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用于级联Z型异质结中定向电荷转移的能量平台:无共催化剂的CO光还原

Energy Platform for Directed Charge Transfer in the Cascade Z-Scheme Heterojunction: CO Photoreduction without a Cocatalyst.

作者信息

Bian Ji, Zhang Ziqing, Feng Jiannan, Thangamuthu Madasamy, Yang Fan, Sun Ling, Li Zhijun, Qu Yang, Tang Dongyan, Lin Zewei, Bai Fuquan, Tang Junwang, Jing Liqiang

机构信息

Department Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education), School of Chemistry and Materials Science, International Joint Research Center and Lab for Catalytic Technology, Heilongjiang University, Harbin, 150080, P. R. China.

School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2021 Sep 13;60(38):20906-20914. doi: 10.1002/anie.202106929. Epub 2021 Aug 13.

Abstract

A universal strategy is developed to construct a cascade Z-Scheme system, in which an effective energy platform is the core to direct charge transfer and separation, blocking the unexpected type-II charge transfer pathway. The dimension-matched (001)TiO -g-C N /BiVO nanosheet heterojunction (T-CN/BVNS) is the first such model. The optimized cascade Z-Scheme exhibits ≈19-fold photoactivity improvement for CO reduction to CO in the absence of cocatalysts and costly sacrificial agents under visible-light irradiation, compared with BVNS, which is also superior to other reported Z-Scheme systems even with noble metals as mediators. The experimental results and DFT calculations based on van der Waals structural models on the ultrafast timescale reveal that the introduced T as the platform prolongs the lifetimes of spatially separated electrons and holes and does not compromise their reduction and oxidation potentials.

摘要

开发了一种通用策略来构建级联Z型体系,其中有效的能量平台是引导电荷转移和分离的核心,阻断了意外的II型电荷转移途径。尺寸匹配的(001)TiO₂-g-C₃N₄/BiVO₄纳米片异质结(T-CN/BVNS)是首个此类模型。与BVNS相比,优化后的级联Z型体系在可见光照射下,在没有助催化剂和昂贵牺牲剂的情况下,将CO还原为CO的光活性提高了约19倍,即使以贵金属作为介质,该体系也优于其他报道的Z型体系。基于超快时间尺度上的范德华结构模型的实验结果和DFT计算表明,引入的TiO₂作为平台延长了空间分离的电子和空穴的寿命,且不影响它们的还原和氧化电位。

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