钴掺杂氧化铜/可见光协同活化PMS降解罗丹明B及其机理研究

doi:10.15541/jim20210090

无机材料学报 ›› 2021, Vol. 36 ›› Issue (11): 1171-1177.DOI: 10.15541/jim20210090

钴掺杂氧化铜/可见光协同活化PMS降解罗丹明B及其机理研究

兰青¹^,²(), 孙盛睿¹, 吴萍¹, 杨庆峰³(), 刘阳桥¹()

1.中国科学院上海硅酸盐研究所, 上海200050
2.中国科学院大学, 北京 100049
3.中国科学院上海高等研究院, 上海 201210

收稿日期:2021-02-08 修回日期:2021-03-15 出版日期:2021-11-20 网络出版日期:2021-03-15
通讯作者: 刘阳桥, 研究员. E-mail: yqliu@mail.sic.ac.cn;杨庆峰, 研究员. E-mail: yangqf@sari.ac.cn
作者简介:兰青(1996-), 男, 硕士研究生. E-mail: lanqing@student.sic.ac.cn
基金资助:
国家自然科学基金(51878647);国家自然科学基金(61574148)

Co-doped CuO/Visible Light Synergistic Activation of PMS for Degradation of Rhodamine B and Its Mechanism

LAN Qing¹^,²(), SUN Shengrui¹, WU Ping¹, YANG Qingfeng³(), LIU Yangqiao¹()

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China

Received:2021-02-08 Revised:2021-03-15 Published:2021-11-20 Online:2021-03-15
Contact: LIU Yangqiao, professor. E-mail: yqliu@mail.sic.ac.cn;YANG Qingfeng, professor. E-mail: yangqf@sari.ac.cn
About author:LAN Qing(1996-), male, Master candidate. E-mail: lanqing@student.sic.ac.cn
Supported by:
National Natural Science Foundation of China(51878647);National Natural Science Foundation of China(61574148)

摘要/Abstract

摘要：

元素掺杂是提升催化剂性能的重要方法。研究采用快速沉淀法制备了钴掺杂氧化铜(Co-doped CuO)纳米催化材料, 在可见光条件下, 20 min内其活化的过氧硫酸氢钾复合盐(PMS)对罗丹明B染料的降解率达到96%以上, 远优于同等条件制备的CuO。本研究还考察了溶液pH、染料初始浓度、催化剂用量等对降解效率影响。钴掺杂后氧化铜纳米颗粒由三维针梭状结构转变为近二维薄带状结构。同时钴掺杂提高了CuO的平带电位进而提升了电荷转移效率。XPS及EPR结果表明钴掺杂能够提高CuO的氧空位含量进而提升催化活性。捕获剂实验结果表明反应过程中的主要活性物种为空穴(h⁺_VB), 且羟基自由基(•OH)、单线态氧(¹O₂)、超氧自由基(•O₂^-)、硫酸根自由基(SO₄^-•)也参与了降解反应。最后, 本文初步阐明了Co-doped CuO协同可见光活化PMS降解有机污染物的反应机理。

关键词: 染料降解, 钴掺杂, 过氧硫酸氢钾复合盐(PMS), CuO

Abstract:

Elemental doping is an important method for improving the efficiency of catalysts. In this study, cobalt-doped CuO catalysts were prepared using a rapid precipitation method for the effective degradation of organic pollutants by photo-assisted activation of potassium peroxymonosulfate (PMS). The Co-doped CuO catalyst demonstrated degradation efficiency as high as 96% within 20 min reaction under visible light conditions, which is much higher than that of the undoped CuO. Cobalt doping transformed copper oxide nanoparticles from a three-dimensional needle-shape structure to a near-two-dimensional thin ribbon-like structure. Cobalt doping increases the flat-band potential of CuO and thus enhances the charge transfer efficiency. Furthermore, the effects of solution pH, initial dye concentration and catalyst dosage on the degradation efficiency were also investigated. XPS and EPR results show that cobalt doping can increase the oxygen vacancy content in CuO and thus improves the activation properties. The result of the trapping agent experiments indicates that main active species in the reaction are holes, while hydroxyl radicals, singlet oxygen, superoxide radicals and sulfate radicals are also involved. Finally, the reaction mechanism for the photo-assisted Co-doped CuO activated PMS degradation of RhB are generally proposed.

Key words: dye degradation, cobalt doping, potassium peroxymonosulfate, CuO

中图分类号:

TQ034

兰青, 孙盛睿, 吴萍, 杨庆峰, 刘阳桥. 钴掺杂氧化铜/可见光协同活化PMS降解罗丹明B及其机理研究[J]. 无机材料学报, 2021, 36(11): 1171-1177.

LAN Qing, SUN Shengrui, WU Ping, YANG Qingfeng, LIU Yangqiao. Co-doped CuO/Visible Light Synergistic Activation of PMS for Degradation of Rhodamine B and Its Mechanism[J]. Journal of Inorganic Materials, 2021, 36(11): 1171-1177.

图/表 9

图1 Co-doped CuO和CuO-S的XRD图谱

Fig. 1 XRD patterns of CuO-S and Co-doped CuO

图2 CuO-S(a)和Co-doped CuO(b)的SEM照片

Fig. 2 SEM images of CuO-S (a) and Co-doped CuO (b) catalysts

图3 光照条件下Co-doped CuO和CuO-S的催化性能对比

Fig. 3 Comparison of the catalytic performance of Co-doped CuO and CuO-S under visible light illumination (PMS concentration=0.4 g/L; Initial RhB concentration=25 mg/L, catalyst dosage=0.4 g/L)

图4 催化剂用量(a)、染料初始浓度(b)、pH(c)对RhB降解效率的影响, 循环实验结果(d)

Fig. 4 Influences of catalyst dosage (a), initial dye concentration (b), solution pH (c) on catalytic performance, the recycling experiment results (d)

图5 CuO-S及Co-doped CuO的电化学阻抗谱(a), 光电流曲线(插图为莫特-肖特基曲线)(b), 漫反射图谱(c)以及Zeta电位曲线(d)

Fig. 5 Electrochemical impedance spectra (a), photocurrent(inset showing Mott-Schottky) curves (b), Diffuse reflection spectra (c), Zeta potential curves (d) of CuO-S and Co-doped CuO

图6 反应前后Co-doped CuO的Co2p(a)、Cu2p(b)、O1s(c) XPS谱图, Co-doped CuO和CuO-S反应前的O1s(d)、Cu2p(e)XPS谱图

Fig. 6 Comparation of XPS spectra of Co-doped CuO before and after reaction (Co2p (a), Cu2p (b), O1s (c)) XPS spectra of catalysts Co-doped CuO and CuO-S before reaction(O1s (d), Cu2p (e))

图7 CuO-S和Co-doped CuO的电磁顺磁共振谱图

Fig. 7 EPR spectra of CuO-S and Co-doped CuO

图8 Co-doped CuO的自由基捕获剂实验

Fig. 8 Free radical capture experiments of Co-doped CuO

图9 Co-doped CuO活化PMS降解反应机理示意图

Fig. 9 Proposed reaction mechanism for photo-assisted Co-doped CuO activated PMS degradation

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钴掺杂氧化铜/可见光协同活化PMS降解罗丹明B及其机理研究

Co-doped CuO/Visible Light Synergistic Activation of PMS for Degradation of Rhodamine B and Its Mechanism

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