铜基硫族化合物电催化二氧化碳还原制甲酸盐的研究进展

doi:10.19964/j.issn.1006-4990.2021-0622

摘要/Abstract

摘要：

因电催化二氧化碳还原反应（CO₂ reduction reaction,CO₂RR）助于降低大气二氧化碳浓度缓解环境问题,还可以生产高附加值化学品,引起了广泛关注。甲酸盐作为二氧化碳电还原的重要产物之一,在化工、燃料电池等领域广泛应用。铜基硫族化合物（Cu_xS）由于价格便宜、催化性能优异等优点有着广阔的应用前景,基于此研究者们在纳米结构调控、电解液优化和反应气组分控制等方面展开了大量研究以提升其在电催化CO₂RR中的催化活性和甲酸盐产物选择性。主要从催化剂结构设计、催化影响要素、催化反应机理等多角度综述了近期Cu_xS在电催化CO₂RR领域的研究进展,提出了Cu_xS在CO₂RR领域中主要面临的挑战;展望了Cu_xS族催化剂作为高活性、高稳定性二氧化碳电还原催化剂的发展前景。

关键词: 电催化, 二氧化碳电还原, 铜基硫族化合物, 甲酸盐

Abstract:

Electrocatalytic caybon dioxide reduction reaction（CO₂RR） has attracted widespread attention for its help in reducing atmospheric CO₂ concentration to alleviate environmental problems and producing high value-added chemicals.As one of the most important products of CO₂ electroreduction,formate is widely used in chemical industry,fuel cell and other fields.Cu-based chalcogenides（Cu_xS） have broad application prospects due to their low price and excellent catalytic performance.Based on this,researchers have devoted much effort to nanostructure regulation,electrolytes optimization and feed composition control to promote the catalytic activities and formate selectivity of Cu-based chalcogenides toward electrocatalytic CO₂RR.Recent advances in structural design of catalysts,influential factors and catalytic mechanism for Cu_xS in CO₂ electroreduction were reviewed.And the main challenges that Cu_xS faces in the CO₂RR field were also pointed out.The development prospect of Cu_xS catalysts as electrocatalysts for CO₂ reduction with high activity and stability was prospected.

Key words: electrocatalysis, carbon dioxide electroreduction, Cu-based chalcogenides, formate

中图分类号:

O643.32

陈婧娟,吕琳,万厚钊,王浩. 铜基硫族化合物电催化二氧化碳还原制甲酸盐的研究进展[J]. 无机盐工业, 2021, 53(12): 14-20.

CHEN Jingjuan,LÜ Lin,WAN Houzhao,WANG Hao. Recent progress on Cu-based chalcogenides for electrocatalytic carbon dioxide reduction to formate[J]. Inorganic Chemicals Industry, 2021, 53(12): 14-20.

