Switching O-O bond formation mechanism between WNA and I2M pathways by modifying the Ru-bda backbone ligands of water-oxidation catalysts  

作　　者：Biaobiao Zhang Shaoqi Zhan Tianqi Liu Linqin Wang A.Ken Inge Lele Duan Brian J.J.Timmer Oleksandr Kravchenko Fei Li Marten S.G.Ahlquist Licheng Sun 

机构地区：[1]Department of Chemistry,KTH Royal Institute of Technology,10044 Stockholm,Sweden [2]Department of Theoretical Chemistry&Biology,School of Engineering Sciences in Chemistry Biotechnology and Health,KTH Royal Institute of Technology,10691 Stockholm,Sweden [3]Department of Materials and Environmental Chemistry,Stockholm University,10691 Stockholm,Sweden [4]Department of Chemistry,Southern University of Science and Technology(SUSTech),Shenzhen 518055,Guangdong,China [5]State Key Laboratory of Fine Chemicals,Institute of Artificial Photosynthesis,DUT–KTH Joint Education and Research Center on Molecular Devices,Dalian University of Technology(DUT),Dalian 116024,Liaoning,China

出　　处：《Journal of Energy Chemistry》2021年第3期815-821,共7页能源化学（英文版）

基　　金：the financial support from the Swedish Research Council(2017-00935);Swedish Energy Agency;the Knut and Alice Wallenberg Foundation;the National Natural Science Foundation of China(21120102036);the National Basic Research Program of China(973 program,2014CB239402);the China Scholarship Council(CSC)。

摘　　要：Understanding the seven coordination and O-O coupling pathway of the distinguished Ru-bda catalysts is essential for the development of next generation efficient water-oxidation catalysts based on earthabundant metals.This work reports the synthesis,characterization and catalytic properties of a monomeric ruthenium catalyst Ru-bnda(H2 bnda=2,2’-bi(nicotinic acid)-6,6’-dicarboxylic acid)featuring steric hindrance and enhanced hydrophilicity on the backbone.Combining experimental evidence with systematic density functional theory calculations on the Ru-bnda and related catalysts Ru-bda(H_(2)bda=2,2’-bipyridine-6,6’-dicarboxylic acid),Ru-pda(H_(2)pda=1,10-phenanthroline-2,9-dicarboxylic acid),and Ru-biqa(H_(2)biqa=(1,1’-biisoquinoline)-3,3’-dicarboxylic acid),we emphasized that seven coordination clearly determines presence of Ru^(Ⅴ)=O with high spin density on the ORu^(Ⅴ)=O atom,i.e.oxo with radical properties,which is one of the necessary conditions for reacting through the O-O coupling pathway.However,an additional factor to make the condition sufficient is the favorable intermolecular faceto-face interaction for the generation of the pre-reactive[Ru^(Ⅴ)=O…O=Ru^(Ⅴ)],which may be significantly influenced by the secondary coordination environments.This work provides a new understanding of the structure-activity relationship of water-oxidation catalysts and their potential to adopt I2M pathway for O-O bond formation.

关 键 词：Water oxidation Oxygen evolution RUTHENIUM O-O bond formation 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学]