Khan Ruqia, Chakraborty Jeet, Singh Rawat Kuber, Morent Rino, De Geyter Nathalie, Van Speybroeck Veronique, Van Der Voort Pascal
Center for Ordered Materials, Organometallics and Catalysis (COMOC), Department of Chemistry, Ghent University, Krijgslaan 281-S3, 9000, Ghent, Belgium.
Department of Chemistry, Quaid-i-Azam University, Islamabad, 45320, Pakistan.
Angew Chem Int Ed Engl. 2023 Nov 20;62(47):e202313836. doi: 10.1002/anie.202313836. Epub 2023 Oct 19.
Electrochemical two-electron water oxidation (2e WOR) is gaining surging research traction for sustainable hydrogen peroxide production. However, the strong oxidizing environment and thermodynamically competitive side-reaction (4e WOR) posit as thresholds for the 2e WOR. We herein report a custom-crafted covalent triazine network possessing strong oxidizing properties as a proof-of-concept metal-free functional organic network electrocatalyst for catalyzing 2e WOR. As the first-of-its-kind, the material shows a maximum of 89.9 % Faradaic Efficiency and 1428 μmol/h/cm H O production rate at 3.0 V bias potential (vs reversible hydrogen electrode, RHE), which are either better or comparable to the state-of-the-art electrocatalysts. We have experimentally confirmed a stepwise 2e WOR mechanism which was further computationally endorsed by density functional theory studies.
电化学双电子水氧化（2e WOR）在可持续生产过氧化氢方面正获得越来越多的研究关注。然而，强氧化环境和热力学上具有竞争性的副反应（4e WOR）成为了2e WOR的门槛。我们在此报告一种定制的具有强氧化性质的共价三嗪网络，作为催化2e WOR的概念验证无金属功能有机网络电催化剂。作为同类中的首个材料，该材料在3.0 V偏置电位（相对于可逆氢电极，RHE）下表现出最高89.9%的法拉第效率和1428 μmol/h/cm H₂O的产率，与目前最先进的电催化剂相比，要么更好，要么相当。我们通过实验证实了一种逐步的2e WOR机制，该机制进一步得到了密度泛函理论研究的计算支持。
