Research progress on microenvironment regulation of metal-organic framework photocatalyst

doi:10.11949/0438-1157.20190601

Abstract

Abstract:

Metal organic framework materials (MOFs) are a class of inorganic metal centers and organic ligands formed by self-assembly of crystalline porous materials. MOFs combine high crystallinity and electron mobility of inorganic materials with high specific surface area, porosity and modifiability of organic materials, thus exhibiting broad application prospects in the field of photocatalysis. The research on MOFs photocatalytic materials in recent years is reviewed centering on the regulation of physical and chemical microenvironment. The regulation of physical microenvironment has been focused on micromorphology regulation, noble metal deposition and heterostructure construction, meanwhile the regulation of chemical microenvironment has been focused on metal site regulation and organic ligand regulation. In addition, in order to provide ideas for rational design and controllable preparation of high-performance MOF photocatalysts, the future development of MOF photocatalytic materials is also prospected.

Key words: metal-organic frameworks, microenvironment, catalyst, photochemistry, solar energy

摘要：

金属有机框架材料（MOFs）是一类无机金属中心和有机配体自组装形成的晶体多孔材料，既有无机材料高结晶度、高电子迁移率等特点，又兼具有机材料高比表面积、高孔隙率、强可修饰性等特点，在光催化领域显示出广阔的应用前景。围绕物理化学微环境调控，对近年来MOFs光催化材料的研究进行了详细综述。其中，物理微环境的调控重点介绍了微观形貌调控、贵金属沉积和异质结构建三个方面；化学微环境调控重点介绍了金属位点调控与有机配体调控两个方面。此外，对MOFs光催化材料的未来发展进行展望，以期为高性能MOFs光催化剂的理性设计和可控制备等方面的研究提供思路。

关键词: 金属有机框架材料, 微环境, 催化剂, 光化学, 太阳能

CLC Number:

O 643

Ke AN, Dong YANG, Zhanfeng ZHAO, Hanjie REN, Yao CHEN, Zhiyuan ZHOU, Zhongyi JIANG. Research progress on microenvironment regulation of metal-organic framework photocatalyst[J]. CIESC Journal, 2019, 70(10): 3776-3790.

安珂, 杨冬, 赵展烽, 任汉杰, 陈瑶, 周致远, 姜忠义. 金属有机框架光催化剂微环境调控研究进展[J]. 化工学报, 2019, 70(10): 3776-3790.

Figures/Tables 16

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催化剂种类	物理微环境调控	应用领域	光催化活性	参考文献
NH₂-MIL-125	沉积Pt	CO₂还原	587.5 μmol?h^–1?g^–1	Sun等^[48]
UiO-66	沉积Au@Pd	产氢	42000 ml?h^–1?g^–1	Wen等^[49]
Co-ZIF-9	沉积Ag	CO₂还原	56800 μmol?h^–1?g^–1	Chen等^[50]
MIL-125	沉积Pt和Au	产氢	1743.0 μmol?h^–1?g^–1	Xiao等^[51]
UiO-66	复合g-C₃N₄	产氢	比物理混合性能高17倍	Wang等^[52]
MIL-53	复合 g-C₃N₄	Cr(Ⅵ)还原	比MIL-53性能高2.0倍	Huang等^[53]
ZIF-8	复合 g-C₃N₄	CO₂还原	0.75 μmol?h^–1?g^–1	Liu等^[54]
NH₂-UiO-66	复合TpPa-1-COF	产氢	23.41 μmol?h^–1?g^–1	Zhang等^[55]
NH₂-MIL-125或NH₂-UiO-66	复合B-CTF-1	产氢	360 μmol?h^–1?g^–1	Li等^[56]
NH₂-MIL-68	复合TPA-COF	降解罗丹明B	降解率100%(40 min)	Peng等^[57]
NH₂-MIL-125	复合LZU1	苯乙烯加氢	转化率100%(15 min)	Sun等^[58]
NH₂-MIL-125	复合TTB-TTA	降解甲基橙	降解率100%(20 min)	He等^[59]
Ru-MOF	形貌调控	CO₂还原	77.2 μmol?h^–1?g^–1	Zhang等^[60]
Cd-TBAPy	形貌调控	全解水	产氧速率1634 μmol?h^–1?g^–1	Xiao等^[61]
Ni-MOF	形貌调控	产氢	45201 μmol?h^–1?g^–1	Qiao等^[62]
ZIF-67	形貌调控	CO₂还原	3890 μmol?h^–1?g^–1	Wang等^[63]
Ni-MOF	缺陷构造	CO₂还原	16000 μmol?h^–1?g^–1	Niu等^[64]
NH₂-MIL-125	孔道封装Co(Ⅱ)	产氢	比NH₂-MIL-125高32倍	Jiang等^[65]

