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

所属专题：【虚拟专辑】碳中和(2020~2021)；【能源环境】量子点；【能源环境】CO2绿色转换

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

参考文献 28

[1]	LI X D, WANG S M, LI L, et al. Progress and perspective for in situ studies of CO₂ reduction. Journal of the American Chemical Society, 2020, 142: 9567-9581.
[2]	BIRDJA Y Y, PEREZ-GALLENT E, FIGUEIREDO M, et al. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels. Nature Energy, 2019, 4: 732-745. DOI URL
[3]	VASILEFF A, ZHENG Y, QIAO S Z. Carbon solving carbon's problems: recent progress of nanostructured carbon-based catalysts for the electrochemical reduction of CO₂. Advanced Energy Materials, 2017, 7(21): 1700759. DOI URL
[4]	SHAO P, YI L C, CHEN S M, et al. Metal-organic frameworks for electrochemical reduction of carbon dioxide: the role of metal centers. Journal of Energy Chemistry, 2020, 40: 156-170. DOI URL
[5]	ZHANG L, ZHAO Z J, GONG J. Nanostructured materials for heterogeneous electrocatalytic CO₂ reduction and their related reaction mechanisms. Angewandte Chemie International Edition, 2017, 56(38): 11326-11353. DOI URL
[6]	MISTRY H, RESKE R, ZENG Z H, et al. Exceptional size- dependent activity enhancement in the electroreduction of CO₂ over Au nanoparticles. Journal of the American Chemical Society, 2014, 136(47): 16473-16476. DOI URL
[7]	TYO E C, VAJDA S. Catalysis by clusters with precise numbers of atoms. Nature Nanotechnology, 2015, 10(7): 577-588. DOI URL
[8]	GAO D F, ZHOU H, WANG J, et al. Size-dependent electrocatalytic reduction of CO₂ over Pd nanoparticles. Journal of the American Chemical Society, 2015, 137(13): 4288-4291. DOI URL
[9]	LIU S G, HUANG S P. Size effects and active sites of Cu nanoparticle catalysts for CO₂ electroreduction. Applied Surface Science, 2019, 475: 20-27. DOI URL
[10]	LEE C H, KANAN M W. Controlling H⁺ vs CO₂ reduction selectivity on Pb electrodes. ACS Catalysis, 2014, 5(1): 465-469. DOI URL
[11]	LI Z D, HE D, YAN X X, et al. Size-dependent nickel-based electrocatalysts for selective CO₂ reduction. Angewandte Chemie International Edition, 2020, 59: 2-8. DOI URL
[12]	RESKE R, MISTRY H, BEHAFARID F, et al. Particle size effects in the catalytic electroreduction of CO₂ on Cu nanoparticles. Journal of the American Chemical Society, 2014, 136(19): 6978-6986. DOI URL
[13]	LÜ K L, SUO W Q, SHAO M D, et al. Nitrogen doped MoS₂ and nitrogen doped carbon dots composite catalyst for electroreduction CO₂ to CO with high Faradaic efficiency. Nano Energy, 2019, 63: 103834. DOI URL
[14]	LIU M, LIU M X, WANG X M, et al. Quantum-dot-derived catalysts for CO₂ reduction reaction. Joule, 2019, 3(7): 1703-1718. DOI URL
[15]	WU J J, MA S C, SUN J, et al. A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates. Nature Communication, 2016, 7: 13869. DOI URL
[16]	TIAN J J, WANG M, SHEN M, et al. Highly efficient and selective CO₂ electro-reduction to HCOOH on Sn particle- decorated polymeric carbon nitride. ChemSusChem, 2020, 13(23): 6442-6448.
[17]	WEN G B, LEE D U, REN B H, et al. Orbital interactions in Bi-Sn bimetallic electrocatalysts for highly selective electrochemical CO₂ reduction toward formate production. Advanced Energy Materials, 2018, 8(31): 1802427. DOI URL
[18]	LI P X, FU W Z, ZHUANG P Y, et al. Amorphous Sn/crystalline SnS₂ nanosheets via in situ electrochemical reduction methodology for highly efficient ambient N₂ fixation. Small, 2019, 15(40): 1902535. DOI URL
[19]	TIAN J J, ZHANG L X, WANG M, et al. Remarkably enhanced H₂ evolution activity of oxidized graphitic carbon nitride by an extremely facile K₂CO₃-activation approach. Applied Catalysis B: Environmental, 2018, 232: 322-329. DOI URL
[20]	WEN J, XIE J, CHEN X, et al. A review on g-C₃N₄-based photocatalysts. Applied Surface Science, 2017, 391: 72-123. DOI URL
[21]	LAI Q, YUAN W Y, HUANG W J, et al. Sn/SnO_x electrode catalyst with mesoporous structure for efficient electroreduction of CO₂ to formate. Applied Surface Science, 2020, 508: 145221. DOI URL
[22]	LIU S B, XIAO J, LU X F, et al. Efficient electrochemical reduction of CO₂ to HCOOH over Sub-2 nm SnO₂ quantum wires with exposed grain boundaries. Angewandte Chemie International Edition, 2019, 58: 8499-8503. DOI URL
[23]	LUC W, COLLINS C, WANG S W, et al. Ag-Sn bimetallic catalyst with a core-shell structure for CO₂ reduction. Journal of the American Chemical Society, 2017, 139(5): 1885-1893. DOI URL
[24]	BANG J H, CHOI M S, MIRZAEI A, et al. Selective NO₂ sensor based on Bi₂O₃ branched SnO₂ nanowires. Sensors and Actuators B: Chemical, 2018, 274: 356-369. DOI URL
[25]	MA Y, WANG Z, XU X, et al. Review on porous nanomaterials for adsorption and photocatalytic conversion of CO₂. Chinese Journal of Catalysis, 2017, 38(12): 1956-1969. DOI URL
[26]	CHEN Z, GAO M R, DUAN N, et al. Tuning adsorption strength of CO₂ and its intermediates on tin oxide-based electrocatalyst for efficient CO₂ reduction towards carbonaceous products. Applied Catalysis B: Environmental, 2020, 277: 119252. DOI URL
[27]	NGUYEN T N, SALEHI M, LE Q, et al. Fundamentals of electrochemical CO₂ reduction on single-metal-atom catalysts. ACS Catalysis, 2020, 10(17): 10068-10095. DOI URL
[28]	HE R, YUAN X, SHAO P F, et al. Hybridiztion of defective tin disulfide nanosheets and silver nanowires enables efficient electrochemical reduction of CO₂ into formate and syngas. Small, 2019, 15(50): 1904882. DOI URL

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