二氧化碳电化学还原反应器的研究进展

doi:10.16085/j.issn.1000-6613.2019-0383

摘要/Abstract

摘要：

电化学还原二氧化碳（CO₂）可实现CO₂的资源化转化，是实现自然界“碳循环”、缓解因CO₂过度排放所引起诸多环境问题的关键技术。本文综述了CO₂电还原反应器的研究发展现状，并依据电解质的不同对比分析了各反应器的结构、传质特征及与之匹配阴极的CO₂转化活性与选择性。研究指出膜电极构型反应器是当前CO₂电还原反应器发展的主要方向，其电解质材料的优选不仅决定于其离子选择性与电导率，还需考虑电催化材料的性质与膜电极效率。最后，提出膜电极构型反应器内的过程强化技术与自支撑结构的阴极设计将成为CO₂还原研究发展的新方向。

关键词: 电催化, 二氧化碳电还原, 膜电极型反应器, 二氧化碳, 反应器, 电化学

Abstract:

CO₂electro-catalytic reduction reaction can realize carbon resources conversion, which is the key to achieve global “carbon cycle” and to alleviate many environment problems originated from excessive CO₂emissions. On this account, research progress in the CO₂ electro-reduction reactors is reviewed in this paper. the structure, mass transfer characteristics and CO₂ conversion activity and selectivity of the reactor and its matching cathode are compared and analyzed according to the different electrolytes. It is suggested that the major progress of the reactor locates in the membrane electrode assembly type (MEA-type) electrolytic cell. The optimization of electrolyte materials depends not only on its ion selectivity and conductivity, but also on the properties of electrocatalytic materials and membrane electrode efficiency. Finally, process intensification technology in the MEA-type electrolytic cell as well as the matched self-supporting cathode are regarded as the potential research direction in the CO₂ electro-reduction reactors.

Key words: electrocatalysis, carbon dioxide electro-reduction, membrane electrode assembly (MEA) type reactor, carbon dioxide, reactors, electrochemistry

中图分类号:

O646

李冰玉,毛庆,赵健,杜兆龙,刘松,黄延强. 二氧化碳电化学还原反应器的研究进展[J]. 化工进展, 2019, 38(11): 4901-4910.

Bingyu LI,Qing MAO,Jian ZHAO,Zhaolong DU,Song LIU,Yanqiang HUANG. Research progress in CO₂ electroreduction reactor[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4901-4910.

