锡量子点制备及其电催化还原二氧化碳产甲酸性能

doi:10.15541/jim20210177

无机材料学报 ›› 2021, Vol. 36 ›› Issue (12): 1337-1342.DOI: 10.15541/jim20210177 CSTR: 32189.14.10.15541/jim20210177

所属专题：【虚拟专辑】碳中和(2020~2021)

锡量子点制备及其电催化还原二氧化碳产甲酸性能

田建建¹^,²(), 马霞¹^,², 王敏¹, 姚鹤良¹, 华子乐¹, 张玲霞¹^,²^,³()

1.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海200050
2.中国科学院大学材料科学与光电工程中心, 北京100864
3.国科大杭州高等研究院化学与材料科学学院, 杭州 310024

收稿日期:2021-03-19 修回日期:2021-05-07 出版日期:2021-12-20 网络出版日期:2021-05-25
通讯作者: 张玲霞, 研究员. E-mail: zhlingxia@mail.sic.ac.cn
作者简介:田建建(1989-), 女, 博士. E-mail: tianshujian11@163.com

Sn Quantum Dots for Electrocatalytic Reduction of CO₂ to HCOOH

TIAN Jianjian¹^,²(), MA Xia¹^,², WANG Min¹, YAO Heliang¹, HUA Zile¹, ZHANG Lingxia¹^,²^,³()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China

Received:2021-03-19 Revised:2021-05-07 Published:2021-12-20 Online:2021-05-25
Contact: ZHANG Lingxia, professor. E-mail: zhlingxia@mail.sic.ac.cn
About author:TIAN Jianjian (1989-), female, PhD. E-mail: tianshujian11@163.com
Supported by:
National Key R&D Program of China(2017YFE0127400);National Natural Science Foundation of China(51872317);National Natural Science Foundation of China(21835007);Science and Technology Commission of Shanghai(20520711900)

摘要/Abstract

摘要：

锡基材料在自然界含量丰富、价格低廉, 在电催化还原CO₂制液体燃料反应中具有巨大潜力。但是较低的产物选择性和较差的稳定性限制了其应用。本工作制备的锡量子点电催化剂(Sn-QDs), 具有高效、高稳定性和高选择性的电催化还原CO₂产HCOOH活性。Sn-QDs的平均颗粒尺寸仅为2~3 nm, 结晶性良好。小的颗粒尺寸增大了电化学活性面积(ECSA), Sn-QDs的ECSA约为锡颗粒的4.4倍。ECSA增大以及CO₂还原反应动力学加速, 促进了CO₂电化学转化。在-1.0 V (vs RHE)下, Sn-QDs/CN催化剂的HCOOH法拉第效率(FE_HCOOH)达到95%, 并且在宽约0.5 V的电势范围内能够保持在83%以上。此外, Sn-QDs/CN可以在24 h内保持良好的电化学稳定性。

关键词: CO₂还原, 锡量子点, HCOOH, 电催化剂

Abstract:

Sn based materials, as low-cost and earth-abundant electrocatalysts, are potential candidates for CO₂ reduction reaction (CO₂RR) into liquid fuels. Unfortunately, the low selectivity and stability limits their applications. Herein, we developed an electrocatalyst of Sn quantum dots (Sn-QDs) for efficient, durable and highly selective CO₂ reduction to HCOOH. The Sn-QDs were conﬁrmed with high crystallinity and an average size of only 2-3 nm. Small particle size endowed the electrocatalyst with improved electrochemical active surface area (ECSA), which was about 4.4 times of that of Sn particle. This enlarged ECSA as well as accelerated CO₂RR kinetics favored the electrochemical conversion of CO₂. The Faradaic efﬁciency of HCOOH (FE_HCOOH) on Sn-QDs/CN reached up to 95% at -1.0 V (vs RHE), which exceeded 83% in the recorded wide potential window of 0.5 V. Moreover, the Sn-QDs electrocatalyst exhibited good electrochemical durability for 24 h.

Key words: CO₂reduction, Sn quantum dots, HCOOH, electrocatalyst

中图分类号:

TQ174

田建建, 马霞, 王敏, 姚鹤良, 华子乐, 张玲霞. 锡量子点制备及其电催化还原二氧化碳产甲酸性能[J]. 无机材料学报, 2021, 36(12): 1337-1342.

TIAN Jianjian, MA Xia, WANG Min, YAO Heliang, HUA Zile, ZHANG Lingxia. Sn Quantum Dots for Electrocatalytic Reduction of CO₂ to HCOOH[J]. Journal of Inorganic Materials, 2021, 36(12): 1337-1342.

