金属有机框架材料吸附VOCs影响因素研究进展

doi:10.16085/j.issn.1000-6613.2020-0474

摘要/Abstract

摘要：

挥发性有机化合物（VOCs）对环境和人体健康均具有严重危害，而吸附法作为有效的VOCs脱除技术已得到广泛应用。在众多吸附剂中，金属有机框架材料（MOFs）以其极大的比表面积、可调节的孔径和可修饰性等优势，在VOCs脱除领域展示出良好的应用前景。本文首先介绍了在吸附过程中涉及到的吸附机理，从影响因素角度回顾了近年MOFs在VOCs吸附方面的研究进展。按照吸附质与吸附剂的几何结构、改性官能团、MOFs的金属位点、酸碱、水和碳材料复合等多个方面剖析了吸附过程中的影响因素，并将其分为内部影响因素和外部影响因素两大部分。针对影响因素归纳了提高吸附量的主要方法，并对MOFs吸附VOCs的吸附量进行了汇总。最后总结并展望了未来应用MOFs吸附VOCs的研究发展方向，期望为深入研究VOCs脱除技术提供有价值的参考。

关键词: 金属有机框架, 吸附, 有机化合物, 影响因素

Abstract:

Volatile organic compounds (VOCs) is a pollutant that is severely harmful for the environment and the human health. Fortunately, the adsorption method has obvious advantages in VOCs removal and has been widely used. Metal-organic frameworks (MOFs) have good application prospects in the field of VOCs removal because of its high surface area, adjustable pore size, and wonderful modification and so on. This article first introduced the adsorption mechanism involved in the adsorption process, and reviewed the recent research progress of MOFs in the adsorption of VOCs from the perspective of influencing factors. According to the geometric structure of adsorbate and adsorbent, modified functional groups, metal sites of MOFs, acid-base, water and carbon material composite, the influencing factors in the adsorption process were analyzed and divided into internal influencing factors and external factors. The main methods to increase the adsorption capacity of VOCs by MOFs were summarized according to the influencing factors. At the end of this paper the MOFs adsorption of VOCs was summarized and looked forward to the application prospect of adsorption VOCs by MOFs. These will be provided some valuable references to remove VOCs from flue gas by sorbents.

Key words: mental organic frameworks, adsorption, organic compounds, influence factors

中图分类号:

X511

杨建成, 王诗宁, 杨硕, 杨明涛, 沈伯雄, 张笑. 金属有机框架材料吸附VOCs影响因素研究进展[J]. 化工进展, 2021, 40(1): 463-476.

Jiancheng YANG, Shining WANG, Shuo YANG, Mingtao YANG, Boxiong SHEN, Xiao ZHANG. Influence factors of VOCs adsorption on metal-organic frameworks: the reviews[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 463-476.

图/表 12

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吸附剂	吸附质	相互作用力	参考文献
MIL-101	苯	π-π	[40]
	甲苯	π-π、阳离子-π	[32]
	丙酮	静电力、范德华力	[41]
HKUST-1	丙酮	静电力、范德华力	[38]
	苯	π-π	[38]
HKUST-1/ZSM-5复合材料	苯	阳离子-π	[42]
UiO-66(NH₂)	甲苯	弱氢键	[26]
ZIF-67	甲苯	弱氢键	[26]
CMP-200-In/Mg	CH₄、C₂H₄	范德华力	[33]
	C₂H₃Cl、C₂H₂Cl₂、CH₂Cl₂、CHCl₃	卤素键、静电力	[33]
MOF-177	苯	π-π	[36]
	丙酮	静电力、范德华力	[36]

吸附剂	吸附质	相互作用力	参考文献
MIL-101	苯	π-π	[40]
	甲苯	π-π、阳离子-π	[32]
	丙酮	静电力、范德华力	[41]
HKUST-1	丙酮	静电力、范德华力	[38]
	苯	π-π	[38]
HKUST-1/ZSM-5复合材料	苯	阳离子-π	[42]
UiO-66(NH₂)	甲苯	弱氢键	[26]
ZIF-67	甲苯	弱氢键	[26]
CMP-200-In/Mg	CH₄、C₂H₄	范德华力	[33]
	C₂H₃Cl、C₂H₂Cl₂、CH₂Cl₂、CHCl₃	卤素键、静电力	[33]
MOF-177	苯	π-π	[36]
	丙酮	静电力、范德华力	[36]

