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      The Growth Mechanism of a Conductive MOF Thin Film in Spray‐based Layer‐by‐layer Liquid Phase Epitaxy

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          Abstract

          The layer‐by‐layer liquid‐phase epitaxy (LBL‐LPE) method is widely used in preparing metal–organic framework (MOF) thin films with the merits of controlling thickness and out‐of‐plane orientation for superior performances in applications. The LBL‐LPE growth mechanism related to the grain boundary, structure defect, and orientation is critical but very challenging to study. In this work, a novel “in‐plane self‐limiting and self‐repairing” thin‐film growth mechanism is demonstrated by the combination study of the grain boundary, structure defect, and orientation of Cu 3(HHTP) 2‐xC thin film via microscopic analysis techniques and electrical measurements. This mechanism results a desired high‐quality MOF thin film with preferred in‐plane orientations at its bottom for the first time and is very helpful for optimizing the LBL‐LPE method, understanding the growth cycle‐dependent properties of MOF thin film, and inspiring the investigations of the biomimetic self‐repairing materials.

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          Electrically Conductive Metal–Organic Frameworks

          Metal–organic frameworks (MOFs) are intrinsically porous extended solids formed by coordination bonding between organic ligands and metal ions or clusters. High electrical conductivity is rare in MOFs, yet it allows for diverse applications in electrocatalysis, charge storage, and chemiresistive sensing, among others. In this Review, we discuss the efforts undertaken so far to achieve efficient charge transport in MOFs. We focus on four common strategies that have been harnessed toward high conductivities. In the “through-bond” approach, continuous chains of coordination bonds between the metal centers and ligands’ functional groups create charge transport pathways. In the “extended conjugation” approach, the metals and entire ligands form large delocalized systems. The “through-space” approach harnesses the π–π stacking interactions between organic moieties. The “guest-promoted” approach utilizes the inherent porosity of MOFs and host–guest interactions. Studies utilizing less defined transport pathways are also evaluated. For each approach, we give a systematic overview of the structures and transport properties of relevant materials. We consider the benefits and limitations of strategies developed thus far and provide an overview of outstanding challenges in conductive MOFs.
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            Electrically Conductive Porous Metal-Organic Frameworks

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              MOF-Based Membranes for Gas Separations

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                Author and article information

                Contributors
                Journal
                Angewandte Chemie International Edition
                Angew Chem Int Ed
                Wiley
                1433-7851
                1521-3773
                October 24 2022
                September 21 2022
                October 24 2022
                : 61
                : 43
                Affiliations
                [1 ] State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou Fujian 350002 China
                [2 ] University of Chinese Academy of Sciences Beijing 100049 China
                [3 ] Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou Fujian 350108 China
                Article
                10.1002/anie.202212797
                3c739fa0-0bda-4896-8e58-f330172a832a
                © 2022

                http://onlinelibrary.wiley.com/termsAndConditions#vor

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