2D/2D Black Phosphorus/g-C3N4 S-Scheme Heterojunction Photocatalysts for CO2 Reduction Investigated using DFT Calculations

Citation: Xingang Fei, Haiyan Tan, Bei Cheng, Bicheng Zhu, Liuyang Zhang. 2D/2D Black Phosphorus/g-C₃N₄ S-Scheme Heterojunction Photocatalysts for CO₂ Reduction Investigated using DFT Calculations[J]. Acta Physico-Chimica Sinica, 2021, 37(6): 201002. doi: 10.3866/PKU.WHXB202010027 shu

理论计算研究二维/二维BP/g-C₃N₄异质结的光催化CO₂还原性能

费新刚 ^1, ,
谭海燕 ^{2,
,} ,
程蓓 ^1, ,
朱必成 ^{1,
,} ,
张留洋 ^{1,
,}

1.
武汉理工大学，材料复合新技术国家重点实验室，武汉 430070
2.
湖北民族大学，化学与环境工程学院，湖北恩施 445000

通讯作者: 谭海燕, Jftanhaiyan@sina.com
朱必成, zhubicheng1991@whut.edu.cn
张留洋, zly2017@whut.edu.cn

基金项目:
国家重点研发计划 2018YFB1502001

国家自然科学基金 51872220

国家自然科学基金 21905219

国家自然科学基金 51932007

国家自然科学基金 U1905215

国家自然科学基金 21871217

国家自然科学基金 U1705251

博士后创新人才支持计划 BX20180231

中国博士后科学基金 2020M672432

摘要: 光催化二氧化碳还原成烃类化合物是解决能源短缺和环境污染的重要途径。而构建复合物光催化剂可以有效地解决单一光催化剂的缺点，并且提高二氧化碳还原活性。尽管对复合物光催化剂已经做了很多研究，然而对其活性增强的内在机制还缺乏理论认识。本文采用密度泛函理论计算方法研究了二维/二维BP/g-C₃N₄复合模型的电子性质和CO₂还原反应过程。通过对能带位置和界面电子相互作用的综合分析发现，在BP/g-C₃N₄异质结中，光生载流子的迁移遵循S型异质结光催化机制。与单一的g-C₃N₄相比，这种异质结可以实现光生载流子的高效分离并且拥有良好的氧化还原能力。此外，通过对比研究CO₂在g-C₃N₄和BP/g-C₃N₄还原反应过程发现，异质结使CO₂还原反应的最大能垒从1.48 eV降低到1.22 eV。因此，BP/g-C₃N₄异质结在理论上被证明是一种优良的CO₂还原光催化剂。这项工作有助于了解BP改性对g-C₃N₄光催化活性的影响，也为其他高性能CO₂还原光催化剂的设计提供理论依据。

关键词:

English

2D/2D Black Phosphorus/g-C₃N₄ S-Scheme Heterojunction Photocatalysts for CO₂ Reduction Investigated using DFT Calculations

Xingang Fei ^1, ,
Haiyan Tan ^{2,
,} ,
Bei Cheng ^1, ,
Bicheng Zhu ^{1,
,} ,
Liuyang Zhang ^{1,
,}

1.
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2.
School of Chemistry and Environmental Engineering, Hubei University for Nationalities, Enshi 445000, Hubei Province, China

Corresponding author: Haiyan Tan, Jftanhaiyan@sina.com Bicheng Zhu, zhubicheng1991@whut.edu.cn Liuyang Zhang, zly2017@whut.edu.cn

Received Date: 13 October 2020
Accepted Date: 04 November 2020
Revised Date: 04 November 2020
Available Online: 15 June 2021
Fund Project:

Abstract: Photocatalytic reduction of CO₂ to hydrocarbon compounds is a promising method for addressing energy shortages and environmental pollution. Considerable efforts have been devoted to exploring valid strategies to enhance photocatalytic efficiency. Among various modification methods, the hybridization of different photocatalysts is effective for addressing the shortcomings of a single photocatalyst and enhancing its CO₂ reduction performance. In addition, metal-free materials such as g-C₃N₄ and black phosphorus (BP) are attractive because of their unique structures and electronic properties. Many experimental results have verified the superior photocatalytic activity of a BP/g-C₃N₄ composite. However, theoretical understanding of the intrinsic mechanism of the activity enhancement is still lacking. Herein, the geometric structures, optical absorption, electronic properties, and CO₂ reduction reaction processes of 2D/2D BP/g-C₃N₄ composite models are investigated using density functional theory calculations. The composite model consists of a monolayer of BP and a tri-s-triazine-based monolayer of g-C₃N₄. Based on the calculated work function, it is inferred that electrons transfer from g-C₃N₄ to BP owing to the higher Fermi level of g-C₃N₄ compared with that of BP. Furthermore, the charge density difference suggests the formation of a built-in electric field at the interface, which is conducive to the separation of photogenerated electron-hole pairs. The optical absorption coefficient demonstrates that the light absorption of the composite is significantly higher than that of its single-component counterpart. Integrated analysis of the band edge potential and interfacial electronic interaction indicates that the migration of photogenerated charge carriers in the BP/g-C₃N₄ hybrid follows the S-scheme photocatalytic mechanism. Under visible-light irradiation, the photogenerated electrons on BP recombine with the photogenerated holes on g-C₃N₄, leaving photogenerated electrons and holes in the conduction band of g-C₃N₄ and the valence band of BP, respectively. Compared with pristine g-C₃N₄, this S-scheme heterojunction allows efficient separation of photogenerated charge carriers while effectively preserving strong redox abilities. Additionally, the possible reaction path for CO₂ reduction on g-C₃N₄ and BP/g-C₃N₄ is discussed by computing the free energy of each step. It was found that CO₂ reduction on the composite occurs most readily on the g-C₃N₄ side. The reaction path on the composite is different from that on g-C₃N₄. The heterojunction reduces the maximum energy barrier for CO₂ reduction from 1.48 to 1.22 eV, following the optimal reaction path. Consequently, the BP/g-C₃N₄ heterojunction is theoretically proven to be an excellent CO₂ reduction photocatalyst. This work is helpful for understanding the effect of BP modification on the photocatalytic activity of g-C₃N₄. It also provides a theoretical basis for the design of other high-performance CO₂ reduction photocatalysts.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

理论计算研究二维/二维BP/g-C₃N₄异质结的光催化CO₂还原性能

通讯作者: 谭海燕, Jftanhaiyan@sina.com
朱必成, zhubicheng1991@whut.edu.cn
张留洋, zly2017@whut.edu.cn

English

2D/2D Black Phosphorus/g-C₃N₄ S-Scheme Heterojunction Photocatalysts for CO₂ Reduction Investigated using DFT Calculations

Corresponding author: Haiyan Tan, Jftanhaiyan@sina.com Bicheng Zhu, zhubicheng1991@whut.edu.cn Liuyang Zhang, zly2017@whut.edu.cn

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理论计算研究二维/二维BP/g-C3N4异质结的光催化CO2还原性能

通讯作者: 谭海燕, Jftanhaiyan@sina.com 朱必成, zhubicheng1991@whut.edu.cn 张留洋, zly2017@whut.edu.cn

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