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化学进展 2022, Vol. 34 Issue (5): 1191-1202 DOI: 10.7536/PC210728 前一篇   后一篇

• 综述 •

提高非均相芬顿催化活性策略、研究进展及启示

高文艳1, 赵玄1, 周曦琳1, 宋雅然1, 张庆瑞1,2,*()   

  1. 1.燕山大学 河北省水体重金属深度修复与资源利用重点实验室 秦皇岛 066004
    2.燕山大学亚稳材料制备科学与技术国家重点实验室 秦皇岛 066004
  • 收稿日期:2021-07-22 修回日期:2021-11-05 出版日期:2022-05-24 发布日期:2021-12-02
  • 通讯作者: 张庆瑞
  • 基金资助:
    国家自然科学基金项目(21876145); 河北省高等学校百名优秀创新人才支持计划(SLRC2019041)
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Strategies, Research Progress and Enlightenment of Enhancing the Heterogeneous Fenton Catalytic Reactivity: A Critical Review

Wenyan Gao1, Xuan Zhao1, Xilin Zhou1, Yaran Song1, Qingrui Zhang1,2()   

  1. 1. Hebei Key Laboratory of Heavy Metal Deep-Remediation in Water and Resource Reuse, Yanshan University,Qinhuangdao 066004, China
    2. State Key Laboratory of Metastable Science and Technology, Yanshan University, Qinhuangdao 066004, China
  • Received:2021-07-22 Revised:2021-11-05 Online:2022-05-24 Published:2021-12-02
  • Contact: Qingrui Zhang
  • Supported by:
    National Natural Science Foundation of China(21876145); Support Program for One Hundred Outstanding Innovative Talents in Higher Education Institutions in Hebei Province(SLRC2019041)

非均相芬顿反应由于固体芬顿催化剂与H2O2反应生成高活性羟基自由基,在去除难降解有机物方面得到了广泛的关注。与均相芬顿相比,其具有pH响应范围广、催化剂稳定性和可重复使用性好以及产泥量少等优点。然而,非均相芬顿反应仍存在一些缺陷,如金属离子析出、H2O2有效利用率低和Fe(Ⅱ)生成速率慢等,阻碍了非均相芬顿在实际废水处理中的应用。为解决这些问题研究者做了大量的工作,本文综述了非均相芬顿反应机制,总结了加速Fe(Ⅱ)生成和促进H2O2分解的策略,以期为开展非均相芬顿催化剂的研究提供技术支持。

关键词： 非均相芬顿, Fe(Ⅲ)/Fe(Ⅱ)循环, 过氧化氢, 羟基自由基

Heterogeneous Fenton reactions have attracted tremendous attention for recalcitrant organic contaminants removal, as the reaction between solid Fenton catalysts and H2O2 can generate highly reactive hydroxyl radicals. Additionally, compared to the homogeneous Fenton reaction, it has the advantages of wide pH response range, good catalyst stability and reusability, as well as less-production of iron sludge. However, some defects of heterogeneous Fenton reaction, such as metal ion precipitation, low effective utilization of H2O2 and slow formation rate of Fe(Ⅱ), limiting its application in real wastewater treatment. Therefore, numbers of research have introduced numerous techniques to overcome these drawbacks. In the present review, we summarize the mechanism of homogeneous and heterogeneous Fenton reaction. We also elucidate the strategies for accelerating the formation of Fe(Ⅱ) and promoting the decomposition of H2O2. We believe this review will provide a new insight into the future direction research in the heterogeneous Fenton catalyst.

