Preparation of SnO2/GDE Cathodes and Their Electrocatalytic Reduction of CO2 to Produce Formic Acid †

doi:10.7503/cjcu20190516

Abstract

Abstract:

The SnO₂ gas diffusion electrodes(SnO₂/GDE) were prepared by low temperature hydrothermal synthesis. Their physicochemical properties and catalytic performance for reduction of CO₂ to produce formic acid were studied. The results of scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy showed that the catalysts prepared at 60, 75 and 100 ℃ were all nano-SnO₂ powder with good dispersibility, and the particle sizes were 7.9, 11.8 and 12.9 nm, respectively. Cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy results showed that the electrodes had excellent electrocatalytic activity, and their electrochemically active surface area was 150, 470, 240 cm ², respectively, the resistance after fitting was 8.5, 3.9, and 6.6 Ω·cm ², respectively. With electrical charge of 500 C passed at applied potential of -1.8 V(vs. SCE),, the electrodes showed higher electrocatalytic performance for reduction of CO₂ to produce formic acid. For the best electrode that prepared at 75 ℃, the current density of formic acid production was 22.8 mA/cm ², and the Faraday efficiency of formic acid production was as high as 93.5%; after 20 h of electrolysis of this electrode, the current density of formic acid production could be maintained at 12.8 mA/cm ², and the Faraday efficiency of formic acid production was stable at about 65%, indicating that the preparation of SnO₂ catalysts by low-temperature hydrothermal synthesis has great competitiveness.

Key words: CO₂, Electrocatalytic reduction, Low temperature hydrothermal synthesis, SnO₂/gas diffusion electrode

CLC Number:

O646

TrendMD:

ZHUO Mengning,LI Fei,JIANG Hao,CHEN Qianwen,LI Peng,WANG Lizhang. Preparation of SnO₂/GDE Cathodes and Their Electrocatalytic Reduction of CO₂ to Produce Formic Acid ^†[J]. Chem. J. Chinese Universities, 2020, 41(3): 530.

Figures/Tables 11

Fig.1 SEM images of SnO2-60/GDE(A), SnO2-75/GDE(B) and SnO2-100/GDE(C)

Fig.2 XRD patterns of SnO2-T/GDE

Fig.3 XPS survey(A, C, E) and high resolution spectra of Sn3d(B, D, F) of SnO2-T/GDE (A), (B) SnO2-60/GDE; (C), (D) SnO2-75/GDE; (E), (F) SnO2-100/GDE.

Fig.4 Cyclic voltammetric scan of SnO2-T/GDE in N2 and CO2 environments Scanning rate: 50 mV/s; potential window: -0.3—1.8 V(vs. SCE); electrolyte: 0.1 mol/L KHCO3 solution. (A) SnO2-60/GDE; (B) SnO2-75/GDE; (C) SnO2-100/GDE; (D) SnO2-T/GDE in the CO2 environment.

Fig.5 Linear sweep voltammetry of SnO2-T/GDE in N2 and CO2 environments Scanning rate: 50 mV/s; Potential window: -0.3—1.8 V vs. SCE; electrolyte: 0.1 mol/L KHCO3 solution. (A) SnO2-60/GDE; (B) SnO2-75/GDE; (C) SnO2-100/GDE; (D) SnO2-T/GDE in the CO2 environment.

Fig.6 Linear relationship between current density difference and scan rate of SnO2-T/GDE at -0.4 V(vs. SCE) Potential window: -0.3—-0.5 V(vs. SCE); electrolyte: N2 satarated 0.1 mol/L KHCO3 solution. (A) SnO2-60/GDE; (B) SnO2-75/GDE; (C) SnO2-100/GDE.

Fig.7 Nyquist plots(A) and bode plots(B) of SnO2-T/GDE in 0.1 mol/L KHCO3 solution with saturated CO2 at -1.5 V(vs. SCE)

Electrode	R_s/(Ω·cm²)	R_ct/(Ω·cm²)	Error(%)
SnO₂-60/GDE	4.8	8.5	1.6
SnO₂-75/GDE	4.8	3.9	1.3
SnO₂-100/GDE	4.5	6.6	1.5

Fig.8 Faradic efficiency(A), current density(B) and production yield(C) of formic acid in CO2 saturared 0.1 mol/L KHCO3 solution over SnO2-T/GDE at -1.8 V(vs. SCE) a. SnO2-60/GDE; b. SnO2-75/GDE; c. SnO2-100/GDE.

Preparation condition	Electrolysis potential/V	Electrolysis time/h	FE(%)	Current density/(mA·cm^-2)	Ref.
180 ℃, 24 h	-1.7(vs. SHE) ^a	1	62	12.5	[21]
120 ℃, 6 h	-1.8(vs. SCE) ^a	1	60	9	[33]
100 ℃, 8 h	-1.5(vs. SHE) ^a	1	87.1	10	[24]
60 ℃, 10 h	-1.8(vs. SCE)	1.21 ^b	46.5	11.4	This work
75 ℃, 10 h	-1.8(vs. SCE)	1.76 ^b	93.5	22.8	This work
100 ℃, 10 h	-1.8(vs. SCE)	1.57 ^b	62.1	12.8	This work

Fig.9 SnO2-75/GDE electrode reaction reduction CO2 current density and formic acid Faraday efficiency change with electrolysis time

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Preparation of SnO₂/GDE Cathodes and Their Electrocatalytic Reduction of CO₂ to Produce Formic Acid ^†

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