金属-有机框架MIL-88A（Fe）及其复合材料在水处理中的研究进展

doi:10.19894/j.issn.1000-0518.220259

摘要/Abstract

摘要：

具有多重功能的金属-有机框架MIL-88A（Fe）作为一种新兴的材料在水处理领域具有一定的应用潜力。利用MIL-88A（Fe）独特的理化特性（如多孔结构、不饱和金属位点、优良的可见光吸收能力），将其和其它功能材料（如碳材料、无机半导体材料）异质复合，可以提升MIL-88A（Fe）的吸附及催化性能。详细综述了MIL-88A（Fe）及其复合材料作为吸附剂和催化剂在水处理中的应用，总结它们吸附去除污染物（尤其是重金属离子）的机制、介绍了它们作为光催化技术、类芬顿技术、过二硫酸盐高级氧化技术和催化臭氧技术的催化剂来降解水体中有机污染物的反应机理。指出基于MIL-88A（Fe）的功能材料处理水体污染存在适用pH范围窄和难回收利用等问题。未来研究需优化MIL-88A（Fe）的制备条件来提高产率和保证MIL-88A（Fe）的规整形貌、小尺寸和高结晶度，通过表面包裹技术改善MIL-88A（Fe）的稳定性以及赋予MIL-88A（Fe）磁性来提升回收利用性能。另外，需要根据目标有机污染物的结构和水质条件，合理调控基于MIL-88A（Fe）的高级氧化过程中自由基途径和非自由基途径对目标物的降解贡献，以期达到最佳去污效果。

关键词: 金属有机框架, MIL-88A（Fe）, 高级氧化, 废水处理, 机理

Abstract:

As an emerging material， multifunctional metal-organic framework MIL-88A（Fe） poses a potential application in water treatment. Considering the unique physical and chemical properties of MIL-88A（Fe）（i.e. porous structure， unsaturated metal sites and excellent visible light absorption ability）， MIL-88A（Fe） can heterogeneously combine with other functional materials （i.e. carbon materials， inorganic semiconductor materials） to improve its adsorption and catalytic performance. This paper reviews the application of MIL-88A（Fe） and its composites as adsorbents and catalysts in water treatment. The mechanism of adsorption removal of pollutants in water by MIL-88A（Fe） and its composites （especially heavy metal ions） is summarized， and the reaction mechanism for degradation of organic pollutants in water by MIL-88A（Fe） and its composites in photocatalytic technology， Fenton-like technology， peroxydisulfate advanced oxidation technology and ozone-catalytic technology is introduced. It is pointed out that the MIL-88A（Fe）-based functional materials have problems such as narrow applicable pH range and difficulty in recycling in the process of wastewater treatment. Future research needs to optimize the preparation condition of MIL-88A（Fe） to improve the yield and ensure the regular morphology， small size and high crystallinity of MIL-88A（Fe）， improve the stability of MIL-88A（Fe） by surface coating technology， and enhance the recycling performance of MIL-88A（Fe） by endowing its magnetic property. In addition， according to the structure of the target organic pollutants and water quality condition， it is necessary to reasonably adjust the degradation contribution of the free radical pathway and the non-radical pathway to the target pollutant in the MIL-88A（Fe）-based advanced oxidation process， thus achieving the best decontamination effect.

Key words: Metal-organic framework, MIL-88A（Fe）, Advanced oxidation, Wastewater treatment, Mechanism

中图分类号:

O643

王华宇, 张超, 陈柯铭, 葛明. 金属-有机框架MIL-88A（Fe）及其复合材料在水处理中的研究进展[J]. 应用化学, 2023, 40(2): 155-168.

Hua-Yu WANG, Chao ZHANG, Ke-Ming CHEN, Ming GE. Research Progress of Metal-organic Framework MIL-88A（Fe） and Its Composites in Water Treatment[J]. Chinese Journal of Applied Chemistry, 2023, 40(2): 155-168.

