Molecular and heterogenized dinuclear Ir-Cp^* water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands

作     者：Chiara Domestici Leonardo Tensi Francesco Zaccaria Nade Kissimina Massimiliano Valentini Roberto D'Amato Ferdinando Costantino Cristiano Zuccaccia Alceo Macchioni Chiara Domestici;Leonardo Tensi;Francesco Zaccaria;Nade Kissimina;Massimiliano Valentini;Roberto D'Amato;Ferdinando Costantino;Cristiano Zuccaccia;Alceo Macchioni

作者机构：Department of ChemistryBiology and BiotechnologyUniversity of Perugia and CIRCCPerugia 06123Italy école Supérieure d'Ingénieurs de RennesUniversity of Rennes 1Rennes 35042France Department of ChemistrySultan Qaboos UniversityMuscat 123Oman 

出 版 物：《Science Bulletin》 (科学通报（英文版）)

年 卷 期：2020年第65卷第19期

页      面：1614-1625,M0003页

核心收录：

学科分类：081704[工学-应用化学] 081705[工学-工业催化] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：financially supported by PRIN 2015(20154X9ATP_004) University of Perugia and MIUR(AMIS,“Dipartimenti di Eccellenza–2018–2022”Program) INSTM and CIRCC for a post-doctoral grant University of Perugia for hospitality and the Erasmus Programme for financial support 

主　　题：Renewable fuels Water oxidation Homogeneous catalysis Heterogenized catalysts Organometallic chemistry Dinuclear complexes 

摘      要：The development of efficient water oxidation catalysts(WOCs)is of key importance in order to drive sustainable reductive processes aimed at producing renewable ***,two novel dinuclear complexes,[(Cp^*Ir)2(μ-κ^3-O,N,O-H4-EDTMP)](Ir-H4-EDTMP,H4-EDTMP^4-=ethylenediamine tetra(methylene phosphonate))and[(Cp^*Ir)2(μ-κ^3-O,N,O-EDTA)](Ir-EDTA,EDTA^4-=ethylenediaminetetraacetate),were synthesized and completely characterized in solution,by multinuclear and multidimensional NMR spectroscopy,and in the solid state,by single crystal X-Ray *** were supported onto rutile TiO2 nanocrystals obtaining Ir-H4-EDTMP@TiO2 and Ir-EDTA@TiO2 hybrid *** molecular complexes and hybrid materials were found to be efficient catalysts for WO driven by NaIO4,providing almost quantitative yields,and TON values only limited by the amount of NaIO4 *** for the molecular catalysts,Ir-H4-EDTMP(TOF up to 184 min^-1)exhibited much higher activity than Ir-EDTA(TOF up to 19 min^-1),likely owing to the higher propensity of the former to generate a coordination vacancy through the dissociation of a Ir–OP bond(2.123A,significantly longer than Ir–OC,2.0913A),which is a necessary step to activate these saturated ***-H4-EDTMP@TiO2(up to 33 min^-1)and IrEDTA@TiO2(up to 41 min^-1)hybrid materials showed similar activity that was only marginally reduced in the second and third catalytic runs carried out after having separated the supernatant,which did not show any sign of activity,*** observed TOF values for hybrid materials are higher than those reported for analogous systems deriving from heterogenized mononuclear *** suggests that supporting dinuclear molecular precursors could be a successful strategy to obtain efficient heterogenized water oxidation catalysts.