1. School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China; Institute of Eco-Chongming, Shanghai 202162, China 2. Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China 3. School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China; Institute of Eco-Chongming, Shanghai 202162, China; Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Electrocatalytic CO2 reduction (ECR) offers an attractive approach to realizing carbon neutrality and producing valuable chemicals and fuels using CO2 as the feedstock. However, the lack of cost-effective electrocatalysts with better performances has seriously hindered its application. Herein, a one-step co-electrodeposition method was used to introduce Zn, a metal with weak *CO binding energy, into Cu to form Cu/Zn intermetallic catalysts (Cu/Zn IMCs). It was shown that, using an H-cell, the high Faradaic efficiency of C2+ hydrocarbons/alcohols () could be achieved in ECR by adjusting the surface metal components and the applied potential. In suitable conditions, FEC2+ and current density could be as high as 75% and 40 mA/cm2, respectively. Compared with the Cu catalyst, the Cu/Zn IMCs have a lower interfacial charge transfer resistance and a larger electrochemically active surface area (ECSA), which accelerate the reaction. Moreover, the *CO formed on Zn sites can move to Cu sites due to its weak binding with *CO, and thus enhance the C–C coupling on the Cu surface to form C2+ products.
M He, Y Sun, B Han. Green carbon science: Efficient carbon resource processing, utilization, and recycling towards carbon neutrality. Angewandte Chemie International Edition, 2022, 61(15): e202112835 https://doi.org/10.1002/anie.202112835
2
S Payra, S Shenoy, C Chakraborty. et al.. Structure-sensitive electrocatalytic reduction of CO2 to methanol over carbon-supported intermetallic PtZn nano-alloys. ACS Applied Materials & Interfaces, 2020, 12(17): 19402–19414 https://doi.org/10.1021/acsami.0c00521
3
P Pinthong, P Klongklaew, P Praserthdam. et al.. Effect of the nanostructured Zn/Cu electrocatalyst morphology on the electrochemical reduction of CO2 to value-added chemicals. Nanomaterials, 2021, 11(7): 1671–1682 https://doi.org/10.3390/nano11071671
4
M Pori, I Arčon, Jurković D Lašič. et al.. Synthesis of a Cu/ZnO nanocomposite by electroless plating for the catalytic conversion of CO2 to methanol. Catalysis Letters, 2019, 149(5): 1427–1439 https://doi.org/10.1007/s10562-019-02717-7
5
X Wang, Q Hu, G Li. et al.. Recent advances and perspectives of electrochemical CO2 reduction toward C2+ products on Cu-based catalysts. Electrochemical Energy Reviews, 2022, 5(S2): 28–71 https://doi.org/10.1007/s41918-022-00171-5
6
G Keerthiga, R Chetty. Electrochemical reduction of carbon dioxide on zinc-modified copper electrodes. Journal of the Electrochemical Society, 2017, 164(4): H164–H169 https://doi.org/10.1149/2.0421704jes
7
P F Sui, M R Gao, S Liu. et al.. Carbon dioxide valorization via formate electrosynthesis in a wide potential window. Advanced Functional Materials, 2022, 32(32): 2203794–2203802 https://doi.org/10.1002/adfm.202203794
8
L Wang, H Peng, S Lamaison. et al.. Bimetallic effects on Zn-Cu electrocatalysts enhance activity and selectivity for the conversion of CO2 to CO. Chem Catalysis, 2021, 1(3): 663–680 https://doi.org/10.1016/j.checat.2021.05.006
9
Y Yan, L Ke, Y Ding. et al.. Recent advances in Cu-based catalysts for electroreduction of carbon dioxide. Materials Chemistry Frontiers, 2021, 5(6): 2668–2683 https://doi.org/10.1039/D0QM01127D
10
W Wang, J Han, Y Sun. et al.. Metal-free SeBN ternary-doped porous carbon as efficient electrocatalysts for CO2 reduction reaction. ACS Applied Energy Materials, 2022, 5(9): 10518–10525 https://doi.org/10.1021/acsaem.2c01201
11
X Tan, C Yu, Y Ren. et al.. Recent advances in innovative strategies for the CO2 electroreduction reaction. Energy & Environmental Science, 2021, 14(2): 765–780 https://doi.org/10.1039/D0EE02981E
12
