DOI: 10.1016/j.scib.2020.06.015
论文题名: Molecular and heterogenized dinuclear Ir-Cp* water oxidation catalysts bearing EDTA or EDTMP as bridging and anchoring ligands
作者: Domestici C. ; Tensi L. ; Zaccaria F. ; Kissimina N. ; Valentini M. ; D'Amato R. ; Costantino F. ; Zuccaccia C. ; Macchioni A.
刊名: Science Bulletin
ISSN: 20959273
出版年: 2020
卷: 65, 期: 19 起始页码: 1614
结束页码: 1625
语种: 英语
中文关键词: 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
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, [(Cp*Ir)2(μ-κ3-O,N,O-H4-EDTMP)] (Ir-H4-EDTMP, H4-EDTMP4− = ethylenediamine tetra(methylene phosphonate)) and [(Cp*Ir)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 Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/169878
Appears in Collections: 气候变化与战略
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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
Recommended Citation:
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]. Science Bulletin,2020-01-01,65(19)