“双碳”目标下Janus In2S2X光催化还原CO2的密度泛函理论研究

doi:10.6023/A23040155

摘要/Abstract

CO₂光催化还原转化为可利用的化工产品能够有效地缓解温室效应和资源短缺两大问题, 有助于实现“碳达峰”和“碳中和”的伟大目标. 然而由于量子效率和产物选择性等问题的影响, 目前仍然无法将其大规模应用于工业生产. 其中光催化剂具有关键作用. 金属硫化物因具有良好的光吸收能力和带边电位, 被认为是一类具有巨大应用前景的光催化剂. 本工作以Janus In₂S₂X为基础, 在表面引入了不同浓度的空位缺陷, 分析了其稳定构型、电子结构以及吸收光谱. 计算CO₂还原路径发现, 空位浓度可以有效调控还原产物的选择性, 具有单空位和双空位表面的催化剂分别将CO₂还原为HCOOH和HCHO, 进一步揭示了空位浓度对催化性能的影响机理. 这项工作为实验设计和制备高效的光催化剂提供了一定的理论指导.

关键词: Janus In₂S₂X, 光催化, 空位浓度, CO₂还原, 选择性

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

引用此文

吴宇晗, 张栋栋, 尹宏宇, 陈正男, 赵文, 匙玉华. “双碳”目标下Janus In₂S₂X光催化还原CO₂的密度泛函理论研究[J]. 化学学报, 2023, 81(9): 1148-1156.

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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图/表 13

图式1. 光催化还原CO2助力实现“双碳”目标

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

图1. (a~c)分别为In2S3、In2S2Se和In2S2Te晶胞的俯视图、侧视图和主视图; (d~f)分别为In2S3、In2S2Se和In2S2Te晶胞的声子谱

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

图2. (a) In2S3、(b) In2S2Se和(c) In2S2Te晶胞的PBE泛函作用下的能带结构和分波态密度(PDOS). 在In2S3的PDOS中, 顶层的S原子用Sx表示, S1和S2分别代表中间的S原子和底部的S原子, In1和In2分别代表上层和下层In原子. (d) In2S3、(e) In2S2Se和(f) In2S2Te晶胞的CBM(左)和VBM(右)的局域电荷密度侧视图

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

图3. In2S3、In2S2Se和In2S2Te晶胞相对于两个表面真空能级的带边电位; 灰色虚线是氢电极电位和氧电极电位, 红色虚线分别表示CO2 还原到HCOOH和HCHO的电极电位

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

图4. In2S3、In2S2Se和In2S2Te晶胞的吸收光谱图

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

图5. (a) 4×4×1 Janus In2S2X (X=Se, Te)超胞顶端空位示意图. (b) In2S2X表面上双空位的空位形成能

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

图6. (a~c) In2S2Se和(d~f) In2S2Te单层完美、单和双空位结构的能带结构和PDOS (a~c) In2S2Se和(d~f) In2S2Te单层完美、单和双空位结构的能带结构和PDOS

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

图7. In2S2Se (a~c)和In2S2Te (d~f)单层完美、单空位和双空位结构的表面静电势, 红色虚线是费米能级

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

图8. 完美(pure)、单空位(Vs)和双空位(Vd)结构的In2S2Se和In2S2Te相对于真空能级的带边电位(灰色虚线是氢电极电位和氧电极电位、红色虚线分别表示CO2还原为HCOOH和HCHO的电极电位)

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

图9. 完美、单空位和双空位结构的(a) In2S2Se和(b) In2S2Te的吸收光谱

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

图10. CO2在Vs-In2S2X表面被还原为HCOOH的(a)吉布斯自由能变化(△G)和(b, c)反应路径

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

图11. CO2在Vd-In2S2X表面被还原为HCHO的(a)吉布斯自由能变化(△G)和(b, c)反应路径

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

图12. (a) Vd-In2S2Se和(b) Vd-In2S2Te第一次加氢反应后的反应中间体结构. 空位处的三个原子分别用In4、In5和In6来区分. CHOO*中的两个O原子也分别用O1和O2来区分

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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