Research progress in polymer-metal-organic frameworks

doi:10.11949/0438-1157.20201415

Abstract

Abstract:

Metal-organic frameworks (MOFs) have received extensive attention due to their advantages such as large porosity, high specific surface area, and regular and adjustable pore structure. The processability of MOFs is limited by poor thermoplasticity and mechanical properties, which seriously handicaps their further industrial application. In order to solve this problem, researchers used polymers as a component of porous materials to synthesize a three-dimensional and highly porous monolithic material—polyMOFs by direct or indirect methods. PolyMOFs can combine the excellent functionality of MOFs with the processability of polymers, and have broad application prospects in the fields of gas separation, biomedicine, and catalysis. In this paper, three synthetic methods of polyMOFs are reviewed, including postsynthetic polymerization and single-crystal to single-crystal transformations and direct synthesis. The characteristics and shortcomings of the three methods are summarized, and the future development direction of polyMOFs is prospected.

Key words: polyMOFs, postsynthetic polymerization, single-crystal to single-crystal transformations, direct synthesis

摘要：

金属有机框架（MOFs）因其大孔隙率、高比表面积和规则可调的孔径结构等优势受到了广泛关注，然而该材料较差的热塑性和力学性能限制了其可加工性，不利于大规模工业应用。为解决此问题，研究者们将聚合物作为多孔材料的一部分，通过直接或间接的方法合成了一种三维且高度多孔的材料——聚合物-金属有机框架（polymer-metal-organic frameworks， polyMOFs）。此材料兼具MOFs出色的性能与聚合物的可加工性，在气体分离、生物医用和催化等领域具有广阔的应用前景。本文综述了polyMOFs的三种合成方法，包括合成后聚合、单晶到单晶转换和直接合成法，介绍了三种方法的特点与不足，并展望了未来polyMOFs的发展方向。

关键词: 聚合物-金属有机框架, 合成后聚合, 单晶到单晶转换, 直接合成

CLC Number:

TQ 028.8

ZHANG Jiahe, YUAN Ye, WANG Ming, WANG Zhi, WANG Jixiao. Research progress in polymer-metal-organic frameworks[J]. CIESC Journal, 2021, 72(2): 709-726.

张家赫, 原野, 王明, 王志, 王纪孝. 聚合物-金属有机框架材料的研究进展[J]. 化工学报, 2021, 72(2): 709-726.

Figures/Tables 16

Fig.1 The number of papers on polyMOFs published from 2000 to 2019(Database source: Web of Science; search using keywords: MOFs, polymers, polyMOFs)

Fig.2 Schematic illustration of cross-linking of the organic linkers in MOF (AzM) and subsequent decomposition to obtain polymer gel (PG) (a). Molecular structures of the organic ligand (AzTPDC) and the cross-linkers (b) [52]

Fig.3 DNA functionalization of UiO-66-N3 nanoparticles, using DNA functionalized with dibenzylcyclooctyne (DBCO) (a). Nanoparticle uptake per cell determined by ICP-MS (b)[33]

Fig.4 Schematic illustration of sequence-regulated radical copolymerization using PCPs[63]

Fig.5 Schematic representation of the preparation of P@MOF[35]

Fig.6 Synthetic route to PMMA@IRMOF-3@MOF-5[75]

Fig.7 Schematic diagram for the transformation from 1D coordination polymer chains to 3D frameworks by heating[79]

Fig.8 Schematic diagram for the transformation from 1D staggered-sculls chains to 3D frameworks through [2+2] photodimerization[80]

Fig.9 The strategy described herein to convert a one-dimensional (linear), non-porous, mostly amorphous polymer into a three-dimensional, porous, crystalline polyMOF hybrid material[88]

Fig.10 Comparison of para-substituted (top) and ortho-substituted (bottom) polymer ligands (a). Synthesis of o-pbdc-xa-u and subsequent formation of polyIRMOF-1 (b)[91]

Fig.11 Effect of block copolymer architecture and mass fractions on polyMOFs morphology[100]

Fig.12 In situ synthesis protocol of PEI-g-ZIF-8 nanoparticles (a). Structure illustration of PEI-g-ZIF-8 nanoparticles(only showing some main linkers of Hmim and PEI) (b)[38]

Table 1 Comparison of doping amount and gas separation performance of two mixed matrix membranes

混合基质膜	掺杂量/%(质量)	气体分离性能^①		文献
混合基质膜	掺杂量/%(质量)	CO₂渗透速率/GPU	CO₂/N₂分离因子	文献
PVAm/ZIF-8/PSf	13.1	600	95	[101]
PVAm/PEI-g-ZIF-8/PSf	20	1600	75	[38]

Fig.13 The main structure of each independent MPF-1 framework (a). The polymer segments of the main MPF-1 framework (b). The structure of PVAmacid (c) [39]

Fig.14 Construction of MMP frameworks using the PDCS process (a). Independent frameworks of MMP-1 and MMP-2 (b). Independent frameworks of MMP-3 and MMP-4 (c)[40]

Table 2 Typical polyMOFs synthesized by different methods and their advantages and disadvantages

合成方法		polyMOF材料	优点	缺点	文献
合成后聚合	点击化学法	polySURMOF	反应条件温和；催化剂高效稳定；反应速率高，几乎无副产物	铜盐作催化剂时后处理烦琐, 不易从产物中去除；环炔与叠氮的反应便于后处理但效率相对较低	[53]
	点击化学法	UiO-66-N₃-DNA-Conjugate	反应条件温和；催化剂高效稳定；反应速率高，几乎无副产物	铜盐作催化剂时后处理烦琐, 不易从产物中去除；环炔与叠氮的反应便于后处理但效率相对较低	[33]
	MOFs孔道内聚合	聚乙烯型polyMOFs	polyMOFs中的聚合物结构可控、分子量分布窄	易堵塞孔道，降低孔隙率	[36,54,60,62-68]
	表面接枝法	P@MOF	操作方便，步骤简单；大大提升MOFs表面的聚合物质量分数；有效改善MOFs的机械性与稳定性	对侧链的分子量分布及接枝密度的控制难度较大；接枝效率较低；易堵塞MOFs孔道	[35]
		terpolymer@ZIF-8@BA			[32]
		PMMA-g-GMA-UiO-66			[37]
		PMMA@IRMOF-3@MOF-5			[75]
单晶到单晶转换		MOPF	操作简单且效率较高；能够可逆地合成polyMOFs	金属与聚合物结合处易断裂，往往制备的polyMOFs的热稳定性和化学稳定性较差	[85]
		[Zn(poly-bppcb)(bdc)]_n			[84]
		[Zn₂(S-poly-bppcb)(obc)₂]? 2.5H₂O			[86]
直接合成法		MPF-1	合成步骤简单；材料结构可控；有效提升MOFs的稳定性与功能性	分离过程烦琐；产率较低	[39]
		MMPs			[40]
		HMMP-1			[102]
		PEI-g-ZIF-8			[38]
		polyIRMOF-1			[88,93-94,97-98,100] [87,90,94,100]
		polyUiO-66, polyUiO-67,polyUiO-68			[88,93-94,97-98,100] [87,90,94,100]
		[Zn₂(BME-bdc)₂(bpy)]_n, [Zn₇(bdc)₆(H₂O)₆(bpe)₂(NO₃)₂]_n			[89]

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