Modulating Oxygen Affinity to Enhance Liquid Products for the Electrochemical Reduction of Carbon Monoxide

Abstract

Electrocatalytic CO reduction (COR) offers a promising alternative approach for synthesizing valuable chemicals, potentially at a lower carbon intensity as compared to conventional chemical production. Cu-based catalysts have shown encouraging selectivity and activity toward multi-carbon (C₂₊) products, albeit typically in the form of a mixture. Steering COR selectivity toward specific types of C₂₊ products, such as liquid products with high energy density, remains a challenge. In this study, we developed a Cu/Zn bimetallic catalyst composite and demonstrated enhanced selectivity toward liquid products as compared to reference CuO and Cu-based catalysts, approaching 60% at a high current density of 300 mA/cm². Our investigation highlights that the introduction of Zn promoted the emergence of a Cu/Zn heterojunction interface during COR. Density functional theory simulations were used to rationalize the observed differences in selectivity, revealing that interface plays a crucial role in diminishing the oxygen adsorption at the Cu-sites and modifying the adsorption energy of COR reaction intermediates, consequently leading to enhanced selectivity toward liquid products.

Keywords

C2 liquid production / CO ₂/CO reduction / copper/zinc / electrocatalysts / oxygen affinity

References

[1] H. Arakawa, M. Aresta, J. N. Armor, et al., “Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities,” Chemical Reviews 101, no. 4 (2001): 953–996.

[2] Y. Y. Birdja, E. Pérez-Gallent, M. C. Figueiredo, A. J. Göttle, F. Calle-Vallejo, and M. T. M. Koper, “Advances and Challenges in Understanding the Electrocatalytic Conversion of Carbon Dioxide to Fuels,” Nature Energy 4, no. 9 (2019): 732–745.

[3] E. S. Sanz-Pérez, C. R. Murdock, S. A. Didas, and C. W. Jones, “Direct Capture of CO₂ From Ambient Air,” Chemical Reviews 116, no. 19 (2016): 11840–11876.

[4] Y. Zhao, X. Liu, J. Chen, et al., “Promote Electroreduction of CO₂ via Catalyst Valence State Manipulation by Surface-Capping Ligand,” Proceedings of the National Academy of Sciences 120, no. 22 (2023): e2218040120.

[5] D. Raciti and C. Wang, “Recent Advances in CO₂ Reduction Electrocatalysis on Copper,” ACS Energy Letters 3, no. 7 (2018): 1545–1556.

[6] S. Nitopi, E. Bertheussen, S. B. Scott, et al., “Progress and Perspectives of Electrochemical CO₂ Reduction on Copper in Aqueous Electrolyte,” Chemical Reviews 119, no. 12 (2019): 7610–7672.

[7] G. Wang, J. Chen, Y. Ding, et al., “Electrocatalysis for CO₂ Conversion: From Fundamentals to Value-Added Products,” Chemical Society Reviews 50, no. 8 (2021): 4993–5061.

[8] W. Fu, Y. Li, J. Chen, et al., “Preserving Molecular Tuning for Enhanced Electrocatalytic CO₂-to-Ethanol Conversion,” Angewandte Chemie International Edition 63, no. 47 (2024): e202407992.

[9] S. Popović, M. Smiljanić, P. Jovanovič, J. Vavra, R. Buonsanti, and N. Hodnik, “Stability and Degradation Mechanisms of Copper-Based Catalysts for Electrochemical CO₂ Reduction,” Angewandte Chemie International Edition 59, no. 51 (2020): 14736–14746.

[10] K. P. Kuhl, E. R. Cave, D. N. Abram, and T. F. Jaramillo, “New Insights Into the Electrochemical Reduction of Carbon Dioxide on Metallic Copper Surfaces,” Energy & Environmental Science 5, no. 5 (2012): 7050.

[11] J. Yu, J. Wang, Y. Ma, et al., “Recent Progresses in Electrochemical Carbon Dioxide Reduction on Copper-Based Catalysts Toward Multicarbon Products,” Advanced Functional Materials 31, no. 37 (2021): 2102151.

