Identification of intrinsic vacancies and polarization effect on ternary halo-sulfur-bismuth compounds for efficient CO2 photoreduction under near-infrared light irradiation

IF 19.5 1区 材料科学 Q1 CHEMISTRY, PHYSICAL
Carbon Energy Pub Date : 2024-07-05 DOI:10.1002/cey2.598
Jun Li, Qingqing Chai, Ranran Niu, Wenfeng Pan, Zhiquan Chen, Liang Wang, Kai Wang, Zhongyi Liu, Yifeng Liu, Yao Xiao, Bin Liu
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引用次数: 0

Abstract

Ternary halo-sulfur bismuth compound Bi19X3S27 (X = Cl, Br, I) with distinct electronic structure and full-spectrum light-harvesting properties show great application potential in the CO2 photoreduction field. However, the relationship between photocatalytic CO2 reduction performance and the function of halogens in Bi19X3S27 is still poorly understood. Herein, a series of Bi19X3S27 nanorod photocatalysts with intrinsic X and S dual vacancies were developed, which showed significant near-infrared (NIR) light responses. The types and concentrations of intrinsic vacancies were confirmed and quantified by positron annihilation spectrometry and electron spin resonance spectroscopy. Experimental results showed that Br atoms and intrinsic vacancies (dual Br-S) in Bi19Br3S27 could greatly enhance the internal polarized electric field and improve the transfer and separation of photogenerated carriers compared with Bi19Cl3S27 and Bi19I3S27. Theoretical calculations revealed that Br atoms in Bi19Br3S27 could facilitate CO2 adsorption and activation and decrease the formation energy of reactive hydrogen. Among Bi19X3S27 nanorods, Bi19Br3S27 nanorods revealed the highest CO2 photoreduction activity with CO yield rate of 28.68 and 2.28 μmol gcatalyst−1 h−1 with full-spectrum and NIR lights, respectively. This work presents an atomic understanding of the intrinsic vacancies and halogen-mediated CO2 photoreduction mechanism.

Abstract Image

Abstract Image

鉴定三元卤硫铋化合物的本征空位和极化效应,以便在近红外光照射下高效进行二氧化碳光氧化还原
三元卤硫铋化合物 Bi19X3S27(X = Cl、Br、I)具有独特的电子结构和全光谱采光特性,在二氧化碳光催化领域具有巨大的应用潜力。然而,人们对光催化还原 CO2 性能与 Bi19X3S27 中卤素功能之间的关系还知之甚少。本文开发了一系列具有固有 X 和 S 双空位的 Bi19X3S27 纳米棒光催化剂,其对近红外(NIR)光有显著的响应。正电子湮灭光谱法和电子自旋共振光谱法确认并量化了本征空位的类型和浓度。实验结果表明,与 Bi19Cl3S27 和 Bi19I3S27 相比,Bi19Br3S27 中的 Br 原子和本征空位(双 Br-S)能极大地增强内部极化电场,改善光生载流子的转移和分离。理论计算显示,Bi19Br3S27 中的 Br 原子可以促进 CO2 的吸附和活化,降低活性氢的形成能。在 Bi19X3S27 纳米棒中,Bi19Br3S27 纳米棒的 CO2 光还原活性最高,在全光谱光和近红外光下的 CO 产率分别为 28.68 和 2.28 μmol gcatalyst-1 h-1。这项工作从原子角度揭示了本征空位和卤素介导的 CO2 光还原机制。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Carbon Energy
Carbon Energy Multiple-
CiteScore
25.70
自引率
10.70%
发文量
116
审稿时长
4 weeks
期刊介绍: Carbon Energy is an international journal that focuses on cutting-edge energy technology involving carbon utilization and carbon emission control. It provides a platform for researchers to communicate their findings and critical opinions and aims to bring together the communities of advanced material and energy. The journal covers a broad range of energy technologies, including energy storage, photocatalysis, electrocatalysis, photoelectrocatalysis, and thermocatalysis. It covers all forms of energy, from conventional electric and thermal energy to those that catalyze chemical and biological transformations. Additionally, Carbon Energy promotes new technologies for controlling carbon emissions and the green production of carbon materials. The journal welcomes innovative interdisciplinary research with wide impact. It is indexed in various databases, including Advanced Technologies & Aerospace Collection/Database, Biological Science Collection/Database, CAS, DOAJ, Environmental Science Collection/Database, Web of Science and Technology Collection.
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