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Pore Geometry and Surface Engineering of Covalent Organic Frameworks for Anhydrous Proton Conduction
Authors:Liqin Hao  Shuping Jia  Xueling Qiao  En Lin  Yi Yang  Prof Yao Chen  Prof Peng Cheng  Prof Zhenjie Zhang
Institution:1. State Key Laboratory of Medicinal Chemical biology, College of Chemistry, Nankai University, Tianjin, 300071 China;2. State Key Laboratory of Medicinal Chemical biology, College of Chemistry, Nankai University, Tianjin, 300071 China

State Key Laboratory of Medicinal Chemical biology, Nankai University, Tianjin, 300071 China;3. State Key Laboratory of Medicinal Chemical biology, College of Chemistry, Nankai University, Tianjin, 300071 China

Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center, Frontiers Science, Center for New Organic Matter, Nankai University, Tianjin, 300071 China

Abstract:Developing new materials for anhydrous proton conduction under high-temperature conditions is significant and challenging. Herein, we create a series of highly crystalline covalent organic frameworks (COFs) via a pore engineering approach. We simultaneously engineer the pore geometry (generating concave dodecagonal nanopores) and pore surface (installing multiple functional groups such as −C=N−, −OH, −N=N− and −CF3) to improve the utilization efficiency and host–guest interaction of proton carriers, hence benefiting the enhancement of anhydrous proton conduction. Upon loading with H3PO4, COFs can realize a proton conductivity of 2.33×10−2 S cm−1 under anhydrous conditions, among the highest values of all COF materials. These materials demonstrate good stability and maintain high proton conductivity over a wide temperature range (80–160 °C). This work paves a new way for designing COFs for anhydrous proton conduction applications, which shows great potential as high-temperature proton exchange membranes.
Keywords:1D Channels  Anhydrous Proton Conduction  Covalent Organic Frameworks  Pore Engineering
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