Five 3D Co(II)-MOFs constructed from 5-(2-methylimidazol-1-yl) isophthalic acid and different bis(imidazole) ligands and one of their derivatives as an efficient electrocatalyst for ORR,Dalton Transactions

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Five 3D Co(II)-MOFs constructed from 5-(2-methylimidazol-1-yl) isophthalic acid and different bis(imidazole) ligands and one of their derivatives as an efficient electrocatalyst for ORR
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-10-22 , DOI: 10.1039/d2dt02383k
Ming-Xing Yang ₁ , Rong-Zhi Yan ₁ , Li-Juan Chen ₁ , Shen Lin ₁

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In this work, four different bis(imidazole) ligands, namely 1,4-bis(1-imidazolyl)benzene (bib), 4,4′-bis(1-imidazolyl)biphenyl (bibp), 1,4-bis (imidazol-1-ylmethylene)benzene) (bimb) and 4,4′-bis(imidazol-1-yl)diphenyl ether (bidpe), were used as the second ligand to give rise to the structural diversity of a coordination polymer based on the cobalt-miipa (H₂miipa = 5-(2-methylimidazol-1-yl) isophthalic acid) system. In compound 1, miipa²⁻ coordinates to Co(II) atoms to form the Co-miipa 3D network. On introducing linear bis(imidazole) ligands with different lengths and rigidities into the Co(II)-miipa system, the obtained compounds 2–4 form similar three-fold interpenetrating 3D MOFs constructed from the Co(II)-miipa layers pillared by bis(imidazole) ligands. While introducing the V-shaped half-flexible bis(imidazole) ligands, the obtained compound 5 exhibits a 2D double-layered network built from the Co(II)-miipa 1D quadrangular prism linked by the bis(imidazole) ligand. Each 2D double layer is further interlocked with two neighboring ones to produce an interesting 3D framework. Significantly, CoNC-5 derived from a mixture of dicyandiamide (DCD) and compound 5 with a low void volume shows a superior electrocatalytic performance for the oxygen reduction reaction. The E_onset (0.974 V) and E_1/2 (0.830 V) of CoNC-5 in O₂-saturated 0.1 M KOH at 1600 rpm and 5 mV s⁻¹ are superior to those of Pt/C (0.968 and 0.799 V). The J_L value of CoNC-5 (J_L = 5.29 mA cm⁻²) is higher than that of Pt/C (5.09 mA cm⁻²).

中文翻译：

由 5-(2-甲基咪唑-1-基) 间苯二甲酸和不同的双 (咪唑) 配体及其衍生物之一构建的五种 3D Co(II)-MOF 作为 ORR 的有效电催化剂

在这项工作中，四种不同的双（咪唑）配体，即 1,4-双（1-咪唑基）苯（bib）、4,4'-双（1-咪唑基）联苯（bibp）、1,4-双（咪唑-1-基亚甲基）苯）（bimb）和 4,4'-双（咪唑-1-基）二苯醚（bidpe）被用作第二配体以产生基于配位聚合物的结构多样性钴-miipa（H ₂ miipa = 5-（2-甲基咪唑-1-基）间苯二甲酸）系统。在化合物1中，miipa ²⁻与 Co( II ) 原子配位形成 Co-miipa 3D 网络。将不同长度和刚度的线性双（咪唑）配体引入Co（II）-miipa体系，得到化合物2-4形成类似的三重互穿 3D MOF，由双（咪唑）配体支撑的 Co（II）-miipa 层构成。在引入 V 形半柔性双（咪唑）配体的同时，所得化合物5显示出由双（咪唑）配体连接的 Co( II )-miipa 一维四棱柱构建的二维双层网络。每个 2D 双层进一步与两个相邻的双层互锁以产生有趣的 3D 框架。值得注意的是，源自双氰胺 (DCD) 和化合物5的混合物的 CoNC-5具有低空隙体积，显示出优异的氧还原反应电催化性能。E_开始( 0.974 V) 和E _1/2在 1600 rpm 和 5 mV s ^-1下，O₂饱和的 0.1 M KOH中 CoNC-5 (0.830 V)优于 Pt/C（0.968 和 0.799 V）。CoNC-5的J _L值（J _L = 5.29 mA cm ^-2）高于Pt/C的J L 值（5.09 mA cm ^-2）。

更新日期：2022-10-22

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