图/表 7

表1 合成MIL-88A（Fe）的方法

Table 1 Method for synthesis of MIL-88A（Fe）

Method	Synthesis process	Advantage	Disadvantage
Ultrasoundmethod^［5］	Through high-frequency vibration， the bubbles and bursts were rapidly generated in the mixed solution of FeCl₃·6H₂O and fumaric acid， and the temperature of the local solution was increased to synthesize MIL-88A（Fe）^［5］	The operation is simple and the time-consuming is relatively short^［5］	The product morphology is irregular and the yield is low^［5］
Hydrothermal/solvothermal method^［6］	FeCl₃·6H₂O and fumaric acid were completely dissolved in water/DMF according to a certain proportion， and the mixed solution was put into an autoclave and heated at 65~105 ℃ for 12 h or longer^［6］	The operation is simple， the crystal morphology of MIL-88（Fe） is good， and the yield is high^［6］	High energy consumption and time-consuming
Microwave method^［7］	The energy is transferred to the reaction solution by microwave radiation， and the temperature of the reaction solution was increased after absorbing the energy， thereby generating MIL-88A（Fe）	The operation is simple and the time-consuming is short， and it is one of the convenient and quick methods for the preparation of MIL-88A（Fe） in large quantities^［7］	The crystallization rate is too fast to obtain a product with a regular morphology
Room temperature stirring method^［8］	The reaction solution was continuously stirred for a certain period of time at room temperature. During this process， FeCl₃·6H₂O and fumaric acid reacted slowly to form MIL-88A（Fe）^［8］	Simple operation and low energy consumption^［8］	It takes a long time， the product is difficult to separate out， and the yield is low
Mechanicalgrindingmethod^［9］	The reaction occured by the input of mechanical energy to the reactant， generally referring to the solid reaction. FeCl₃·6HO and pure water were added into the mortar， grind to completely dissolve the metal salt， then adding fumaric acid and continue grinding to obtain MIL-88A（Fe）	No organic solvent is used， the yield is high and the product particle size is small^［9］	The product is less crystalline and may contain amorphous impurities

表1 合成MIL-88A（Fe）的方法

Table 1 Method for synthesis of MIL-88A（Fe）

Method	Synthesis process	Advantage	Disadvantage
Ultrasoundmethod^［5］	Through high-frequency vibration， the bubbles and bursts were rapidly generated in the mixed solution of FeCl₃·6H₂O and fumaric acid， and the temperature of the local solution was increased to synthesize MIL-88A（Fe）^［5］	The operation is simple and the time-consuming is relatively short^［5］	The product morphology is irregular and the yield is low^［5］
Hydrothermal/solvothermal method^［6］	FeCl₃·6H₂O and fumaric acid were completely dissolved in water/DMF according to a certain proportion， and the mixed solution was put into an autoclave and heated at 65~105 ℃ for 12 h or longer^［6］	The operation is simple， the crystal morphology of MIL-88（Fe） is good， and the yield is high^［6］	High energy consumption and time-consuming
Microwave method^［7］	The energy is transferred to the reaction solution by microwave radiation， and the temperature of the reaction solution was increased after absorbing the energy， thereby generating MIL-88A（Fe）	The operation is simple and the time-consuming is short， and it is one of the convenient and quick methods for the preparation of MIL-88A（Fe） in large quantities^［7］	The crystallization rate is too fast to obtain a product with a regular morphology
Room temperature stirring method^［8］	The reaction solution was continuously stirred for a certain period of time at room temperature. During this process， FeCl₃·6H₂O and fumaric acid reacted slowly to form MIL-88A（Fe）^［8］	Simple operation and low energy consumption^［8］	It takes a long time， the product is difficult to separate out， and the yield is low
Mechanicalgrindingmethod^［9］	The reaction occured by the input of mechanical energy to the reactant， generally referring to the solid reaction. FeCl₃·6HO and pure water were added into the mortar， grind to completely dissolve the metal salt， then adding fumaric acid and continue grinding to obtain MIL-88A（Fe）	No organic solvent is used， the yield is high and the product particle size is small^［9］	The product is less crystalline and may contain amorphous impurities

图1 （a） MIL-88A（Fe）/Bi2WO6 Ⅱ型异质结［16］；（b） Z型Bi2SeO5/rGO/MIL-88A（Fe）光催化体系［17］

Fig.1 （a） Type II heterojunction of MIL-88A（Fe）/Bi2WO6［16］；（b） Z-type photocatalytic system of Bi2SeO5/rGO/MIL-88A（Fe）［17］

