基于流动池的电化学二氧化碳还原研究进展

doi:10.13208/j.electrochem.200443

摘要/Abstract

摘要：

采用电化学方法将二氧化碳（CO₂）还原转化为基础化学品或碳基燃料是目前极具前景的碳资源利用新方式. 考虑到该技术未来的发展方向和大规模应用需求,人们亟需开发具有高转化效率和高稳定性的电解设备. 在本文中,作者详细介绍了现阶段发展的两种流动池的结构特点及性能优势,阐述了每种反应体系的内在局限性, 深入分析了整个反应体系所用组件（电解池、气体扩散电极、离子交换膜）对于性能的影响. 最后,针对目前该领域存在的挑战及未来发展趋势进行了总结与展望.

关键词: 二氧化碳还原, 电催化, 流动池, 电流密度

Abstract:

Electrochemical carbon dioxide reduction (CO₂RR) is an appealing approach to convert atmospheric CO₂ to value-added fuels and industrial chemicals, and may play an important role during the transition to a carbon-neutral economy. In order to make this technology commercially viable, it is essential to pursue CO₂RR in flow reactors instead of conventional H-type reactors, and to combine electrocatalyst development with system engineering. In this review, we overview the cell configurations and performance advantages of the two types of flow reactors, analyze their shortcomings, and discuss the effects of their different components including gas diffusion electrode and ion exchange membrane. A brief perspective is offered at the end for the possible future research directions in this emerging field.

Key words: CO₂ reduction, electrocatalysis, flow cell, current density

中图分类号:

O646.5

范佳, 韩娜, 李彦光. 基于流动池的电化学二氧化碳还原研究进展[J]. 电化学（中英文）, 2020, 26(4): 510-520.

FAN Jia, HAN Na, LI Yan-guang. Electrochemical Carbon Dioxide Reduction in Flow Cells[J]. Journal of Electrochemistry, 2020, 26(4): 510-520.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200443