图/表 7

参考文献 64

1	IPCC . Climate change 2014: mitigation of climate change[M].United Kingdom and New York, NY, USA: Cambridge University Press, 2014:1-1454.
2	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.
	JING W Y , MAO Q , SHI Y , et al . Research progress of electro-catalytic reduction of CO₂ to hydrocarbons[J]. Chemical Industry and Engineering Progress, 2017, 36(6): 2150-2157.
3	王付燕, 孙洪志, 宋名秀, 等 . 二氧化碳的氨化反应研究进展[J]. 化工进展, 2014, 33(1):209-212.
	WANG F Y , SUN H Z , SONG M X , et al . Research progress on ammoniation reaction of carbon dioxide[J]. Chemical Industry and Engineering Progress, 2014, 33(1): 209-212.
4	赵丹, 王文珍, 贾新刚, 等 . 二氧化碳合成有机碳酸酯和聚碳酸丙烯酯的研究进展[J]. 现代化工, 2015, 35(7): 32-36.
	ZHAO D , WANG W Z , JIA X G , et al . Research progress in synthesis of organic carbonates and polypropylene carbonates from carbon dioxide[J]. Modern Chemical Industry, 2015, 35(7): 32-36.
5	SHIRONITAA S , KARASUDAA K , SATOA K , et al . Methanol generation by CO₂ reduction at a Pt-Ru/C electrocatalyst using a membrane electrode assembly[J]. Journal of Power Sources, 2013, 240(10): 404-410.
6	牛量, 于涛, 张晓, 等 . 甲烷二氧化碳重整制合成气催化剂的研究进展[J]. 吉林化工学院学报, 2018, 35(11): 8-13.
	NIU L , YU T , ZHANG X , et al . Research progress in catalysts for methane carbon dioxide reforming to syngas[J]. Journal of Jilin Institute of Chemical Technology, 2018, 35(11): 8-13.
7	LIU R , TIAN H , YANG A , et al . Preparation of HZSM-5 membrane packed CuO-ZnO-Al₂O₃ nanoparticles for catalysing carbon dioxide hydrogenation to dimethyl ether[J]. Applied Surface Science, 2015, 345: 1-9.
8	LINGAMPALLI S R , MONIS AYYUB M , MAGESH G , et al . Photocatalytic reduction of CO₂ by employing ZnO/Ag_1- _x Cu _x /CdS and related heterostructures[J]. Chemical Physics Letters, 2018, 691(1): 28-32.
9	LI B , NIU W , CHENG Y , et al . Preparation of Cu₂O modified TiO₂ nanopowder and its application to the visible light photoelectrocatalytic reduction of CO₂ to CH₃OH[J]. Chemical Physics Letters, 2018, 700: 57-63.
10	WEEKES D M , SALVATORE D A , REYES A , et al . Electrolytic CO₂ reduction in a flow cell[J]. Accounts of Chemical Research, 2018, 51(4): 910-918.
11	CENTI G , PERATHONER S , WINE G , et al . Electrocatalytic conversion of CO₂ to long carbon-chain hydrocarbons[J]. Green Chemistry, 2007, 9(6): 671.
12	YOO J S, CHRISTENSEN R , VEGGE T , et al . Theoretical insight into the trends that guide the electrochemical reduction of carbon dioxide to formic acid[J]. ChemSusChem, 2016, 9(4): 358-363.
13	ROSEN J , HUTCHINGS G S , LU Q , et al . Mechanistic insights into the electrochemical reduction of CO₂ to CO on nanostructured Ag surfaces[J]. ACS Catalysis, 2015, 5(7): 4293-4299.
14	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: 12123.
15	HE J , JOHNSON N J J , HUANG A . Electrocatalytic alloys for CO₂ reduction[J]. ChemSusChem, 2017, 11(1):48-57.
16	YANG H B , HUNG S F , LIU S , et al . Atomically dispersed Ni(i) as the active site for electrochemical CO₂ reduction[J]. Naure Energy, 2018, 3(2): 140-147.
17	ZHENG X L , JI Y F , TANG J , et al . Theory-guided Sn/Cu alloying for efficient CO₂ electroreduction at low overpotentials[J]. Nature Catalysis, 2019(2): 55-61.
18	CAO-THANG D , THOMAS B , MD G K, et al . CO₂ electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface[J]. Science, 2018, 360: 783-787.
19	WHIPPLE D T , FINKE E C , KENIS P J A . Microfluidic reactor for the electrochemical reduction of carbon dioxide: the effect of pH[J]. Electrochemical and Solid-State Letters, 2010, 13(9): B109-B111.
20	XIE Y M , JIE X, LIU D D , et al . Electrolysis of carbon dioxide in a solid oxide electrolyzer with silver-gadolinium-doped ceria cathode[J]. Journal of the Electrochemical Society, 2015, 162(4): F397-F402.
21	LAGUNA-BERCERO M A . Recent advances in high temperature electrolysis using solid oxide fuel cells: a review[J]. Journal of Power Sources, 2012, 203: 4-16.
22	HORI Y , ITO H, OKANO K , et al . Silver-coated ion exchange membrane electrode applied to electrochemical reduction of carbon dioxide[J]. Electrochimica Acta, 2003, 48(18): 2651-2657.
