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Authors

Chang ZHU, 1. CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China;2. University of Chinese Academy of Sciences, Beijing, 100049, China;
Wei CHEN, 1. CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China;Follow
Yan-fang SONG, 1. CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China;
Xiao DONG, 1. CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China;
Gui-hua LI, 1. CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China;
Wei WEI, 1. CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China;3. School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, China;Follow
Yu-han SUN, 1. CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China;3. School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, China;Follow

Corresponding Author

Wei CHEN(chenw@sari.ac.cn);
Wei WEI(weiwei@sari.ac.cn);
Yu-han SUN(sunyh@sari.ac.cn)

Abstract

Electrochemical conversion of carbon dioxide (CO2) driven by renewable electricity that can meet both carbon emission reduction and renewable energy utilization has been rapidly developed in recent years. Copper (Cu) catalyst has long been a promising candidate for CO2 electroreduction applications because of its natural abundance and specific capability of producing a substantial amount of C2 products. However, various metallic Cu electrodes reported have been significantly influenced by the adsorption of certain cation/anion ions, resulting in wide-span catalytic activities and selectivity for various products. In addition, a recent report demonstrated that by virtue of gas-diffusion flow cell with Cu cathode, remarkable ethylene production was achieved in CO2 electroreduction. It is, therefore, desirable to systematically investigate the effect of reaction conditions on the performances of Cu-catalyzed CO2 electroreduction. Here we chose the commercial Cu particles with an average size of 600 nm as the catalyst for CO2 electroreduction and investigated the electrocatalytic performances under various reaction conditions, including the commonly used electrolyte solutions, the different potassium hydrogen carbonate (KHCO3) concentrations, as well as H-type and gas-diffusion flow cells. The results of linear sweep voltammetry and potentiostatic CO2 electrolysis showed that KHCO3 as an electrolyte solution with a concentration of 0.5 mol?L-1 offered good catalytic activities and high current densities, and the gas-diffusion flow cell could further improve the Faradaic efficiencies and partial current densities of the main products formate and CO. This work provides a fundamental insight to the electrocatalytic conversion of CO2 reduction from the view of reaction conditions.

Graphical Abstract

Keywords

CO2 electroreduction, copper catalyst, reaction conditions, gas-diffusion electrode

Publication Date

2020-12-28

Online Available Date

2020-04-15

Revised Date

2020-02-25

Received Date

2019-12-30

References

[1] Caldeira K, Wickett M E . Anthropogenic carbon and ocean pH[J]. Nature, 2003,425(6956):365.
doi: 10.1038/425365a URL pmid: 14508477

[2] White J W C, Ciais P, Figge R A , et al. A high-resolution record of atmospheric CO2 content from carbon isotopes in peat[J]. Nature, 1994,367(6459):153-156.

[3] Chu S, Majumdar A . Opportunities and challenges for a sustainable energy future[J]. Nature, 2012,488(7411):294-303.

[4] Obama B . The irreversible momentum of clean energy[J]. Science, 2017,355(6321):126-129.

[5] Zhang X R( 张旭锐), Shao X L( 邵晓琳), 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.

[6] Wang L M, Chen W L, Zhang D D , et al. Surface strategies for catalytic CO2 reduction: from two-dimensional materials to nanoclusters to single atoms[J]. Chemical Society Reviews, 2019,48(21):5310-5349.

[7] Song R B, Zhu W, Fu J , et al. Electrode materials engineering in electrocatalytic CO2 reduction: Energy input and conversion efficiency[J]. Advanced Materials, 2019,32(27):1903796.

[8] Askgaard T S, Norskov J K, Ovesen C V , et al. A kinetic model of methanol synjournal[J]. Journal of Catalysis, 1995,156(2):229-242.

[9] Iglesias M L, de Vries C, Claeys M , et al. Chemical energy storage in gaseous hydrocarbons via iron Fischer-Tropsch synjournal from H2/CO2 Kinetics, selectivity and process considerations[J]. Catalysis Today, 2015,242:184-192.

[10] Liu J J, Peng H G, Liu W M , et al. Sn modification on Ni/Al2O3: Designing potent coke-resistant catalysts for methane dry reforming[J]. Chemcatchem, 2014,6(7):2095-2104.

[11] Birdja Y Y, Pérez-Gallent E, Figueiredo M C , et al. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels[J]. Nature Energy, 2019,4(9):732-745.

[12] Zhou W, Cheng K, Kang J C , et al. New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO2 into hydrocarbon chemicals and fuels[J]. Chemical Society Reviews, 2019,48(12):3193-3228.

[13] Liu M, Pang Y J, Zhang B , et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration[J]. Nature, 2016,537(7620):382-386.

[14] Bai X F, Chen W, Zhao C C , et al. Exclusive formation of formic acid from CO2 electroreduction by a tunable Pd-Sn alloy[J]. Angewandte Chemie International Edition, 2017,56(40):12219-12223.

[15] Gao S, Lin Y, Jiao X C , et al. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel[J]. Nature, 2016,529(7584):68-71.
doi: 10.1038/nature16455 URL pmid: 26738592

[16] 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.

[17] Lim D H, Jo J H, Shin D Y , et al. Carbon dioxide conversion into hydrocarbon fuels on defective graphene supported Cu nanoparticles from first principles[J]. Nanoscale, 2014,6(10):5087-5092.