图/表 4

表1

图1

图2

图3

参考文献 59

[1]	SPERRY J S, VENTURASM D, TODD H N, et al. The impact of ris-ing CO₂ and acclimation on the response of US forests to global war-ming[J]. Proceedings of the National Academy of Sciences, 2019, 116(51):25734-25744.
[2]	PETER S C. Reduction of CO₂ to chemicals and fuels:A solution to global warming and energy crisis[J]. ACS Energy Letters, 2018, 3(7):1557-1561.
[3]	王建行, 赵颖颖, 李佳慧, 等. 二氧化碳的捕集、固定与利用的研究进展[J]. 无机盐工业, 2020, 52(4):12-17.
[4]	李书文, 周严, 汪铁林. BiVO₄/rGO复合物的制备及其光催化还原CO₂研究[J]. 无机盐工业, 2020, 51(11):82-87.
[5]	APPEL A M, BERCAW J E, BOCARSLY A B, et al. Frontiers,op-portunities,and challenges in biochemical and chemical catalysis of CO₂ fixation[J]. Chemical Reviews, 2013, 113(8):6621-6658.
[6]	GALADIMA A, MURAZA O. Catalytic thermal conversion of CO₂ into fuels:Perspective and challenges[J]. Renewable and Sustain-able Energy Reviews, 2019, 115.Doi: 10.1016/j.rser.2019.109333.
[7]	常若鹏, 胡旭, 贺雷, 等. 络合物法制备镍-氮共掺杂炭基二氧化碳电催化剂[J]. 无机盐工业, 2021, 53(9):97-103.
[8]	胡旭, 董灵玉, 李文翠, 等. 光化学法制备过渡金属—氮共掺杂多孔炭基CO₂电还原催化剂[J]. 无机盐工业, 2021, 53(6):8-13.
[9]	KIBRIA M G, EDWARDS J P, GABARDO C M, et al. Electroche-mical CO₂ reduction into chemical feedstocks:From mechanistic electrocatalysis models to system design[J]. Advanced Materials, 2019, 31(31).Doi: 10.1002/adma.201807166.
[10]	ZHANG W, HU Y, MA L, et al. Progress and perspective of electro-catalytic CO₂ reduction for renewable carbonaceous fuels and che-micals[J]. Advanced Science, 2018, 5(1).Doi: 10.1002/advs.201700275.
[11]	景维云, 毛庆, 石越, 等. CO₂电催化还原制烃类产物的研究进展[J]. 化工进展, 2017, 36(6):2150-2157.
[12]	FINN C, SCHNITTGER S, YELLOWLEES L J, et al. Molecular approaches to the electrochemical reduction of carbon dioxide[J]. Chemical Communications, 2012, 48(10):1392-1399.
[13]	FRANCKE R, SCHILLE B, ROEMELT M. Homogeneously catalyz-ed electroreduction of carbon dioxide-methods,mechanisms,and catalysts[J]. Chemical Reviews, 2018, 118(9):4631-4701.
[14]	AN L, CHEN R. Direct formate fuel cells:A review[J]. Journal of Power Sources, 2016, 320:127-139.
[15]	GRUBEL K, JEONG H, YOON C W, et al. Challenges and oppor-tunities for using formate to store,transport,and use hydrogen[J]. Journal of Energy Chemistry, 2020, 41:216-224.
[16]	ZHENG X, DE LUNA P, DE ARQUER F P G, et al. Sulfur-modu-lated tin sites enable highly selective electrochemical reduction of CO₂ to formate[J]. Joule, 2017, 1(4):794-805.
[17]	ZHANG S, KANG P, MEYER T J. Nanostructured tin catalysts for selective electrochemical reduction of carbon dioxide to formate[J]. Journal of the American Chemical Society, 2014, 136(5):1734-1737.
[18]	WU D, WANG X, FU X-Z, et al. Ultrasmall Bi nanoparticles con-fined in carbon nanosheets as highly active and durable catalysts for CO₂ electroreduction[J]. Applied Catalysis B:Environmental, 2021, 284.Doi: 10.1016/j.apcatb.2020.119723.
[19]	DENG P, YANG F, WANG Z, et al. Metal-organic framework-de-rived carbon nanorods encapsulating bismuth oxides for rapid and selective CO₂ electroreduction to formate[J]. Angewandte Chemie International Edition, 2020, 59(27):10807-10813.
[20]	ZHANG A, LIANG Y, LI H, et al. In-situ surface reconstruction of InN nanosheets for efficient CO₂ electroreduction into formate[J]. Nano Letters, 2020, 20(11):8229-8235.
[21]	CHI L-P, NIU Z-Z, ZHANG X-L, et al. Stabilizing indium sulfide for CO₂ electroreduction to formate at high rate by zinc incorporation[J]. Nature Communications, 2021, 12(1):1-9.
[22]	CHATTERJEE S, GRIEGO C, HART J L, et al. Free standing nano-porous palladium alloys as CO poisoning tolerant electrocatalysts for the electrochemical reduction of CO₂ to formate[J]. ACS Catal-ysis, 2019, 9(6):5290-5301.
[23]	LV H, LV F, QIN H, et al. Single-crystalline mesoporous palladium and palladium-copper nanocubes for highly efficient electrochemi-cal CO₂ reduction[J]. CCS Chemistry, 2021, 3:1435-1444.
[24]	YANG W, CHEN S, REN W, et al. Nanostructured amalgams with tuneable silver-mercury bonding sites for selective electroreduc-tion of carbon dioxide into formate and carbon monoxide[J]. Jour-nal of Materials Chemistry A, 2019, 7(26):15907-15912.
[25]	ARROCHA-ARCOS A, CERVANTES-ALCALÁR, HUERTA-MIRANDA G, et al. Electrochemical reduction of bicarbonate to formate with silver nanoparticles and silver nanoclusters supported on multiwalled carbon nanotubes[J]. Electrochimica Acta, 2017, 246:1082-1087.
[26]	LV L, HE X, WANG J, et al. Charge localization to optimize reac-tant adsorption on KCu₇S₄/CuO interfacial structure toward selec-tive CO₂ electroreduction[J]. Applied Catalysis B:Environmental, 2021, 298.Doi: 10.1016/j.apcatb.2021.120531.
[27]	CHEN Y, CHEN K, FU J, et al. Recent advances in the utilization of copper sulfide compounds for electrochemical CO₂ reduction[J]. Nano Materials Science, 2020, 2(3):235-247.
[28]	HUANG Y, DENG Y, HANDOKO A D, et al. Rational design of sulfur-doped copper catalysts for the selective electroreduction of carbon dioxide to formate[J]. ChemSusChem, 2018, 11(1):320-326.
[29]	LI D, HUANG L, LIU T, et al. Electrochemical reduction of carbon dioxide to formate via nano-prism assembled CuO microspher-es[J]. Chemosphere, 2019, 237.Doi: 10.1016/j.chemosphere.2019.124527.
[30]	LI D, LIU T, YAN Z, et al. MOF-derived Cu₂O/Cu nanospheres an-chored in nitrogen-doped hollow porous carbon framework for in-creasing the selectivity and activity of electrochemical CO₂-to-formate conversion[J]. ACS Applied Materials & Interfaces, 2020, 12(6):7030-7037.
[31]	ZHAO Z, PENG X, LIU X, et al. Efficient and stable electroreduc-tion of CO₂ to CH₄ on CuS nanosheet arrays[J]. Journal of Materials Chemistry A, 2017, 5(38):20239-20243.