23	HSU C Y, KUO M H, KUO P L . Preparation, characterization, and properties of poly(styrene-b-sulfonated isoprene)s membranes for proton exchange membrane fuel cells (PEMFCs)[J]. Journal of Membrane Science, 2015, 484: 146-153.
24	BEVILACQUA M , FILIPPI J , MILLER H A , et al . Recent technological progress in CO₂ electroreduction to fuels and energy carriers in aqueous environments[J]. Energy Technology, 2015, 3(3): 197-210.
25	HERNÁNDEZ S , FARKHONDEHFAL M , SASTRE F , et al . Syngas production from electrochemical reduction of CO₂: current status and prospective implementation[J]. Green Chemistry, 2017, 19(10): 2326-2346.
26	ENDRŐDI B , BENCSIK G , DARVAS F , et al . Continuous-flow electroreduction of carbon dioxide[J]. Progress in Energy and Combustion Science, 2017, 62: 133-154.
27	DELACOURT C , RIDGWAY P L , KERR J B , et al . Design of an electrochemical cell making syngas (CO+H₂) from CO₂ and H₂O reduction at room temperature[J]. Journal of the Electrochemical Society, 2008, 155(1): B42-B49.
28	DELACOURT C , RIDGWAY P L , NEWMAN J . Mathematical modeling of CO₂ reduction to CO in aqueous electrolytes Ⅰ. Kinetic study on planar silver and gold electrodes[J]. Journal of The Electrochemical Society, 2010, 157(12): B1902-B1910.
29	JIANG K , SIAHROSTAMI S , ZHENG T , et al . Isolated Ni single atoms in graphene nanosheets for high-performance CO₂ reduction[J]. Energy & Environmental Science, 2018, 11(4): 893-903.
30	SMITHA B , SRIDHAR S , KHAN A A . Solid polymer electrolyte membranes for fuel cell applications—A review[J]. Journal of Membrane Science, 2005, 259(1/2): 10-26.
31	VARGAS-BARBOSA N M , GEISE G M , HICKNER M A , et al . Assessing the utility of bipolar membranes for use in photoelectrochemical water-splitting cells[J]. ChemSusChem, 2014, 7(11): 3017-3020.
32	OENER S Z , ARDO S , BOETTCHER S W . Ionic processes in water electrolysis: the role of ion-selective membranes[J]. ACS Energy Letters, 2017, 2(11): 2625-2634.
33	LUO J , VERMAAS D A , BI D , et al . Bipolar membrane-assisted solar water splitting in optimal pH[J]. Advanced Energy Materials, 2016, 6(13): 1600100.
34	LI Y C , ZHOU D , YAN Z , et al . Electrolysis of CO₂ to syngas in bipolar membrane-based electrochemical cells[J]. ACS Energy Letters, 2016, 1: 1149-1153.
35	ZHOU X , LIU R , SUN K , et al . Solar-driven reduction of 1 atm of CO₂ to formate at 10% energy-conversion efficiency by use of a TiO₂-protected Ⅲ-Ⅴ tandem photoanode in conjunction with a bipolar membrane and a Pd/C cathode[J]. ACS Energy Letters, 2016, 1(4): 764-770.
36	VEMAAS D A , SMITH W A . Synergistic electrochemical CO₂ reduction and water oxidation with a bipolar membrane[J]. ACS Energy Letters, 2016, 1(6): 1143-1148.
37	景维云 . CO₂电还原催化剂的筛选及反应器的设计[D].大连: 大连理工大学, 2018.
	JING W Y . Screening of CO₂ electrocatalysts and design of reactors[D].Dalian: Dalian University of Technology, 2018.
38	WU J , RISALVATO F G , SHARMA P P , et al . Electrochemical reduction of carbon dioxide Ⅱ. Design, assembly, and performance of low temperature full electrochemical cells[J]. Journal of the Electrochemical Society, 2013, 160(9): F953-F957.
39	SUBRAMANIAN K , ASOKAN K , JEEVARATHINAM D , et al . Electrochemical membrane reactor for the reduction of carbondioxide to formate[J]. Journal of Applied Electrochemistry, 2007, 37(2): 255-260.
40	INNOCENT B , LIAIGRE D , PASQUIER D , et al . Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium[J]. Journal of Applied Electrochemistry, 2009, 39(2): 227-232.
41	WU J , RISALVATO F G , KE F , et al . Electrochemical reduction of carbon dioxide Ⅰ. Effects of the electrolyte on the horiivity and activity with Sn electrode[J]. Journal of the Electrochemical Society, 2012, 159(7): F353-F359.
42	WU J , RISALVATO F G , MA S , et al . Electrochemical reduction of carbon dioxide Ⅲ. The role of oxide layer thickness on the performance of Sn electrode in a full electrochemical cell[J]. Journal of Materials Chemistry A, 2014, 2(6): 1647-1651.
43	YANG H , KACZUR J J , SAJJAD S D , et al . Electrochemical conversion of CO₂ to formic acid utilizing Sustainion™ membranes[J]. Journal of CO₂ Utilization, 2017, 20: 208-217.
