Self-supported copper-based gas diffusion electrodes improve the local CO2 concentration for efficient electrochemical CO2 reduction
Received date: 15 Oct 2023
Accepted date: 04 Dec 2023
Copyright
Electrochemical CO2 reduction is a sustainable approach in green chemistry that enables the production of valuable chemicals and fuels while mitigating the environmental impact associated with CO2 emissions. Despite its several advantages, this technology suffers from an intrinsically low CO2 solubility in aqueous solutions, resulting in a lower local CO2 concentration near the electrode, which yields lower current densities and restricts product selectivity. Gas diffusion electrodes (GDEs), particularly those with tubular architectures, can solve these issues by increasing the local CO2 concentration and triple-phase interface, providing abundant electroactive sites to achieve superior reaction rates. In this study, robust and self-supported Cu flow-through gas diffusion electrodes (FTGDEs) were synthesized for efficient formate production via electrochemical CO2 reduction. They were further compared with traditional Cu electrodes, and it was found that higher local CO2 concentration due to improved mass transfer, the abundant surface area available for the generation of the triple-phase interface, and the porous structure of Cu FTGDEs enabled high formate Faradaic efficiency (76%) and current density (265 mA·cm–2) at –0.9 V vs. reversible hydrogen electrode (RHE) in 0.5 mol·L–1 KHCO3. The combined phase inversion and calcination process of the Cu FTGDEs helped maintain a stable operation for several hours. The catalytic performance of the Cu FTGDEs was further investigated in a non-gas diffusion configuration to demonstrate the impact of local gas concentration on the activity and performance of electrochemical CO2 reduction. This study demonstrates the potential of flow-through gas-diffusion electrodes to enhance reaction kinetics for the highly efficient and selective reduction of CO2, offering promising applications in sustainable electrochemical processes.
Azeem Mustafa , Bachirou Guene Lougou , Yong Shuai , Zhijiang Wang , Haseeb-ur-Rehman , Samia Razzaq , Wei Wang , Ruming Pan , Jiupeng Zhao . Self-supported copper-based gas diffusion electrodes improve the local CO2 concentration for efficient electrochemical CO2 reduction[J]. Frontiers of Chemical Science and Engineering, 2024 , 18(3) : 29 . DOI: 10.1007/s11705-024-2392-6
1 |
Ruiz-López E , Gandara-Loe J , Baena-Moreno F , Reina T R , Odriozola J A . Electrocatalytic CO2 conversion to C2 products: catalysts design, market perspectives and techno-economic aspects. Renewable & Sustainable Energy Reviews, 2022, 161: 112329
|
2 |
Wang J J , Li X P , Cui B F , Zhang Z , Hu X F , Ding J , Deng Y D , Han X P , Hu W B . A review of non-noble metal-based electrocatalysts for CO2 electroreduction. Rare Metals, 2021, 40(11): 3019–3037
|
3 |
Mustafa A , Lougou B G , Shuai Y , Wang Z , Haseeb-ur-Rehman S , Razzaq W , Wang R , Pan F , Li L . Analyzing the electrochemical reduction of CO and CO2 as reactants to C1 and C2 products on copper-based flow-through gas diffusion electrodes. Journal of Environmental Chemical Engineering, 2023, 11(6): 111528
|
4 |
Wang M , Zhang S , Li M , Han A , Zhu X , Ge Q , Han J , Wang H . Facile synthesis of hierarchical flower-like Ag/Cu2O and Au/Cu2O nanostructures and enhanced catalytic performance in electrochemical reduction of CO2. Frontiers of Chemical Science and Engineering, 2020, 14(5): 813–823
|
5 |
Zhang S , Liu Q , Tang X , Zhou Z , Fan T , You Y , Zhang Q , Zhang S , Luo J , Liu X . Electrocatalytic reduction of NO to NH3 in ionic liquids by P-doped TiO2 nanotubes. Frontiers of Chemical Science and Engineering, 2023, 17(6): 726–734
|
6 |
Zhan L S , Wang Y C , Liu M J , Zhao X , Wu J , Xiong X , Lei Y P . Hydropathy modulation on Bi2S3 for enhanced electrocatalytic CO2 reduction. Rare Metals, 2023, 42(3): 806–812
|
7 |
Lu S , Wang Y , Xiang H , Lei H , Xu B B , Xing L , Yu E H , Liu T X . Mass transfer effect to electrochemical reduction of CO2: electrode, electrocatalyst and electrolyte. Journal of Energy Storage, 2022, 52: 104764
