Electrochemical CO₂ reduction to C₂₊ products over Cu/Zn intermetallic catalysts synthesized by electrodeposition

Abstract

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 ({\mathrm{F}\mathrm{E}}_{{\mathrm{C}}_{2+}}) could be achieved in ECR by adjusting the surface metal components and the applied potential. In suitable conditions, FE_C2+ 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.

Graphical abstract

Keywords

carbon dioxide electroreduction / electrochemistry / co-electrodeposition / intermetallic catalysts / value-added chemicals

References

[1] He M, Sun Y, Han B. Green carbon science: Efficient carbon resource processing, utilization, and recycling towards carbon neutrality. Angewandte Chemie International Edition, 2022, 61(15): e202112835

[2] Payra S, Shenoy S, Chakraborty C. . Structure-sensitive electrocatalytic reduction of CO₂ to methanol over carbon-supported intermetallic PtZn nano-alloys. ACS Applied Materials & Interfaces, 2020, 12(17): 19402–19414

[3] Pinthong P, Klongklaew P, Praserthdam P. . Effect of the nanostructured Zn/Cu electrocatalyst morphology on the electrochemical reduction of CO₂ to value-added chemicals. Nanomaterials, 2021, 11(7): 1671–1682

[4] Pori M, Arčon I, Lašič Jurković D. . Synthesis of a Cu/ZnO nanocomposite by electroless plating for the catalytic conversion of CO₂ to methanol. Catalysis Letters, 2019, 149(5): 1427–1439

[5] Wang X, Hu Q, Li G. . Recent advances and perspectives of electrochemical CO₂ reduction toward C₂₊ products on Cu-based catalysts. Electrochemical Energy Reviews, 2022, 5(S2): 28–71

[6] Keerthiga G, Chetty R. Electrochemical reduction of carbon dioxide on zinc-modified copper electrodes. Journal of the Electrochemical Society, 2017, 164(4): H164–H169

[7] Sui P F, Gao M R, Liu S. . Carbon dioxide valorization via formate electrosynthesis in a wide potential window. Advanced Functional Materials, 2022, 32(32): 2203794–2203802

[8] Wang L, Peng H, Lamaison S. . Bimetallic effects on Zn-Cu electrocatalysts enhance activity and selectivity for the conversion of CO₂ to CO. Chem Catalysis, 2021, 1(3): 663–680

[9] Yan Y, Ke L, Ding Y. . Recent advances in Cu-based catalysts for electroreduction of carbon dioxide. Materials Chemistry Frontiers, 2021, 5(6): 2668–2683

[10] Wang W, Han J, Sun Y. . Metal-free SeBN ternary-doped porous carbon as efficient electrocatalysts for CO₂ reduction reaction. ACS Applied Energy Materials, 2022, 5(9): 10518–10525

[11] Tan X, Yu C, Ren Y. . Recent advances in innovative strategies for the CO₂ electroreduction reaction. Energy & Environmental Science, 2021, 14(2): 765–780

[12] Han J, Ma J, Zhou J. . 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

[13] Wang J, Wang G, Zhang J. . Inversely tuning the CO₂ electroreduction and hydrogen evolution activity on metal oxide via heteroatom doping. Angewandte Chemie International Edition, 2021, 60(14): 7602–7606

[14] Kim D, Resasco J, Yu Y. . Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nature Communications, 2014, 5(1): 4948

[15] Zhu C, Kais S, Zeng X C. . 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

[16] Zhang Y, Wang X, Zheng S. . 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

[17] Zhao Y, Zhang X G, Bodappa N. . 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

[18] Mun Y, Lee S, Cho A. . 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

[19] Juntrapirom S, Santatiwongchai J, Watwiangkham A. . 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

[20] Zhong X, Liang S, Yang T. . Sn dopants with synergistic oxygen vacancies boost CO₂ electroreduction on CuO nanosheets to CO at low overpotential. ACS Nano, 2022, 16(11): 19210–19219

[21] Zhu Z, Yu Z L, Gao W Y. . Controlled synthesis of intermetallic Au₂Bi nanocrystals and Au₂Bi/Bi hetero-nanocrystals with promoted electrocatalytic CO₂ reduction properties. ChemSusChem, 2022, 15(10): 202200211

