Triggering Asymmetric Layer Displacement Polarization and Redox Dual-Sites Activation by Inside-Out Anion Substitution for Efficient CO2 Photoreduction
{"title":"Triggering Asymmetric Layer Displacement Polarization and Redox Dual-Sites Activation by Inside-Out Anion Substitution for Efficient CO2 Photoreduction","authors":"Yutang Yu, Zijian Zhu, Fang Chen, Tianyi Ma, Hongwei Huang","doi":"10.1002/adma.202413835","DOIUrl":null,"url":null,"abstract":"Sluggish bulk charge transfer and barren catalytic sites severely hinder the CO<sub>2</sub> photoreduction process. Seeking strategies for accelerating charge dynamics and activating reduction and oxidation sites synchronously presents a huge challenge. Herein, an inside-out chlorine (Cl) ions substitution strategy on the layered polar Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> is proposed for achieving layer structure-dependent polarization effect and redox dual-sites activation. Cl ions in the bulk phase shrink the halogen layer interspace by 8‰, triggering asymmetric [Bi<sub>4</sub>O<sub>5</sub>]<sup>2+</sup> layer displacement polarization, prolonging the average photocharge lifetime to 201.8 ps. Meanwhile, surface substituted Cl ions enhance the electron-donating capability of neighboring Bi atoms, activating the intrinsic Bi reduction sites, and increasing H<sub>2</sub>O molecule adsorption on nearby intrinsic O oxidation site (cal. by 0.105 eV), also self-donating as an alien oxidation site. Besides, Cl upshifts the p-band center closer to the Fermi level, facilitating the reactant adsorption. Therefore, the energy barrier for CO<sub>2</sub> activation and rate-limiting <sup>*</sup>COOH intermediate formation steps are significantly decreased. Without cocatalysts and sacrificial reagents, inside-out Cl-substituted Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> delivers a remarkable CO<sub>2</sub>-to-CO photoreduction rate of 50.18 µmol g<sup>−1</sup> h<sup>−1</sup>, being one of the state-of-the-art catalysts. This finding offers insights into exploiting polarization at the molecular-level and enhances understanding of catalytic site activation.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":null,"pages":null},"PeriodicalIF":27.4000,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/adma.202413835","RegionNum":1,"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
Sluggish bulk charge transfer and barren catalytic sites severely hinder the CO2 photoreduction process. Seeking strategies for accelerating charge dynamics and activating reduction and oxidation sites synchronously presents a huge challenge. Herein, an inside-out chlorine (Cl) ions substitution strategy on the layered polar Bi4O5Br2 is proposed for achieving layer structure-dependent polarization effect and redox dual-sites activation. Cl ions in the bulk phase shrink the halogen layer interspace by 8‰, triggering asymmetric [Bi4O5]2+ layer displacement polarization, prolonging the average photocharge lifetime to 201.8 ps. Meanwhile, surface substituted Cl ions enhance the electron-donating capability of neighboring Bi atoms, activating the intrinsic Bi reduction sites, and increasing H2O molecule adsorption on nearby intrinsic O oxidation site (cal. by 0.105 eV), also self-donating as an alien oxidation site. Besides, Cl upshifts the p-band center closer to the Fermi level, facilitating the reactant adsorption. Therefore, the energy barrier for CO2 activation and rate-limiting *COOH intermediate formation steps are significantly decreased. Without cocatalysts and sacrificial reagents, inside-out Cl-substituted Bi4O5Br2 delivers a remarkable CO2-to-CO photoreduction rate of 50.18 µmol g−1 h−1, being one of the state-of-the-art catalysts. This finding offers insights into exploiting polarization at the molecular-level and enhances understanding of catalytic site activation.
期刊介绍:
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