J Han, J Ma, J Zhou. et al.. Insight into the effect of surface coverage of carbon support on selective CO2 electroreduction to C2H4 over copper-based catalyst. Applied Surface Science, 2023, 609(30): 155394–155401 https://doi.org/10.1016/j.apsusc.2022.155394
13
J Wang, G Wang, J Zhang. et al.. Inversely tuning the CO2 electroreduction and hydrogen evolution activity on metal oxide via heteroatom doping. Angewandte Chemie International Edition, 2021, 60(14): 7602–7606 https://doi.org/10.1002/anie.202016022
14
D Kim, J Resasco, Y Yu. et al.. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nature Communications, 2014, 5(1): 4948 https://doi.org/10.1038/ncomms5948
15
C Zhu, S Kais, X C Zeng. et al.. Interfaces select specific stereochemical conformations: The isomerization of glyoxal at the liquid water interface. Journal of the American Chemical Society, 2017, 139(1): 27–30 https://doi.org/10.1021/jacs.6b10208
16
Y Zhang, X Wang, S Zheng. et al.. Hierarchical cross-linked carbon aerogels with transition metal-nitrogen sites for highly efficient industrial-level CO2 electroreduction. Advanced Functional Materials, 2021, 31(45): 2104377–2104386 https://doi.org/10.1002/adfm.202104377
17
Y Zhao, X G Zhang, N Bodappa. et al.. Elucidating electrochemical CO2 reduction reaction processes on Cu(hkl) single-crystal surfaces by in situ Raman spectroscopy. Energy & Environmental Science, 2022, 15(9): 3968–3977 https://doi.org/10.1039/D2EE01334G
18
Y Mun, S Lee, A Cho. et al.. Cu-Pd alloy nanoparticles as highly selective catalysts for efficient electrochemical reduction of CO2 to CO. Applied Catalysis B: Environmental, 2019, 5(246): 82–88 https://doi.org/10.1016/j.apcatb.2019.01.021
19
S Juntrapirom, J Santatiwongchai, A Watwiangkham. et al.. Tuning CuZn interfaces in metal–organic framework-derived electrocatalysts for enhancement of CO2 conversion to C2 products. Catalysis Science & Technology, 2021, 11(24): 8065–8078 https://doi.org/10.1039/D1CY01839F
20
X Zhong, S Liang, T Yang. et al.. Sn dopants with synergistic oxygen vacancies boost CO2 electroreduction on CuO nanosheets to CO at low overpotential. ACS Nano, 2022, 16(11): 19210–19219 https://doi.org/10.1021/acsnano.2c08436
21
Z Zhu, Z L Yu, W Y Gao. et al.. Controlled synthesis of intermetallic Au2Bi nanocrystals and Au2Bi/Bi hetero-nanocrystals with promoted electrocatalytic CO2 reduction properties. ChemSusChem, 2022, 15(10): 202200211 https://doi.org/10.1002/cssc.202200211
22
S Kuang, M Li, X Chen. et al.. Intermetallic CuAu nanoalloy for stable electrochemical CO2 reduction. Chinese Chemical Letters, 2023, 34(7): 108013–108016 https://doi.org/10.1016/j.cclet.2022.108013
23
S Jia, Q Zhu, M Chu. et al.. Hierarchical metal-polymer hybrids for enhanced CO2 electroreduction. Angewandte Chemie International Edition, 2021, 60(19): 10977–10982 https://doi.org/10.1002/anie.202102193
24
M Awais, S Kamal, F Ijaz. et al.. Improved catalytic performance of aspergillus flavus laccase immobilized on the zinc ferrite nanoparticles. Catalysis Letters, 2023, 5(153): 1240–1249 https://doi.org/10.1007/s10562-022-04067-3
25
S Yan, C Peng, C Yang. et al.. Electron localization and lattice strain induced by surface lithium doping enable ampere-level electrosynthesis of formate from CO2. Angewandte Chemie International Edition, 2021, 60(49): 25741–25745 https://doi.org/10.1002/anie.202111351
26
M Chen, S Wan, L Zhong. et al.. Dynamic restructuring of Cu-doped SnS2 nanoflowers for highly selective electrochemical CO2 reduction to formate. Angewandte Chemie International Edition, 2021, 60(50): 26233–26237 https://doi.org/10.1002/anie.202111905
27
D L T Nguyen, M S Jee, D H Won. et al.. Effect of halides on nanoporous Zn-based catalysts for highly efficient electroreduction of CO2 to CO. Catalysis Communications, 2018, 114(114): 109–113 https://doi.org/10.1016/j.catcom.2018.06.020
28
B Qin, Y Li, H Fu. et al.. Electrochemical reduction of CO2 into tunable syngas production by regulating the crystal facets of earth-abundant Zn catalyst. ACS Applied Materials & Interfaces, 2018, 10(24): 20530–20539 https://doi.org/10.1021/acsami.8b04809
