Ruan Guilin, Pahar Suraj, Fridman Natalia, Maayan Galia
Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.
Inorg Chem. 2025 Mar 10;64(9):4267-4274. doi: 10.1021/acs.inorgchem.4c04501. Epub 2025 Feb 23.
A dinuclear Cu-peptoid, Cu(), having a diol side chain was developed as a homogeneous electrocatalyst for oxygen evolution reaction (OER) at neutral pH. The molecular structure of Cu() was characterized and concluded by ESI-MS, UV-vis, and single-crystal X-ray diffraction. Electrochemical, spectroscopic, and mechanistic studies revealed that borate buffer (the solution medium) has a minor effect during electrocatalysis; however, the diol side chain promotes a second coordination sphere effect via multiple hydrogen bonds which highly stabilize the complex, leading to an OER. Based on these observations and the collected data, we also suggest two different and unique mechanism pathways: a major one, which involves interactions of radical intermediates, which is buffer independent, and a minor one that resembles water nucleophilic attack (WNA) and is assisted by the borate buffer.
一种具有二醇侧链的双核铜类肽Cu（）被开发为在中性pH值下用于析氧反应（OER）的均相电催化剂。通过电喷雾电离质谱（ESI-MS）、紫外可见光谱（UV-vis）和单晶X射线衍射对Cu（）的分子结构进行了表征和总结。电化学、光谱和机理研究表明，硼酸盐缓冲液（溶液介质）在电催化过程中影响较小；然而，二醇侧链通过多个氢键促进第二配位球效应，从而高度稳定该配合物，导致析氧反应的发生。基于这些观察结果和收集到的数据，我们还提出了两种不同且独特的机理途径：一种主要途径涉及自由基中间体的相互作用，与缓冲液无关；另一种次要途径类似于水亲核攻击（WNA），并由硼酸盐缓冲液辅助。