Contents

1 Introduction

2 Homogeneous and heterogeneous Fenton reaction mechanism

2.1 Homogeneous Fenton reaction mechanism

2.2 Heterogeneous Fenton reaction mechanism

3 Development of heterogeneous Fenton catalysts

3.1 Zero valent metal catalyst system

3.2 In situ doping catalysis system of metal ions

3.3 Cocatalyst

3.4 Two center catalytic system

4 Physical field assisted heterogeneous Fenton reaction

5 Conclusion and outlook

Key words: heterogeneous Fenton, Fe(Ⅲ)/Fe(Ⅱ) recycling, hydrogen peroxide, hydroxyl radicals
()
图1 均相Fenton氧化有机物的反应机理[21]
Fig. 1 Reaction mechanism for the Fenton process[21].Copyright 2019, ELSEVIER
图2 铁系非均相Fenton氧化的界面机理催化剂:①浸出铁的均相反应和②非均相反应在催化剂的表面[19]
Fig.2 Interfacial mechanisms of heterogeneous Fenton oxidation using iron-basedcatalyst:① homogeneous reaction through the leached iron and ②heterogeneous reaction at the surface of the catalyst[19]. Copyright 2016, ELSEVIER
图3 (a)完全被H原子覆盖的FeOCl(100)表面的结构和H原子还原 Fe c u s 3 +示意图;(b)H原子和质子(H+)部分覆盖的FeOCl(100)表面结构[31]
Fig.3 (a) Structure of FeOCl(100) surface fully covered by H atoms and schematic illustration of H atom reduction effect for surface Fe c u s 3 + sites. (b) structure of FeOCl(100) surface with H atom and proton (H+) co-covered, illustrating formation of active [ Fe c u s 2 +- Fe c u s 3 +] unit[31].Copyright 2019, SCI
图4 H原子覆盖FeOCl(100)表面Fenton反应机理示意图:(a)H2O2脱氢和·OOH脱附为[ Fe c u s 2 +- Fe c u s 3 +]单元;(b)[ Fe c u s 2 +- Fe c u 3 + s]单元共催化H2O2吸附和分解,包括在H质子或表面吸附的H偶联作用下·OH在 Fe c u 3 + s上解吸和OH-在 Fe c u 2 + s上中和[31]
Fig.4 Schematic illustration of Fenton reaction mechanism on proton pre-covered FeOCl(100) surface: (a) formation of [ Fe c u s 2 + - Fe c u s 3 +] unit as aresult of H2O2 dehydrogenation and ·OOH desorption process. (b) H2O2 adsorption and decomposition co-catalyzed by [ Fe c u s 2 +- Fe c u 3 + s] unit, as well as OH desorption into radicals on Fe c u s 3 + site and OH- neutralization reaction on Fe c u s 2 + site by coupling with proton or surface-adsorbed H[31]. Copyright 2019, SCI
图5 非均相Fenton催化体系降解苯酚可能存在的反应机制[32]
Fig.5 Possible heterogeneous Fenton reaction mechanism during phenol degradation[32]. Copyright 2015, SCI
图6 纳米Fe@Fe2O3催化Fenton氧化原理[37]
Fig. 6 Possible molecular oxygen activation pathway over the Fe@Fe2O3 nanowires[37]. Copyright 2013, ACS
图7 纳米Fe@Fe2O3催化Fenton去除Cr(Ⅵ)机理[38]
Fig. 7 Illustration of the anoxic Cr(Ⅵ) removal by core-shell Fe@Fe2O3 nanowires[38]. Copyright 2015, ACS
图8 Cu掺杂Fe3O4@γ-Al2O3催化Fenton降解Ni-EDTA机制[40]
Fig. 8 Mechanism of Fenton degradation of Ni-EDTA catalyzed by Cu doped Fe3O4@γ-Al2O3[40]. Copyright 2019, ELSEVISR
图9 Fe@Fe2O3/H2O2/HA体系降解有机物机理[45]
Fig. 9 Schematic illustration for the degradation mechanisms in the Fe@Fe2O3/H2O2/HA system[45].Copyright 2019, ELSEVIER
图10 MoS2助Fenton催化反应杀菌机理[46]
Fig. 10 The proposed bactericidal mechanism of the MoS2 co-catalytic Fenton reaction[46]. Copyright 2018, ELSEVIER
图11 C@M与MIL-88B-Fe反应机制[47]
Fig. 11 The comparison chart of reaction mechanism for C@M and MIL-88B-Fe[47]. Copyright 2019, SCI
图12 磷酸盐促核壳纳米Fe@Fe2O3生成H2O2的示意图[48]
Fig. 12 Schematic illustration for enhanced H2O2 generation with Fe@Fe2O3 core-shell nanowires in the presence of phosphate[48]. Copyright 2017, ACS
图13 d-TiCuAl-SiO2Ns表面类原电池双反应中心Fenton催化反应机制[49]
Fig. 13 The Fenton-like reaction mechanism on the surface galv-anic-like cells of d-TiCuAl-SiO2Ns[49]. Copyright 2017, RSC
图14 CN-Cu(Ⅱ)-CuAlO2类原电池双反应中心Fenton催化反应机制[50]
Fig. 14 Fenton catalytic reaction mechanism of CN-Cu(Ⅱ)-CuAlO2 type primary battery double reaction center[50]. Copyright 2018, ACS
图15 可见光驱动TiO2/Fe2TiO5/Fe2O3去除不同有机污染物的PFR机理[55]
Fig. 15 Visible-light-driven PFR mechanism of TiO2/Fe2TiO5/Fe2O3 for the removal of different organic pollutants[55]. Copyright 2017, SCI
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