催化剂种类	物理微环境调控	应用领域	光催化活性	参考文献
NH₂-MIL-125	沉积Pt	CO₂还原	587.5 μmol?h^–1?g^–1	Sun等^[48]
UiO-66	沉积Au@Pd	产氢	42000 ml?h^–1?g^–1	Wen等^[49]
Co-ZIF-9	沉积Ag	CO₂还原	56800 μmol?h^–1?g^–1	Chen等^[50]
MIL-125	沉积Pt和Au	产氢	1743.0 μmol?h^–1?g^–1	Xiao等^[51]
UiO-66	复合g-C₃N₄	产氢	比物理混合性能高17倍	Wang等^[52]
MIL-53	复合 g-C₃N₄	Cr(Ⅵ)还原	比MIL-53性能高2.0倍	Huang等^[53]
ZIF-8	复合 g-C₃N₄	CO₂还原	0.75 μmol?h^–1?g^–1	Liu等^[54]
NH₂-UiO-66	复合TpPa-1-COF	产氢	23.41 μmol?h^–1?g^–1	Zhang等^[55]
NH₂-MIL-125或NH₂-UiO-66	复合B-CTF-1	产氢	360 μmol?h^–1?g^–1	Li等^[56]
NH₂-MIL-68	复合TPA-COF	降解罗丹明B	降解率100%(40 min)	Peng等^[57]
NH₂-MIL-125	复合LZU1	苯乙烯加氢	转化率100%(15 min)	Sun等^[58]
NH₂-MIL-125	复合TTB-TTA	降解甲基橙	降解率100%(20 min)	He等^[59]
Ru-MOF	形貌调控	CO₂还原	77.2 μmol?h^–1?g^–1	Zhang等^[60]
Cd-TBAPy	形貌调控	全解水	产氧速率1634 μmol?h^–1?g^–1	Xiao等^[61]
Ni-MOF	形貌调控	产氢	45201 μmol?h^–1?g^–1	Qiao等^[62]
ZIF-67	形貌调控	CO₂还原	3890 μmol?h^–1?g^–1	Wang等^[63]
Ni-MOF	缺陷构造	CO₂还原	16000 μmol?h^–1?g^–1	Niu等^[64]
NH₂-MIL-125	孔道封装Co(Ⅱ)	产氢	比NH₂-MIL-125高32倍	Jiang等^[65]

催化剂种类	化学微环境调控	应用领域	光催化活性	参考文献
MIL100、MOF-74	Sc、Zn、Mg与Ti离子交换	降解亚甲基蓝	降解率＞98%(3 min)	Zou等^[85]
NH₂-UiO-66	Ti、Zr离子交换	CO₂还原	最高转换数为6.50	Lee等^[86]
NH₂-UiO-66	Ti、Zr离子交换	产氢	389 μmol?h^-1?mol^-1	Sun等^[87]
NH₂-UiO-66	Ti、Zr离子交换	还原Se(Ⅵ)	还原率100%	Tu等^[88]
M(tpbpc)_0.5(bdc)_0.5·H₂O	Co、Zn离子交换	降解甲基橙	降解率100%(1.5 h)	Liu等^[89]
Pd/MlL-101	Ce、Cr离子交换	产氢	495 μmol?h^-1?g^-1	Wen等^[90]
UiO-66	Zr、Ga离子交换	CO₂还原	9.06 μmol?h^-1	Lee等^[91]
UiO-68	配体H₂mtpdc引入H₂etpdc	CDC反应	产率93%	Li等^[92]
Zn-PYIs	配体BCIP转换PYIs	醛α-烷基化	转化率74%	Wu等^[93]
NH₂-MIL-125	配体ATA中引入氨基	CO₂还原	16.28 μmol?h^-1?g^-1	Fu等^[94]
NH₂-UiO-66	配体ATA中混合DTA	CO₂还原	41.4 μmol?h^-1?g^-1	Sun等^[95]
UiO-67	配体H₂bpdc引入Mn(bpy)(CO)₃Br	CO₂还原	量子产率13.8%	Fei等^[96]

催化剂种类	化学微环境调控	应用领域	光催化活性	参考文献
MIL100、MOF-74	Sc、Zn、Mg与Ti离子交换	降解亚甲基蓝	降解率＞98%(3 min)	Zou等^[85]
NH₂-UiO-66	Ti、Zr离子交换	CO₂还原	最高转换数为6.50	Lee等^[86]
NH₂-UiO-66	Ti、Zr离子交换	产氢	389 μmol?h^-1?mol^-1	Sun等^[87]
NH₂-UiO-66	Ti、Zr离子交换	还原Se(Ⅵ)	还原率100%	Tu等^[88]
M(tpbpc)_0.5(bdc)_0.5·H₂O	Co、Zn离子交换	降解甲基橙	降解率100%(1.5 h)	Liu等^[89]
Pd/MlL-101	Ce、Cr离子交换	产氢	495 μmol?h^-1?g^-1	Wen等^[90]
UiO-66	Zr、Ga离子交换	CO₂还原	9.06 μmol?h^-1	Lee等^[91]
UiO-68	配体H₂mtpdc引入H₂etpdc	CDC反应	产率93%	Li等^[92]
Zn-PYIs	配体BCIP转换PYIs	醛α-烷基化	转化率74%	Wu等^[93]
NH₂-MIL-125	配体ATA中引入氨基	CO₂还原	16.28 μmol?h^-1?g^-1	Fu等^[94]
NH₂-UiO-66	配体ATA中混合DTA	CO₂还原	41.4 μmol?h^-1?g^-1	Sun等^[95]
UiO-67	配体H₂bpdc引入Mn(bpy)(CO)₃Br	CO₂还原	量子产率13.8%	Fei等^[96]

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