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Multiple Strategies to Fabricate a Highly Stable 2D CuIICuI–Organic Framework with High Proton Conductivity
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-10-17 , DOI: 10.1021/acs.inorgchem.1c02312 Lijia Zhao 1, 2 , Rong-Rong Zhu 1, 2 , Shuyu Wang 1, 2 , Liancheng He 1, 2 , Lin Du 1, 2 , Qi-Hua Zhao 1, 2
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-10-17 , DOI: 10.1021/acs.inorgchem.1c02312 Lijia Zhao 1, 2 , Rong-Rong Zhu 1, 2 , Shuyu Wang 1, 2 , Liancheng He 1, 2 , Lin Du 1, 2 , Qi-Hua Zhao 1, 2
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Using multifunctional organic ligands with multiple acidic groups (carboxylate and sulfonate groups) to synthesize metal–organic frameworks (MOFs) bearing effective H-bond networks is a promising strategy to obtain highly proton conductive materials. In this work, a highly stable two-dimensional MOF, [CuII5CuI2(μ3-OH)4(H2O)6(L)2(H2L)2]·3H2O (denoted as YCu161; H3L = 6-sulfonaphthalene-1,4-dicarboxylic acid) containing mixed-valence [CuII5CuI2(μ3-OH)4]8+ subunits, was successfully prepared. It exhibited excellent stability and temperature- and humidity-dependent proton conduction properties. Its optimal proton conductivity reached 1.84 × 10–3 S cm–1 at 90 °C and 98% relative humidity. On the basis of a crystal structure analysis, water vapor adsorption test results, and activation energy calculations, we deduced the proton conduction pathway and mechanism. Apparently, uncoordinated sulfonic and carboxyl groups and a network of abundant H-bonds inside the framework were responsible for the efficient proton transfer. Therefore, the strategy of selecting suitable bifunctional ligands to construct two-dimensional Cu-cluster-based MOFs with excellent proton conductivity is feasible.
中文翻译：
制备具有高质子电导率的高度稳定的二维 CuIICuI-有机框架的多种策略
使用具有多个酸性基团（羧酸根和磺酸根）的多功能有机配体来合成具有有效氢键网络的金属有机骨架（MOF）是获得高质子导电材料的一种很有前景的策略。在这项工作中，高度稳定的二维 MOF，[Cu II 5 Cu I 2 (μ 3 -OH) 4 (H 2 O) 6 (L) 2 (H 2 L) 2 ]·3H 2 O（表示为YCu161 ; H 3 L = 6-磺萘-1,4-二羧酸) 含有混合价 [Cu II 5 Cu I2 (μ 3 -OH) 4 ] 8+亚基制备成功。它表现出优异的稳定性和温度和湿度相关的质子传导特性。其最佳质子电导率达到 1.84 × 10 –3 S cm –1在 90 °C 和 98% 的相对湿度下。在晶体结构分析、水蒸气吸附试验结果和活化能计算的基础上，我们推导出质子传导途径和机制。显然，未配位的磺酸基和羧基以及框架内丰富的氢键网络是有效质子转移的原因。因此，选择合适的双功能配体构建具有优异质子传导性的二维Cu簇基MOFs的策略是可行的。
更新日期：2021-11-01
中文翻译：
制备具有高质子电导率的高度稳定的二维 CuIICuI-有机框架的多种策略
使用具有多个酸性基团（羧酸根和磺酸根）的多功能有机配体来合成具有有效氢键网络的金属有机骨架（MOF）是获得高质子导电材料的一种很有前景的策略。在这项工作中，高度稳定的二维 MOF，[Cu II 5 Cu I 2 (μ 3 -OH) 4 (H 2 O) 6 (L) 2 (H 2 L) 2 ]·3H 2 O（表示为YCu161 ; H 3 L = 6-磺萘-1,4-二羧酸) 含有混合价 [Cu II 5 Cu I2 (μ 3 -OH) 4 ] 8+亚基制备成功。它表现出优异的稳定性和温度和湿度相关的质子传导特性。其最佳质子电导率达到 1.84 × 10 –3 S cm –1在 90 °C 和 98% 的相对湿度下。在晶体结构分析、水蒸气吸附试验结果和活化能计算的基础上，我们推导出质子传导途径和机制。显然，未配位的磺酸基和羧基以及框架内丰富的氢键网络是有效质子转移的原因。因此，选择合适的双功能配体构建具有优异质子传导性的二维Cu簇基MOFs的策略是可行的。
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