CO2电催化还原制烃类产物的研究进展

doi:10.16085/j.issn.1000-6613.2017.06.026

化工进展 ›› 2017, Vol. 36 ›› Issue (06): 2150-2157.DOI: 10.16085/j.issn.1000-6613.2017.06.026

CO₂电催化还原制烃类产物的研究进展

景维云¹, 毛庆¹, 石越¹, 杜兆龙², 肖宇², 刘松³, 徐金铭³, 黄延强³

1 大连理工大学化工学院, 辽宁大连 116023;
2 全球能源互联网研究院, 北京 102200;
3 中国科学院大连化学物理研究所航天催化与新材料研究室, 辽宁大连 116023

收稿日期:2016-11-17 修回日期:2017-01-09 出版日期:2017-06-05 发布日期:2017-06-05
通讯作者: 毛庆,黄延强
作者简介:景维云(1993—),男,硕士研究生。E-mail:jingweiyun@mail.dlut.edu.cn。
基金资助:
国家自然科学基金（21403029）、国家电网公司科技项目（SGRI-DL-71-16-015）、科技部重大研发计划（2016YFB0600902）、辽宁省教育厅科学研究一般项目（L2014022）及辽宁省自然科学基金（201602162）项目。

Research progress of electro-catalytic reduction of CO₂ to hydrocarbons

JING Weiyun¹, MAO Qing¹, SHI Yue¹, DU Zhaolong², XIAO Yu², LIU Song³, XU Jinming³, HUANG Yanqiang³

1 School of Chemical Engineering, Dalian University of Technology, Dalian 116023, Liaoning, China;
2 Global Energy Interconnection Research Institute, Beijing 102200, China;
3 Laboratory of Aerospace Catalysts and New Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2016-11-17 Revised:2017-01-09 Online:2017-06-05 Published:2017-06-05

摘要/Abstract

摘要： 应用可再生能源驱动CO₂电催化还原制备燃料，是目前清洁能源发展最具前景的方向之一。本文综述了以气态烃类（CH₄、C₂H₄）为目标产物的CO₂电催化还原的研究进展，分别介绍了电催化材料、电解质溶液以及反应机理的研究现状。指出在水溶液电解质中，电催化材料需兼具烃类产物的高选择性与电化学析氢反应的抑制能力，Cu与Cu基材料是电催化材料的首选，Cu的氧化物由于其丰富的结构特征拓宽了电催化材料优选范围。水溶液电解质的性质会显著影响CO₂电催化还原产物的选择性；非水溶液或痕水溶液电解质由于可以显著抑制析氢反应，将会进一步拓宽电催化材料的优选范围。最后介绍了CO₂电催化还原机理研究的现状，指出原位电化学谱学方法的应用与CO₂电催化还原机理模型研究工作的开展，将成为人们深入认识以烃类为目标产物的CO₂电催化还原反应的关键，并有利于指导电催化材料与电解质材料的研究开发。

关键词: 二氧化碳, 碳氢化合物, 电化学

Abstract: Electroreduction of CO₂ into useful fuels,especially those driven by renewable energy,is one of the most promising strategies for clean energy development. Current researches of the electro-catalytic reduction of carbon dioxide to hydrocarbons(CH₄,C₂H₄)is reviewed. It covers the research status of electro-catalytic materials,electrolyte solution and the reaction mechanisms. Among aqueous electrolytes,copper and copper based materials are preferred as they have both high selectivity in the hydrocarbons transfer and inhibiting ability of hydrogen evolution reaction (HER). Copper oxides provides more options of the electro-catalytic materials due to their multiplex structural features. Aqueous electrolytes have significant effects on the selection of the electro-catalytic reduction products,while non-aqueous or trace-aqueous electrolytes are promising because of their significant inhibition ability of the HER. Finally,the research status of the reaction mechanisms are introduced. It is suggested that the application of in-situ spectroscopy techniques and the modeling work based on the reaction kinetics are highly demanded,which would be helpful to guide the development of the electro-catalysts and the electrolytes.

Key words: carbon dioxide, hydrocarbon, electrochemistry

中图分类号:

O646

景维云, 毛庆, 石越, 杜兆龙, 肖宇, 刘松, 徐金铭, 黄延强. CO₂电催化还原制烃类产物的研究进展[J]. 化工进展, 2017, 36(06): 2150-2157.

