气候变化领域集成服务门户(CCPortal): Molecular and heterogenized dinuclear Ir-Cp* water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands

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DOI	10.1016/j.scib.2020.06.015
	*Molecular and heterogenized dinuclear Ir-Cp water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands**
	Domestici C.; Tensi L.; Zaccaria F.; Kissimina N.; Valentini M.; D'Amato R.; Costantino F.; Zuccaccia C.; Macchioni A.
发表日期	2020
ISSN	20959273
起始页码	1614
结束页码	1625
卷号	65 期号:19
英文摘要	The development of efficient water oxidation catalysts (WOCs) is of key importance in order to drive sustainable reductive processes aimed at producing renewable fuels. Herein, two novel dinuclear complexes, [(CpIr)2(μ-κ3-O,N,O-H4-EDTMP)] (Ir-H4-EDTMP, H4-EDTMP4− = ethylenediamine tetra(methylene phosphonate)) and [(CpIr)2(μ-κ3-O,N,O-EDTA)] (Ir-EDTA, EDTA4− = ethylenediaminetetraacetate), were synthesized and completely characterized in solution, by multinuclear and multidimensional NMR spectroscopy, and in the solid state, by single crystal X-Ray diffraction. They were supported onto rutile TiO2 nanocrystals obtaining Ir-H4-EDTMP@TiO2 and Ir-EDTA@TiO2 hybrid materials. Both 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 used. As 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 (2.123 Å, significantly longer than Ir–OC, 2.0913 Å), which is a necessary step to activate these saturated complexes. Ir-H4-EDTMP@TiO2 (up to 33 min−1) and Ir-EDTA@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, instead. The observed TOF values for hybrid materials are higher than those reported for analogous systems deriving from heterogenized mononuclear complexes. This suggests that supporting dinuclear molecular precursors could be a successful strategy to obtain efficient heterogenized water oxidation catalysts. © 2020 Science China Press
关键词	Dinuclear complexes Heterogenized catalysts Homogeneous catalysis Organometallic chemistry Renewable fuels Water oxidation
英文关键词	Catalysts; Coordination reactions; Iridium compounds; Nuclear magnetic resonance spectroscopy; Oxidation; Oxide minerals; Single crystals; Sodium compounds; Titanium dioxide; Efficient catalysts; Molecular catalysts; Molecular complexes; Molecular precursor; Mononuclear complexes; Multidimensional NMR; Single crystal x-ray diffraction; Water oxidation catalysts; Hybrid materials
语种	英语
来源期刊	Science Bulletin
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/207022
作者单位	Department of Chemistry, Biology and Biotechnology, University of Perugia and CIRCC, Perugia, 06123, Italy; École Supérieure d'Ingénieurs de Rennes, University of Rennes 1, Rennes, 35042, France; Department of Chemistry, Sultan Qaboos University, Muscat, 123, Oman
推荐引用方式 GB/T 7714	Domestici C.,Tensi L.,Zaccaria F.,et al. Molecular and heterogenized dinuclear Ir-Cp* water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands[J],2020,65(19).
APA	Domestici C..,Tensi L..,Zaccaria F..,Kissimina N..,Valentini M..,...&Macchioni A..(2020).Molecular and heterogenized dinuclear Ir-Cp* water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands.Science Bulletin,65(19).
MLA	Domestici C.,et al."Molecular and heterogenized dinuclear Ir-Cp* water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands".Science Bulletin 65.19(2020).