44	KÖLELI F , ATILAN T , PALAMUT N , et al . Electrochemical reduction of CO₂ at Pb- and Sn-electrodes in a fixed-bed reactor in aqueous K₂CO₃, and KHCO₃ media[J]. Journal of Applied Electrochemistry, 2003, 33(5): 447-450.
45	KÖLELI F , BALUN D . Reduction of CO₂ under high pressure and high temperature on Pb-granule electrodes in a fixed-bed reactor in aqueous medium[J]. Applied Catalysis A: General, 2004, 274(1/2): 237-242.
46	MERINO-GARCIA I , ALVAREZ-GUERRA E , ALBO J , et al . Electrochemical membrane reactors for the utilisation of carbon dioxide[J]. Chemical Engineering Journal, 2016, 305: 104-120.
47	HARA K , KUDO A , SAKATA T . Electrochemical reduction of high pressure carbon dioxide on Fe electrodes at large current density[J]. Journal of Electroanalytical Chemistry, 1995, 386(1): 257-260.
48	LIU Z C , MASEL R I , CHEN Q M , et al . Electrochemical generation of syngas from water and carbon dioxide at industrially important rates[J]. Journal of CO₂ Utilization, 2016, 15(9): 50-56.
49	AZUMA M , HASHIMOTO K , HIRAMOTO M , et al . Electrochemical reduction of carbon dioxide on various metal electrodes in low-temperature aqueous KHCO₃ media[J]. Journal of Electrochemical Society, 1990, 137(6): 1772-1778.
50	DUFEK E J , LISTER T E , STONE S G , et al . Operation of a pressurized system for continuous reduction of CO₂ [J]. Journal of the Electrochemical Society, 2012, 159(9): F514-F517.
51	GABARDO C M , SEIFITOKALDANI A , EDWARDS J P , et al . Combined high alkalinity and pressurization enable efficient CO₂ electroreduction to CO[J]. Energy & Environmental Science, 2018, 11: 2531-3539.
52	GUNATHUNGE C M , OVALLE V J , WAEGELE M M . Probing promoting effects of alkali cations on the reduction of CO at the aqueous electrolyte/copper interface[J]. Physical Chemistry Chemical Physics, 2017, 19(44): 30166.
53	SALVATORE D A , WEEKS D M , HE J , et al . Electrolysis of gaseous CO₂ to CO in a flow cell with a bipolar membrane[J]. ACS Energy Letters, 2017, 3(1): 149-154.
54	OGURA K , WATANABE H . Reduction of carbon monoxide on a mediated and partially immersed electrode[J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1985, 81: 1569-1576.
55	LI J , CHEN G , ZHU Y , et al . Efficient electrocatalytic CO₂ reduction on a three-phase interface[J]. Nature Catalysis, 2018, 1: 592-600.
56	WENG L C , BELL A T , WEBER A Z . Modeling gas-diffusion electrodes for CO₂ reduction[J]. Physical Chemistry Chemical Physics, 2018, 20: 16973-16984.
57	COOK R L , MACDUFF R C , SAMMELLS A F . High-rate gas-phase CO₂ reduction to ethylene and methane using gas-diffusion electrodes[J]. Journal of the Electrochemical Society, 1990, 137(2): 607-608.
58	KIM B , HILLMAN F , ARIYOSHI M , et al . Effects of composition of the micro porous layer and the substrate on performance in the electrochemical reduction of CO₂ to CO[J]. Journal of Power Sources, 2016, 312: 192-198.
59	BITAR Z , FECANT A , TRELA-BAUDOT E , et al . Electrocatalytic reduction of carbon dioxide on indium coated gas diffusion electrodes-comparison with indium foil[J]. Applied Catalysis B: Environmental, 2016, 189: 172-180.
60	HORI Y . Electrochemical CO₂ reduction on metal electrodes[J]. Modern Aspects of Electrochemistry, 2008, 42: 89-189
61	JHONG H , BRUSHETT F R , KENIS P J A . The effects of catalyst layer deposition methodology on electrode performance[J]. Advanced Energy Materials, 2013, 3(5): 589-599.
62	YU S H , CHOE S , KIM M J , et al . Electrodeposited Ag catalysts for the electrochemical reduction of CO₂ to CO[J]. Applied Catalysis B: Environmental, 2017, 208: 35-43.
63	YU S H , MYUNG J K , TAEHO L , et al . Direct formation of dendritic Ag catalyst on a gas diffusion layer for electrochemical CO₂ reduction to CO and H₂ [J]. Hydrogen Energy, 2018, 43: 11315-11325.
64	ZHAO C M , WANG Y , LI Z J , et al . Solid-diffusion synthesis of single-atom catalysts directly from bulk metal for efficient CO₂ reduction[J]. Joule, 2018, 3: 1-11.

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