Saha Rajat, Sharma Amitosh, Siddiqui Anjila I, Benmansour Samia, Ortega-Castro Joaquín, Frontera Antonio, Mondal Biswajit, Lah Myoung Soo, Gómez García Carlos J
Departamento de Química Inorgánica, Universidad de Valencia Dr Moliner 50, Burjasot Valencia 46100 Spain
Department of Chemistry, Ulsan National Institute of Science and Technology Ulsan 44919 Republic of Korea.
Chem Sci. 2025 Apr 30;16(21):9501-9508. doi: 10.1039/d5sc02474a. eCollection 2025 May 28.
Proton coupled electron transfer (PCET) is considered as the elementary step of several chemical, electrochemical and biological processes and thus the development of dual conducting materials has recently become a major focus in Chemical Science. Herein, we report the highly selective electrocatalytic oxygen reduction to water by the stable dual conducting metal-organic material (MOM) [Cu(INA)(HO)] (INA = isonicotinate). Structural analysis reveals the important role of both, hydrogen bonding and π-interactions, in the formation of a supramolecular 3D network. Theoretical calculations show that hydrogen bonding interactions among the coordinated water molecules and deprotonated carboxylate oxygen atoms induce proton transport (2.26 ± 0.10 × 10 S cm at 98% RH) while weak intermolecular π-interactions (π-π and anion-π) provide the pathway for electron transport (1.4 ± 0.1 × 10 S cm at 400 K). Such dual proton and electron conductivity leads to a selective oxygen reduction reaction (ORR) to water in an alkaline medium. To the best of our knowledge, this is the first report on electrocatalytic ORR by a dual-conducting metal-organic material.
质子耦合电子转移（PCET）被认为是多种化学、电化学和生物过程的基本步骤，因此双导电材料的开发近来已成为化学科学的一个主要研究重点。在此，我们报道了稳定的双导电金属有机材料（MOM）[Cu(INA)(HO)]（INA = 异烟酸）对氧气还原为水具有高度选择性的电催化作用。结构分析揭示了氢键和π相互作用在超分子三维网络形成过程中的重要作用。理论计算表明，配位水分子与去质子化羧酸根氧原子之间的氢键相互作用诱导质子传输（在98%相对湿度下为2.26 ± 0.10 × 10 S cm），而弱分子间π相互作用（π-π和阴离子-π）为电子传输提供了途径（在400 K下为1.4 ± 0.1 × 10 S cm）。这种质子和电子的双导电性导致在碱性介质中氧气选择性还原为水的反应（ORR）。据我们所知，这是关于双导电金属有机材料电催化ORR的首次报道。
