α,β,γ,δ,ε,η-Bi2O3电子结构和光学性质的第一性原理研究

doi:10.7503/cjcu20160028

摘要/Abstract

摘要：

基于密度泛函理论的CASTEP模块研究了α, β, γ, δ, ε和η-Bi₂O₃晶型, 计算分析了其几何结构、能带结构、电子态密度和光学性质. 结果表明, α, ε和η相均为层状结构, 其中, α和ε相为单层—Bi—O—结构, 而η相为双层—Bi—O—结构; β, γ和δ相为—Bi_m—O_n—交错结构, 其中δ相交错尤为密集, 呈现导体特性. 各晶相的导带均由Bi 6p态构成, 价带由O₂_p态起主导作用. 电势电位分析结果表明, 6种晶相价带电位均在H₂O/O₂之下, 具有强氧化能力, 与实验报道的光催化氧化能力大小顺序γ-Bi₂O₃>β-Bi₂O₃>α-Bi₂O₃>δ-Bi₂O₃一致, 而导带还原电位低于H₂/H₂O, 预测纯Bi₂O₃很难具备催化产氢能力. 光学性质分析发现, γ和δ相的起始响应波长较大, 说明其应具备红外激发的性质. 这些结果可为获得偏红外激发和较宽光谱响应的Bi₂O₃材料研究提供理论基础, 为研发和应用Bi₂O₃及其复合物提供重要的指导.

关键词: Bi2O3晶相, 第一性原理, 电子结构, 光学性质

Abstract:

A theoretical investigation on the geometric structures, band structures, densities of states and optical properties of Bi₂O₃ in six crystalline phases(α, β, γ, δ, ε and η) was carried out using CASTEP(Cambridge Sequential Total Energy Package) module based on the density functional theory. The calculation results show that the α, ε and η phases belong to the layered structure, in which α and ε phases are —Bi—O— single-layer structure and η phase is consisted of the —Bi—O— double-layers structure, while the β, γ, and δ phases are —Bi_m—O_n— staggered structure, in which the δ phase is intensively staggered and its band structure exhibits the conductor characteristic. The conduction bands of all the six crystalline phases are mainly generated by Bi₆_p states, while the valence bands are contributed by O₂_p states. The potential of the six phases are lower than the H₂O/O₂, indicating that they have the higher oxidative ability, which is in good agreement with the reported experimental result(γ-Bi₂O₃>β-Bi₂O₃>α-Bi₂O₃>δ-Bi₂O₃) of the photocatalytic oxidative ability. The reduction potential of the conduction band is lower than H₂/H₂O, we thus speculate that pure Bi₂O₃ has hardly the catalytic ability of hydrogen production. The γ and δ phases have the longer initial response wavelengths, implying that they should have the infrared excitation property. Our calculations can provide basic and reliable theoretical data for the synthesis and study of Bi₂O₃ materials with partial infrared excitation and wide spectral response range, and afford significant guidance for the development and application in the Bi₂O₃-based materials.

Key words: Bi2O3 crystalline phase, First-principle, Electronic structure, Optical property

中图分类号:

O641

TrendMD:

李坦, 张小超, 王凯, 李瑞, 樊彩梅. α,β,γ,δ,ε,η-Bi₂O₃电子结构和光学性质的第一性原理研究. 高等学校化学学报, 2016, 37(5): 920.

LI Tan, ZHANG Xiaochao, WANG Kai, LI Rui, FAN Caimei. First-principle Calculations on Electronic Structures and Optical Properties of α, β, γ, δ, ε, η-Bi₂ $O 3 †$ . Chem. J. Chinese Universities, 2016, 37(5): 920.

图/表 11

Table 1 Crystal lattice parameters of α, β, γ, δ, ε, η-Bi2 O3[5-7,9]

Species	Crystal system	Space group	Unit cell parameter	V₀/nm³
α-Bi₂O₃	Monoclinic	P2₁/c	a=0.58496(3) nm, b=0.81648(4) nm, c=0.75101(4) nm,	0.330235
			α=γ=90°, β=112.977(3)°
β-Bi₂O₃	Tetragonal	P $4 ˉ$ 2₁c	a=b=0.5738(3) nm, c=0.5731(8) nm, α=β=γ=90°	0.343153
γ-Bi₂O₃	Cubic	I23	a=b=c=1.025 nm, α=γ=β=90^o	0.343153
δ-Bi₂O₃	Cubic	Fm $3 ˉ$ m	a=b=c=0.56595(4) nm, α=β=γ=90°	0.181277
ε-Bi₂O₃	Orthorhombic	Pbnb	a=0.49555(1) nm, b=0.55854(2) nm, c=1.27299(3) nm,	0.352347
			α=β=γ=90°
η-Bi₂O₃	Hexagonal	P $3 ˉ$ m1	a=b=0.3878(1) nm, c=0.6303(1) nm, α=β=90°, γ=120°	0.082096

Table 1 Crystal lattice parameters of α, β, γ, δ, ε, η-Bi2 O3[5-7,9]

