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用于高效光催化CO还原的无机铜基卤化物钙钛矿

Inorganic Copper-Based Halide Perovskite for Efficient Photocatalytic CO Reduction.

作者信息

Zhao Hai-Bing, Liao Jin-Feng, Teng Yuan, Chen Hong-Yan, Kuang Dai-Bin

机构信息

MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-sen University, Guangzhou 510006, P. R. China.

School of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, People's Republic of China.

出版信息

ACS Appl Mater Interfaces. 2022 Sep 28;14(38):43354-43361. doi: 10.1021/acsami.2c12695. Epub 2022 Sep 19.

Abstract

In view of the toxicity of the Pb element, exploring eco-friendly Pb-free halide perovskites with excellent photoelectric properties is of great research and practical application significance. Herein, copper-based halide perovskite CsCuCl and the corresponding Br-substituted sample (CsCuClBr) are designed and explored as the catalysts for photocatalytic CO reduction for the first time. A facile antisolvent recrystallization process with pre-prepared single crystals as the precursor is employed to controllably synthesize CsCuCl and CsCuClBr microcrystals (MCs). The electronic structure and charge transfer property analysis by theoretical and experimental investigation reveal that CsCuCl possesses a satisfying bandgap (1.92 eV) and conduction band minimum (CBM) to harvest the sunlight and drive the conversion of CO to CH and CO. The Br substitution can not only narrow the bandgap but also facilitate the transportation of charge carriers. Thus, a total electron consumption rate of 44.71 μmol g h is achieved for CsCuClBr MCs, which is much better than that of same-sized CsPbBr microcrystals or even better than many perovskite nanocrystal photocatalysts. This study suggests that Cu-based perovskites can serve as promising candidates for artificial photosynthesis or other photocatalytic applications, which may propose a new thought to construct lead-free, low-cost photocatalysts.

摘要

鉴于铅元素的毒性,探索具有优异光电性能的环保无铅卤化物钙钛矿具有重大的研究和实际应用意义。在此,首次设计并探索了铜基卤化物钙钛矿CsCuCl及其相应的Br取代样品(CsCuClBr)作为光催化CO还原的催化剂。采用以预制备的单晶为前驱体的简便反溶剂重结晶过程,可控地合成了CsCuCl和CsCuClBr微晶(MCs)。通过理论和实验研究进行的电子结构和电荷转移性质分析表明,CsCuCl具有令人满意的带隙(1.92 eV)和导带最小值(CBM),能够捕获太阳光并驱动CO转化为CH和CO。Br取代不仅可以缩小带隙,还能促进电荷载流子的传输。因此,CsCuClBr MCs实现了44.71 μmol g⁻¹ h⁻¹的总电子消耗率,这比相同尺寸的CsPbBr微晶要好得多,甚至优于许多钙钛矿纳米晶光催化剂。这项研究表明,铜基钙钛矿可作为人工光合作用或其他光催化应用的有前途的候选材料,这可能为构建无铅、低成本的光催化剂提出新思路。

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