四元BiMnVO5的合成、电子结构与可见光催化性能研究

doi:10.15541/jim20210263

无机材料学报 ›› 2022, Vol. 37 ›› Issue (1): 58-64.DOI: 10.15541/jim20210263 CSTR: 32189.14.10.15541/jim20210263

四元BiMnVO₅的合成、电子结构与可见光催化性能研究

张弦(), 张策, 姜文君, 冯德强, 姚伟()

中国空间技术研究院钱学森空间技术实验室, 北京 100094

收稿日期:2021-04-21 修回日期:2021-07-02 出版日期:2022-01-20 网络出版日期:2021-07-12
通讯作者: 姚伟, 研究员. E-mail: yaowei@qxslab.cn
作者简介:张弦(1989-), 男, 博士, 高级工程师. E-mail: zhangxian@qxslab.cn
基金资助:
国家自然科学基金(22001263);中国航天科技集团钱学森青年创新基金(Y-KC-JT-QXS-012)

Synthesis, Electronic Structure and Visible Light Photocatalytic Performance of Quaternary BiMnVO₅

ZHANG Xian(), ZHANG Ce, JIANG Wenjun, FENG Deqiang, YAO Wei()

Qian Xuesen Laboratory of Space Technology, China Academy of Space Technology, Beijing 100094, China

Received:2021-04-21 Revised:2021-07-02 Published:2022-01-20 Online:2021-07-12
Contact: YAO Wei, professor. E-mail: yaowei@qxslab.cn
About author:ZHANG Xian(1989-), male, PhD, senior engineer. E-mail: zhangxian@qxslab.cn
Supported by:
National Natural Science Foundation of China(22001263);Qian Xuesen Youth Innovation Fund(Y-KC-JT-QXS-012)

摘要/Abstract

摘要：

光催化去除水体中的有机污染物在污水净化领域具有广阔的应用前景。本研究分别采用水热法和固相法合成了四元BiMnVO₅可见光催化剂, 对催化剂的形貌结构和光学性质进行了表征分析, 并计算了其电子结构。结果表明, 水热法可以快速合成高纯度、高结晶度的BiMnVO₅。BiMnVO₅为直接带隙半导体, 禁带宽度为1.8 eV, 与第一性原理计算结果一致。态密度分析结果表明, 其光吸收可归因于从Mn3d/O2p到V3d的电子跃迁。光催化实验结果显示, 水热法合成的BiMnVO₅催化剂的催化活性最高, 可见光照射4 h后, 亚甲基蓝的降解率为98%。羟基自由基和光生空穴是光催化过程中的主要活性物。经过5次循环利用后,该催化剂对亚甲基蓝的降解率仍可达85%, 且形貌结构不变, 表现出良好的稳定性。

关键词: BiMnVO₅半导体, 水热法, 电子结构, 光催化

Abstract:

Removal of organic pollutants from water bodies by photocatalysis has broad application prospects in the field of sewage purification. In this study, the quaternary BiMnVO₅ was synthesized by hydrothermal method and solid-state reaction, respectively. The morphology, structure and optical properties of the catalysts were characterized, and the electronic structure was calculated. Results showed that the hydrothermal method can rapidly synthesize pure BiMnVO₅ with high crystallinity. BiMnVO₅ is a semiconductor with a direct band gap of 1.8 eV, which is consistent with the results of first-principles calculations. Analysis of the density of states further reveals that the optical absorption band are attributed to the transitions from Mn3d/O2p to V3d. The photocatalytic results show that the BiMnVO₅ synthesized by hydrothermal method exhibits the highest catalytic activity. About 98% Methylene Blue (MB) is degraded when exposed to visible light for 4 h. The hydroxyl radicals and photo-generated holes are proved to be the main active substances in the photocatalytic process. After 5 cycles, it still maintains capacity of degrading 85% MB in 4 h under visible light irradiation, while its morphology and structure remain unchanged, which indicates BiMnVO₅ a good photocatalyst with reliable stability.

Key words: BiMnVO₅ semiconductor, hydrothermal method, electronic structure, photocatalysis

中图分类号:

TQ174

张弦, 张策, 姜文君, 冯德强, 姚伟. 四元BiMnVO₅的合成、电子结构与可见光催化性能研究[J]. 无机材料学报, 2022, 37(1): 58-64.

ZHANG Xian, ZHANG Ce, JIANG Wenjun, FENG Deqiang, YAO Wei. Synthesis, Electronic Structure and Visible Light Photocatalytic Performance of Quaternary BiMnVO₅[J]. Journal of Inorganic Materials, 2022, 37(1): 58-64.

图/表 9

图1 MnO、BiVO4和BiMnVO5能带结构示意图

Fig. 1 Schematic band structure of MnO, BiVO4 and BiMnVO5

图2 水热法合成BiMnVO5粉体的SEM照片与EDX元素分布

Fig. 2 SEM images and EDX elemental mappings of the hydrothermal synthesized BiMnVO5 powder

图3 (a)BiMnVO5粉体的XRD谱图和(b)BiMnVO5的晶体结构

Fig. 3 (a) XRD patterns of the as-synthesized BiMnVO5 powders, and (b) crystal structure of BiMnVO5

图4 BiMnVO5粉体的(a)Bi4f、(b)Mn2p、(c)V2p和(d)O1s XPS图谱

Fig. 4 (a) Bi4f, (b) Mn2p, (c) V2p, and (d) O1s XPS spectra of the as-synthesized BiMnVO5 powders

图5 BiVO4、BMVO-S和BMVO-H催化剂的(a)紫外-可见-近红外漫反射光谱和(b) [F(R)hn]2随hn的变化曲线

Fig. 5 (a) UV-Vis diffuse reflection spectra and (b) [F(R)hn]2 vs hν curves of BMVO-S and BMVO-H photocatalysts

图6 BiMnVO5的能带结构(a)和态密度(b)

Fig. 6 (a) Band structure and (b) density of states of BiMnVO5

图7 BMVO-H样品的XPS价带谱(插图为VB、CB和Ef的相对位置)

Fig. 7 XPS valance band of BMVO-H sample with inset showing the relative positions of VB, CB and Ef

图8 (a)不同催化条件下MB浓度随时间变化曲线和(b)加入不同捕捉剂后MB浓度随时间变化曲线

Fig. 8 (a) Curves of MB concentration vs time under different catalytic conditions, and (b) curves of MB concentration vs time with different scavengers

图9 (a)BMVO-H样品可见光催化降解MB的重复试验, (b)5次循环后BMVO-H样品的SEM照片和 (c)5次循环前后BMVO-H样品的XRD图谱

Fig. 9 (a) Repeated test for visible light degradation of MB for BMVO-H sample, (b) SEM image of BMVO-H sample after 5 cycles, and (c) XRD patterns of BMVO-H sample before and after 5 cycles

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四元BiMnVO₅的合成、电子结构与可见光催化性能研究

Synthesis, Electronic Structure and Visible Light Photocatalytic Performance of Quaternary BiMnVO₅

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