Species	Crystal system	Space group	Unit cell parameter	V₀/nm³
α-Bi₂O₃	Monoclinic	P2₁/c	a=0.58496(3) nm, b=0.81648(4) nm, c=0.75101(4) nm,	0.330235
			α=γ=90°, β=112.977(3)°
β-Bi₂O₃	Tetragonal	P $4 ˉ$ 2₁c	a=b=0.5738(3) nm, c=0.5731(8) nm, α=β=γ=90°	0.343153
γ-Bi₂O₃	Cubic	I23	a=b=c=1.025 nm, α=γ=β=90^o	0.343153
δ-Bi₂O₃	Cubic	Fm $3 ˉ$ m	a=b=c=0.56595(4) nm, α=β=γ=90°	0.181277
ε-Bi₂O₃	Orthorhombic	Pbnb	a=0.49555(1) nm, b=0.55854(2) nm, c=1.27299(3) nm,	0.352347
			α=β=γ=90°
η-Bi₂O₃	Hexagonal	P $3 ˉ$ m1	a=b=0.3878(1) nm, c=0.6303(1) nm, α=β=90°, γ=120°	0.082096

Fig.1 Structure models of α-Bi2O3(A), β-Bi2O3(B), γ-Bi2O3(C), δ-Bi2O3(D), ε-Bi2O3(E) and η-Bi2O3(F)

Table 2 Comparison for the lattice parameters of α, β, γ, δ, ε and η-Bi2O3

Species	Function	a/nm	b/nm	c/nm	α/(°)	β/(°)	γ/(°)	E_Total/eV
α-Bi₂O₃	Experimental data	0.58496	0.81648	0.75101	90	112.98	90
	GGA(PBE)	0.58688	0.81297	0.74127	90	112.13	90	-6452.1483
	GGA(RPBE)	0.58964	0.82923	0.74865	90	112.35	90	-6457.8904
	GGA(PW91)	0.58699	0.81178	0.74147	90	112.24	90	-6458.9497
	GGA(WC)	0.58410	0.79654	0.73246	90	111.90	90	-6442.5043
	LDA(CA-PZ)	0.56575	0.77129	0.71422	90	112.57	90	-6474.4689
β-Bi₂O₃	Experimental data	0.7738	0.7738	0.5731	90	90	90
	GGA(PBE)	0.79805	0.79805	0.56081	90	90	90	-6451.4282
	GGA(RPBE)	0.81264	0.81264	0.57354	90	90	90	-6457.4546
	GGA(PW91)	0.79418	0.79418	0.56212	90	90	90	-6458.2178
	GGA(WC)	0.76856	0.76856	0.54938	90	90	90	-6441.6260
	LDA(CA-PZ)	0.7471	0.7471	0.52843	90	90	90	-6474.0463
γ-Bi₂O₃	Experimental data	1.025	1.025	1.025	90	90	90
	GGA(PBE)	1.02482	1.02482	1.02482	90	90	90	-17905.0688
	GGA(RPBE)	1.04211	1.04211	1.04211	90	90	90	-17921.4047
	GGA(PW91)	1.02284	1.02284	1.02284	90	90	90	-17923.5416
	GGA(WC)	1.00512	1.00512	1.00512	90	90	90	-17878.6071
	LDA(CA-PZ)	0.9768	0.9768	0.9768	90	90	90	-17976.4001
δ-Bi₂O₃	Experimental data	0.56595	0.56595	0.56595	90	90	90
	GGA(PBE)	0.61886	0.61886	0.61886	90	90	90	-14461.6655
	GGA(RPBE)	0.61992	0.61992	0.61992	90	90	90	-14472.1577
	GGA(PW91)	0.61873	0.61873	0.61873	90	90	90	-14477.5683
	GGA(WC)	0.61716	0.61716	0.61716	90	90	90	-14441.4486
	LDA(CA-PZ)	0.61703	0.61703	0.61703	90	90	90	-14469.0378
ε-Bi₂O₃	Experimental data	0.49555	0.55854	1.27299	90	90	90
	GGA(PBE)	0.52672	0.58311	1.32275	90	90	90	-6442.5117
	GGA(RPBE)	0.52768	0.5792	1.31738	90	90	90	-6454.1838
	GGA(PW91)	0.52626	0.59106	1.29263	90	90	90	-6449.5727
	GGA(WC)	0.50199	0.58217	1.30291	90	90	90	-6430.6840
	LDA(CA-PZ)	0.52219	0.5814	1.28529	90	90	90	-6463.4572
η-Bi₂O₃	Experimental data	0.38781	0.38781	0.63031	90	90	120
	GGA(PBE)	0.38434	0.38434	0.59898	90	90	120	-1612.6690
	GGA(RPBE)	0.38559	0.38559	0.60292	90	90	120	-1613.9926
	GGA(PW91)	0.38414	0.38414	0.5994	90	90	120	-1614.3683
	GGA(WC)	0.38261	0.38261	0.59165	90	90	120	-1610.3816
	LDA(CA-PZ)	0.37171	0.37171	0.56963	90	90	120	-1618.1124

