Electrochemical Spectroscopy Analysis for Kinetics of the CO2 Electroreduction Reaction on Ni Single Atom Catalysts †

doi:10.7503/cjcu20190699

Abstract

Abstract:

Single site mechanism and bi-function mechanism were both put forward for CO₂ electro-reduction reaction(CO₂RR) on the carbon-nitride anchoring Ni single atoms catalysts. The former is specific to the CO₂RR only on the active site Ni and the latter considers both reductions on the Ni site and water spitting on the anchoring carbon nitride site. Kinetic analysis of the CO₂RR as well as sensitivity analysis for the model parameters were both performed by means of static CO₂RR models and experimental polarizations. Electrochemical impedance spectroscopy(EIS) and total harmonic distortion(THD) spectroscopy were also simulated using dynamic CO₂RR models to explore its linear and nonlinear frequency response behaviors, respectively. It is suggested that CO₂ concentration is the most sensitive parameters to CO₂RR performance. The elemental step to form COOH_ads is the rate determines step as the CO₂RR follows the single site mechanism. As for the bi-function mechanism, both CO_2,ads electro-reduction on the Ni site and water splitting on the carbon nitride site are rate-determining steps of the CO₂RR. Transient simulation of CO₂RR reveals that the EIS is able to tell the difference of the single site mechanism from the bi-function mechanism theoretically over the THD spectroscopy.

Key words: CO₂ Electro-reduction reaction(CO₂RR) mechanism, Electrochemical impedance spectroscopy(EIS), Nonlinear frequency response analysis, Total harmonic distortion(THD) spectroscopy

CLC Number:

O646

TrendMD:

MAO Qing,ZHAO Jian,LIU Song,GUO Chang,LI Bingyu,XU Keyi,CAO Ziqiang,HUANG Yanqiang. Electrochemical Spectroscopy Analysis for Kinetics of the CO₂ Electroreduction Reaction on Ni Single Atom Catalysts ^†[J]. Chem. J. Chinese Universities, 2020, 41(5): 1058.

Figures/Tables 10

Mechanism	K₁₀₁	K₁₀₂	K₂₀₁	K₂₀₂	K₃₀₁	K₃₀₂
Single site mechanism	6.5×10¹	9.3×10⁰	6.3×10^-6	6.9×10^-15	1.6×10^-3	6.0×10^-12
bi-Function mechanism	6.6×10²	4.2×10²	2.5×10^-5	5.9×10^-5	3.0×10^-5	4.3×10^-2

Model parameter	Target parameter
Model parameter	$θ C O 2$	$θ COOH$	$E c$
CO₂ concentration	-0.7357	-0.7357	0.1745
KHCO₃ concentration	0	0	-0.0152
CO concentration	0	0	-0.0079
Limiting coverage of active site Ni	-0.5	-0.5	0.0396

Model parameter	Target parameter
Model parameter	$θ C O 2$	$θ COOH$	$E c$
CO₂ concentration	-0.7357	-0.7357	0.1745
KHCO₃ concentration	0	0	-0.0152
CO concentration	0	0	-0.0079
Limiting coverage of active site Ni	-0.5	-0.5	0.0396

Model parameter	Target parameter
Model parameter	$θ C O 2$	$θ H$	$E c$
CO₂ concentration	-0.7563	0.0294	0.1779
KHCO₃ concentration	0	0	-0.0153
CO concentration	0	0	-0.0079
Limiting coverage of active site N	0	-0.5	0.0316
Limiting coverage of active site Ni	-0.5	0.0193	0.0308

Model parameter	Target parameter
Model parameter	$θ C O 2$	$θ H$	$E c$
CO₂ concentration	-0.7563	0.0294	0.1779
KHCO₃ concentration	0	0	-0.0153
CO concentration	0	0	-0.0079
Limiting coverage of active site N	0	-0.5	0.0316
Limiting coverage of active site Ni	-0.5	0.0193	0.0308

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Electrochemical Spectroscopy Analysis for Kinetics of the CO₂ Electroreduction Reaction on Ni Single Atom Catalysts ^†

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