Catalytic Mechanism of Ionic Liquid for CO2 Electrochemical Reduction†

doi:10.7503/cjcu20150514

Abstract

Abstract:

In 1-butyl-3-methylimidazolium trifluoromethanesulfonate([Bmim][CF₃SO₃])/propylene carbo-nate(PC) solution, the rate-determining step and catalytic mechanism of ionic liquid for CO₂ electrochemical reduction on gold electrode were studied by cyclic voltammetry, electrochemical impedance spectroscopy and impedance simulation. Experimental results show that the rate-determining step for CO₂ reduction is the formation of C radical by one-electron transfer. Due to the catalytic effect of ionic liquid, the onset potential of CO₂ reduction in [Bmim][CF₃SO₃]/PC shifts positively by 239 mV comparing to that occurred in tetrabuty-lammonium trifluoromethanesulfonate([Bu₄N][CF₃SO₃])/PC catholyte. The catalytic mechanism of ionic liquid is proposed as follows: firstly, the cation of ionic liquid([Bmim]⁺) adsorbed on the Au electrode and lead to the formation of ionic liquid film; then, CO₂ in catholyte diffuses from the bulk solution to the surface of cathode. After transfer through the ionic liquid film adsorbed on the surface of Au electrode, CO₂ is reduced to C radical via single electron transfer. The generated C radical further react with cation [Bmim]⁺ and induce the formation of [Bmim-CO₂]_ad. Through this route, the activation energy of CO₂ electrochemical reduction is reduced. Hence the overpotential of CO₂ electrochemical reduction is reduced substantially.

Key words: Carbon dioxide, Electrochemical reduction, Ionic liquid, Electrochemical impedance, Catalytic mechanism

CLC Number:

O646

TrendMD:

YANG Dongwei, LI Lu, WANG Qin, WANG Xiaochun, LI Qingyuan, SHI Jin. Catalytic Mechanism of Ionic Liquid for CO₂ Electrochemical Reduction^†[J]. Chem. J. Chinese Universities, 2016, 37(1): 94.

Figures/Tables 7

Fig.1 Schematic of the electrolysis cell for CO2 reduction

Fig.2 Cyclic voltammograms in [Bu4N][CF3SO3]/PC(A) and [Bmim][CF3SO3]/PC(B)^ Scan rate: 20 mV/s. a. Blank; b. 10 mmol/L ferrocene.

Fig.3 Cyclic voltammograms of CO2 electrochemical reduction in [Bu4N][CF3SO3]/PC(a) and [Bmim][CF3SO3]/PC(b)^Scan rate: 50 mV/s.

Fig.4 EIS of CO2 electrochemical reduction in [Bu4N][CF3SO3]/PC(A) and [Bmim][CF3SO3]/PC(B) catholytes

Fig.5 Equivalent circuits for CO2 reduction in [Bu4N][CF3SO3]/PC(A) and [Bmim][CF3SO3]/PC catholyte(B)

Table 1 Parameter values of elements in the equivalent circuit model

Catholyte	R_s/(Ω·cm²)	C/(μF·cm^-2)	R₁/(Ω·cm²)	W/(Ω·cm²)	Q/(μF·cm^-2)	n	R₂/(Ω·cm²)
[Bu₄N][CF₃SO₃]/PC	68.66	0.2438	148.6	0.001126
[Bmim][CF₃SO₃]/PC	5.175	0.311	15.4	0.0258	65.06	0.8	29.68

Fig.6 Mechanism of CO2 electrochemical reduction in [Bmim][CF3SO3]/PC catholyte

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Catalytic Mechanism of Ionic Liquid for CO₂ Electrochemical Reduction^†

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