Table 2 Comparison for the lattice parameters of α, β, γ, δ, ε and η-Bi2O3

Species	Function	a/nm	b/nm	c/nm	α/(°)	β/(°)	γ/(°)	E_Total/eV
α-Bi₂O₃	Experimental data	0.58496	0.81648	0.75101	90	112.98	90
	GGA(PBE)	0.58688	0.81297	0.74127	90	112.13	90	-6452.1483
	GGA(RPBE)	0.58964	0.82923	0.74865	90	112.35	90	-6457.8904
	GGA(PW91)	0.58699	0.81178	0.74147	90	112.24	90	-6458.9497
	GGA(WC)	0.58410	0.79654	0.73246	90	111.90	90	-6442.5043
	LDA(CA-PZ)	0.56575	0.77129	0.71422	90	112.57	90	-6474.4689
β-Bi₂O₃	Experimental data	0.7738	0.7738	0.5731	90	90	90
	GGA(PBE)	0.79805	0.79805	0.56081	90	90	90	-6451.4282
	GGA(RPBE)	0.81264	0.81264	0.57354	90	90	90	-6457.4546
	GGA(PW91)	0.79418	0.79418	0.56212	90	90	90	-6458.2178
	GGA(WC)	0.76856	0.76856	0.54938	90	90	90	-6441.6260
	LDA(CA-PZ)	0.7471	0.7471	0.52843	90	90	90	-6474.0463
γ-Bi₂O₃	Experimental data	1.025	1.025	1.025	90	90	90
	GGA(PBE)	1.02482	1.02482	1.02482	90	90	90	-17905.0688
	GGA(RPBE)	1.04211	1.04211	1.04211	90	90	90	-17921.4047
	GGA(PW91)	1.02284	1.02284	1.02284	90	90	90	-17923.5416
	GGA(WC)	1.00512	1.00512	1.00512	90	90	90	-17878.6071
	LDA(CA-PZ)	0.9768	0.9768	0.9768	90	90	90	-17976.4001
δ-Bi₂O₃	Experimental data	0.56595	0.56595	0.56595	90	90	90
	GGA(PBE)	0.61886	0.61886	0.61886	90	90	90	-14461.6655
	GGA(RPBE)	0.61992	0.61992	0.61992	90	90	90	-14472.1577
	GGA(PW91)	0.61873	0.61873	0.61873	90	90	90	-14477.5683
	GGA(WC)	0.61716	0.61716	0.61716	90	90	90	-14441.4486
	LDA(CA-PZ)	0.61703	0.61703	0.61703	90	90	90	-14469.0378
ε-Bi₂O₃	Experimental data	0.49555	0.55854	1.27299	90	90	90
	GGA(PBE)	0.52672	0.58311	1.32275	90	90	90	-6442.5117
	GGA(RPBE)	0.52768	0.5792	1.31738	90	90	90	-6454.1838
	GGA(PW91)	0.52626	0.59106	1.29263	90	90	90	-6449.5727
	GGA(WC)	0.50199	0.58217	1.30291	90	90	90	-6430.6840
	LDA(CA-PZ)	0.52219	0.5814	1.28529	90	90	90	-6463.4572
η-Bi₂O₃	Experimental data	0.38781	0.38781	0.63031	90	90	120
	GGA(PBE)	0.38434	0.38434	0.59898	90	90	120	-1612.6690
	GGA(RPBE)	0.38559	0.38559	0.60292	90	90	120	-1613.9926
	GGA(PW91)	0.38414	0.38414	0.5994	90	90	120	-1614.3683
	GGA(WC)	0.38261	0.38261	0.59165	90	90	120	-1610.3816
	LDA(CA-PZ)	0.37171	0.37171	0.56963	90	90	120	-1618.1124

Fig.2 Calculated band structure(A), total density of states(B) and partial density of states(C,D) for α-Bi2O3

Fig.3 Calculated band structure(A), total density of states(B) and partial density of states(C,D) for β-Bi2O3

Fig.4 Calculated band structure(A), total density of states(B) and partial density of states(C,D) for γ-Bi2O3

Fig.5 Calculated band structure(A), total density of states(B) and partial density of states(C,D) for δ-Bi2O3

Fig.6 Calculated band structure(A), total density of states(B) and partial density of states(C,D) for ε-Bi2O3

Fig.7 Calculated band structure(A), total density of states(B) and partial density of states(C,D) for η-Bi2O3

Fig.8 Calculated electric potential of α, β, γ,δ, ε, η-Bi2O3 and TiO2

Fig.9 Calculated absorption spectra(A1—F1) and conductivity(A2—F2) of α-Bi2O3(A), β-Bi2O3(B),γ-Bi2O3(C), δ-Bi2O3(D), ε-Bi2O3(E), η-Bi2O3(F) along respective direction of polarization

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α,β,γ,δ,ε,η-Bi₂O₃电子结构和光学性质的第一性原理研究

First-principle Calculations on Electronic Structures and Optical Properties of α, β, γ, δ, ε, η-Bi₂ $O 3 †$

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