JING Weiyun, MAO Qing, SHI Yue, DU Zhaolong, XIAO Yu, LIU Song, XU Jinming, HUANG Yanqiang. Research progress of electro-catalytic reduction of CO₂ to hydrocarbons[J]. Chemical Industry and Engineering Progress, 2017, 36(06): 2150-2157.

参考文献

[1] QIAO J,LIU Y,HONG F,et al. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels[J]. Chemical Society Reviews,2014,43(2):631-675.
[2] BARD A J,PARSONS R,JORDAN J. Standard potentials in aqueous solution[M]. Florida:CRC Press,1985.
[3] KUHL K P,CAVE E R,ABRAM D N,et al. New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces[J]. Energy & Environmental Science,2012,5(5):7050-7059.
[4] HORI Y,KIKUCHI K,SUZUKI S. Production of CO and CH₄ in electrochemical reduction of CO₂ at metal electrodes in aqueous hydrogencarbonate solution[J]. Chemistry Letters,1985(11):1695-1698.
[5] LI C W,CISTON J, KANAN M W. Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper[J]. Nature,2014,508(7497):504-507.
[6] HORI Y,MURATA A,TAKAHASHI R,et al. Electroreduction of carbon monoxide to methane and ethylene at a copper electrode in aqueous solutions at ambient temperature and pressure[J]. Journal of the American Chemical Society,1987,109(16):5022-5023.
[7] HOSHI N,UCHIDA T,MIZUNURA T,et al. Atomic arrangement dependence of reduction rates of carbon dioxide on iridium single crystal electrodes[J]. Journal of Electroanalytical Chemistry,1995,381(1):261-264.
[8] TAKAHASHI I,KOGA O,HOSHI N,et al. Electrochemical reduction of CO₂,at copper single crystal Cu(S)-[n (111)×(111)] and Cu(S)-[n(110)×(100)] electrodes[J]. Journal of Electroanalytical Chemistry,2002,533(1/2):135-143.
[9] HORI Y,TAKAHASHI I,KOGA O,et al. Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes[J]. Journal of Molecular Catalysis A:Chemical,2003,199(1/2):39-47.
[10] DELACOURT Charles. Electrochemical reduction of carbon dioxide and water to syngas (CO+H₂) at room temperature[D]. Berkeley:Department of Chemical Engineering,University of California Berkeley,2006-2007.
[11] HORI Y,KONISHI H,FUTAMURA T,et al. Deactivation of copper electrode in electrochemical reduction of CO₂[J]. Electrochimica Acta,2005,50(27):5354-5369.
[12] MANTHIRAM K,BEBERWYCK B J,ALIVISATOS A P. Enhanced electrochemical methanation of carbon dioxide with a dispersible nanoscale copper catalyst[J]. Journal of the American Chemical Society,2014,136(38):13319-13325.
[13] BATURINA O A, LU Q,PADILLA M A,et al. CO₂ electroreduction to hydrocarbons on carbon-supported Cu nanoparticles[J]. ACS Catalysis,2014,4(10):3682-3695.
[14] HEIZ U,SANCHEZ A,ABBET S,et al. Catalytic oxidation of carbon monoxide on monodispersed platinum clusters:each atom counts[J]. Journal of the American Chemical Society,1999,121(13):3214-3217.
[15] LOIUDICE A,LOBACCARO P, KAMALI E A,et al. Tailoring copper nanocrystals towards C₂products in electrochemical CO₂ reduction[J]. Angewandte Chemie International Edition,2016,55(19):5789-5792.
[16] ROBERTS F S,KUHL K P,NILSSON A. High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts[J]. Angewandte Chemie,2015,127(17):5268-5271.
[17] RACITI D,LIVI K J,WANG C. Highly dense Cu nanowires for low-overpotential CO₂reduction[J]. Nano Letters,2015,15(10):6829-6835.
[18] TANG W,PETERSON A,VARELA A S,et al. The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO₂ electroreduction[J]. Physical Chemistry Chemical Physics, 2012,14(1):76-81.
[19] MISTRY H,VARELA A S,BONIFACIO C S,et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene[J]. Nature Communications,2016,7. DOI:10.1038/ncomms 12123.
