推进MOF产业化应用：宏量制备与成型

doi:10.11949/0438-1157.20240819

摘要/Abstract

摘要：

金属-有机框架（MOF）是一类由金属离子或金属簇与有机配体通过配位键形成的新型多孔材料。它们展现出结构多样、高比表面积、高孔隙率、结构与性质多样化调控等优点。近年来，MOF在吸附、分离、催化和传感等不同领域的应用逐渐受到关注。然而，MOF宏量制备面临着合成条件严苛、反应时间延长、产量低以及成本高等化学工程领域的挑战。因此，研究人员正在探索各种新的合成方法，如水热/溶剂热法、常温快速合成法、溶剂回流法、碱辅助法、机械化学法、电化学法、微波辅助法、超声波辅助法、喷雾干燥法、干凝胶转化法、加速老化法等。以此为主题，综述了宏量制备MOF的方法，并对成本、环境影响、安全性和可行性进行了评价，也简要讨论了MOF成型加工技术的最新进展，展望了未来MOF材料在宏量制备与成型方面的挑战与机遇。

关键词: 金属-有机框架, 化工新材料, 宏量制备, 加工成型, 工业应用, 制备, 安全, 多孔介质

Abstract:

Metal-organic frameworks (MOF) are a new type of porous materials constructed by metal ions or metal clusters with organic ligands through coordination bonds. They show advantages such as diverse structures, high specific surface area, high porosity, and diversified regulation of structures and properties. In recent years, MOF has gradually attracted attention in different fields such as adsorption/separation, catalysis, and sensing. However, the scale-up preparation of MOF faces many challenges, including stringent synthesis conditions, prolonged reaction times, reduced yields, and increased costs. Therefore, researchers are exploring various new synthesis methods, such as hydrothermal/solvothermal, rapid room temperature synthesis, solvent reflux, base-assisted, mechanochemical, electrochemical, microwave-assisted, spray-drying, ultrasonic, dry gel conversion, and accelerated aging methods. Thus, the methods for scale-up preparation of MOF are reviewed, and factors like cost, environmental impact, safety, and practical feasibility are assessed. Additionally, the article will briefly discuss advances in MOF shaping technologies to accelerate progress in those fields. The future challenges and opportunities for scale-up preparation and shaping of MOF materials are envisioned.

Key words: metal-organic frameworks (MOF), chemical new materials, scale-up preparation, material forming, industrial application, preparation, safety, porous medium

中图分类号:

TQ 028.1

安昊天, 韩章烨, 陆慕瑶, 周阿武, 李建荣. 推进MOF产业化应用：宏量制备与成型[J]. 化工学报, 2025, 76(5): 2011-2025.

Haotian AN, Zhangye HAN, Muyao LU, Awu ZHOU, Jianrong LI. Promoting industrial application of MOF: scale-up preparation and shaping[J]. CIESC Journal, 2025, 76(5): 2011-2025.

图/表 14

图1 宏量制备MOF要兼顾科学与工程两方面

Fig.1 Both science and engineering should be considered in the scale-up preparation of MOF

图2 水热/溶剂热法与流动式合成结合的装置示意图[20]

Fig.2 Hydrothermal/solvothermal synthesis combined with a flow synthesis device[20]

图3 宏量制备Cu-AD-SA：(a)原料；(b)产物；(c)反应装置[25]

Fig.3 Large-scale synthesis of Cu-AD-SA: (a) the starting materials; (b) the products; (c) the reaction setup[25]

图4 (a) MOF-303结构示意图；(b) 在200 L反应容器中合成3.5 kg规模的MOF-303[28]

Fig.4 (a) Schematic of MOF-303 structure; (b) Synthesis of 3.5 kg scale MOF-303 in a 200 L reaction vessel[28]

图5 (a)用于UiO-66-NH2连续生产的双螺杆挤出装置示意图； (b)水辅助机械化学绿色合成Zr-MOF示意图[38]

Fig.5 (a) TSE setup used for continuous mechanochemical synthesis of UiO-66-NH2; (b) Water-assisted mechanochemical procedure for green synthesis of zirconium MOF[38]

图6 (a)高熵-ZIF的机械化学合成示意图；(b)高熵-ZIF的TEM图像和EDS元素分布图[39]

Fig.6 (a) Schematic of mechanochemical synthesis of high-entropy ZIFs; (b) TEM image and EDS elemental distribution of high-entropy ZIFs[39]

图7 在羧基功能化的ITO电极表面直接电化学合成MIL-101(Fe)薄膜[45]

Fig.7 Surface functionalization of ITO electrodes with carboxylic acid groups enables direct electrosynthesis of MIL-101（Fe） films on the inert conducting support[45]

图8 MOF-808_15（红色）、MOF-808_60（蓝色）和 MOF-808_120（绿色）的：(a)用于制备MOF-808（实线）和对照材料（虚线）的受控加热斜率；(b) 粉末X射线衍射图；(c) 77 K下的N2吸附曲线；(d) SEM照片（比例尺：1 μm）[59]

Fig.8 MOF-808_15 (red), MOF-808_60 (blue) and MOF-808_120 (green): (a) controlled-heating ramp used in the preparation of MOF-808 (continuous lines) and control materials (dashed lines); (b) powder X-ray diffractograms; (c) N2 adsorption at 77 K; (d) SEM images (scale bar: 1 μm)[59]

