含铋复合氧化物可见光催化材料研究进展

doi:10.3724/SP.J.1077.2012.00011

摘要/Abstract

摘要：

光催化材料因可以利用太阳能净化环境, 受到广泛关注. 一些含铋复合氧化物半导体可直接被可见光激发, 更有效地利用太阳能, 实现有机污染物的矿化, 成为近期光催化材料研究领域的热点之一. 本文概述了Bi₂WO₆、BiVO₄和Bi₂MoO₆三种常见的含铋复合氧化物可见光催化材料体系的近期研究进展. 通过合成方法的优选、晶粒成核和生长的调节, 实现晶粒尺寸、形貌、结晶度等微结构的控制, 从而获得小尺寸、高表面积的光催化材料, 无论是在有机染料、苯酚和乙醛等多种模拟污染物的矿化, 还是抗菌等方面, 它们皆呈现出优秀的可见光催化性能. 通过进一步发展, 含铋复合氧化物有望实现在环境净化领域的应用.

关键词: 含铋复合氧化物, 光催化, 可见光, 环境净化, 综述

Abstract:

Photocatalysts could utilize solar energy to remedy environmental pollutions thus attract world wide attention. Some bismuth-containing complex oxides could be activated by visible light and mineralize organic pollutants. In this paper we reviewed recent progresses on the development of Bi₂WO₆, BiVO₄ and Bi₂MoO₆ photocatalysts. By controlling the particle size, morphology, crystallinity and other microstructures via different methods, the photocatalytic activities in the degradation of organic dyes, colorless model pollutants such as phenol and acetaldehyde, and disinfection of these visible light induced photocatalysts were greatly enhanced. Through further development, bismuth- containing complex oxides are hopeful to be applied in the field of environmental remediation.

Key words: bismuth containing complex oxides, photocatalyst, visible light, environmental remediation, review

中图分类号:

TB322

王文中, 尚萌, 尹文宗, 任佳, 周林. 含铋复合氧化物可见光催化材料研究进展[J]. 无机材料学报, 2012, 27(1): 11-18.

WANG Wen-Zhong, SHANG Meng, YIN Wen-Zong, REN Jia, ZHOU Lin. Recent Progress on the Bismuth Containing Complex Oxide Photocatalysts[J]. Journal of Inorganic Materials, 2012, 27(1): 11-18.

图/表 11

图1 Bi2WO6的晶体结构示意图和能带结构图[6]

Fig. 1 Schematic structure of Bi2WO6 photocatalyst and energy band diagram of Bi2WO6 calculated by the DFT method[6]

图2 160℃水热24 h制备的Bi2WO6的XRD图谱(A)和TEM照片(B)[19]

Fig. 2 XRD pattern (A) and TEM image (B) of Bi2WO6 prepared by hydrothermal method at 160℃ for 24 h[19]

图 3 (A) Bi2WO6的紫外-可见漫反射光谱; (B) RhB水溶液的紫外-可见光降解; (C) 不同Bi2WO6的光催化性能对比(用于对比的钨酸铋分别采用固相法,传统水热法, 柠檬酸铋铵为铋源水热法合成; (D) 可见光下光催化降解RhB的循环稳定性[19]

Fig. 3 (A) UV-Vis diffuse reflectance spectra of the Bi2WO6 nanosheet; (B) Temporal change of UV-Vis spectrum of RhB aqueous solution; (C) Comparison of the photocatalytic activities of different Bi2WO6 and blank test (the Bi2WO6 used for comparison are prepared by solid-state reaction, traditional hydrothermal, and hydrothermal method using Bi(NH3)2C6H7O7 as Bi source, respectively; (D) Cycling runs in the photocatalytic degradation of RhB in the presence of Bi2WO6 nanosheet under visible-light[19]

图4 (A) 碳球的TEM照片; (B) Bi2WO6纳米笼的SEM照片; (C) 光催化材料的活性对比; (D) RhB的紫外-可见吸收光谱随光照时间的变化[26]

Fig. 4 (A) TEM image of carbon spheres; (B) SEM image of Bi2WO6 nanocages; (C) The photo-degradation efficiencies of RhB as a function of irradiation time by different photocatalysts; (D) The temporal evolution of the spectra during the photodegradation of RhB mediated by the Bi2WO6 nanocages under visible light (λ > 420 nm)[26]

图 5 纳米纤维(a)热处理前和(b)热处理后的SEM照片; (c) 可见光下降解乙醛时CO2浓度随光照时间的变化; (d) 降解水中氨氮的性能对比[29]