[20] XIE M S, XIA B Y,LI Y,et al. Amino acid modified copper electrodes for the enhanced selective electroreduction of carbon dioxide towards hydrocarbons[J]. Energy & Environmental Science,2016,9(5):1687-1695.
[21] WANG Z,YANG G,ZHANG Z,et al. Selectivity on etching: creation of high-energy facets on copper nanocrystals for CO₂ electrochemical reduction[J]. ACS Nano,2016,10(4):4559-4564.
[22] LI C W,KANAN M W. CO₂ reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu₂O films[J]. Journal of the American Chemical Society,2012,134(17):7231-7234.
[23] KAS R,KORTLEVER R,MILBRAT A,et al. Electrochemical CO₂ reduction on Cu₂O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons[J]. Physical Chemistry Chemical Physics,2014,16(24):12194-201.
[24] CHEN C S,WAN J H,YEO B S. Electrochemical reduction of carbon dioxide to ethane using nanostructured Cu₂O-derived copper catalyst and palladium (Ⅱ) chloride[J]. Journal of Physical Chemistry C,2015,119(48):26875-26882.
[25] LEE S,KIM D,LEE J. Electrocatalytic production of C3-C4 compounds by conversion of CO₂ on a chloride-induced bi-phasic Cu₂O-Cu catalyst[J]. Angewandte Chemie,2015,127(49):14914-14918.
[26] KUDELSKI A,KEDZIERZAWSKI P, BUKOWSKA J,et al. An SERS investigation of CO intermediate adsorption on a modified Cu-Zr amorphous alloy during CO₂ reduction[J]. Russian Journal of Electrochemistry,2000,36(11):1186-1188.
[27] WATANABE M,SHIBATA M,KATOH A,et al. Design of alloy electrocatalysts for CO₂ reduction:improved energy efficiency,selectivity,and reaction rate for the CO₂ electroreduction on Cu alloy electrodes[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry,1991,305(2):319-328.
[28] ZHAO X,LUO B,LONG R,et al. Composition-dependent activity of Cu-Pt alloy nanocubes for electrocatalytic CO₂ reduction[J]. Journal of Materials Chemistry A,2015,3(8):4134-4138.
[29] MONZÓ J,MALEWSKI Y,KORTLEVER R,et al. Enhanced electrocatalytic activity of Au@Cu core@shell nanoparticles towards CO₂ reduction[J]. Journal of Materials Chemistry A,2015,3(47):23690-23698.
[30] LI Q,ZHU W,FU J,et al. Controlled assembly of Cu nanoparticles on pyridinic-N rich graphene for electrochemical reduction of CO₂to ethylene[J]. Nano Energy,2016,24:1-9.
[31] TORELLI D A,FRANCIS S A,CROMPTON J C,et al. Nickel-gallium-catalyzed electrochemical reduction of CO₂ to highly reduced products at low overpotentials[J]. ACS Catalysis,2016,6(3):2100-2104.
[32] SUN X,KANG X,ZHU Q, et al. Very highly efficient reduction of CO₂ to CH₄ using metal-free N-doped carbon electrodes[J]. Chemical Science, 2016,7(4):2883-2887.
[33] MURATA A,HORI Y. Product selectivity affected by cationic species in electrochemical reduction of CO₂ and CO at a Cu electrode[J].Bulletin of the Chemical Society of Japan,1991,64(1):123-127.
[34] HORI Y,MURATA A,TAKAHASHI R. Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution[J]. Journal of the Chemical Society,Faraday Transactions 1:Physical Chemistry in Condensed Phases,1989,85(8):2309-2326.
[35] VARELA A S,KROSCHEL M,REIER T,et al. Controlling the selectivity of CO₂ electroreduction on copper:the effect of the electrolyte concentration and the importance of the local pH[J]. Catalysis Today,2016,260:8-13.
[36] VARELA A S,JU W,REIER T,et al. Tuning the catalytic activity and selectivity of Cu for CO₂ electroreduction in the presence of halides[J]. ACS Catalysis,2016,6(4):2136-2144.
