Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction:   Experimental and Theoretical Evidence for a Homolytic Hydrogen-Evolution   Reaction

doi:10.1002/anie.201510001

CORC > 北京大学 > 化学与分子工程学院

	Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction: Experimental and Theoretical Evidence for a Homolytic Hydrogen-Evolution Reaction
	Han, Yongzhen ; Fang, Huayi ; Jing, Huize ; Sun, Huiling ; Lei, Haitao ; Lai, Wenzhen ; Cao, Rui
刊名	ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
	2016
关键词	bimetallic reactions electrocatalysis homolysis hydrogen evolution nickel porphyrins COBALT CORROLE CATALYST MOLYBDENUM-OXO CATALYST IRON-ONLY HYDROGENASE H-2 PRODUCTION ELECTRON-TRANSFER SPECTRAL CHARACTERIZATION GENERATING HYDROGEN LOW OVERPOTENTIALS AQUEOUS-SOLUTION WATER REDUCTION
DOI	10.1002/anie.201510001
英文摘要	A nickel(II) porphyrin Ni-P (P=porphyrin) bearing four meso-C6F5 groups to improve solubility and activity was used to explore different hydrogen-evolution-reaction (HER) mechanisms. Doubly reduced Ni-P ([Ni-P](2-)) was involved in H-2 production from acetic acid, whereas a singly reduced species ([Ni-P](-)) initiated HER with stronger trifluoroacetic acid (TFA). High activity and stability of Ni-P were observed in catalysis, with a remarkable i(c)/i(p) value of 77 with TFA at a scan rate of 100 mVs(-1) and 20 degrees C. Electrochemical, stopped-flow, and theoretical studies indicated that a hydride species [H-Ni-P] is formed by oxidative protonation of [Ni-P](-). Subsequent rapid bimetallic homolysis to give H-2 and Ni-P is probably involved in the catalytic cycle. HER cycling through this one-electron-reduction and homolysis mechanism has been proposed previously but rarely validated. The present results could thus have broad implications for the design of new exquisite cycles for H-2 generation.; National Natural Science Foundation of China [21101170, 21573139]; Fundamental Research Funds for the Central Universities; Renmin University of China; "Thousand Young Talents" program in China; SCI(E); EI; PubMed; ARTICLE; wenzhenlai@ruc.edu.cn; ruicao@ruc.edu.cn; 18; 5457-5462; 55
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/434319]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Han, Yongzhen,Fang, Huayi,Jing, Huize,et al. Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction: Experimental and Theoretical Evidence for a Homolytic Hydrogen-Evolution Reaction[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2016.
APA	Han, Yongzhen.,Fang, Huayi.,Jing, Huize.,Sun, Huiling.,Lei, Haitao.,...&Cao, Rui.(2016).Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction: Experimental and Theoretical Evidence for a Homolytic Hydrogen-Evolution Reaction.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION.
MLA	Han, Yongzhen,et al."Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction: Experimental and Theoretical Evidence for a Homolytic Hydrogen-Evolution Reaction".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2016).