{"title":"Single-atom modified graphene cocatalyst for enhanced photocatalytic CO2 reduction on halide perovskite","authors":"","doi":"10.1016/S1872-2067(24)60081-1","DOIUrl":null,"url":null,"abstract":"<div><p>Metal halide perovskite (MHP) has become one of the most promising materials for photocatalytic CO<sub>2</sub> reduction owing to the wide light absorption range, negative conduction band position and high reduction ability. However, photoreduction of CO<sub>2</sub> by MHP remains a challenge because of the slow charge separation and transfer. Herein, a cobalt single-atom modified nitrogen-doped graphene (Co-NG) cocatalyst is prepared for enhanced photocatalytic CO<sub>2</sub> reduction of bismuth-based MHP Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub>. The optimal Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub>/Co-NG composite exhibits the CO production rate of 123.16 μmol g<sup>–1</sup> h<sup>–1</sup>, which is 17.3 times higher than that of Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub>. Moreover, the Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub>/Co-NG composite photocatalyst exhibits nearly 100% CO selectivity as well as impressive long-term stability. Charge carrier dynamic characterizations such as Kelvin probe force microscopy (KPFM), single-particle PL microscope and transient absorption (TA) spectroscopy demonstrate the vital role of Co-NG cocatalyst in accelerating the transfer and separation of photogenerated charges and improving photocatalytic performance. The reaction mechanism has been demonstrated by <em>in situ</em> diffuse reflectance infrared Fourier-transform spectroscopy measurement. In addition, <em>in situ</em> X-ray photoelectron spectroscopy test and theoretical calculation reveal the reaction reactive sites and reaction energy barriers, demonstrating that the introduction of Co-NG promotes the formation of *COOH intermediate, providing sufficient evidence for the highly selective generation of CO. This work provides an effective single-atom-based cocatalyst modification strategy for photocatalytic CO<sub>2</sub> reduction and is expected to shed light on other photocatalytic applications.</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/S1872206724600811","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
Metal halide perovskite (MHP) has become one of the most promising materials for photocatalytic CO2 reduction owing to the wide light absorption range, negative conduction band position and high reduction ability. However, photoreduction of CO2 by MHP remains a challenge because of the slow charge separation and transfer. Herein, a cobalt single-atom modified nitrogen-doped graphene (Co-NG) cocatalyst is prepared for enhanced photocatalytic CO2 reduction of bismuth-based MHP Cs3Bi2Br9. The optimal Cs3Bi2Br9/Co-NG composite exhibits the CO production rate of 123.16 μmol g–1 h–1, which is 17.3 times higher than that of Cs3Bi2Br9. Moreover, the Cs3Bi2Br9/Co-NG composite photocatalyst exhibits nearly 100% CO selectivity as well as impressive long-term stability. Charge carrier dynamic characterizations such as Kelvin probe force microscopy (KPFM), single-particle PL microscope and transient absorption (TA) spectroscopy demonstrate the vital role of Co-NG cocatalyst in accelerating the transfer and separation of photogenerated charges and improving photocatalytic performance. The reaction mechanism has been demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy measurement. In addition, in situ X-ray photoelectron spectroscopy test and theoretical calculation reveal the reaction reactive sites and reaction energy barriers, demonstrating that the introduction of Co-NG promotes the formation of *COOH intermediate, providing sufficient evidence for the highly selective generation of CO. This work provides an effective single-atom-based cocatalyst modification strategy for photocatalytic CO2 reduction and is expected to shed light on other photocatalytic applications.
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.