Metal–organic framework (MOF) solids with their variable functionalities are relevant for energy conversion technologies. However, the development of electroactive and stable MOFs for electrocatalysis still faces challenges. Here, a molecularly engineered MOF system featuring a 2D coordination network based on mercaptan–metal links (e.g., nickel, as for Ni(DMBD)-MOF) is designed. The crystal structure is solved from microcrystals by a continuous-rotation electron diffraction (cRED) technique. Computational results indicate a metallic electronic structure of Ni(DMBD)-MOF due to the Ni–S coordination, highlighting the effective design of the thiol ligand for enhancing electroconductivity. Additionally, both experimental and theoretical studies indicate that (DMBD)-MOF offers advantages in the electrocatalytic oxygen evolution reaction (OER) over non-thiol (e.g., 1,4-benzene dicarboxylic acid) analog (BDC)-MOF, because it poses fewer energy barriers during the rate-limiting *O intermediate formation step. Iron-substituted NiFe(DMBD)-MOF achieves a current density of 100 mA cm⁻² at a small overpotential of 280 mV, indicating a new MOF platform for efficient OER catalysis.

中文翻译：

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金属有机骨架的分子工程作为水氧化的高效电化学催化剂

具有可变功能的金属有机骨架 (MOF) 固体与能量转换技术相关。然而，开发用于电催化的电活性和稳定的 MOFs 仍然面临挑战。在这里，设计了一个分子工程 MOF 系统，具有基于硫醇-金属链（例如，镍，对于 Ni(DMBD)-MOF）的二维配位网络。通过连续旋转电子衍射 (cRED) 技术从微晶解析晶体结构。计算结果表明，由于 Ni-S 配位，Ni(DMBD)-MOF 具有金属电子结构，突出了硫醇配体的有效设计以增强导电性。此外，实验和理论研究均表明，(DMBD)-MOF 在电催化析氧反应 (OER) 方面优于非硫醇（例如，1,4-苯二甲酸）类似物 (BDC)-MOF，因为它产生的能量更少限速 *O 中间形成步骤中的障碍。铁取代的 NiFe(DMBD)-MOF 实现了 100 mA cm 的电流密度^-2在 280 mV 的小过电势下，表明新的 MOF 平台可用于高效的 OER 催化。