[18] Keerthiga G, Viswanathan B, Chetty R . Electrochemical reduction of CO2 on electrodeposited Cu electrodes crystalline phase sensitivity on selectivity[J]. Catalysis Today, 2015,245:68-73.

[19] Chen C S, Handoko A D, Wan J H , et al. Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals[J]. Catalysis Science & Technology, 2015,5(1):161-168.

[20] Lei W( 雷文), Xiao W P( 肖卫平), Wang D L( 王得丽 ), et al. Recent progress in copper-based catalysts for electrochemical CO2 reduction[J]. Journal of Electrochemistry( 电化学), 2019,25(4):455-466.

[21] 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, 1985,14:1695-1698.

[22] 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.

[23] 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.

[24] Garza A J, Bell A T, Head-Gordon M, Mechanism of CO2 reduction at copper surfaces: Pathways to C2 products[J]. ACS Catalysis, 2018,8(2):1490-1499.

[25] Ren S X, 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

[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] Weng L C, Bell A T, Weber A Z . Modeling gas-diffusion electrodes for CO2 reduction[J]. Physical Chemistry Chemical Physics, 2018,20(25):16973-16984.
doi: 10.1039/c8cp01319e URL pmid: 29900441

[28] 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.

[29] 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.
doi: 10.1038/ncomms12123 URL pmid: 27356485

[30] Reske R, Mistry H, Behafarid F , et al. Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles[J]. Journal of the American Chemical Society, 2014,136(19):6978-6986.
doi: 10.1021/ja500328k URL pmid: 24746172

[31] Birdja Y Y, Pérez-Gallent E, Figueiredo M C , et al. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels[J]. Nature Energy, 2019,4(9):732-745.

[32] Spurgeon J M, Kumar B . A comparative technoeconomic analysis of pathways for commercial electrochemical CO2 reduction to liquid products[J]. Energy & Environmental Science, 2018,11(6), 1536-1551.

[33] Min X, Kanan M W . Pd-catalyzed electrohydrogenation of carbon dioxide to formate: high mass activity at low overpotential and identification of the deactivation pathway[J]. Journal of the American Chemical Society, 2015,137(14):4701-4708.
doi: 10.1021/ja511890h URL pmid: 25812119

[34] Gao D F, Scholten F, Roldan Cuenya B . Improved CO2 Electroreduction performance on plasma-activated Cu catalysts via electrolyte design: Halide effect[J]. ACS Catalysis, 2017,7(8):5112-5120.

[35] 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.

[36] Irina V C, Sathish P . Activation of CO2 at the electrodeelectrolyte interface by a co-adsorbed cation and an electric field[J]. Physical Chemistry Chemical Physics, 2019,21(17), 8797-8807.
doi: 10.1039/c8cp07807f URL pmid: 30968884

[37] Yoon Y, Hall A S, Surendranath Y . Tuning of silver catalyst mesostructure promotes selective carbon dioxide conversion into fuels[J]. Angewandte Chemie International Edition. 2016,55(49):15282-15286.
doi: 10.1002/anie.201607942 URL pmid: 27862743

[38] Zhu C Q, Wang Q N, Wu C . Rapid and scalable synjournal of bismuth dendrites on copper mesh as a high-performance cathode for electroreduction of CO2 to formate[J]. Journal of CO2 Utilization, 2020,36:96-104.

[39] Singh MR, Clark EL, Bell AT . Effects of electrolyte, catalyst, and membrane composition and operating conditions on the performance of solar-driven electrochemical reduction of carbon dioxide[J]. Physical Chemistry Che-micalPhysics, 2015,17(29), 18924-18936.

[40] 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.

[41] Zhuang T T, Liang Z Q, Seifitokaldani A , et al. Steering post-C-C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols[J]. Nature Catalysis, 2018,1(6):421-428.

[42] Gao S, Sun Z T, Liu W , et al. Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction[J]. Nature Communications, 2017,8:14503.
doi: 10.1038/ncomms14503 URL pmid: 28220847

[43] Zhao C N, Dai X Y, Yao T , et al. Ionic exchange of metal-organic frameworks to access single nickel sites for efficient electroreduction of CO2[J]. Journal of the American Chemical Society, 2017,139(24):8078-8081.
doi: 10.1021/jacs.7b02736 URL pmid: 28595012

[44] Dunwell M, Lu Q, Heyes J M , et al. The central role of bicarbonate in the electrochemical reduction of carbon dioxide on gold[J]. Journal of the American Chemical Society, 2017,139(10):3774-3783.
doi: 10.1021/jacs.6b13287 URL pmid: 28211683

[45] 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.

[46] 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.

[47] Li F W, Thevenon A, Rosas-Hernandez A , et al. Molecular tuning of CO2-to-ethylene conversion[J]. Nature, 2019,577(7791):509-513.
doi: 10.1038/s41586-019-1782-2 URL pmid: 31747679

[48] Singh M R, Kwon Y, Lum Y , et al. Hydrolysis of electrolyte cations enhances the electrochemical reduction of CO2 over Ag and Cu[J]. Journal of the American Chemical Society, 2016,138(39):13006-13012.
doi: 10.1021/jacs.6b07612 URL pmid: 27626299

[49] Li Q Y, Shi F, Shen F X , et al. Electrochemical reduction of CO2 into CO in N-methyl pyrrolidone/tetrabutylammonium perchlorate in two-compartment electrolysis cell[J]. Journal of Electroanalytical Chemistry, 2016,785:229-134.

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