{"title":"Surface and Defect Engineering Coupling of Halide Double Perovskite Cs2NaBiCl6 for Efficient CO2 Photoreduction","authors":"Jiacheng Pi, Xiaofang Jia, Zhangwen Long, Shuai Yang, Hao Wu, Dacheng Zhou, Qi Wang, Huibin Zheng, Yong Yang, Junying Zhang, Jianbei Qiu","doi":"10.1002/aenm.202202074","DOIUrl":null,"url":null,"abstract":"<p>Non-toxic halide double perovskite materials have many advantages of lead halide perovskite. Whereas, they usually exhibit poor stability and very low intrinsic photocatalytic CO<sub>2</sub> reduction activity due to the insufficient separation of photogenerated charges and the lack of active sites. In this work, stable chlorine-deficient 3D hierarchical Cs<sub>2</sub>NaBiCl<sub>6</sub> porous microspheres assembled by highly crystalline nanoflakes were prepared by a simple grinding method. An unprecedented CO yield of 30.22 µmol g<sup>−1</sup> h<sup>−1</sup> was achieved in the gas-solid photocatalytic reduction of CO<sub>2</sub> without sacrificial agents, which is the highest value among lead-free halide perovskite photocatalysts. Experimental results and density-functional theory calculations show that the chlorine vacancy plays the triple role of suppressing photogenerated electron-holes recombination, enhancing CO<sub>2</sub> adsorption, and significantly reducing the free energy barrier for the key intermediate COOH* generation. In comparison with the pristine Cs<sub>2</sub>NaBiCl<sub>6</sub>, coupling of surface and defect engineering of the hierarchical sample brings 12.34 times enhancement of CO<sub>2</sub> photoreduction activity. This work proposes a simple method to synthesize a chlorine-vacancy rich 3D hierarchical lead-free halide perovskite and offers a new design idea to substantially enhance the photocatalytic activity, opening a door for the prospective contribution of these materials to carbon neutralization.</p>","PeriodicalId":111,"journal":{"name":"Advanced Energy Materials","volume":"12 43","pages":""},"PeriodicalIF":24.4000,"publicationDate":"2022-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"24","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/aenm.202202074","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 24
Abstract
Non-toxic halide double perovskite materials have many advantages of lead halide perovskite. Whereas, they usually exhibit poor stability and very low intrinsic photocatalytic CO2 reduction activity due to the insufficient separation of photogenerated charges and the lack of active sites. In this work, stable chlorine-deficient 3D hierarchical Cs2NaBiCl6 porous microspheres assembled by highly crystalline nanoflakes were prepared by a simple grinding method. An unprecedented CO yield of 30.22 µmol g−1 h−1 was achieved in the gas-solid photocatalytic reduction of CO2 without sacrificial agents, which is the highest value among lead-free halide perovskite photocatalysts. Experimental results and density-functional theory calculations show that the chlorine vacancy plays the triple role of suppressing photogenerated electron-holes recombination, enhancing CO2 adsorption, and significantly reducing the free energy barrier for the key intermediate COOH* generation. In comparison with the pristine Cs2NaBiCl6, coupling of surface and defect engineering of the hierarchical sample brings 12.34 times enhancement of CO2 photoreduction activity. This work proposes a simple method to synthesize a chlorine-vacancy rich 3D hierarchical lead-free halide perovskite and offers a new design idea to substantially enhance the photocatalytic activity, opening a door for the prospective contribution of these materials to carbon neutralization.
期刊介绍:
Established in 2011, Advanced Energy Materials is an international, interdisciplinary, English-language journal that focuses on materials used in energy harvesting, conversion, and storage. It is regarded as a top-quality journal alongside Advanced Materials, Advanced Functional Materials, and Small.
With a 2022 Impact Factor of 27.8, Advanced Energy Materials is considered a prime source for the best energy-related research. The journal covers a wide range of topics in energy-related research, including organic and inorganic photovoltaics, batteries and supercapacitors, fuel cells, hydrogen generation and storage, thermoelectrics, water splitting and photocatalysis, solar fuels and thermosolar power, magnetocalorics, and piezoelectronics.
The readership of Advanced Energy Materials includes materials scientists, chemists, physicists, and engineers in both academia and industry. The journal is indexed in various databases and collections, such as Advanced Technologies & Aerospace Database, FIZ Karlsruhe, INSPEC (IET), Science Citation Index Expanded, Technology Collection, and Web of Science, among others.