Kulesa Krista M, Padilha Diego S, Thapa Bishnu, Mazumder Shivnath, Losovyj Yaroslav, Schlegel H Bernhard, Scarpellini Marciela, Verani Cláudio N
Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, MI 48202, USA.
Instituto de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ 21941-611, Brazil.
J Inorg Biochem. 2023 May;242:112162. doi: 10.1016/j.jinorgbio.2023.112162. Epub 2023 Feb 15.
The prototypical drug carrier [Co(L)Cl]PF (1), where L is a tripodal amine bound to pyridine and methyl-imidazoles, had its electrocatalytic water splitting activity studied under different pH conditions. This species contains a high-spin 3d Co metal center, and is capable of generating both H from water reduction and O from water oxidation Turnover numbers reach 390 after 3 h for water reduction. Initial water oxidation activity is molecular, with TONs of 71 at pH 7 and 103 at pH 11.5. The results reveal that species 1 can undergo several redox transformations, including reduction to the 3d Co species that precedes a 3d hydride for water reduction, as well as nominal CoO and Co-OOH species required for water oxidation. Post-catalytic analyses confirm the molecular nature of reduction and support initial molecular activity for oxidation.
典型的药物载体[Co(L)Cl]PF（1），其中L是与吡啶和甲基咪唑相连的三脚架胺，在不同pH条件下研究了其电催化水分解活性。该物种包含一个高自旋3d钴金属中心，能够通过水还原产生氢气并通过水氧化产生氧气。水还原反应3小时后的周转数达到390。初始水氧化活性是分子性的，在pH为7时TON为71，在pH为11.5时TON为103。结果表明，物种1可以经历几种氧化还原转变，包括还原为水还原前的3d钴物种，以及水氧化所需的名义上的CoO和Co-OOH物种。催化后分析证实了还原的分子性质，并支持氧化的初始分子活性。