图/表 13

Fig. 1 XRD patterns of Sn-QDs/CN and CN

Fig. 2 TEM images at different magnifications (a, b) and corresponding EDS line scanning spectra (c) of Sn-p/CN; TEM image (inset: magnified image) (d), HRTEM image (e) and Sn-QDs size distribution (f) of Sn-QDs/CN

Fig. 3 High-resolution Sn3d (a) and O1s (b) XPS spectra of Sn-QDs/CN

Fig. 4 LSV curves of the Sn-QDs/CN electrode in Ar-(dotted line) and CO2-saturated (solid line) 0.1 mol·L-1 KHCO3 electrolyte at a scan rate of 30 mV·s-1 (a), and Faradaic efﬁciencies of HCOOH on Sn-QDs/CN and Sn-p/CN at a series of potentials (b)

Fig. 5 Charging current density differences plotted against scan rates (a), electrochemical impedance spectra with inset showing the corresponding equivalent circuit (b), Tafel plots for HCOOH production on Sn-QDs/CN and Sn-p/CN (c), and the stability of Sn-QDs/CN catalyst at -1.0 V for 24 h in CO2-saturated 0.1 mol·L-1 KHCO3 (d)

Table S1 Comparison of various Sn-based catalysts for CO2-to-HCOOH conversion

Electrocatalyst	Electrolyte	Potential /V (vs. RHE)	FE_HCOOH /%	Current density /(mA·cm^-2)	Stability/h	Ref.
Sn-QDs/CN	0.1 mol·L^-1 KHCO₃	-1.0	95	3.3	24	This work
Sn quantum sheets confined in graphene	0.1 mol·L^-1 NaHCO₃	-1.2	89	21.1	50	[1]
Nano-SnO₂/graphene	0.1 mol·L^-1 NaHCO₃	-1.2	93.6	10	-	[2]
SnO₂ nanoparticles (< 5 nm)	0.1 mol·L^-1 KHCO₃	-1.2	64	147	-	[3]
SnO₂ nanoparticles (~500 nm)	0.1 mol·L^-1 KHCO₃	-1.2	83.5	7.56	-	[4]
SnO₂ nanoparticles (100 nm)	0.5 mol·L^-1 KHCO₃	-0.9	80	12	-	[5]
SnO₂ nanoparticles (8-20 nm)	0.1 mol·L^-1 KHCO₃	-1.06	82	15.3	5	[6]
SnO₂@N-CNW	0.5 mol·L^-1 NaHCO₃	-0.8	90	13	20	[7]
SnO₂@N-rGO	0.5 mol·L^-1 NaHCO₃	-0.8	89	21.3	20	[8]
SnO₂/PC	0.5 mol·L^-1 KHCO₃	-0.86	92	29	10	[9]
SnO₂⊃NC@EEG	0.1 mol·L^-1 KHCO₃	-1.2	81.2	13.4	10	[10]
SnO/C	0.5 mol·L^-1 KHCO₃	-0.86	75	27.2	-	[11]

Fig. S1 1H NMR spectrum of the cathodic electrolyte after CO2RR (a), and linear relationship between HCOOH concentration and relative peak area ratio (vs. DMSO) (b)

Fig. S2 High-resolution N1s XPS spectra of Sn-QDs and CN

Fig. S3 i-t curves of CO2RR on Sn-QDs/CN at different applied potentials (a), and Faradaic efficiencies of HCOOH, CO and H2 at different applied potentials on the Sn-QDs/CN electrode (b)

Table S2 Fitted data of EIS for Sn-QDs/CN and Sn-p/CN

Parameter	R_s/Ω	R_ct/Ω	CPE-T	CPE-P
Sn-QDs/CN	102.6	276.3	1.2×10^-5	0.85
Sn-p/CN	96.74	336.9	1.1×10^-5	0.89

Fig. S4 Faradaic efficiencies of CO and H2 at different applied potentials on CN

Fig. S5 LSV curves of Sn-p/CN and Sn-QDs/CN in CO2-saturated 0.1 mol·L-1 KHCO3 electrolyte at a scan rate of 30 mV·s-1

Fig. S6 Proposed possible reaction pathway of CO2-to-HCOOH conversion on Sn-QDs/CN

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锡量子点制备及其电催化还原二氧化碳产甲酸性能

Sn Quantum Dots for Electrocatalytic Reduction of CO₂ to HCOOH

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锡量子点制备及其电催化还原二氧化碳产甲酸性能

Sn Quantum Dots for Electrocatalytic Reduction of CO2 to HCOOH

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Sn Quantum Dots for Electrocatalytic Reduction of CO₂ to HCOOH