天津大学胡文平团队开发了聚合物辅助的空间受限策略用于足尺合成柔性金属有机框架基复合薄膜。相关研究成果发表在2021年10月13日出版的《美国化学会杂志》。

在气-液界面，通过在水表面铺展超薄的油层作为反应器，金属-有机框架（MOF）薄膜的有限合成得到了广泛的发展。然而，该界面容易受到各种干扰，无法合成大面积晶体MOF薄膜。

该文中，研究人员开发了一种聚合物辅助的空间受限策略，通过将聚甲基丙烯酸甲酯（PMMA）混合到油层中来合成大面积薄膜，从而改善了气液界面的稳定性和水面上油层的自收缩。同时，合成的MOFs作为准固体基质固定在油层边缘，保持了较大的铺展面积。由于该协同效应，研究人员合成了横向尺寸为英尺（0.66英尺）的独立MOF基薄膜，是迄今为止报道的最大尺寸。此外，由于两种组分的相分离，MOF–PMMA复合膜结合了MOF的导电性（1.13 S/m）和PMMA柔韧性，并表现出优异的机械性能。

更重要的是，该策略可以扩展到其它MOF、配位聚合物（CP）甚至无机材料复合膜的制备，从而为实际应用中各种复合膜的设计和大规模合成带来希望。

附：英文原文

Title: Polymer-Assisted Space-Confined Strategy for the Foot-Scale Synthesis of Flexible Metal–Organic Framework-Based Composite Films

Author: Kuo Yuan, Tianqun Song, Chenhuai Yang, Jun Guo, Qisheng Sun, Ye Zou, Fei Jiao, Lujiang Li, Xiaotao Zhang, Huanli Dong, Liqiang Li, Wenping Hu

Issue&Volume: October 13, 2021

Abstract: At the gas–liquid interface, the confined synthesis of metal–organic framework (MOF) films has been extensively developed by spreading an ultrathin oil layer on the aqueous surface as a reactor. However, this interface is susceptible to various disturbances and incapable of synthesizing large-area crystalline MOF films. Herein, we developed a polymer-assisted space-confined strategy to synthesize large-area films by blending poly(methyl methacrylate) (PMMA) into the oil layer, which improved the stability of the gas–liquid interface and the self-shrinkage of the oil layer on the water surface. Meanwhile, the as-synthesized MOFs as a quasi-solid substrate immobilized the edge of the oil layer, which maintained a large spreading area. Thanks to this synergistic effect, we synthesized the freestanding MOF-based film with a foot-level (0.66 ft) lateral dimension, which is the largest size reported so far. Besides, due to the phase separation of the two components, the MOF–PMMA composite film combined the conductivity of MOFs (1.13 S/m) with the flexibility of PMMA and exhibited excellent mechanical properties. More importantly, this strategy could be extended to the preparation of other MOFs, coordination polymers (CPs), and even inorganic material composite films, bringing light to the design and large-scale synthesis of various composite films for practical applications.

DOI: 10.1021/jacs.1c07033

Source: https://pubs.acs.org/doi/10.1021/jacs.1c07033