[12] Y. Xiao, M. Wang, H. Yang, et al., “Multi-Shell Copper Catalysts for Selective Electroreduction of CO₂ to Multicarbon Chemicals,” Advanced Energy Materials 14, no. 1 (2024): 2302556.

[13] J. Chen, H. Qiu, Y. Zhao, et al., “Selective and Stable CO₂ Electroreduction at High Rates via Control of Local H₂O/CO₂ Ratio,” Nature Communications 15, no. 1 (2024): 5893.

[14] D. Ren, B. S.-H. Ang, and B. S. Yeo, “Tuning the Selectivity of Carbon Dioxide Electroreduction Toward Ethanol on Oxide-Derived Cu_xZn Catalysts,” ACS Catalysis 6, no. 12 (2016): 8239–8247.

[15] P. Wang, H. Yang, C. Tang, et al., “Boosting Electrocatalytic CO₂–to–Ethanol Production via Asymmetric C–C Coupling,” Nature Communications 13, no. 1 (2022): 3754.

[16] A. N. Kuhn, H. Zhao, U. O. Nwabara, et al., “Engineering Silver-Enriched Copper Core-Shell Electrocatalysts to Enhance the Production of Ethylene and C₂₊ Chemicals From Carbon Dioxide at Low Cell Potentials,” Advanced Functional Materials 31, no. 26 (2021): 2101668.

[17] D. Wang, H. D. Jung, S. Liu, et al., “Revealing the Structural Evolution of CuAg Composites During Electrochemical Carbon Monoxide Reduction,” Nature Communications 15, no. 1 (2024): 4692.

[18] C. G Morales-Guio, E. R. Cave, S. A. Nitopi, et al., “Improved CO₂ Reduction Activity Towards C₂₊ Alcohols on a Tandem Gold on Copper Electrocatalyst,” Nature Catalysis 1, no. 10 (2018): 764–771.

[19] S. Ma, M. Sadakiyo, M. Heima, et al., “Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu–Pd Catalysts With Different Mixing Patterns,” Journal of the American Chemical Society 139, no. 1 (2017): 47–50.

[20] J. Zeng, T. Rino, K. Bejtka, et al., “Coupled Copper–Zinc Catalysts for Electrochemical Reduction of Carbon Dioxide,” Chemsuschem 13, no. 16 (2020): 4128–4139.

[21] Y. Baek, H. Song, D. Hong, et al., “Electrochemical Carbon Dioxide Reduction on Copper–Zinc Alloys: Ethanol and Ethylene Selectivity Analysis,” Journal of Materials Chemistry A 10, no. 17 (2022): 9393–9401.

[22] S. B. Varandili, D. Stoian, J. Vavra, et al., “Elucidating the Structure-Dependent Selectivity of CuZn Towards Methane and Ethanol in CO₂ Electroreduction Using Tailored Cu/ZnO Precatalysts,” Chemical Science 12, no. 43 (2021): 14484–14493.

[23] J. Chen, L. Chen, J. Chen, et al., “Enhancing CO Diffusion for Selective Acetate Production via CO Reduction on Copper Catalyst,” Applied Catalysis, B: Environmental 343 (2024): 123551.

[24] W. Wei, X. Feng, R. Wang, R. Zheng, D. Yang, and H. Chen, “Electrochemical Driven Phase Segregation Enabled Dual-Ion Removal Battery Deionization Electrode,” Nano Letters 21, no. 11 (2021): 4830–4837.

[25] K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, and R. G. Hennig, “Implicit Solvation Model for Density-Functional Study of Nanocrystal Surfaces and Reaction Pathways,” Journal of Chemical Physics 140, no. 8 (2014): 084106.

[26] K. Mathew, V. S. C. Kolluru, S. Mula, S. N. Steinmann, and R. G. Hennig, “Implicit Self-Consistent Electrolyte Model in Plane-Wave Density-Functional Theory,” Journal of Chemical Physics 151, no. 23 (2019): 234101.

