Fe(III)/rGO/Bi2MoO6复合光催化剂制备及光催化芬顿协同降解苯酚

doi:10.15541/jim20200437

无机材料学报 ›› 2021, Vol. 36 ›› Issue (6): 615-622.DOI: 10.15541/jim20200437 CSTR: 32189.14.10.15541/jim20200437

Fe(III)/rGO/Bi₂MoO₆复合光催化剂制备及光催化芬顿协同降解苯酚

安伟佳¹(), 李静¹^,², 王淑瑶¹, 胡金山¹, 蔺在元², 崔文权¹(), 刘利¹, 解珺³, 梁英华¹()

1.华北理工大学化学工程学院, 河北省环境光电催化材料重点实验室, 唐山 063210
2.唐山中地地质工程有限公司, 唐山 063009
3.河北省地矿局第二地质大队, 唐山 063009

收稿日期:2020-08-10 修回日期:2020-11-12 出版日期:2021-06-20 网络出版日期:2020-12-10
通讯作者: 崔文权, 教授. E-mail: wkcui@ncst.edu.cn; 梁英华, 教授. E-mail: liangyh@ncst.edu.cn
作者简介:安伟佳(1989-), 男, 高级实验师, E-mail: anweijia@ncst.edu.cn
基金资助:
国家自然科学基金(51672081);河北省自然科学基金(B2018209356);河北省自然科学基金高端钢铁冶金联合基金(B2020209008);河北省教育厅基金(QN2018056)

Fe(III)/rGO/Bi₂MoO₆ Composite Photocatalyst Preparation and Phenol Degradation by Photocatalytic Fenton Synergy

AN Weijia¹(), LI Jing¹^,², WANG Shuyao¹, HU Jinshan¹, LIN Zaiyuan², CUI Wenquan¹(), LIU Li¹, XIE Jun³, LIANG Yinghua¹()

1. College of Chemical Engineering, Hebei Key Laboratory for Environment Photocatalytic and Electrocatalytic Materials, North China University of Science and Technology, Tangshan 063210, China
2. Tangshan Zhongdi Geological Engineering Co., Ltd., Tangshan 063009, China
3. The Second Geological Team of Hebei Bureau of Geology and Mineral Resources, Tangshan 063009, China

Received:2020-08-10 Revised:2020-11-12 Published:2021-06-20 Online:2020-12-10
Contact: CUI Wenquan, professor. E-mail: wkcui@ncst.edu.cn; LIANG Yinghua, professor. E-mail: liangyh@ncst.edu.cn
About author:AN Weijia(1989-), male, senior laboratory technician. E-mail: anweijia@ncst.edu.cn
Supported by:
National Natural Science Foundation of China(51672081);Natural Science Foundation of Hebei Province(B2018209356);Natural Science Foundation-Steel and Iron Foundation of Hebei Province(B2020209008);Youth Fund Project of Hebei Province Department of Education(QN2018056)

摘要/Abstract

摘要：

光催化-芬顿技术耦合可高效降解有机污染物。本研究采用溶剂热法制备了Fe(III)掺杂rGO/Bi₂MoO₆复合催化剂(Fe(III)/rGO/Bi₂MoO₆), 通过外加H₂O₂构建了光催化-芬顿协同体系, 可见光照射3 h后对苯酚的降解率(82%)远高于单独光催化(18%)或芬顿反应(48%), 进一步优化条件对苯酚可实现完全降解。这主要是通过Fe得失电子实现价态的转变, 并以此作为桥梁实现光催化-芬顿的协同作用。同时石墨烯的优异导电性能不仅克服了光催化中光生电子空穴难以分离的问题, 而且促进了Fe³⁺/Fe²⁺的循环反应, 促使芬顿反应产生更多的羟基自由基(?OH), 进一步提高了苯酚的降解效率。实验考察了Fe(III)含量、催化剂投加量、H₂O₂含量以及pH等因素对协同降解效果的影响。淬灭实验证明?OH是协同降解体系中最主要的活性物种, ?O₂^-和h⁺对降解活性也会产生一定的影响, 结合实验结果提出了Fe(III)/rGO/Bi₂MoO₆光催化-芬顿协同降解苯酚的机理。

关键词: Fe(III)/rGO/Bi₂MoO₆, 光催化-芬顿, 协同, 降解

Abstract:

The photocatalysis-Fenton technology coupling can efficiently degrade organic pollutants. In this study, Fe(III)-doped rGO/Bi₂MoO₆ composite catalyst (Fe(III)/rGO/Bi₂MoO₆) was prepared by solvothermal method, and the photocatalysis-Fenton synergy system was constructed by adding H₂O₂. The phenol degradation activity under 3 h visible light irradation is 82%, much higher than that of photocatalysis alone (18%) or renton reaction (48%), and further optimization can achieve full degration of phenol. This can be mainly attributed to the transformation of the valence state through the gain and loss of Fe electrons, which serves as a bridge to realize the photocatalysis- Fenton synergy. Meanwhile, the excellent electrical conductivity of graphene overcomes the difficulty of separating photo-generated electron holes in photocatalysis, and promotes the cyclic reaction of Fe³⁺/Fe²⁺, and then accelerates the Fenton reaction to produce more free hydroxyl groups (?OH), which further improves the degradation efficiency. Effects of Fe(III) content, catalyst dosage, H₂O₂ content, and pH on the synergy degradation performance were investigated. The quenching experiment proves that ?OH is one of the main active species in the degradation system, while ?O₂^- and H⁺ also have a certain effect on the degradation activity. The mechanism of Fe(III)/rGO/Bi₂MoO₆ photocatalysis-Fenton synergy degradation is also proposed based on the present experimental results.

