水热法制备Cu掺杂可见光催化剂BiVO4及其光催化性能研究

doi:10.3724/SP.J.1077.2012.00019

无机材料学报 ›› 2012, Vol. 27 ›› Issue (1): 19-25.DOI: 10.3724/SP.J.1077.2012.00019

水热法制备Cu掺杂可见光催化剂BiVO₄及其光催化性能研究

陈渊^1,2, 周科朝¹, 黄苏萍¹, 李志友¹, 刘国聪^2,3

(1. 中南大学粉末冶金国家重点实验室, 长沙 410083; 2. 玉林师范学院新材料研发和化学生物传感技术所, 玉林 537000; 3. 中南大学化学化工学院, 长沙 410083)

收稿日期:2011-01-11 修回日期:2011-03-12 出版日期:2012-01-09 网络出版日期:2011-12-19
作者简介:陈渊(1971-), 女, 硕士, 副教授. E-mail: chenyuan197191@163.com
基金资助:
广西科学技术研究和开发项目(2010GXNSFB013018);广西高校优秀人才资助项目(2009G033);广西教育厅科研项目(200911LX368);玉林师范学院重点科研项目(2010YJZD13;2011YJD14)

Preparation and Photocatalytic Activity of Cu-doped BiVO₄ Photocatalysts Fabricated by Hydrothermal Method

CHEN Yuan^1,2, ZHOU Ke-Chao¹, HUANG Su-Ping¹, LI Zhi-You¹, LIU Guo-Cong^2,3

(1. State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China; 2. Institute of Advanced Materials & Chembiosensing Technology, Yulin Normal Univesty, Yulin 537000, China; 3. College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China)

Received:2011-01-11 Revised:2011-03-12 Published:2012-01-09 Online:2011-12-19
Supported by:
Technology Research and Exploitation of Guangxi Province (2010GXNSFB013018);Excellent Talents in Guangxi High Education (G2009033);Programs of Education Bureau of Guangxi Province (200911LX368);Key Foundation of Yulin Nornal University (2010YJZD13;2011YJD14)

摘要/Abstract

摘要：

以Bi(NO₃)₃·5H₂O、NH₄VO₃、Cu(NO₃)₂·3H₂O为原料, 采用水热法合成了Cu-BiVO₄光催化剂, 并利用X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)、紫外漫反射(UV-Vis)等测试手段对催化剂进行了表征. 结果表明, 提高前驱液pH值, 可得到单斜晶系白钨矿型Cu-BiVO₄光催化剂, BiVO₄的晶型结构并未随着Cu掺入量的增加而改变. 光催化剂中的Cu元素以CuO和Cu₂O的形式存在. Cu的引入使可见光吸收带发生红移, 吸收强度明显提高. 可见光催化降解亚甲基蓝溶液的结果表明, Cu掺杂有利于提高BiVO₄的活性. 其中pH值为5.0、Cu掺入量为1.0wt%的BiVO₄具有最好的光催化效果, 可见光照射60 min后, 对初始浓度为10 mg/L的亚甲基蓝溶液的最高降解率由纯BiVO₄的57.4%提高到97.8%. 并对Cu掺入后光催化活性提高的机理进行了分析.

关键词: 水热法, Cu-BiVO₄, 光催化, 亚甲基蓝, 制备

Abstract:

Cu-BiVO₄ photocatalysts were prepared by hydrothermal method using Bi(NO₃)₃·5H₂O, NH₄VO₃ and Cu(NO₃)₂·3H₂O as raw materials. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscope (XPS) and UV-Vis diffusion reflectance spectra (UV-Vis). The results show that highly crystalline monoclinic scheelite structure of Cu-BiVO₄ is obtained by increasing the pH value, and the crystal structures of BiVO₄ are no change with the increasing of Cu dopant. XPS results reveal that the doped Cu species exists in the form of CuO and Cu₂O. The Cu-BiVO₄ catalyst has a significant red-shift in the absorption band in the visible region, and the absorption intensity increases greatly for the composite catalyst compared with pure BiVO₄. The Cu-BiVO₄ photocatalysts enhance the photocatalytic activities for degradation of methylene blue (MB) under visible light irradiation. When pH value is 5.0 and Cu dopant is 1.0wt%, the photocatalytic activities reach the maximum. After visible light irradiation for 60 min, the removal rate of MB by Cu-BiVO₄(1.0wt% Cu) at 10 mg/L initial concentration increases to 97.8% while the removal rate of MB by pure BiVO₄ is only 54.7%. The mechanism of enhanced photocatalytic activity is also discussed.

Key words: hydrothermal method, Cu-BiVO₄, photocatalytic, methylene blue, preparation

中图分类号:

O643

陈渊, 周科朝, 黄苏萍, 李志友, 刘国聪. 水热法制备Cu掺杂可见光催化剂BiVO₄及其光催化性能研究[J]. 无机材料学报, 2012, 27(1): 19-25.

CHEN Yuan, ZHOU Ke-Chao, HUANG Su-Ping, LI Zhi-You, LIU Guo-Cong. Preparation and Photocatalytic Activity of Cu-doped BiVO₄ Photocatalysts Fabricated by Hydrothermal Method[J]. Journal of Inorganic Materials, 2012, 27(1): 19-25.

图/表 8

图1 不同pH值下制得的Cu-BiVO4(5.0wt% Cu)的XRD图谱

Fig. 1 XRD patterns of Cu-BiVO4 samples prepared under different pH values

图2 不同pH下制得的Cu-BiVO4(5.0wt% Cu)的SEM照片和EDS图谱

Fig. 2 SEM images and EDS spectrum of Cu-BiVO4 samples prepared under different pH values

图3 不同Cu掺入量Cu-BiVO4的XRD图谱

Fig. 3 XRD patterns of of Cu/BiVO4 samples doped with different Cu amounts

图4 不同掺Cu量Cu-BiVO4的SEM照片

Fig. 4 SEM images of Cu-BiVO4 samples doped with different Cu amounts

图5 Cu-BiVO4(5.0wt% Cu)的XPS图谱

Fig. 5 XPS spectra of Cu-BiVO4 (5.0wt% Cu)

图6 (a)不同Cu掺入量Cu-BiVO4的紫外吸收光谱, (b) Cu-BiVO4光催化剂的禁带宽度

Fig. 6 (a) UV-Vis diffuse reflectance spectra of Cu-BiVO4 samples doped with different Cu amounts, (b) band gap of photocatalysts

图7 Cu掺入量对Cu-BiVO4催化剂降解MB的影响

Fig. 7 Effects of Cu dopants in the Cu/BiVO4 on MB degradation efficiency

图8 可见光下MB 吸收光谱的变化

Fig. 8 Absorbance changes of MB under visible-light irradiation

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水热法制备Cu掺杂可见光催化剂BiVO₄及其光催化性能研究

Preparation and Photocatalytic Activity of Cu-doped BiVO₄ Photocatalysts Fabricated by Hydrothermal Method

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