng, Mingrong Shen, Ronglei Fan","doi":"10.1002/smll.202502226","DOIUrl":null,"url":null,"abstract":"<p>Integrating nanostructured catalysts with semiconductors is a prevalent strategy for the design of photoelectrochemical (PEC) photocathodes toward CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR). However, it is still a challenge to achieve high efficiency and selectivity due to the incompatible catalyst/semiconductor heterogeneous interface. Here, it is proposed that engineering oxygen vacancy in the TiO<sub>2</sub> interlayer plays a multifunctional role in boosting the PEC activity and selectivity for the CO<sub>2</sub>RR on a Bi catalyst modified Si photocathode (denoted as Si/dT/Bi). It is discovered that oxygen vacancy in the TiO<sub>2</sub> interlayer accelerates the carrier transport. These oxygen vacancies also promote the growth of the Bi-based catalysts as sponge-like nanostructures during the photoelectro-deposition process. Numerous PEC experimental results combined with in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy reveal that these sponge-like Bi nano-catalysts on Si/dT/Bi photocathode provide a high density of active sites for CO<sub>2</sub> adsorption and promote the kinetics for HCOOH production by accelerating the formation of the key intermediate of *OCHO. This oxygen vacancy engineering in interlayer provides a unique route for future advancements in CO<sub>2</sub> reduction technologies.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":"21 15","pages":""},"PeriodicalIF":13.0000,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/smll.202502226","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Integrating nanostructured catalysts with semiconductors is a prevalent strategy for the design of photoelectrochemical (PEC) photocathodes toward CO2 reduction reaction (CO2RR). However, it is still a challenge to achieve high efficiency and selectivity due to the incompatible catalyst/semiconductor heterogeneous interface. Here, it is proposed that engineering oxygen vacancy in the TiO2 interlayer plays a multifunctional role in boosting the PEC activity and selectivity for the CO2RR on a Bi catalyst modified Si photocathode (denoted as Si/dT/Bi). It is discovered that oxygen vacancy in the TiO2 interlayer accelerates the carrier transport. These oxygen vacancies also promote the growth of the Bi-based catalysts as sponge-like nanostructures during the photoelectro-deposition process. Numerous PEC experimental results combined with in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy reveal that these sponge-like Bi nano-catalysts on Si/dT/Bi photocathode provide a high density of active sites for CO2 adsorption and promote the kinetics for HCOOH production by accelerating the formation of the key intermediate of *OCHO. This oxygen vacancy engineering in interlayer provides a unique route for future advancements in CO2 reduction technologies.
期刊介绍:
Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments.
With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology.
Small's readership includes biochemists, biologists, biomedical scientists, chemists, engineers, information technologists, materials scientists, physicists, and theoreticians alike.