[32]	PENG C, LUO G, ZHANG J, et al. Double sulfur vacancies by lithi-um tuning enhance CO₂ electroreduction to n-propanol[J]. Nature Communications, 2021, 12(1):1-8.
[33]	ZHANG X, SA R, ZHOU F, et al. Metal-organic framework-derived CuS nanocages for selective CO₂ electroreduction to formate[J]. CCS Chemistry, 2021, 3:199-207.
[34]	SHAO P, CI S, YI L, et al. Hollow CuS microcube electrocatalysts for CO₂ reduction reaction[J]. ChemElectroChem, 2017, 4(10):2593-2598.
[35]	YANG D, ZUO S, YANG H, et al. Single-unit-cell catalysis of CO₂ electroreduction over sub-1 nm Cu₉S₅ nanowires[J]. Advanced Energy Materials, 2021, 11(16).Doi: 10.1002/aenm.202100272.
[36]	SHINAGAWA T, LARRAZÁBAL G O, MARTÍN A J, et al. Sulfur-modified copper catalysts for the electrochemical reduction of car-bon dioxide to formate[J]. ACS Catalysis, 2018, 8(2):837-844.
[37]	CHEN J, TU Y, ZOU Y, et al. Morphology and composition-contro-llable synjournal of copper sulfide nanocrystals for electrochemical reduction of CO₂ to HCOOH[J]. Materials Letters, 2021, 284. Doi: 10.1016/j.matlet.2020.128919.
[38]	LV L, LI Z, WAN H, et al. Achieving low-energy consumption wa-ter-to-hydrogen conversion via urea electrolysis over a bifunctional electrode of hierarchical cuprous sulfide@nickel selenide nanoarrays[J]. Journal of Colloid and Interface Science, 2021, 592:13-21.
[39]	AN L, LI Y, LUO M, et al. Atomic-level coupled interfaces and la-ttice distortion on CuS/NiS₂ nanocrystals boost oxygen catalysis for flexible Zn-air batteries[J]. Advanced Functional Materials, 2017, 27(42).Doi: 10.1002/adfm.201703779.
[40]	LIANG R, SHU C, HU A, et al. Interface engineering induced se-lenide lattice distortion boosting catalytic activity of heterogeneous CoSe₂@NiSe₂ for lithium-oxygen battery[J]. Chemical Engineer-ing Journal, 2020, 393.Doi: 10.1016/j.cej.2020.124592.
[41]	WANG S, KOU T, VARLEY J B, et al. Cu₂O/CuS nanocomposites show excellent selectivity and stability for formate generation via electrochemical reduction of carbon dioxide[J]. ACS Materials Letters, 2020, 3(1):100-109.
[42]	WANG W, WANG Z, YANG R, et al. In situ phase separation into coupled interfaces for promoting CO₂ electroreduction to formate over a wide potential window[J]. Angewandte Chemie International Edition, 2021, 60(42):22940-22947.
[43]	BANERJEE S, ZHANG Z-Q, HALL A S, et al. Surfactant perturba-tion of cation interactions at the electrode-electrolyte interface in carbon dioxide reduction[J]. ACS Catalysis, 2020, 10(17):9907-9914.
[44]	ZHONG Y, XU Y, MA J, et al. An artificial electrode/electrolyte interface for CO₂ electroreduction by cation surfactant self-assem-bly[J]. Angewandte Chemie International Edition, 2020, 59(43):19095-19101.
[45]	WAKERLEY D, LAMAISON S, OZANAM F, et al. Bio-inspired hydrophobicity promotes CO₂ reduction on a Cu surface[J]. Nature Materials, 2019, 18(11):1222-1227.
[46]	XING Z, HU L, RIPATTI D S, et al. Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment[J]. Nature Communications, 2021, 12(1):1-11.
[47]	GOLRU S S, BIDDINGER E J. Effect of anion in diluted imidazoli-um-based ionic liquid/buffer electrolytes for CO₂ electroreduction on copper[J]. Electrochimica Acta, 2020, 361.Doi: 10.1016/j.elec-tacta.2020.136787.
[48]	LI J, KUANG Y, MENG Y, et al. Electroreduction of CO₂ to formate on a copper-based electrocatalyst at high pressures with high en-ergy conversion efficiency[J]. Journal of the American Chemical Society, 2020, 142(16):7276-7282.
[49]	LIM J W, DONG W J, PARK J Y, et al. Spontaneously formed CuS_x catalysts for selective and stable electrochemical reduction of in-dustrial CO₂ gas to formate[J]. ACS Applied Materials & Interfac-es, 2020, 12(20):22891-22900.
[50]	LUC W, KO B H, KATTEL S, et al. SO₂-induced selectivity change in CO₂ electroreduction[J]. Journal of the American Chemical Society, 2019, 141(25):9902-9909.
[51]	WANG X, DE ARAUJO J F, JU W, et al. Mechanistic reaction path-ways of enhanced ethylene yields during electroreduction of CO₂-CO co-feeds on Cu and Cu-tandem electrocatalysts[J]. Nature Na-notechnology, 2019, 14(11):1063-1070.
[52]	HE M, LI C, ZHANG H, et al. Oxygen induced promotion of elec-trochemical reduction of CO₂ via co-electrolysis[J]. Nature Com-munications, 2020, 11(1):1-10.
[53]	LU X, JIANG Z, YUAN X, et al. A bio-inspired O₂-tolerant cataly-tic CO₂ reduction electrode[J]. Science Bulletin, 2019, 64(24):1890-1895.
[54]	KO B H, HASA B, SHIN H, et al. The impact of nitrogen oxides on electrochemical carbon dioxide reduction[J]. Nature Communica-tions, 2020, 11(1):1-9.
[55]	DENG Y, HUANG Y, REN D, et al. On the role of sulfur for the se-lective electrochemical reduction of CO₂ to formate on CuS_x cataly-sts[J]. ACS Applied Materials & Interfaces, 2018, 10(34):28572-28581.
[56]	LIU D, LIU Y, LI M. Understanding how atomic sulfur controls the selectivity of the electroreduction of CO₂ to formic acid on meta-llic Cu surfaces[J]. The Journal of Physical Chemistry C, 2020, 124(11):6145-6153.
[57]	LIU S-Q, GAO M-R, FENG R-F, et al. Electronic delocalization of bismuth oxide induced by sulfur doping for efficient CO₂ electro-reduction to formate[J]. ACS Catalysis, 2021, 11(12):7604-7612.
[58]	DOU T, QIN Y, ZHANG F, et al. CuS nanosheet arrays for electro-chemical CO₂ reduction with surface reconstruction and the effect on selective formation of formate[J]. ACS Applied Energy Materi-als, 2021, 4(5):4376-4384.
[59]	PHILLIPS K R, KATAYAMA Y, HWANG J, et al. Sulfide-derived copper for electrochemical conversion of CO₂ to formic acid[J]. The Journal of Physical Chemistry Letters, 2018, 9(15):4407-4412.

