氧缺陷Bi2WO6-x可见光催化剂的制备和性能

doi:10.15541/jim20140446

摘要/Abstract

摘要：

采用乙二醇溶剂热法原位制备氧缺陷Bi₂WO_6-_x催化剂, 利用XRD、SEM、N₂吸附-脱附、XPS、ESR、UV-Vis DRS、PL及电化学方法对样品的理化性能进行了表征, 考察了样品在可见光下(λ > 400 nm)对气相苯的光催化降解性能。结果表明: 乙二醇溶剂热法制备的催化剂具有较大比表面积, 形成了Bi-O_v和W-O_v氧缺陷中心; 缺陷的生成改变了催化剂的能带结构, 缩小其光响应带隙宽度, 并有效抑制了光生电子-空穴对的复合, 催化剂的活性增强。Bi₂WO_6-_x降解苯的转化率和矿化率分别为52.5%和80.6%, 是Bi₂WO₆的1.72倍和1.84倍。

关键词: Bi2WO6, 溶剂热法, 氧缺陷, 可见光

Abstract:

Oxygen-deficient Bi₂WO_6-_x catalyst was prepared in situ by a solvothermal method using ethylene glycol as the solvent. The physicochemical properties of the as-prepared catalyst were characterized by XRD, SEM, N₂ isothermal, XPS, ESR, UV-Vis DRS, PL and electrochemical analyses. The photocatalytic activity of catalysts was evaluated by the degradation of gaseous benzene under visible-light irradiation (λ > 400 nm). The results indicate that the oxygen-deficient Bi₂WO_6-_x with a larger specific surface area possesses Bi-O_v and W-O_v oxygen vacancies. The formation of oxygen defects narrows optical bandgap of Bi₂WO₆ and hinders photoinduced electron-hole pairs from recombination, which enhances the photocatalytic activity. The conversion and mineralization rates of benzene on the as-prepared Bi₂WO_6-_x are increased up to 52.5% and 80.6%, respectively, which are correspondingly 1.72 and 1.84 times as high as those on the pristine Bi₂WO₆.

Key words: Bi2WO6, solvothermal method, oxygen vacancies, visible light

中图分类号:

O643

卢青, 华罗光, 陈亦琳, 高碧芬, 林碧洲. 氧缺陷Bi₂WO_6-_x可见光催化剂的制备和性能[J]. 无机材料学报, 2015, 30(4): 413-419.

LU Qing, HUA Luo-Guang, CHEN Yi-Lin, GAO Bi-Fen, LIN Bi-Zhou. Preparation and Property of Oxygen-deficient Bi₂WO_6-_x Photocatalyst Active in Visible Light[J]. Journal of Inorganic Materials, 2015, 30(4): 413-419.

图/表 10

图1 催化剂的XRD图谱

Fig. 1 XRD patterns of the catalysts

图2 BWO (a)和BWO-v (b)的SEM照片

Fig. 2 SEM images of BWO (a) and BWO-v (b)

图3 催化剂的N2吸附-脱附曲线及孔径分布曲线

Fig. 3 N2 adsorption isotherm curves of the catalysts Insert shows the corresponding pore size distributions

图4 催化剂样品的XPS图谱和ESR图谱

Fig. 4 XPS (a-c) and ESR (d) spectra of the catalysts

表1 催化剂的XPS数据拟合分析

Table 1 XPS fitting data of catalysts

Sample	Bi4f				W4f				O1s
Sample	Position /eV	Area	FWHM /eV	Assignment	Position /eV	Area	FWHM /eV	Assignment	Position /eV	Area	FWHM /eV	Assignment
BWO	159.00	295327	1.09	Bi₂WO₆, 4f_7/2	35.25	56766	0.96	Bi₂WO₆, 4f_7/2	530.09	46363	1.24	O_{lattice, Bi}-Bi
	164.30	221495	1.12	Bi₂WO₆, 4f_5/2	37.40	42574	0.94	Bi₂WO₆, 4f_5/2	530.67	82916	1.57	O_{lattice, W}-W
									532.20	14983	1.65	OH, O₂
BWO-v	158.85	180241	1.18	Bi₂WO₆, 4f_7/2	35.00	34737	1.03	Bi₂WO₆, 4f_7/2	531.11	24118	1.22	O_{lattice, Bi}-Bi
	164.15	135181	1.21	Bi₂WO₆, 4f_5/2	37.15	26053	1.00	Bi₂WO₆, 4f_5/2	530.69	47240	1.58	O_{lattice, W}-W
									532.09	19536	1.87	OH, O₂

表2 催化剂的O1s XPS分析结果

Table 2 Results of O1s XPS analysis of catalysts

Sample	O_{lattice, Bi}: Bi	O_{lattice, W}: W	O_ad : O_total
Bi₂WO₆	0.94	3.77	0.10
Bi₂WO_6-_x	0.89	3.51	0.21

图5 催化剂的紫外-可见光漫反射吸收图谱

Fig. 5 UV-Vis DRS of the catalystsThe inset is (αhv)0.5 vs photon energy (hv) plots for the corresponding catalysts

图6 催化剂的Mott-Schottky曲线

Fig. 6 Mott-Schottky curves of the catalysts The inset shows schematic diagram of bandgap structure of Bi2WO6-x

图7 催化剂的荧光发射光谱 (a) 和光电流曲线(b)

Fig. 7 Photoluminescence spectra (a) and photocurrent curves of the catalysts (b)

图8 催化剂光催化降解苯的活性 (λ > 400 nm)

Fig. 8 Photocatalytic conversion and mineralization of benzene over catalysts under visible light irradiation (λ > 400 nm)

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氧缺陷Bi₂WO_6-_x可见光催化剂的制备和性能

Preparation and Property of Oxygen-deficient Bi₂WO_6-_x Photocatalyst Active in Visible Light

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