DOI: 10.1016/j.jcou.2016.11.009
Scopus记录号: 2-s2.0-85000899984
论文题名: Electrocatalytic reduction of CO2 to CO in the presence of a mononuclear polypyridyl ruthenium(II) complex
作者: Daryanavard M. ; Hadadzadeh H. ; Weil M. ; Farrokhpour H.
刊名: Journal of CO2 Utilization
ISSN: 22129820
出版年: 2017
卷: 17 起始页码: 80
结束页码: 89
语种: 英语
英文关键词: Carbon dioxide
; CO2 reduction
; Computational studies
; Electrocatalyst
; Ruthenium
Scopus关键词: Acetonitrile
; Activation energy
; Carbon
; Catalyst activity
; Chlorine compounds
; Coordination reactions
; Cyclic voltammetry
; Electrocatalysts
; Molecules
; Organic solvents
; Ruthenium
; Ruthenium alloys
; Ruthenium compounds
; X ray analysis
; Acetonitrile solutions
; Computational studies
; Coordination environment
; Electrocatalytic activity
; Electrocatalytic mechanism
; Electrocatalytic reduction
; Polypyridyl ruthenium complexes
; Reduction peak currents
; Carbon dioxide
英文摘要: A new polypyridyl Ru(II) complex, [Ru(tptz)(CH3CN)Cl2] (tptz = 2,4,6-tri(2-pyridyl)-1,3,5-triazine) has been prepared and characterized. It crystallizes with one molecule of acetonitrile and a partly occupied water solvent molecule. X-ray analysis of the complex revealed that the central Ru(II) atom has a distorted octahedral Cl2N3N' coordination environment. The complex was used as an electrocatalyst for the reduction of CO2 to CO in an acetonitrile solution as monitored by cyclic voltammetry. The electrocatalytic activity of the complex was investigated for CO2 reduction under different reaction conditions. The results show that the CO2 reduction peak current increases with increasing concentration of the electrocatalyst from 0.5 to 2 mM, increasing purging time of CO2 from 5 to 30 min, and increasing scan rate from 0.1 to 0.5 V s-1. The catalytic activity of the Ru(II) complex is decreased at lower temperatures because of the relationship between the activation energy and temperature. The suggested electrocatalytic mechanism was confirmed by computational studies. The calculations indicate that the electrocatalytic mechanism includes six steps. The electrocatalyst undergoes two sequential one-electron tptz-based reductions followed by substitution of the CH3CN by CO2 to yield a metallocarboxylate intermediate. This intermediate (RuII(η1-CO22-)) is involved in further tptz-based reductions and an oxide (O2-) transfer to the free CO2 to yield a monocarbonyl Ru(II) complex ([RuII(tptz2-)(CO)Cl2]2-) and the carbonate anion. The monocarbonyl intermediate undergoes a rapid loss of the coordinating CO molecule at room temperature. Finally, the dianionic intermediate reacts with a new molecule CO2 restarting the electrocatalytic cycle. © 2016 Elsevier Ltd. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/52815
Appears in Collections: 影响、适应和脆弱性
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Recommended Citation:
Daryanavard M.,Hadadzadeh H.,Weil M.,et al. Electrocatalytic reduction of CO2 to CO in the presence of a mononuclear polypyridyl ruthenium(II) complex[J]. Journal of CO2 Utilization,2017-01-01,17