Key words: Fe(III)/rGO/Bi₂MoO₆, photocatalysis-Fenton, synergy, degradation

中图分类号:

O643

安伟佳, 李静, 王淑瑶, 胡金山, 蔺在元, 崔文权, 刘利, 解珺, 梁英华. Fe(III)/rGO/Bi₂MoO₆复合光催化剂制备及光催化芬顿协同降解苯酚[J]. 无机材料学报, 2021, 36(6): 615-622.

AN Weijia, LI Jing, WANG Shuyao, HU Jinshan, LIN Zaiyuan, CUI Wenquan, LIU Li, XIE Jun, LIANG Yinghua. Fe(III)/rGO/Bi₂MoO₆ Composite Photocatalyst Preparation and Phenol Degradation by Photocatalytic Fenton Synergy[J]. Journal of Inorganic Materials, 2021, 36(6): 615-622.

图/表 12

图1 (a)Bi2MoO6和(b)rGO/Bi2MoO6的SEM照片; Fe(III)/ rGO/Bi2MoO6的TEM(c)和HRTEM(d)照片

Fig. 1 (a) SEM images of Bi2MoO6 and (b) rGO/Bi2MoO6; TEM (c) and HRTEM (d) images of Fe(III)/rGO/Bi2MoO6

图2 Bi2MoO6、rGO/Bi2MoO6和Fe(III)/rGO/Bi2MoO6的XRD图谱

Fig. 2 XRD patterns of Bi2MoO6, rGO/Bi2MoO6, Fe(III)/rGO/ Bi2MoO6

图3 Bi2MoO6, GO/Bi2MoO6和Fe(III)/rGO/Bi2MoO6样品的XPS谱图

Fig. 3 XPS spectra of the compared composites (a) Full spectrum analysis; (b-f) XPS spectra of various element; (g) XPS spectra of valence band in Bi2MoO6

图4 (a)光催化、芬顿反应和光催化-芬顿协同降解苯酚活性对比; (b)不同条件下降解速率常数

Fig. 4 (a) Phenol degradation activity by photocatalysis, Fenton, and photocatalysis-Fenton synergy, and (b) degradation rate constant over different conditions

图5 (a)光催化-芬顿协同降解的稳定性, (b) 光催化、芬顿反应和光催化-芬顿协同降解苯酚的TOC结果

Fig. 5 (a) Photocatalysis-Fenton synergy degradation stability test, (b) TOC removal of phenol over photocatalysis, Fenton reaction, and photocatalysis-Fenton synergy

图6 不同催化剂加入H2O2 (a)前(b)后的光电流响应曲线

Fig. 6 Photocurrent response curves of different composites (a) before and (b) after adding H2O2

图7 (a)淬灭剂对降解性能的影响, (b)光催化、芬顿和光催化-芬顿协同生成?OH的浓度对比

Fig. 7 (a) Influence of degradation activity with the addition of quenchers, and (b) concentration of ?OH generated at photocatalysis, Fenton and photocatalysis-Fenton synergy

图8 Fe(III)/rGO/Bi2MoO6光催化-芬顿协同降解机理示意图

Fig. 8 Mechanism of photocatalysis-Fenton synergy degradation over Fe(III)/rGO/Bi2MoO6

图S1 样品的(a)紫外-可见漫反射光谱和(b) Kubelka-Munk转换曲线

Fig. S1 (a) Diffusive UV-Vis spectra and (b) Kubelka- Munk conversion curve of the composites

图S2 (a, b)协同作用和光催化, 芬顿反应的降解活性对比

Fig. S2 (a, b) the comparison of degradation activity over synergy and photocatalysis, Fenton

图S3 不同苯酚去除效率的活性对比图

Fig. S3 Comparison of the activity of different phenol removal efficiency (a) different proportions of Fe (III) (C0 = 5 ppm); (b) Different catalyst dosages (C0 = 5 ppm, 20% Fe (III)/rGO/Bi2MoO6); (c) different amounts of hydrogen peroxide (C0 = 5 ppm, 20% Fe (III)/rGO/Bi2MoO6, catalyst concentration: 1.0 g/L); (d) different pH (C0 = 5 ppm, 20 % Fe (III)/rGO/Bi2MoO6, catalyst concentration: 1.0 g/L, H2O2 = 19.5 mmol/L) *ppm=mg/L

图S4 (a, b)不同催化剂的电化学阻抗谱; (b) Fe(III)/rGO/ Bi2MoO6和加入H2O2的电化学阻抗谱

Fig. S4 (a) EIS of different photocatalyst composites; (b) EIS of Fe(III)/rGO/Bi2MoO6 and Fe(III)/rGO/Bi2MoO6 + H2O2

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Fe(III)/rGO/Bi₂MoO₆复合光催化剂制备及光催化芬顿协同降解苯酚

Fe(III)/rGO/Bi₂MoO₆ Composite Photocatalyst Preparation and Phenol Degradation by Photocatalytic Fenton Synergy

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