SnO2/GDE阴极的制备及电催化还原CO2产甲酸性能

doi:10.7503/cjcu20190516

摘要/Abstract

摘要：

采用低温水热合成法制备了碳纸基底的SnO₂气体扩散电极(SnO₂/GDE), 并对其物化特性与催化还原CO₂产甲酸性能进行了研究. 扫描电子显微镜、 X射线衍射及X射线光电子能谱表征结果表明, 在60, 75, 100 ℃下制备的催化剂均为分散性良好的纳米SnO₂粉体, 其粒径分别为7.9, 11.8和12.9 nm. 循环伏安、线性扫描伏安和电化学交流阻抗测试结果显示电极均具有优异的电催化活性, 其电化学活性表面积分别为150, 470, 240 cm ², 通过等效电路拟合后电阻分别为8.5, 3.9, 6.6 Ω·cm ². 在-1.8 V(vs. SCE)电位下电解, 通入电量500 C时, 电极都具有较高电催化还原CO₂产甲酸性能, 而75 ℃下制备的电极性能最佳, 产甲酸电流密度为22.8 mA/cm ² , 产甲酸法拉第效率高达93.5%; 该电极经过20 h长时间电解后, 产甲酸电流密度可维持在12.8 mA/cm ² , 产甲酸法拉第效率稳定在约65%.

关键词: 二氧化碳, 电催化还原, 低温水热合成, 氧化锡气体扩散电极

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

中图分类号:

O646

TrendMD:

卓孟宁,李飞,蒋浩,陈倩文,李鹏,王立章. SnO₂/GDE阴极的制备及电催化还原CO₂产甲酸性能. 高等学校化学学报, 2020, 41(3): 530.

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 ^†. Chem. J. Chinese Universities, 2020, 41(3): 530.

图/表 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)

Table 1 EIS equivalent circuit fitting of SnO2-T/GDE under -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.

Table 2 Comparison of the electrode performances between the reported results and this work with SnO2 as catalyst

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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SnO₂/GDE阴极的制备及电催化还原CO₂产甲酸性能

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

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