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I4/510

图/表 6

图1

表1

图2

图3

图4

图5

参考文献 64

[1]	Gattuso J P, Magnan A, Billé R, et al. Contrasting futures for ocean and society from different anthropogenic CO₂ emissions scenarios[J]. Science, 2015,349(6243):47221-47223.
[2]	Solomon S, Plattner G K, Knutti R, et al. Irreversible climate change due to carbon dioxide emissions[J]. Proceedings of the National Academy of Sciences of the United States of America, 2009,106(6):1704-1709. URL pmid: 19179281
[3]	Mikkelsen M, Jørgensen M, Krebs F C. The teraton challenge. A review of fixation and transformation of carbon dioxide[J]. Energy & Environmental Science, 2010,3(1):43-81.
[4]	Zhu D D, Liu J L, Qiao S Z. Recent advances in inorganic heterogeneous electrocatalysts for reduction of carbon dioxide[J]. Advanced Materials, 2016,28(18):3423-3452. doi: 10.1002/adma.201504766 URL pmid: 26996295
[5]	Ager J W, Lapkin A A. Chemical storage of renewable energy[J]. Science, 2018,360(6390):707-708. doi: 10.1126/science.aat7918 URL pmid: 29773731
[6]	Qiao J L, Liu Y 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. doi: 10.1039/c3cs60323g URL pmid: 24186433
[7]	Han N, Ding P, He L, et al. Promises of main group metal-based nanostructured materials for electrochemical CO₂ reduction to formate[J]. Advanced Energy Materials, 2020,10(11):1902338.
[8]	Wu J H, Huang Y, Ye W, et al. CO₂ reduction: from the electrochemical to photochemical approach[J]. Advanced Science, 2017,4(11):1700194. URL pmid: 29201614
[9]	Costentin C, Robert M, Savéant J M. Catalysis of the electrochemical reduction of carbon dioxide[J]. Chemical Society Reviews, 2013,42(6):2423-2436. doi: 10.1039/c2cs35360a URL pmid: 23232552
[10]	Kortlever R, Shen J, Schouten K J P, et al. Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide[J]. The Journal of Physical Chemistry Letters, 2015,6(20):4073-4082.
[11]	Lu Q, Rosen J, Jiao F. Nanostructured metallic electrocatalysts for carbon dioxide reduction[J]. ChemCatChem, 2015,7(1):38-47.
[12]	Zhang L, Zhao Z J, Gong J. Nanostructured materials for heterogeneous electrocatalytic CO₂ reduction and their related reaction mechanisms[J]. Angewandte Chemie International Edition, 2017,56(38):11326-11353. doi: 10.1002/anie.201612214 URL pmid: 28168799
[13]	Wang Y F, Han P, Lv X M, et al. Defect and interface engineering for aqueous electrocatalytic CO₂ reduction[J]. Joule, 2018,2(12):2551-2582.
[14]	He J F, Johnson N J J, Huang A X, et al. Electrocatalytic alloys for CO₂ reduction[J]. ChemSusChem, 2018,11(1):48-57. doi: 10.1002/cssc.201701825 URL pmid: 29205925
[15]	Wang Y H, Liu J l, Wang Y F, et al. Tuning of CO₂ reduction selectivity on metal electrocatalysts[J]. Small, 2017, 13(43):UNSP 1701809. doi: 10.1002/smll.201700368 URL pmid: 28524361
[16]	Jones J P, Prakash G S, Olah G A. Electrochemical CO₂ reduction: recent advances and current trends[J]. Israel Journal of Chemistry, 2014,54(10):1451-1466. doi: 10.1002/ijch.201400081 URL
[17]	Ringe S, Clark E L, Resasco J, et al. Understanding cation effects in electrochemical CO₂ reduction[J]. Energy & Environmental Science, 2019,12(10):3001-3014.
[18]	Han N, Wang Y, Ma L, et al. Supported cobalt polyphthalocyanine for high-performance electrocatalytic CO₂ reduction[J]. Chem, 2017,3(4):652-664.
[19]	Han N, Wang Y, Yang H, et al. Ultrathin bismuth nano-sheets from in situ topotactic transformation for selective electrocatalytic CO₂ reduction to formate[J]. Nature Com-munications, 2018,9(1):1320.
[20]	Yang H, Han N, Deng J, et al. Selective CO₂ reduction on 2D mesoporous Bi nanosheets[J]. Advanced Energy Materials, 2018,8(35):1801536.
[21]	Yang H, Huang Y, Deng J, et al. Selective electrocatalytic CO₂ reduction enabled by SnO₂ nanoclusters[J]. Journal of Energy Chemistry, 2019,37:93-96.
[22]	Han N, Wang Y, Deng J, et al. Self-templated synjournal of hierarchical mesoporous SnO₂ nanosheets for selective CO₂ reduction[J]. Journal of Materials Chemistry A, 2019,7(3):1267-1272.
[23]	Zhang X R (张旭锐), Shao X L (邵晓玲), Yi J (易金), et al. Statuses, challenges and strategies in the development of low-temperature carbon dioxide electroreduction technology[J]. Journal of Electrochemistry (电化学), 2019,25(4):413-425.