29
J Leverett, T Tran‐Phu, J A Yuwono. et al.. Tuning the coordination structure of Cu–N–C single atom catalysts for simultaneous electrochemical reduction of CO2 and NO3– to urea. Advanced Energy Materials, 2022, 12(32): 2201500–2201508 https://doi.org/10.1002/aenm.202201500
30
S Sirisomboonchai, H Machida, K V Bao Tran. et al.. Efficient CO2 electrochemical reduction by a robust electrocatalyst fabricated by electrodeposition of indium and zinc over copper foam. ACS Applied Energy Materials, 2022, 5(8): 9846–9857 https://doi.org/10.1021/acsaem.2c01564
31
A Xu, B He, H Yu. et al.. A facile solution to mature cathode modified by hydrophobic dimethyl silicon oil (DMS) layer for electro-Fenton processes: Water proof and enhanced oxygen transport. Electrochimica Acta, 2019, 10(308): 158–166 https://doi.org/10.1016/j.electacta.2019.04.047
32
Y Feng, H Yang, Y Zhang. et al.. Te-doped Pd nanocrystal for electrochemical urea production by efficiently coupling carbon dioxide reduction with nitrite reduction. Nano Letters, 2020, 20(11): 8282–8289 https://doi.org/10.1021/acs.nanolett.0c03400
33
D Chen, Z Zhou, C Feng. et al.. An upgraded lithium ion battery based on a polymeric separator incorporated with anode active materials. Advanced Energy Materials, 2019, 9(15): 1803627–1803637 https://doi.org/10.1002/aenm.201803627
34
L Li, X Jin, X Yu. et al.. Bimetallic Cu-Bi catalysts for efficient electroreduction of CO2 to formate. Frontiers in Chemistry, 2022, 10(10): 983778 https://doi.org/10.3389/fchem.2022.983778
35
Y Gao, S Yu, P Zhou. et al.. Promoting electrocatalytic reduction of CO2 to C2H4 production by inhibiting C2H5OH desorption from Cu2O/C composite. Small, 2022, 18(9): 2105212 https://doi.org/10.1002/smll.202105212
36
W Shan, R Liu, H Zhao. et al.. In situ surface-enhanced Raman spectroscopic evidence on the origin of selectivity in CO2 electrocatalytic reduction. ACS Nano, 2020, 14(9): 11363–11372 https://doi.org/10.1021/acsnano.0c03534
37
T T H Hoang, S Verma, S Ma. et al.. Nanoporous copper-silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol. Journal of the American Chemical Society, 2018, 140(17): 5791–5797 https://doi.org/10.1021/jacs.8b01868
38
M Hu, Z Cai, S Yang. et al.. Direct growth of uniform bimetallic core-shell or intermetallic nanoparticles on carbon via a surface-confinement strategy for electrochemical hydrogen evolution reaction. Advanced Functional Materials, 2023, 33(13): 2212097–2212106 https://doi.org/10.1002/adfm.202212097
39
Y Ma, J Yu, M Sun. et al.. Confined growth of silver-copper Janus nanostructures with 100 facets for highly selective tandem electrocatalytic carbon dioxide reduction. Advanced Materials, 2022, 34(19): 2110607 https://doi.org/10.1002/adma.202110607
40
T Yan, P Wang, Z H Xu. et al.. Copper (II) frameworks with varied active site distribution for modulating selectivity of carbon dioxide electroreduction. ACS Applied Materials & Interfaces, 2022, 14(11): 13645–13652 https://doi.org/10.1021/acsami.2c00487
41
J Sang, P Wei, T Liu. et al.. A reconstructed Cu2P2O7 catalyst for selective CO2 electroreduction to multicarbon products. Angewandte Chemie International Edition, 2022, 61(5): e202114238 https://doi.org/10.1002/anie.202114238
42
J Xu, Y Sun, M Lu. et al.. One-step electrodeposition fabrication of Ni3S2 nanosheet arrays on Ni foam as an advanced electrode for asymmetric supercapacitors. Science China Materials, 2019, 62(5): 699–710 https://doi.org/10.1007/s40843-018-9361-0
43
P Grosse, A Yoon, C Rettenmaier. et al.. Dynamic transformation of cubic copper catalysts during CO2 electroreduction and its impact on catalytic selectivity. Nature Communications, 2021, 12(1): 6736–6746 https://doi.org/10.1038/s41467-021-26743-5
44
S Kunze, L C Tanase, M J Prieto. et al.. Plasma-assisted oxidation of Cu(100) and Cu(111). Chemical Science, 2021, 12(42): 14241–14253 https://doi.org/10.1039/D1SC04861A