可能的反应途径	电极电位（vs.SHE）/V
CO₂（g）+4H⁺+4e^-→C（s）+2H₂O（l）	0.210
CO₂（g）+2H₂O（l）+4e^-→C（s）+4OH^-	-0.627
CO₂（g）+2H⁺+2e^-→HCOOH（l）	-0.250
CO₂（g）+H₂O（l）+2e^-→HCOO^-（aq）+OH^-	-1.078
CO₂（g）+2H⁺+2e^-→CO（g）+H₂O（l）	-0.106
CO₂（g）+H₂O（l）+2e^-→CO（g）+2OH^-	-0.934
CO₂（g）+4H⁺+4e^-→CH₂O（l）+H₂O	-0.070
CO₂（g）+3H₂O（l）+4e^-→CH₂O+4OH^-	-0.898
CO₂（g）+6H⁺+6e^-→CH₃OH（l）+H₂O	0.016
CO₂（g）+5H₂O（l）+6e^-→CH₃OH（l）+6OH^-	-0.812
CO₂（g）+8H⁺+8e^-→CH₄（g）+2H₂O	0.169
CO₂（g）+6H₂O（l）+8e^-→CH₄（g）+8OH^-	-0.659
2CO₂（g）+2H⁺+2e^-→H₂C₂O₄（aq）	-0.500
2CO₂（g）+2e^-→C₂O₄^2-（aq）	-0.590
2CO₂（g）+12H⁺+12e^-→CH₂CH₂（g）+4H₂O	0.064
2CO₂（g）+8H₂O（l）+12e^-→CH₂CH₂（g）+12OH^-	-0.764
2CO₂（g）+12H⁺+12e^-→CH₃CH₂OH（l）+3H₂O（l）	0.084
2CO₂（g）+9H₂O（l）+12e^-→CH₃CH₂OH（l）+12OH^-	-0.744

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会