表1 部分MOF宏量制备工作主要参数

Table 1 Some key parameters related to the scale-up synthesis of MOFs

宏量制备方法	典型MOF	温度/℃	时间	溶剂	金属源	时空产率/ (kg/(m³·d))	文献
加速老化法	Cd-MOF	45	4 d	—	CdO	—	[76]
水热法/溶剂热法	UiO-66	120	24 h	DMF	ZrCl₄	—	[19]
	HKUST-1	90	12 min	DMF、乙醇、水	Cu(NO₃)₂·H₂O	5.8	[20]
	MOF-5	120	12 min	DMF	Zn(NO₃)₂·6H₂O	—
	IRMOF-3	120	12 min	DMF	Zn(NO₃)₂·6H₂O	—
	UiO-66	140	15 min	DMF	ZrCl₄	—
常温快速合成法/ 溶剂回流法	UiO-66-(COOH)₂	100	16 h	水	ZrCl₄	96	[21]
	MIP-202(Zr)	120	1 h	水	ZrCl₄	7030	[22]
	MOF-801(Zr)	室温	5.5 h	水	ZrOCl₂·8H₂O	168	[23]
	NKMOF-8-Br	室温	1 min	乙腈	CuI	—	[24]
	Cu-AD-SA	80	24 h	DMF、水	Cu(NO₃)₂·3H₂O	160	[25]
碱辅助法	MOF-5	室温	24 h	DMF	Zn(NO₃)₂·6H₂O	—	[26]
	MIL-53(Al)	室温	7 d	水	Al(NO₃)₃·9H₂O	—
	MOF-74	室温	20 h	水	Zn(CH₃COO)₂·2H₂O	—
	MOF-303	120	6 h	水	AlCl₃·6H₂O	179.5	[28]
机械化学法	ZIF-8	室温	96 h	—	ZnO	—	[33]
	ZIF-8	室温	2 h	水	Zn(CH₃COO)₂·2H₂O	—	[34]
	MOF-74(Zn)	室温	70 min	水	ZnO	—	[35]
	Fe-MIL-88A	室温	10 min	—	FeCl₃·6H₂O	—	[36]
	HKUST-1	室温	—	乙醇	Cu(OH)₂	144000	[37]
	ZIF-8	200	—	—	[ZnCO₃]₂[Zn(OH)₂]₃	144000
	Al-Fum	室温	—	—	Al₂(SO₄)₃·18H₂O	27000
	UiO-66	室温	90 min	水	异丙醇锆	—	[38]
电化学法	Fe-MIL-101	室温	14 h	DMF	FeCl₂	—	[45]
	Fe-MIL-101-NH₂	室温	8 h	DMF	FeCl₂	—
	Fe-MIL-100	室温	18 h	DMF	FeCl₂	—
	Fe-MIL-88B-NH₂	室温	2 h	DMF	FeCl₂	—
微波辅助法	MOF-74 (Ni)	125	60 min	DMF、乙醇、水	Ni(NO₃)₂·6H₂O	—	[57]
微波辅助法	MOF-808	95	1 h	水	ZrOCl₂·8H₂O	—	[59]
超声波辅助法	CPO-27-Co	70	75 min	DMF、水	Co(NO₃)₂·6H₂O	—	[65]
超声波辅助法	MIL-53(Fe)	—	7 min	DMF	FeCl₃·6H₂O	—	[66]
喷雾干燥法	UiO-66	220	—	DMF	乙酰丙酮锆	—	[70]
喷雾干燥法	CID-1	220	—	DMF	Zn(NO₃)₂·4H₂O	—	[70]
干凝胶转换法	MIL-100(Fe)	室温	30 min	水	Fe(NO₃)3·9H₂O	—	[73]

图9 (a)用于海水淡化的MOF-303膜；(b)在α-Al2O3表面上生长的MOF-303膜横截面SEM图[78]

Fig. 9 (a) MOF-303 membrane for seawater desalination; (b) SEM image of the cross-section of MOF-303 membrane grown on α-Al2O3 surface[78]

图10 热压法生产MOF涂层示意图（SBU为次级构建单元）[79]

Fig.10 Schematic presentation of the hot-pressing (HoP) method for MOF coating (SBU is the secondary building unit)[79]

图11 不同形状的3D打印HKUST-1泡沫照片[82]

Fig.11 Photographs of 3D printed HKUST-1 foams with different shapes[82]

图12 粉末和压片成型的(a) MIL-53(Al)（压片、碎片），(b) Cu3(BTC)2（压片、粉末）[84]

Fig.12 Powder and pelletized (a) MIL-53(Al) (tablets, crushed tablets), (b) Cu3(BTC)2 (tablet, powder)[84]

图13 使用不同黏合剂制备的ZUL-300颗粒：(a) ZUL-300（左）和ZUL-300@HPC（右），(b) ZUL-300（左）和ZUL-300@PVB（右），(c) ZUL-300（左）和ZUL-300@PVA（右）[87]

Fig.13 ZUL-300 pellets prepared with different binders: (a) ZUL-300 (left) and ZUL-300@HPC (right), (b) ZUL-300 (left) and ZUL-300@PVB (right), (c) ZUL-300 (left) and ZUL-300@PVA (right)[87]

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