Fig. 5 SEM images of Bi2WO6 nanofibers before calcination (a) and after calcinations (b); (c) photocatalytic degradation of CH3CHO (1×10-4) under visible-light (λ >420 nm); (d) Comparison of the photocatalytic degradation of NH4+/NH3 by different samples[29]

图6 (A) Bi2WO6光催化抗菌对比实验图片: (a)空白样; (b)仅光照; (c)仅有Bi2WO6; (d) Bi2WO6在光照下2 h; (B) E. coli的存活率: (a) Bi2WO6在无光照时(0.5 mg/mL); (b)光照无催化材料; (c) Bi2WO6(0.5 mg/mL)在可见光下; (C) E. coli经Bi2WO6在光照下处理前后的TEM照片(a)处理前, (b)处理后[34]

Fig. 6 (A) Images of colonies on an agar plates: (a) E. coli suspension before reaction; (b) E. coli suspension containing Bi2WO6 in the dark; (c) E. coli suspension without Bi2WO6 under visible light irradiation; (d) E. coli suspension containing Bi2WO6 under visible light irradiation. (B) Survival ratio of E. coli in aqueous dispersions: (a) Bi2WO6 in the dark; (b) No catalyst; and (c) Bi2WO6 under visible light irradiation. (C) TEM images of E. coli irradiated by visible light with Bi2WO6 (a) E. coli before reaction; (b) E. coli treated for 2 h[34]

图7 (a) BiVO4(z-t)和(b) BiVO4(s-t)的能级图[1]

Fig. 7 Total and partial density of states for the BiVO4(z-t) (a) and BiVO4(s-t) (b) [1]

图8 超声化学法制备的BiVO4 的SEM照片(A)和XRD图谱(B), 其中超声时间为(a)30 min; (b)60 min和(c)固相反应制备的BiVO4; (C) 紫外-可见漫反射光谱, 插图为能带估算?αhv?-(hv)曲线; (D) 超声、固相反应制备的 BiVO4和P25的可见光降解甲基橙的吸收光谱及活性对比(插图)[44]

Fig. 8 SEM image (A) and XRD patterns (B) of UR-BiVO4 when ultrasonic time was 30 min (a), 60 min (b) and by solid state reaction; (C) UV-Vis diffuse reflectance spectra of UR-BiVO4 and SSR-BiVO4 samples, Inset: plots of ?αhv? versus photon energy (hv); (D) Changes of UV-Vis spectra of UR-BiVO4 suspended MO solution as a function of irradiation time. Inset: MO concentration changes over UR-BiVO4, SSR-BiVO4 and P25[44]

图9 (A) m-BiVO4空心球的TEM照片; (B) 光催化降解RhB的性能比较: m-BiVO4空心球(a)、液相法制备的BiVO4(b)和固相法制备的BiVO4(c)[45]

Fig. 9 (A) TEM of m-BiVO4 hollow spheres; (B) Comparison of the photodegradation of RhB by HS-BVO (a), AM-BVO (b), and SSR-BVO (c) under visible light (λ>420 nm)[45]

图10 (A) Bi2MoO6空心球的SEM照片; (B) 光催化降解苯酚的性能对比: HS-BMO(a), SSR-BMO(b), 光解(c)[51]

Fig. 10 (A) SEM image of Bi2MoO6 hollow spheres; (B) Photocatalytic degradation of phenol over HS-BMO (a), SSR- BMO (b) and photolysis (c) under visible-light (λ>420 nm) [51]

图11 Bi2MoO6在3 W蓝光LED光照下: (A) RhB的光降解; (B) 苯酚溶液的光降解; (C) 光催化抗菌: (b) Bi2MoO6在3W蓝光LED灯光照下6 h; (c) 空白样; (d) 只有Bi2MoO6; (e)只在3 W蓝光LED光照下[52]

Fig. 11 Photodegradation of RhB (A), phenol (B) and disinfection (C), ((b) Bi2MoO6 under the irradiation for 6 h; (c) control; (d) Bi2MoO6 only; (e) 3W blue LED only) by Bi2MoO6 under 3W blue LED[52]

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[54]	第一作者学术成就介绍:王文中, 男, 博士, 中国科学院上海硅酸盐研究所研究员, 中科院“百人计划”. 主要从事以铋基复合氧化物为主的可见光催化材料的设计、合成、光催化机理及其在环境净化方面的应用等研究工作. 在Angew. Chem. Int. Ed.等SCI期刊上发表论文90篇, 被引用2200余次, h因子26, 申请发明专利10余项. 曾获2007、2008、2009、2011年上海硅酸盐研究所优秀研究生指导教师, 2009年中科院朱李月华优秀教师, 2009年中科院优秀研究生指导教师, 2010年中国科学院上海分院第二届杰出青年科技创新人才.