Redox-Active Ligand Assisted Catalytic Water Oxidation by RuIV =O Intermediate.,Angewandte Chemie International Edition

当前位置： X-MOL 学术 › Angew. Chem. Int. Ed. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Redox-Active Ligand Assisted Catalytic Water Oxidation by RuIV =O Intermediate.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2019-12-26 , DOI: 10.1002/anie.201910614
Jing Shi ₁ , Yu-Hua Guo ₁ , Fei Xie ₁ , Qi-Fa Chen ₁ , Ming-Tian Zhang ₁

Affiliation

Water splitting is one of the most promising solutions for storing solar energy in a chemical bond. Water oxidation is still the bottleneck step because of its inherent difficulty and the limited understanding of the O-O bond formation mechanism. Molecular catalysts provide a platform for understanding this process in depth and have received wide attention since the first Ru-based catalyst was reported in 1982. RuV =O is considered a key intermediate to initiate the O-O bond formation through either a water nucleophilic attack (WNA) pathway or a bimolecular coupling (I2M) pathway. Herein, we report a Ru-based catalyst that displays water oxidation reactivity with RuIV =(O) with the help of a redox-active ligand at pH 7.0. The results of electrochemical studies and DFT calculations disclose that ligand oxidation could significantly improve the reactivity of RuIV =O toward water oxidation. Under these conditions, sustained water oxidation catalysis occurs at reasonable rates with low overpotential (ca. 183 mV).

中文翻译：

RuIV = O中间体的氧化还原活性配体辅助催化水氧化。

分解水是以化学键存储太阳能的最有前途的解决方案之一。由于其固有的困难和对OO键形成机理的了解有限，水氧化仍然是瓶颈步骤。自1982年首次报道钌基催化剂以来，分子催化剂为深入了解这一过程提供了平台，并且受到广泛关注。RuV= O被认为是通过水亲核攻击（WNA）引发OO键形成的关键中间体。）途径或双分子偶联（I2M）途径。本文中，我们报道了一种基于Ru的催化剂，该催化剂在pH 7.0的情况下借助氧化还原活性配体显示出RuIV =（O）的水氧化反应性。电化学研究和DFT计算的结果表明，配体氧化可显着提高RuIV = O对水氧化的反应性。在这些条件下，持续的水氧化催化会以合理的速率发生，且过电位较低（约183 mV）。

更新日期：2020-01-27

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11