[24]	Yang F (杨帆), Deng P L (邓培林), Han Y J (韩优嘉), et al. Copper-based compounds for electrochemical reduction of carbon dioxide[J]. Journal of Electrochemistry (电化学), 2019,25(4):426-444.
[25]	Zhou R (周睿), Han N (韩娜), Li Y G (李彦光). Recent advances in bismuth-based CO₂ reduction electrocatalysts[J]. Journal of Electrochemistry (电化学), 2019,25(4):445-454.
[26]	Salvatore D A, Weekes 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.
[27]	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. doi: 10.1021/acs.accounts.8b00010 URL pmid: 29569896
[28]	Sun Z Y, Ma T, Tao H C, et al. Fundamentals and challenges of electrochemical CO₂ reduction using two-dimensional materials[J]. Chem, 2017,3(4):560-587.
[29]	Lu X, Leung D Y, Wang H, et al. Electrochemical reduction of carbon dioxide to formic acid[J]. ChemElectroChem。 2014,1(5):836-849.
[30]	Gupta N, Gattrell M, MacDougall B, Calculation for the cathode surface concentrations in the electrochemical reduction of CO₂ in KHCO₃ solutions[J]. Journal of Applied Electrochemistry, 2006,36(2):161-172.
[31]	Burdyny T, Smith W A. CO₂ reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions[J]. Energy & Environmental Science, 2019,12(5):1442-1453.
[32]	Jouny M, Lv J J, Cheng T, et al. Formation of carbon-nitrogen bonds in carbon monoxide electrolysis[J]. Nature Chemistry, 2019,11(9):846-851. URL pmid: 31444485
[33]	Tan Y C, Lee K B, Song H, et al. Modulating local CO₂ concentration as a general strategy for enhancing C-C coupling in CO₂ electroreduction[J]. Joule, 2020,4(5):1104-1120.
[34]	Merino Garcia I, Albo J, Irabien A. Tailoring gas-phase CO₂ electroreduction selectivity to hydrocarbons at Cu nanoparticles[J]. Nanotechnology, 2017,29(1):014001. doi: 10.1088/1361-6528/aa994e URL pmid: 29119948
[35]	Dewulf D W, Bard A J. The electrochemical reduction of CO₂ to CH₄ and C₂H₄ at Cu/Nafion electrodes (solid polymer electrolyte structures)[J]. Catalysis Letters, 1988,1(1/3):73-79.
[36]	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.
[37]	Aeshala L M, Uppaluri R, Verma A. Electrochemical conversion of CO₂ to fuels: tuning of the reaction zone using suitable functional groups in a solid polymer electrolyte[J]. Physical Chemistry Chemical Physics, 2014,16(33):17588-17594. doi: 10.1039/c4cp02389g URL pmid: 25025524
[38]	Pǎtru A, Binninger T, Pribyl B, et al. Design principles of bipolar electrochemical co-electrolysis cells for efficient reduction of carbon dioxide from gas phase at low temperature[J]. Journal of The Electrochemical Society, 2019,166(2):F34-F43.
[39]	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(6):1149-1153.
[40]	McDonald M B, Ardo S, Lewis N S, et al. Use of bipolar membranes for maintaining steady state pH gradients in membrane-supported, solar-driven water splitting[J]. Che-mSusChem, 2014,7(11):3021-3027.
[41]	Reiter R S, White W, Ardo S. Communication-electrochemical characterization of commercial bipolar membranes under electrolyte conditions relevant to solar fuels technologies[J]. Journal of The Electrochemical Society, 2016,163(4):H3132-H3134.
[42]	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]. ChemSus-Chem, 2014,7(11):3017-3020.
[43]	Chen C, Kotyk J F K, Sheehan S W, Progress toward commercial application of electrochemical carbon dioxide reduction[J]. Chem, 2018,4(11):2571-2586.
[44]	Gong Q, Ding P, Xu M, et al. Structural defects on converted bismuth oxide nanotubes enable highly active electrocatalysis of carbon dioxide reduction[J]. Nature Co-mmunications, 2019,10(1):2807.
[45]	Jiang K, Sandberg R B, Akey A J, et al. Metal ion cycling of Cu foil for selective C-C coupling in electrochemical CO₂ reduction[J]. Nature Catalysis, 2018,1(2):111-119.
[46]	Jhong H R M, Tornow C E, Smid B, et al. A nitrogen-doped carbon catalyst for electrochemical CO₂ conversion to CO with high selectivity and current density[J]. ChemSusChem, 2017,10(6):1094-1099. doi: 10.1002/cssc.201600843 URL pmid: 27791338
[47]	Liang C, Kim B, Yang S, et al. High efficiency electrochemical reduction of CO₂ beyond the two-electron transfer pathway on grain boundary rich ultra-small SnO₂ nanoparticles[J]. Journal of Materials Chemistry A, 2018,6(22):10313-10319.
