新型二维Zr2CO2/InS异质结可见光催化产氢性能的第一性原理研究

doi:10.15541/jim20190521

摘要/Abstract

摘要：

采用第一性原理计算方法, 系统研究了新型二维Zr₂CO₂/InS异质结的电子结构和光催化性能。计算结果显示, 二维Zr₂CO₂/InS异质结是一种直接带隙半导体材料, 晶格失配率低于3%, 形成能为-0.49 eV, 说明其具有稳定的结构; Zr₂CO₂/InS异质结的带隙值为1.96 eV, 对应较宽的可见光吸收范围, 且吸收系数高达10⁵ cm^-1; 异质结表现出Ⅱ型能带对齐, 价带和导带的带偏置分别为1.24和0.17 eV, 表明光生电子从Zr₂CO₂层转移到InS层, 而光生空穴则与之相反, 从而实现了电子和空穴在空间上的有效分离。另外, InS是间接带隙半导体材料, 能够进一步降低电子和空穴的复合率。综上所述, 新型二维Zr₂CO₂/InS异质结是一种潜在的可见光光催化剂。

关键词: Zr₂CO₂/InS异质结, 电子结构, 光催化性能, 第一性原理计算

Abstract:

Electronic structure and photocatalytic performance of 2D novel Zr₂CO₂/InS heterostructure was systematically investigated using first principle calculations. The calculated results demonstrate that the Zr₂CO₂/InS heterostructure is a direct bandgap semiconductor with a lattice mismatch less than 3% and a formation energy of -0.49 eV, indicating a stable structure. Band gap of the Zr₂CO₂/InS heterostructure is 1.96 eV, which should have a wide visible light absorption range, and the absorption coefficient is up to 10⁵ cm^-1. The heterostructure has a typical type-II band alignment, and its valence band and conduction band offsets are 1.24 and 0.17 eV, respectively, demonstrating the transfer of photo-generated electrons from Zr₂CO₂ layer to InS layer and vice versa for holes, which indicates that the electrons and holes can be separated effectively in space. In addition, InS is an indirect band gap semiconductor material, which can further reduce the recombination of electrons and holes. Therefore, the novel Zr₂CO₂/InS heterostructure is a potential visible-light photocatalyst.

Key words: Zr₂CO₂/InS heterostructure, electronic structure, photocatalytic performance, first principles calculations

中图分类号:

O471.5

赵宇鹏,贺勇,张敏,史俊杰. 新型二维Zr₂CO₂/InS异质结可见光催化产氢性能的第一性原理研究[J]. 无机材料学报, 2020, 35(9): 993-998.

ZHAO Yupeng,HE Yong,ZHANG Min,SHI Junjie. First-principles Study on the Photocatalytic Hydrogen Production of a Novel Two-dimensional Zr₂CO₂/InS Heterostructure[J]. Journal of Inorganic Materials, 2020, 35(9): 993-998.

图/表 6

表1 二维Zr2CO2和InS的晶格常数(a、b)和带隙(Eg)及相应文献报道结果

Table 1 Lattice constants (a, b) and band gaps (Eg) of two-dimensional Zr2CO2 and InS, as well as their corresponding values reported in literatures

		a/nm	b/nm	E_g/eV (GGA)	E_g/eV (GGA-1/2)	E_g/eV (GW)
Zr₂CO₂	This study	0.331	0.331	1.02	2.13
Zr₂CO₂	Previous study	0.331^[18]	0.331^[18]	0.97^[18]		2.13^[15]
InS	This study	0.391	0.391	1.74	3.20
InS	Previous study	0.394^[7]	0.394^[7]	1.74^[7]		3.20^[7]

图1 二维(a)Zr2CO2和(b)InS的俯视图以及(c)Zr2CO2/InS异质结的侧视图

Fig. 1 Top views of 2D (a)Zr2CO2 and (b)InS and side view of (c)Zr2CO2/InS heterostructure

图2 (a)Zr2CO2/InS异质结的投影能带、态密度以及(b)导带底(CBM)和(c)价带顶(VBM)的带分解电荷局域密度分布图 (ρ=3.7×10-2 e·nm-3)

Fig. 2 (a) Projected band structure and density of states of Zr2CO2/InS heterostructure, and band-decomposed charge of local density distributions of (b) conduction band minimum (CBM) and (c) valence band maximum (VBM) for Zr2CO2/InS heterostructure (ρ=3.7×10-2 e·nm-3)

图3 Zr2CO2/InS异质结的差分电荷密度示意图和电子积累及损耗(分别用青色和紫色等值面表示, ρ=1.2×10-1 e·nm-3)

Fig. 3 Schematic diagram of the charge density difference of Zr2CO2/InS heterostructure, and the accumulation and depletion of electrons displaying with cyan and purple color isosurfaces, respectively (ρ=1.2×10-1 e·nm-3) Red curve showing the plane-averaged charge density difference plot; The vdW Gap stands for van der Waals gap

图4 单层InS、Zr2CO2和Zr2CO2/InS异质结构的光吸收系数

Fig. 4 Optical absorption coefficient of monolayer InS, Zr2CO2 and Zr2CO2/InS heterostructure

图5 以标准氢电极(SHE)电位为参考的二维InS、Zr2CO2和Zr2CO2/InS异质结的带隙值与能带偏置

Fig. 5 In contrast to standard hydrogen electrode (SHE) potential, band gaps and band offset of two-dimensional InS and Zr2CO2 in (a) and Zr2CO2/InS heterostructure in (b) VBO: Valence Band Offset, CBO: Conduction Band offset. The dotted lines represent the standard water redox potential

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新型二维Zr₂CO₂/InS异质结可见光催化产氢性能的第一性原理研究

First-principles Study on the Photocatalytic Hydrogen Production of a Novel Two-dimensional Zr₂CO₂/InS Heterostructure

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