Preparation of Cu Doped SnO2 Cathode Material for Electroreduction of Carbon Dioxide at Low Overpotential†

doi:10.7503/cjcu20180226

Abstract

Abstract:

Cu doped SnO₂ was prepared through one-step hydrothermal method with SnCl₄·5H₂O as precursor material and CuCl₂ as dopant. The surface morphology, crystal structure and element composition as well as valence state were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). The properties of the material and the reduction of CO₂ were investigated by cyclic voltammetry, Tafel plot and electrochemical impedance spectroscopy under normal temperature and pressure in 0.5 mol/L NaHCO₃ solution. The results show that SnO₂ has rutile structure and Cu²⁺ ions replace some Sn⁴⁺ ions of SnO₂. Besides, the particles size decreases slightly after doping Cu⁺. Through electrochemical performance evaluation, the best catalytic performance was achieved as the Cu doping content was 1.5%. The current density reached 3.5 mA/cm², the Tafel slope was 55.1 mV/dec and the maximum Faradic efficiency reached 23% when the catalyst loading amount was 0.8 mg. The Faradic efficiency is 12 times that of pure SnO₂. Therefore, the Cu doped SnO₂ can be used as cathode material for electrocatalytic reduction of CO₂.

Key words: Cu doped Sn-oxide, Electrocatalysis, Carbon dioxide reduction, Low overpotential, Formate

CLC Number:

O646

TrendMD:

HU Xueyan,WANG Na,HAO Yuting,XU Zhiqing,WANG Minghui,SHI Gaiqin,YANG Huimin,LIANG Zhenhai. Preparation of Cu Doped SnO₂ Cathode Material for Electroreduction of Carbon Dioxide at Low Overpotential^†[J]. Chem. J. Chinese Universities, 2018, 39(10): 2265.

Figures/Tables 12

Fig.1 Preparation of Cu doped SnO2 material and catalytic schematic diagram

Fig.2 Standard curve of formic acid

Fig.3 SEM images of samples SC0(A) and SC1.5(B)

Fig.4 XRD patterns of different samples

Table 1 XRD parameters of different samples

Sample	D_hkl/nm	d/nm	a/nm	c/nm
SC0	22.2344	0.2587	0.4743	0.3191
SC1	9.3089	0.2586	0.4740	0.3191
SC1.5	8.0839	0.2586	0.4739	0.3191
SC2	11.8905	0.2593	0.4766	0.3199
SC3	12.2344	0.2587	0.4745	0.3192

Fig.5 XPS survey spectrum(A) and O1s(B), Sn3d(C) and Cu2p(D) XPS spectra of sample SC1.5

Fig.6 Cyclic voltammograms of sample SC1.5 in N2 and CO2 saturated 0.5 mol/L NaHCO3 solution(A) and different samples in CO2 saturated 0.5 mol/L NaHCO3 solution(B)

Table 2 Overpotential comparison of different catalysts for electrocatalytic reduction of CO2

Electrode	Electrolyte	Overpotential	Reference
SnO₂ nanowires	0.1 mol/L KHCO₃	0.35 V(vs. RHE)	[3]
Sn electrode	0.1 mol/L NaHCO₃	0.34 V(vs. RHE)	[12]
Cu doped SnO₂	0.5 mol/L NaHCO₃	0.30 V(vs. RHE)	This work

Fig.7 Electrochemical impedance plots of different samples(A) and equivalent circuit diagram(B)

Fig.8 Tafel plots for production of HCOOH

Fig.9 Faradaic efficiency for formateThe inset shows the 1H NMR spectrum of the liquid product.

Fig.10 Current-time curves of cathode materials

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Preparation of Cu Doped SnO₂ Cathode Material for Electroreduction of Carbon Dioxide at Low Overpotential^†

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