[48]	Kopljar D, Wagner N, Klemm E. Transferring electrochemical CO₂ reduction from semi-batch into continuous operation mode using gas diffusion electrodes[J]. Chemical Engineering & Technology, 2016,39(11):2042-2050.
[49]	Dinh C T, Burdyny T, Kibria M G, et al. CO₂ electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface[J]. Science, 2018,360(6390):783-787. doi: 10.1126/science.aas9100 URL pmid: 29773749
[50]	Hoang T T, Verma S, Ma S, et al. Nanoporous copper-silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO₂ to ethylene and ethanol[J]. Journal of the American Chemical Society, 2018,140(17):5791-5797. doi: 10.1021/jacs.8b01868 URL pmid: 29620896
[51]	Lee S, Park G, Lee J. Importance of Ag-Cu biphasic boundaries for selective electrochemical reduction of CO₂ to ethanol[J]. ACS Catalysis, 2017,7(12):8594-8604.
[52]	Ma S, Sadakiyo M, Heima M, et al. Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu-Pd catalysts with different mixing patterns[J]. Journal of the American Chemical Society, 2017,139(1):47-50. doi: 10.1021/jacs.6b10740 URL pmid: 27958727
[53]	Ren S, Joulié D, Salvatore D, et al. Molecular electrocatalysts can mediate fast, selective CO₂ reduction in a flow cell[J]. Science, 2019,365(6451):367-369. doi: 10.1126/science.aax4608 URL pmid: 31346062
[54]	Del Castillo A, Alvarez Guerra M, Solla Gullón J, et al. Sn nanoparticles on gas diffusion electrodes: Synjournal, characterization and use for continuous CO₂ electroreduction to formate[J]. Journal of CO₂ Utilization, 2017,18:222-228.
[55]	De Arquer F P G, Dinh C T, Ozden A, et al. CO₂ electrolysis to multicarbon products at activities greater than 1 A·cm^-2 [J]. Science, 2020,367(6478):661-666. doi: 10.1126/science.aay4217 URL pmid: 32029623
[56]	Lv J J, Jouny M, Luc W, et al. A highly porous copper electrocatalyst for carbon dioxide reduction[J]. Advanced Materials, 2018,30(49):1803111.
[57]	Ma W C, Xie S J, Liu T T, et al. Electrocatalytic reduction of CO₂ to ethylene and ethanol through hydrogen-assisted C-C coupling over fluorine-modified copper[J]. Nature Catalysis, 2020,3(6):478-487.
[58]	Li F, Thevenon A, Rosas Hernández A, et al. Molecular tuning of CO₂-to-ethylene conversion[J]. Nature, 2020,577(7791):509-513. doi: 10.1038/s41586-019-1782-2 URL pmid: 31747679
[59]	Yin Z L, Peng H Q, Wei X, et al. An alkaline polymer electrolyte CO₂ electrolyzer operated with pure water[J]. Energy & Environmental Science, 2019,12(8):2455-2462.
[60]	Ren S, Joulie D, Salvatore D, et al. Molecular electrocatalysts can mediate fast, selective CO₂ reduction in a flow cell[J]. Science, 2019,365(6451):367-369. doi: 10.1126/science.aax4608 URL pmid: 31346062
[61]	Zheng T T, Jiang K, Ta N, et al. Large-scale and highly selective CO₂ electrocatalytic reduction on nickel single-atom catalyst[J]. Joule, 2019,3(1):265-278.
[62]	Gabardo C M, O’Brien C P, Edwards J P, et al. Continuous carbon dioxide electroreduction to concentrated multi-carbon products using a membrane electrode assembly[J]. Joule, 2019,3(11):2777-2791. doi: 10.1016/j.joule.2019.07.021 URL
[63]	Wang X, Wang Z Y, de Arquer FPG, et al. Efficient electrically powered CO₂-to-ethanol via suppression of deoxygenation[J]. Nature Energy, 2020,5(6):478-486.
[64]	Xia C, Zhu P, Jiang Q, et al. Continuous production of pure liquid fuel solutions via electrocatalytic CO₂ reduction using solid-electrolyte devices[J]. Nature Energy, 2019,4(9):776-785.

Reactor type	Characteristic	Advantage	Disadvantage
H-cells	Standard CO₂RR reactors	Suitable for fast screening electrocatalysts, straightforward,low cost	Limited current density, not for commercial use
Flow cells	Three channels for the circulation of CO₂, catholyte and anolyte	No CO₂ solubility and diffusion limit, compatible with alkaline electrolytes, suitable for liquid product production	Susceptible to GDE flooding, impurity deposition or carbonate precipitation
MEAs	No catholyte,zero-gap configuration	Low impedance,suitable for high-pressure operation	Usually challenging to extract liquid products