等价阴-阳离子共掺杂调节ZnO的能带结构及其光催化活性

doi:10.19596/j.cnki.1001-246x.8253

摘要/Abstract

摘要：

采用等价阴-阳离子共掺的方法调节ZnO的能带结构，提高其光催化分解水制氢的效率。计算结果表明：等价阴-阳离子共掺不仅减小了ZnO的带隙，使其在可见光区域的光吸收增强，而且能有效抑制电子-空穴的复合，提高载流子迁移率。（Cd+Te）共掺杂的ZnO是较理想的水分解的光催化剂，因为它具有合适的带隙、较少的电子-空穴复合中心、增强的可见光区域的光吸收和与水氧化还原势相匹配的带边位置。等价阴-阳离子共掺的方法也可运用到其它宽带隙的半导体中以提高光催化活性。

关键词: ZnO, 光催化水分解, 等价阴阳离子共掺, 第一性原理计算, 宽带隙半导体

Abstract:

We propose an isovalent anion-cation codoping approach to improve photoelectrochemical (PEC) water-splitting efficiency of ZnO for hydrogen production. First-principles calculations reveal that the isovalent codoping reduces the band gap to enhance optical absorption in visible light and suppresses electron-hole recombination centers to improve carrier mobility as well. Specifically, (Cd+Te) codoped ZnO may be a strong candidate for PEC water-splitting in virtue of its suitable band gap and matched band edge positions for water redox. This isovalent codoping approach could be applied in other wide-band-gap semiconductors for improving photocatalytic activity.

Key words: ZnO, photoelectrochemical water-splitting, isovalent anion-cation codoping, first-principles calculations, wide-band-gap semiconductors

中图分类号:

O472⁺.3

潘靖, 沈国华. 等价阴-阳离子共掺杂调节ZnO的能带结构及其光催化活性[J]. 计算物理, 2021, 38(3): 371-378.

Jing PAN, Guohua SHEN. Enhanced Photocatalytic Activity of ZnO for Water-splitting with Isovalent Anion-Cation Codoping: First-principles Calculations[J]. Chinese Journal of Computational Physics, 2021, 38(3): 371-378.

图/表 6

Table 1 Average bond lengths (in nm), lattice parameters (in nm), dipole moments (in Debye), band gap (in eV) calculated with PBE method (PBE-Eg in eV) and HSE method (HSE-Eg in eV), calculated BGC, CBM and VBM (in eV) of pure, isovalent monodoped and codoped ZnO

System	bond length			lattice		dipole	PBE-E_g	HSE-E_g	BGC	VBM	CBM
System	Zn-O	Cd-O	Zn-S/Te/Se	a	c	dipole	PBE-E_g	HSE-E_g	BGC	VBM	CBM
ZnO	0.200			0.326	0.524	2.822	0.8	3.37	-5.52	-7.20	-3.83
Cd	0.199	0.217		0.328	0.528	3.356	1.31	3.09
S	0.200		0.223	0.329	0.531	1.502	1.78	3.34
Se	0.200		0.232	0.330	0.534	1.175	1.68	3.18
Te	0.201		0.245	0.332	0.537	0.514	1.49	2.81
(Cd+S)	0.200	0.217	0.222	0.330	0.534	1.916	1.76	2.79	-5.34	-6.74	-3.95
(Cd+Se)	0.200	0.217	0.232	0.330	0.536	2.612	1.40	2.62	-5.10	-6.50	-3.88
(Cd+Te)	0.201	0.219	0.246	0.332	0.538	2.621	1.95	2.18	-4.84	-5.93	-3.75

Fig.1 HSE-calculated (a)-(e) TDOS and (f)-(j) PDOS of pure, Cd-, S-, Se- and Te-doped ZnO (Fermi levels of systems are displayed with dashed lines. The dotted lines indicate the VBM of pure ZnO. The PDOS at conduction band are amplified for clarity.)

Fig.2 HSE-calculated (a)-(d) TDOS and (f)-(j) PDOS of pure, (Cd+S), (Cd+Se) and (Cd+Te)-codoped ZnO (Fermi levels of the systems are displayed with dashed lines. The dotted lines indicate the VBM of pure ZnO. The PDOS at conduction band are amplified for clarity.)

Fig.3 Electrostatic potential V(r) of the (10${\rm{\bar 1}}$0) surface of (Cd+Se) codoped ZnO (The vacuum level corresponds to zero electrostatic potential energy. The dash lines denote

Fig.4 Band edges of pure and (Cd+S), (Cd+Se), (Cd+Te) codoped ZnO in comparison with redox potential of water at pH=7 (The introduction of dopants creates new energy levels that effectively narrow band gap.)

Fig.5 HSE-calculated absorption spectra of pure and isovalent (Cd+S), (Cd+Se) and (Cd+Te) codoped ZnO

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