吸附剂	BET比表面积/m²·g^-1	Langmuir比表面积/m²·g^-1	孔容积/cm3·g^-1	孔尺寸/?
HKUST-1	1568.5	2081.4	0.75	9~10
MOF-177	2970	4170	1.11	9.4
MIL-101	2925	4977	1.56	笼子30~40，窗口12~16
BUT-66	1096	1291	0.46	孔道6，窗口4
BUT-67	984	1141	0.41	孔道7，窗口5.5
AC	1600	—	2	4~4.6
PAF-1	2380	3209	1.99	7~12（三维孔）
ZIF-8	1510	2008	0.85	笼子12.5，窗口3.3
HZSM-5	550	—	0.2	—
Carboxen 1000	1017	1213	0.61	10~12

吸附剂	BET比表面积/m²·g^-1	Langmuir比表面积/m²·g^-1	孔容积/cm3·g^-1	孔尺寸/?
HKUST-1	1568.5	2081.4	0.75	9~10
MOF-177	2970	4170	1.11	9.4
MIL-101	2925	4977	1.56	笼子30~40，窗口12~16
BUT-66	1096	1291	0.46	孔道6，窗口4
BUT-67	984	1141	0.41	孔道7，窗口5.5
AC	1600	—	2	4~4.6
PAF-1	2380	3209	1.99	7~12（三维孔）
ZIF-8	1510	2008	0.85	笼子12.5，窗口3.3
HZSM-5	550	—	0.2	—
Carboxen 1000	1017	1213	0.61	10~12

吸附剂	吸附质	吸附量/mmol·g^-1	温度/K	压力/kPa	参考文献
MIL-Z1	苯^①	3.35	298	1	[49]
	苯^②	2.94	298	1	[49]
	苯^③	2.63	298	1	[49]
HKUST-1	苯	9.1	298	0.05	[49]
	苯^④	6.55	308	0.15	[49]
	苯	9.97	298	0.0521	[38]
	水	26~31	298	0.25-0.3	[38]
	甲苯	1.72	293	101.3	[26]
	甲苯	6.6	298	P/P₀>0.1	[45]
BUT-66	苯	2.54	298	0.012	[28]
Carboxen 1000	苯	2.27	298	0.012	[28]
PDVB	甲苯	5.215	298	101.3	[46]
	乙酸乙酯	1.31	298	101.3	[46]
ZIF-8/PDVB	甲苯	5.9707	298	101.3	[46]
	乙酸乙酯	1.668	298	101.3	[46]
ZIF-8	甲苯	0.84	298	101.3	[46]
	乙酸乙酯	1.1	298	101.3	[46]
	苯	0.03	298	0.012	[28]
MCM-41	苯	10.49	298	10	[28]
MIL-101	苯	15.84	298	10	[28]
	对二甲苯	10.9	288	0.6	[41]
	甲苯	0.626	298	101.3	[32]
	甲苯	22.96	298	101.3	[39]
	甲苯	15.1	298	P/P₀>0.1	[45]
PAF-1	苯	20.59	298	10	[28]
CPM-200-In/Mg	甲醛	13	293	100	[33]
CPM-200-In/Mg-NH₂(site2)	甲醛	13.67	298	100	[33]
CPM-5	甲苯	4.22	298	101.3	[39]
438-MOF	甲醛	7.333	293	100	[33]
活性炭	甲醛	0.3	293	100	[33]
MOF-177	丙酮	10.155	298	100	[36]
	苯	10.256	298	100	[36]
	甲苯	6.359	298	100	[36]
	乙苯	2.557	298	100	[36]
	二甲苯	2.01~2.557	298	100	[36]
	苯乙烯	2.25	298	100	[36]
MIL-100	甲烷	0.36	298	100	[43]
	乙烷	2.22	298	100	[43]
	丙烷	6.78	298	100	[43]
UiO-66	甲苯	1.8	293	101.3	[26]
	二氯甲烷	6.0	298	44	[50]
UiO-66(NH₂)	甲苯	2.739	293	101.3	[26]
ZIF-67	甲苯	2.43	293	101.3	[26]
4A Zeolite	甲苯	0.334	293	101.3	[26]
颗粒活性炭	二甲苯	1.88	298	101.3	[51]
UL-ZSM5	二甲苯	3.5	303	0.6	[52]
MIL-53	甲苯	7.93	298	101.3	[39]