[27] W. Zhang, S. Ding, Z. Yang, et al., “Growth of Novel Nanostructured Copper Oxide (CuO) Films on Copper Foil,” Journal of Crystal Growth 291, no. 2 (2006): 479–484.

[28] D. Raoufi and T. Raoufi, “The Effect of Heat Treatment on the Physical Properties of Sol–Gel Derived ZnO Thin Films,” Applied Surface Science 255, no. 11 (2009): 5812–5817.

[29] S. Park, S. An, H. Ko, C. Jin, and C. Lee, “Synthesis of Nanograined ZnO Nanowires and Their Enhanced Gas Sensing Properties,” ACS Applied Materials & Interfaces 4, no. 7 (2012): 3650–3656.

[30] D. P. Volanti, M. O. Orlandi, J. Andrés, and E. Longo, “Efficient Microwave-Assisted Hydrothermal Synthesis of CuO Sea Urchin-Like Architectures via a Mesoscale Self-Assembly,” CrystEngComm 12, no. 6 (2010): 1696.

[31] J.-J. Lv, M. Jouny, W. Luc, W. Zhu, J. J. Zhu, and F. Jiao, “A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction,” Advanced Materials 30, no. 49 (2018): 1803111.

[32] Y. Zhang, G. Du, X. Wang, et al., “X-Ray Photoelectron Spectroscopy Study of ZnO Films Grown by Metal-Organic Chemical Vapor Deposition,” Journal of Crystal Growth 252, no. 1–3 (2003): 180–183.

[33] A. A. Gabrienko, S. S. Arzumanov, A. V. Toktarev, et al., “Different Efficiency of Zn²⁺ and ZnO Species for Methane Activation on Zn-Modified Zeolite,” ACS Catalysis 7, no. 3 (2017): 1818–1830.

[34] P. Wei, D. Gao, T. Liu, et al., “Coverage-Driven Selectivity Switch From Ethylene to Acetate in High-Rate CO₂/CO Electrolysis,” Nature Nanotechnology 18, no. 3 (2023): 299–306.

[35] D. Grandjean, H. L. Castricum, J. C. van den Heuvel, and B. M. Weckhuysen, “Highly Mixed Phases in Ball-Milled Cu/ZnO Catalysts: An EXAFS and XANES Study,” Journal of Physical Chemistry B 110, no. 34 (2006): 16892–16901.

[36] S. Thomas, I. S. Cole, M. Sridhar, and N. Birbilis, “Revisiting Zinc Passivation in Alkaline Solutions,” Electrochimica Acta 97 (2013): 192–201.

[37] J. Chen and L. Wang, “Effects of the Catalyst Dynamic Changes and Influence of the Reaction Environment on the Performance of Electrochemical CO₂ Reduction,” Advanced Materials 34, no. 25 (2022): 2103900.

[38] L. Chen, J. Chen, L. Fan, et al., “Additive-Assisted Electrodeposition of Cu on Gas Diffusion Electrodes Enables Selective CO₂ Reduction to Multicarbon Products,” ACS Catalysis 13, no. 18 (2023): 11934–11944.

[39] Y. Zhao, Y. Li, J. Chen, et al., “Cu/LaF₃ Interfaces Boost Electrocatalytic CO-to-Acetate Conversion,” ACS Catalysis 14, no. 11 (2024): 8366–8375.

[40] H. Yang, N. Guo, S. Xi, et al., “Potential-Driven Structural Distortion in Cobalt Phthalocyanine for Electrocatalytic CO₂/CO Reduction Towards Methanol,” Nature Communications 15, no. 1 (2024): 7703.

[41] S. Chen, Y. Su, P. Deng, et al., “Highly Selective Carbon Dioxide Electroreduction on Structure-Evolved Copper Perovskite Oxide Toward Methane Production,” ACS Catalysis 10, no. 8 (2020): 4640–4646.

