MOFs材料在光电催化领域应用的研究进展

doi:10.16085/j.issn.1000-6613.2023-0598

摘要/Abstract

摘要：

为满足可持续发展的要求，光电催化在水分解制氢、CO₂还原和污染物降解等方面的应用由于其在储能和运输方面的可预测性优势而成为研究热点。金属有机框架（MOFs）材料具有高比表面积、金属/有机配体丰富、孔体积大、结构和组成可调等优点，在光电催化领域应用中具有巨大的潜力。因此，本文主要从水分解制氢、CO₂还原、有机污染物降解这三个方面，综述了MOFs材料在光电催化领域中的应用研究进展。首先简要介绍了近年来MOFs材料在催化领域的进展，总结了几种MOFs催化剂应用较广的合成方法，并就其优劣进行比较；其次分别介绍了MOF基光电催化剂在这几个应用方面的基本机理和最新研究进展；最后，本文对MOFs材料在光电极中的作用及其在光电催化领域所面临的机遇和挑战进行了简要的总结与展望。

关键词: 金属有机框架, 光电催化, 产氢, CO₂还原, 降解有机污染物

Abstract:

To meet the requirements of sustainable development, photoelectric catalytic decomposition of hydrogen in the water, CO₂ reduction and degradation of pollutants, has become the research hot spot due to its predictability of advantage in energy storage and transport. Metal-organic frameworks (MOFs) material with high specific surface area, metal/organic ligand rich, large pore volume, structure and composition of the advantages of adjustable, has great potential in photoelectric catalysis applications. Therefore, this article mainly reviewed the research progress on the application of MOFs materials in the photoelectric catalysis from the three aspects of hydrogen production from water decomposition, CO₂ reduction and organic pollutants degradation. Firstly, the MOFs materials were introduced in the field of catalysis in recent years. Several widely used MOFs catalyst synthesis methods were summarized, and their advantages and disadvantages were compared. Secondly, a few basic mechanisms and the latest research progress in the application of MOF based photoelectric catalyst was introduced in detail respectively. Finally, the role of MOFs materials in optical electrode and the opportunities and challenges in the field of photoelectric catalysis was carried on the brief summary and outlook.

Key words: metal organic framework, photoelectrocatalyst, hydrogen production, CO₂ reduction, degradation of organic pollutants

中图分类号:

O6-1

葛全倩, 徐迈, 梁铣, 王凤武. MOFs材料在光电催化领域应用的研究进展[J]. 化工进展, 2023, 42(9): 4692-4705.

GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.

图/表 21

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工艺	优点	缺点	实例
溶剂热/水热法	无须特定的设备、结晶度高和形貌好	耗时、溶剂用量大、不经济环保	MIL-125^[59]、UIO-66^[45] 、ZIF-8^[60] 等
电化学法	操作条件简单、合成速度快、能耗低、对设备无特殊要求	产率低、容易产生副产物	MIL-101(Fe)^[61]、HKUST-1^[62]、ZIF-8^[63]等
机械力化学法	合成效率高、反应条件温和	晶体结构差、杂质多	MOF-74^[64]、MOF-5^[65]、MOF-199^[66]等
超声法	经济环保、产率高、反应条件温和	反应不易控制、杂质多	HKUST-1^[67]、ZIF-8^[68]等
微波法	反应时间短、环保、易操作	实验需要精密仪器	MIL-100 (Fe)^[69]、MIL-88B^[69]等

工艺	优点	缺点	实例
溶剂热/水热法	无须特定的设备、结晶度高和形貌好	耗时、溶剂用量大、不经济环保	MIL-125^[59]、UIO-66^[45] 、ZIF-8^[60] 等
电化学法	操作条件简单、合成速度快、能耗低、对设备无特殊要求	产率低、容易产生副产物	MIL-101(Fe)^[61]、HKUST-1^[62]、ZIF-8^[63]等
机械力化学法	合成效率高、反应条件温和	晶体结构差、杂质多	MOF-74^[64]、MOF-5^[65]、MOF-199^[66]等
超声法	经济环保、产率高、反应条件温和	反应不易控制、杂质多	HKUST-1^[67]、ZIF-8^[68]等
微波法	反应时间短、环保、易操作	实验需要精密仪器	MIL-100 (Fe)^[69]、MIL-88B^[69]等

催化剂	金属中心	电解质	光电流密度（vs. RHE 1.230V)/mA·cm^-2	参考文献
TiO₂/NH₂⁃MIL⁃125	Ti	1mol/L NaOH	1.63	[59]
BiVO₄@CoNi⁃MOF	Co/Ni	0.5mol/L Na₂SO₄	3.20	[83]
TiO₂//UiO⁃67	Zr	1mol/L H₂SO₄	2.10	[84]
Co₃O₄@NH₂⁃MOF⁃5/NF	Zn	1mol/L KOH	32.93	[85]
Mn(Ⅱ)-FeBTC/NIF	Fe	0.1mol/L KOH	—	[86]
α-Fe₂O₃@Ag@ZIF-67	Co	0.1mol/L NaOH	1.04	[87]

催化剂	金属中心	电解质	光电流密度（vs. RHE 1.230V)/mA·cm^-2	参考文献
TiO₂/NH₂⁃MIL⁃125	Ti	1mol/L NaOH	1.63	[59]
BiVO₄@CoNi⁃MOF	Co/Ni	0.5mol/L Na₂SO₄	3.20	[83]
TiO₂//UiO⁃67	Zr	1mol/L H₂SO₄	2.10	[84]
Co₃O₄@NH₂⁃MOF⁃5/NF	Zn	1mol/L KOH	32.93	[85]
Mn(Ⅱ)-FeBTC/NIF	Fe	0.1mol/L KOH	—	[86]
α-Fe₂O₃@Ag@ZIF-67	Co	0.1mol/L NaOH	1.04	[87]

催化技术	特点	不足
光催化	需要光照，利用太阳能，经济环保，产品收率高，催化剂可重复使用且高度稳定，反应条件温和，耗能少	电子转移机理复杂，产物选择性差，反应完成时催化剂难以从产物中分离催化剂，需要牺牲供体
电催化	涉及偏置电压，主要在室温下进行反应	催化剂寿命短，需要电能，成本高
光电催化	需要照明，涉及偏置电压，不需要牺牲试剂，成本效益高	催化剂的复合设计