|
8 |
Mustafa A , Lougou B G , Shuai Y , Wang Z , Razzaq S , Zhao J , Tan H . Theoretical insights into the factors affecting the electrochemical reduction of CO2. Sustainable Energy & Fuels, 2020, 4(9): 4352–4369
|
9 |
Rabiee H , Ge L , Zhang X , Hu S , Li M , Yuan Z . Gas diffusion electrodes (GDEs) for electrochemical reduction of carbon dioxide, carbon monoxide, and dinitrogen to value-added products: a review. Energy & Environmental Science, 2021, 14(4): 1959–2008
|
10 |
Nguyen T N , Dinh C T . Gas diffusion electrode design for electrochemical carbon dioxide reduction. Chemical Society Reviews, 2020, 49(21): 7488–7504
|
11 |
Park S , Lee J W , Popov B N . A review of gas diffusion layer in PEM fuel cells: materials and designs. International Journal of Hydrogen Energy, 2012, 37(7): 5850–5865
|
12 |
Omrani R , Shabani B . Gas diffusion layer modifications and treatments for improving the performance of proton exchange membrane fuel cells and electrolysers: a review. International Journal of Hydrogen Energy, 2017, 42(47): 28515–28536
|
13 |
Majlan E H , Rohendi D , Daud W R , Husaini T , Haque M A . Electrode for proton exchange membrane fuel cells: a review. Renewable & Sustainable Energy Reviews, 2018, 89: 117–134
|
14 |
Tan Y C , Lee K B , Song H , Oh J . Modulating local CO2 concentration as a general strategy for enhancing C–C coupling in CO2 electroreduction. Joule, 2020, 4(5): 1104–1120
|
15 |
Bitar Z , Fecant A , Trela-Baudot E , Chardon-Noblat S , Pasquier D . Electrocatalytic reduction of carbon dioxide on indium coated gas diffusion electrodes—comparison with indium foil. Applied Catalysis B: Environmental, 2016, 189: 172–180
|
16 |
Albo J , Irabien A . Cu2O-loaded gas diffusion electrodes for the continuous electrochemical reduction of CO2 to methanol. Journal of Catalysis, 2016, 343: 232–239
|
17 |
Li J J , Zhang Z C K . K+-enhanced electrocatalytic CO2 reduction to multicarbon products in strong acid. Rare Metals, 2022, 41(3): 723–725
|
18 |
Wang J , Zou J , Hu X , Ning S , Wang X , Kang X , Chen S . Heterostructured intermetallic CuSn catalysts: high performance towards the electrochemical reduction of CO2 to formate. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(48): 27514–27521
|
19 |
Yang K , Kas R , Smith W A , Burdyny T . Role of the carbon-based gas diffusion layer on flooding in a gas diffusion electrode cell for electrochemical CO2 reduction. ACS Energy Letters, 2021, 6(1): 33–40
|
20 |
Jhong H R , Brushett F R , Kenis P J . The effects of catalyst layer deposition methodology on electrode performance. Advanced Energy Materials, 2013, 3(5): 589–599
|
21 |
Laoun B , Kasat H A , Ahmad R , Kannan A M . Gas diffusion layer development using design of experiments for the optimization of a proton exchange membrane fuel cell performance. Energy, 2018, 151: 689–695
|
22 |
Higgins D , Hahn C , Xiang C , Jaramillo T F , Weber A Z . Gas-diffusion electrodes for carbon dioxide reduction: a new paradigm. ACS Energy Letters, 2019, 4(1): 317–324
|
23 |
Monteiro M C , Philips M F , Schouten K J , Koper M T . Efficiency and selectivity of CO2 reduction to CO on gold gas diffusion electrodes in acidic media. Nature Communications, 2021, 12(1): 4943
|
24 |
Jiang K , Sandberg R B , Akey A J , Liu X , Bell D C , Nørskov J K , Chan K , Wang H . Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. Nature Catalysis, 2018, 1(2): 111–119
|
25 |
Hou X , Cai Y , Zhang D , Li L , Zhang X , Zhu Z , Peng L , Liu Y , Qiao J . 3D core–shell porous-structured Cu@Sn hybrid electrodes with unprecedented selective CO2-into-formate electroreduction achieving 100%. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(7): 3197–3205
|
26 |
Peterson A A , Abild-Pedersen F , Studt F , Rossmeisl J , Nørskov J K . How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy & Environmental Science, 2010, 3(9): 1311–1315
|
27 |
Durand W J , Peterson A A , Studt F , Abild-Pedersen F , Nørskov J K . Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces. Surface Science, 2011, 605(15-16): 1354–1359
|
28 |
Nitopi S , Bertheussen E , Scott S B , Liu X , Engstfeld A K , Horch S , Seger B , Stephens I E , Chan K , Hahn C .