[37] KAS R,KORTLEVER R,YILMAZ H,et al. Manipulating the hydrocarbon selectivity of copper nanoparticles in CO₂ electroreduction by process conditions[J]. ChemElectroChem,2015,2(3):354-358.
[38] HARA K,TSUNETO A,KUDO A,et al. Electrochemical reduction of CO₂ on a Cu electrode under high pressure factors that determine the product selectivity[J]. Journal of the Electrochemical Society,1994,141(8):2097-2103.
[39] MIZUNO T,OHTA K,KAWAMOTO M,et al. Electrochemical reduction of CO₂ on Cu in 0.1M KOH-methanol[J]. Energy Sources,1997,19(3):249-257.
[40] KANECO S,IIBA K,HIEI N H,et al. Electrochemical reduction of carbon dioxide to ethylene with high Faradaic efficiency at a Cu electrode in CsOH/methanol[J]. Electrochimica Acta,1999,44(26):4701-4706.
[41] MURUGANANTHAN M,KUMARAVEL M, KATSTMATA H,et al. Electrochemical reduction of CO₂ using Cu electrode in methanol/LiClO₄ electrolyte[J]. International Journal of Hydrogen Energy,2015,40(21): 6740-6744.
[42] SEDDON K R. Ionic liquids for clean technology[J]. Journal of Chemical Technology and Biotechnology,1997,68(4):351-356.
[43] 张锁江,吕兴梅. 离子液体从基础研究到工业应用[M]. 北京:科学出版社,2006. ZHANG S J,LV X M. Ionic liquid-from basic research industrial application[M].Beijing:Science Press,2006.
[44] 赵晨辰,何向明,王莉,等.电化学还原CO₂阴极材料研究进展[J]. 化工进展,2013,32(2):373-380. ZHAO C C,HE X M,WANG L,et al. Progress of cathode materials for electrochemical reduction of carbon dioxide[J]. Chemical Industry and Engineering Progress,2013,32(2):373-380.
[45] BLANCHARD L A,HANCU D,BECKMAN E J,et al. Green processing using ionic liquids and CO₂[J]. Nature,1999,399:28-29.
[46] BLANCHARD L A,GU Z,BRENECKE J F. High-pressure phase behavior of ionic liquid/CO₂ systems[J]. The Journal of Physical Chemistry B,2001,105(12):2437-2444.
[47] BATES E D,MAYTON R D,NTAI I,et al. CO₂capture by a task-specific ionic liquid[J]. Journal of the American Chemical Society,2002,124(6):926-927.
[48] BARROSSE-ANTLE L E,COMPTON R G. Reduction of carbon dioxide in 1-butyl-3-methylimidazolium acetate[J]. Chemical Communications,2009,25:3744-3746.
[49] CHU D B,QIN G X,YUAN X M,et al. Fixation of CO₂ by electrocatalytic reduction and electropolymerization in ionic liquid-H₂O solution[J]. ChemSusChem,2008,1(3):205-209.
[50] ZHU J,LIU G,LIU Z,et al. Conducting membranes:unprecedented perovskite oxyfluoride membranes with high-efficiency oxygen ion transport paths for low-temperature oxygen permeation[J]. Advanced Materials,2016,28(18):3510-3510.
[51] HORI Y,TAKAHASHI R,YOSHINAMI Y,et al. Electrochemical reduction of CO at a copper electrode[J]. The Journal of Physical Chemistry B,1997,101(36):7075-7081.
[52] SCHOUTEN K J P,KWON Y,VAN DER HAM C J M,et al. A new mechanism for the selectivity to C₁ and C₂species in the electrochemical reduction of carbon dioxide on copper electrodes[J]. Chemical Science,2011,2(10):1902-1909.
[53] NIE X,ESOPI M R,JANIK M J,et al. Selectivity of CO₂ reduction on copper electrodes: the role of the kinetics of elementary steps[J]. Angewandte Chemie International Edition,2013,52(9):2459-2462.
[54] LUO W,NIE X,JANIK M J,et al. Facet dependence of CO₂ reduction paths on Cu electrodes[J]. ACS Catalysis,2015,6(1):219-229.
[55] AMEPELLI C,GENOVESE C,MAREPALLY B C,et al. Electrocatalytic conversion of CO to produce solar fuels in electrolyte or electrolyte-less configurations of PEC cells[J]. Faraday Discussions,2015,183:125-145.

CO₂电催化还原制烃类产物的研究进展

Research progress of electro-catalytic reduction of CO₂ to hydrocarbons

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