Density Functional Theory Study of Janus In2S2X Photocatalytic Reduction of CO2 under “Double Carbon” Target

doi:10.6023/A23040155

Abstract

Photocatalytic reduction of CO₂ into usable chemical products can effectively alleviate the two major problems of greenhouse effect and resource shortage, and help to achieve the great goals of “carbon peak” and “carbon neutrality”. However, due to the influence of quantum efficiency and low product selectivity, it is still not possible to apply it to large-scale industrial production. Among them, the photocatalyst plays a key role. Metal sulfides are considered to be a class of promising photocatalysts due to their good light absorption ability and reduction potential. Based on the research of two-dimensional (2D) In₂S₃, a 2D In₂S₂X (X=Se, Te) Janus structure is designed using density functional theory (DFT). In₂S₂X not only possesses suitable band edge positions and moderate bandgap for photocatalytic CO₂ reduction, but also has excellent visible light absorption. Moreover, the valence band maximum (VBM) and conduction band minimum (CBM) of In₂S₂X are contributed by the bottom and top atoms, respectively, so that the reduction and oxidation reactions are spatially separated and the photocatalytic efficiency is improved. In particular, due to the intrinsic polarization, the direction of the built-in electric field generated by In₂S₂X is just opposite to the direction of electronic transition, which can improve the carrier mobility. On this basis, different concentrations of vacancy defects are introduced on the surface, and its stable configuration, electronic structure and absorption spectrum are analyzed. Calculation of the CO₂ reduction pathways reveal that the vacancy concentration can effectively regulate the selectivity of reduction products, and the catalysts with single-vacancy and double-vacancy surfaces reduced CO₂ to HCOOH and HCHO, respectively. The mechanism of the effect of vacancy concentration on the catalytic performance is further revealed. Vs-In₂S₂Se and Vd-In₂S₂Te show more excellent photocatalytic performance in the process of reducing CO₂ to HCOOH and HCHO, respectively. This work provides some theoretical guidance for experimental design and preparation of highly efficient photocatalysts.

Key words: Janus In₂S₂X, photocatalysis, vacancy concentration, CO₂ reduction, selectivity

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Yuhan Wu, Dongdong Zhang, Hongyu Yin, Zhengnan Chen, Wen Zhao, Yuhua Chi. Density Functional Theory Study of Janus In₂S₂X Photocatalytic Reduction of CO₂ under “Double Carbon” Target[J]. Acta Chimica Sinica, 2023, 81(9): 1148-1156.

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Fig. & Tab. 13

Scheme 1. Photocatalytic reduction of CO2 to help achieve the goal of “double carbon”

Figure 1. Top view, side view and front view of (a) In2S3, (b) In2S2Se and (c) In2S2Te unit cell. Phonon band structures of (d) In2S3, (e) In2S2Se and (f) In2S2Te monolayer, respectively

Figure 2. Band structure and projected density of states (PDOS) under PBE functional of (a) In2S3, (b) In2S2Se and (c) In2S2Te unit cell. In the PDOS of In2S3, the S atom in the top layer is denoted by Sx. S1 and S2 represent the middle S atom and the bottom S atom respectively, and In1 and In2 represent the upper and lower In atoms respectively. Side view of the local charge density of the CBM (left) and VBM (right) of the unit cells of (d) In2S3, (e) In2S2Se, and (f) In2S2Te

Figure 3. Band edge positions of In2S3, In2S2Se and In2S2Te unit cell relative to the vacuum level of two surfaces. The gray dashed lines are the standard redox potential levels of water-splitting. The red dashed lines are reduction potential of CO2 reduction to HCCOH (up) and HCHO (down), respectively

Figure 4. Absorption spectra of In2S3, In2S2Se and In2S2Te unit cell

Figure 5. (a) Schematic diagram of apical vacancy sites of 4×4×1 Janus In2S2X (X=Se, Te) supercells. (b) Vacancy formation energies of double vacancies on the In2S2X surface

Figure 6. Band structures and PDOS of pure, single and double vacancies structures of (a~c) In2S2Se and (d~f) In2S2Te monolayer

Figure 7. The vacuum energy level difference of pure, monovacancy and double vacancies structures of (a~c) In2S2Se and (d~f) In2S2Te monolayer. The red lines are Fermi levels

Figure 8. Band edge positions of pure, single (Vs) and double (Vd) vacancies structure of In2S2Se and In2S2Te monolayer relative to the vacuum level. The gray dashed lines are the standard redox potential levels of water-splitting. The red dashed lines are reduction potential of CO2 reduction to HCCOH (up) and HCHO (down), respectively

Figure 9. Absorption spectra of (a) In2S2Se and (b) In2S2Te monolayer with pure, single and double vacancies

Figure 10. (a) The Gibbs free energy changes (△G) and (b, c) the reaction paths of CO2 photoreduction to HCOOH for single structures of In2S2Se and In2S2Te monolayer, respectively

Figure 11. (a) The Gibbs free energy changes and (b, c) the reaction paths of CO2 photoreduction to CH2O for double vacancies structures of In2S2Se and In2S2Te monolayer, respectively

Figure 12. Reaction intermediate structures after the first hydrogenation reaction of (a) Vd-In2S2Se and (b) Vd-In2S2Te. The three In atoms at the vacancy are distinguished by In4, In5, and In6, respectively. The two O atoms in the CHOO* are also distinguished by O1 and O2, respectively

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“双碳”目标下Janus In₂S₂X光催化还原CO₂的密度泛函理论研究

Density Functional Theory Study of Janus In₂S₂X Photocatalytic Reduction of CO₂ under “Double Carbon” Target

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“双碳”目标下Janus In2S2X光催化还原CO2的密度泛函理论研究