|
29 |
Zhao J , Xue S , Barber J , Zhou Y , Meng J , Ke X . An overview of Cu-based heterogeneous electrocatalysts for CO2 reduction. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2020, 8(9): 4700–4734
|
30 |
Reske R , Mistry H , Behafarid F , Roldan Cuenya B , Strasser P . Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles. Journal of the American Chemical Society, 2014, 136(19): 6978–6986
|
31 |
Firet N J , Burdyny T , Nesbitt N T , Chandrashekar S , Longo A , Smith W A . Copper and silver gas diffusion electrodes performing CO2 reduction studied through operando X-ray absorption spectroscopy. Catalysis Science & Technology, 2020, 10(17): 5870–5885
|
32 |
Paul S , Kao Y L , Ni L , Ehnert R , Herrmann-Geppert I , van de Krol R , Stark R W , Jaegermann W , Kramm U I , Bogdanoff P . Influence of the metal center in M–N–C catalysts on the CO2 reduction reaction on gas diffusion electrodes. ACS Catalysis, 2021, 11(9): 5850–5864
|
33 |
Weng L C , Bell A T , Weber A Z . Modeling gas-diffusion electrodes for CO2 reduction. Physical Chemistry Chemical Physics, 2018, 20(25): 16973–16984
|
34 |
Abdinejad M , Motlagh M K , Noroozifar M , Kraatz H B . Electroreduction of carbon dioxide to formate using highly efficient bimetallic Sn-Pd aerogels. Materials Advances, 2022, 3(2): 1224–1230
|
35 |
Zhu C , Song Y , Dong X , Li G , Chen A , Chen W , Wu G , Li S , Wei W , Sun Y . Ampere-level CO2 reduction to multicarbon products over a copper gas penetration electrode. Energy & Environmental Science, 2022, 15(12): 5391–5404
|
36 |
Ikeda S , Ito K , Noda H . Electrochemical reduction of carbon dioxide using gas diffusion electrodes loaded with fine catalysts. American Institute of Physics: AIP Conference Proceedings, 2009, 1136(1): 108–113
|
37 |
Yang H , Li S , Xu Q . Efficient strategies for promoting the electrochemical reduction of CO2 to C2+ products over Cu-based catalysts. Chinese Journal of Catalysis, 2023, 48: 32–65
|
38 |
Varela A S , Kroschel M , Reier T , Strasser P . Controlling the selectivity of CO2 electroreduction on copper: the effect of the electrolyte concentration and the importance of the local pH. Catalysis Today, 2016, 260: 8–13
|
39 |
Klinkova A , De Luna P , Dinh C T , Voznyy O , Larin E M , Kumacheva E , Sargent E H . Rational design of efficient palladium catalysts for electroreduction of carbon dioxide to formate. ACS Catalysis, 2016, 6(12): 8115–8120
|
40 |
Li F , Chen L , Knowles G P , MacFarlane D R , Zhang J . Hierarchical mesoporous SnO2 nanosheets on carbon cloth: a robust and flexible electrocatalyst for CO2 reduction with high efficiency and selectivity. Angewandte Chemie International Edition, 2017, 56(2): 505–509
|
41 |
Huang Y , Deng Y , Handoko A D , Goh G K , Yeo B S . Rational design of sulfur‐doped copper catalysts for the selective electroreduction of carbon dioxide to formate. ChemSusChem, 2018, 11(1): 320–326
|
42 |
Shinagawa T , Larrazábal G O , Martín A J , Krumeich F , Perez-Ramirez J . Sulfur-modified copper catalysts for the electrochemical reduction of carbon dioxide to formate. ACS Catalysis, 2018, 8(2): 837–844
|
43 |
Duarte M , De Mot B , Hereijgers J , Breugelmans T . Electrochemical reduction of CO2: effect of convective CO2 supply in gas diffusion electrodes. ChemElectroChem, 2019, 6(22): 5596–5602
|
44 |
de Sousa L , Benes N E , Mul G . Evaluating the effects of membranes, cell designs, and flow configurations on the performance of Cu-GDEs in converting CO2 to CO. ACS ES&T Engineering, 2022, 2(11): 2034–2042
|
45 |
Marcandalli G , Goyal A , Koper M T . Electrolyte effects on the faradaic efficiency of CO2 reduction to CO on a gold electrode. ACS Catalysis, 2021, 11(9): 4936–4945
|
46 |
Ye K , Zhang G , Ma X Y , Deng C , Huang X , Yuan C , Meng G , Cai W B , Jiang K . Resolving local reaction environment toward an optimized CO2-to-CO conversion performance. Energy & Environmental Science, 2022, 15(2): 749–759
|
47 |
Jouny M , Luc W , Jiao F . High-rate electroreduction of carbon monoxide to multi-carbon products. Nature Catalysis, 2018, 1(10): 748–755
|
48 |
Peng L , Wang Y , Wang Y , Xu N , Lou W , Liu P , Cai D , Huang H , Qiao J . Separated growth of Bi-Cu bimetallic electrocatalysts on defective copper foam for highly converting CO2 to formate with alkaline anion-exchange membrane beyond KHCO3 electrolyte. Applied Catalysis B: Environmental, 2021, 288: 120003
|
49 |
Ye K , Zhang G , Ni B , Guo L , Deng C , Zhuang X , Zhao C , Cai W B , Jiang K . Steering CO2 electrolysis selectivity by modulating the local reaction environment: an online DEMS approach for Cu electrodes. eScience, 2023, 3(4): 100143
|
50 |
Zhang G , Ye K , Ni B , Jiang K . Steering the products distribution of CO2 electrolysis: a perspective on extrinsic tuning knobs. Chem Catalysis, 2023, 3(9): 100746
|
/
〈 | 〉 |