图 2 合成各种形貌MIL-88A（Fe）的反应条件示意图［6］

Fig.2 Schematic diagram of the reaction conditions for the synthesis of MIL-88A（Fe） with various morphologies［6］

图3 （a） MIL-88A（Fe）活化PDS降解OG的机制［63］；（b）可见光协助MIL-88A（Fe）活化PDS去除水中TC的反应机理［65］

Fig.3 （a） The mechanism of MIL-88A（Fe）?-activated PDS to degrade OG［63］；（b） The reaction mechanism of visible light-assisted MIL-88A（Fe）-activated PDS to remove TC in water［65］

图 4 MIL-88A（Fe）光催化及催化活化H2O2/PDS/O3产生反应活性物种

Fig.4 MIL-88A（Fe） photocatalysis and catalytic activation of H2O2/PDS/O3 to generate reactive species

表2 基于MIL-88A（Fe）的水处理技术的优缺点对比

Table 2 Comparison of advantages and disadvantages of water treatment technology based on MIL-88A（Fe）

Technology category	Advantage	Disadvantage
Adsorption	MIL-88A（Fe） has a larger specific surface area and pore size， and has an abnormal expansion of 85% in water， which expands its internal channels and pores， and bonds easily with heavy metal ions^［11-12］	MIL-88A（Fe） is not easy to desorb after adsorbing heavy metals， and the recycling rate is low
Photocatalytic	MIL-88A（Fe） has a wide range of visible light response and can utilize solar energy； the regular morphology of MIL-88A（Fe） is easy to construct a high activity composite catalyst with other photocatalysts^［35-40］	High energy consumption for continuous light irradiation
Fenton-like	The exposed crystal face of MIL-88A（Fe） is easy to control， and the catalytic activation efficiency of H₂O₂ is efficient^［6，42］	The ?OH generated by catalytic activation of H₂O₂ can destroy the structure of MIL-88A（Fe）， and at the same time Fe ions can beleached， which leads to a decrease in stability
PDS advanced oxidation	MIL-88A（Fe） has many reactive sites to catalyze activation of PDS^［58-60］	During the reaction， the rate of Fe（Ⅲ） reduction to Fe（Ⅱ） is slow， and a large amount of SO $4 2 -$ ions are left in water after the reaction
Catalytic O₃ oxidation	MIL-88A（Fe） has many Lewis acid sites， which can efficiently catalyze O₃ to produce a variety of reactive species^［67-68］	O₃ is not easy to transport and needs to be prepared on site， which increases the cost of equipment

表2 基于MIL-88A（Fe）的水处理技术的优缺点对比

Table 2 Comparison of advantages and disadvantages of water treatment technology based on MIL-88A（Fe）

Technology category	Advantage	Disadvantage
Adsorption	MIL-88A（Fe） has a larger specific surface area and pore size， and has an abnormal expansion of 85% in water， which expands its internal channels and pores， and bonds easily with heavy metal ions^［11-12］	MIL-88A（Fe） is not easy to desorb after adsorbing heavy metals， and the recycling rate is low
Photocatalytic	MIL-88A（Fe） has a wide range of visible light response and can utilize solar energy； the regular morphology of MIL-88A（Fe） is easy to construct a high activity composite catalyst with other photocatalysts^［35-40］	High energy consumption for continuous light irradiation
Fenton-like	The exposed crystal face of MIL-88A（Fe） is easy to control， and the catalytic activation efficiency of H₂O₂ is efficient^［6，42］	The ?OH generated by catalytic activation of H₂O₂ can destroy the structure of MIL-88A（Fe）， and at the same time Fe ions can beleached， which leads to a decrease in stability
PDS advanced oxidation	MIL-88A（Fe） has many reactive sites to catalyze activation of PDS^［58-60］	During the reaction， the rate of Fe（Ⅲ） reduction to Fe（Ⅱ） is slow， and a large amount of SO $4 2 -$ ions are left in water after the reaction
Catalytic O₃ oxidation	MIL-88A（Fe） has many Lewis acid sites， which can efficiently catalyze O₃ to produce a variety of reactive species^［67-68］	O₃ is not easy to transport and needs to be prepared on site， which increases the cost of equipment

图 5 基于MIL-88A（Fe）的水处理技术的未来发展方向

Fig.5 The future development direction of water treatment technology based on MIL-88A（Fe）

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