[22] Kuang S, Li M, Chen X. . Intermetallic CuAu nanoalloy for stable electrochemical CO₂ reduction. Chinese Chemical Letters, 2023, 34(7): 108013–108016

[23] Jia S, Zhu Q, Chu M. . Hierarchical metal-polymer hybrids for enhanced CO₂ electroreduction. Angewandte Chemie International Edition, 2021, 60(19): 10977–10982

[24] Awais M, Kamal S, Ijaz F. . Improved catalytic performance of aspergillus flavus laccase immobilized on the zinc ferrite nanoparticles. Catalysis Letters, 2023, 5(153): 1240–1249

[25] Yan S, Peng C, Yang C. . 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

[26] Chen M, Wan S, Zhong L. . Dynamic restructuring of Cu-doped SnS₂ nanoflowers for highly selective electrochemical CO₂ reduction to formate. Angewandte Chemie International Edition, 2021, 60(50): 26233–26237

[27] Nguyen D L T, Jee M S, Won D H. . Effect of halides on nanoporous Zn-based catalysts for highly efficient electroreduction of CO₂ to CO. Catalysis Communications, 2018, 114(114): 109–113

[28] Qin B, Li Y, Fu H. . 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

[29] Leverett J, Tran‐Phu T, Yuwono J A. . Tuning the coordination structure of Cu–N–C single atom catalysts for simultaneous electrochemical reduction of CO₂ and NO^3– to urea. Advanced Energy Materials, 2022, 12(32): 2201500–2201508

[30] Sirisomboonchai S, Machida H, Bao Tran K V. . 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

[31] Xu A, He B, Yu H. . 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

[32] Feng Y, Yang H, Zhang Y. . Te-doped Pd nanocrystal for electrochemical urea production by efficiently coupling carbon dioxide reduction with nitrite reduction. Nano Letters, 2020, 20(11): 8282–8289

[33] Chen D, Zhou Z, Feng C. . An upgraded lithium ion battery based on a polymeric separator incorporated with anode active materials. Advanced Energy Materials, 2019, 9(15): 1803627–1803637

[34] Li L, Jin X, Yu X. . Bimetallic Cu-Bi catalysts for efficient electroreduction of CO₂ to formate. Frontiers in Chemistry, 2022, 10(10): 983778

[35] Gao Y, Yu S, Zhou P. . Promoting electrocatalytic reduction of CO₂ to C₂H₄ production by inhibiting C₂H₅OH desorption from Cu₂O/C composite. Small, 2022, 18(9): 2105212

[36] Shan W, Liu R, Zhao H. . In situ surface-enhanced Raman spectroscopic evidence on the origin of selectivity in CO₂ electrocatalytic reduction. ACS Nano, 2020, 14(9): 11363–11372

[37] Hoang T T H, Verma S, Ma S. . 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

[38] Hu M, Cai Z, Yang S. . 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

[39] Ma Y, Yu J, Sun M. . Confined growth of silver-copper Janus nanostructures with 100 facets for highly selective tandem electrocatalytic carbon dioxide reduction. Advanced Materials, 2022, 34(19): 2110607

[40] Yan T, Wang P, Xu Z H. . Copper (II) frameworks with varied active site distribution for modulating selectivity of carbon dioxide electroreduction. ACS Applied Materials & Interfaces, 2022, 14(11): 13645–13652

[41] Sang J, Wei P, Liu T. . A reconstructed Cu₂P₂O₇ catalyst for selective CO₂ electroreduction to multicarbon products. Angewandte Chemie International Edition, 2022, 61(5): e202114238

[42] Xu J, Sun Y, Lu M. . 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

[43] Grosse P, Yoon A, Rettenmaier C. . Dynamic transformation of cubic copper catalysts during CO₂ electroreduction and its impact on catalytic selectivity. Nature Communications, 2021, 12(1): 6736–6746

[44] Kunze S, Tanase L C, Prieto M J. . Plasma-assisted oxidation of Cu(100) and Cu(111). Chemical Science, 2021, 12(42): 14241–14253

RIGHTS & PERMISSIONS

Higher Education Press 2023