[42] G. A. Cerrón-Calle, A. S. Fajardo, C. M. Sánchez-Sánchez, and S. Garcia-Segura, “Highly Reactive Cu-Pt Bimetallic 3D-Electrocatalyst for Selective Nitrate Reduction to Ammonia,” Applied Catalysis, B: Environmental 302 (2022): 120844.

[43] S. S. Shinde, N. K. Wagh, C. H. Lee, et al., “Scaling-Up Insights for Zinc–Air Battery Technologies Realizing Reversible Zinc Anodes,” Advanced Materials 35, no. 48 (2023): 2303509.

[44] C.-J. Chang, S.-F. Hung, C.-S. Hsu, et al., “Quantitatively Unraveling the Redox Shuttle of Spontaneous Oxidation/Electroreduction of CuO_x on Silver Nanowires Using In Situ X-Ray Absorption Spectroscopy,” ACS Central Science 5, no. 12 (2019): 1998–2009.

[45] S.-C. Lin, C.-C. Chang, S.-Y. Chiu, et al., “Operando Time-Resolved X-Ray Absorption Spectroscopy Reveals the Chemical Nature Enabling Highly Selective CO₂ Reduction,” Nature Communications 11, no. 1 (2020): 3525.

[46] Y. Zeng, X. Zhang, R. Qin, et al., “Dendrite-Free Zinc Deposition Induced by Multifunctional CNT Frameworks for Stable Flexible Zn-Ion Batteries,” Advanced Materials 31, no. 36 (2019): 1903675.

[47] S. J. Kim, Y. I. Kim, B. Lamichhane, et al., “Flat-Surface-Assisted and Self-Regulated Oxidation Resistance of Cu(111),” Nature 603, no. 7901 (2022): 434–438.

[48] R. Kortlever, J. Shen, K. J. P. Schouten, F. Calle-Vallejo, and M. T. M. Koper, “Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide,” Journal of Physical Chemistry Letters 6, no. 20 (2015): 4073–4082.

[49] F. Calle-Vallejo and M. T. M. Koper, “Theoretical Considerations on the Electroreduction of CO to C₂ Species on Cu(100) Electrodes,” Angewandte Chemie International Edition 52, no. 28 (2013): 7282–7285.

[50] P. Deshlahra, E. E. Wolf, and W. F. Schneider, “A Periodic Density Functional Theory Analysis of CO Chemisorption on Pt(111) in the Presence of Uniform Electric Fields,” Journal of Physical Chemistry A 113, no. 16 (2009): 4125–4133.

[51] H. Zhang, W. A. Goddard, Q. Lu, and M.-J. Cheng, “The Importance of Grand-Canonical Quantum Mechanical Methods to Describe the Effect of Electrode Potential on the Stability of Intermediates Involved in Both Electrochemical CO₂ Reduction and Hydrogen Evolution,” Physical Chemistry Chemical Physics 20, no. 4 (2018): 2549–2557.

[52] D. Cheng, Z.-J. Zhao, G. Zhang, et al., “The Nature of Active Sites for Carbon Dioxide Electroreduction Over Oxide-Derived Copper Catalysts,” Nature Communications 12, no. 1 (2021): 395.

[53] Y. Zheng, A. Vasileff, X. Zhou, Y. Jiao, M. Jaroniec, and S. Z. Qiao, “Understanding the Roadmap for Electrochemical Reduction of CO₂ to Multi-Carbon Oxygenates and Hydrocarbons on Copper-Based Catalysts,” Journal of the American Chemical Society 141, no. 19 (2019): 7646–7659.

[54] H. H. Heenen, H. Shin, G. Kastlunger, et al., “The Mechanism for Acetate Formation in Electrochemical CO₂ Reduction on Cu: Selectivity With Potential, pH, and Nanostructuring,” Energy & Environmental Science 15, no. 9 (2022): 3978.

[55] M. Jun, D. Kim, M. Kim, M. Kim, T. Kwon, and K. Lee, “Polymer-Covered Copper Catalysts Alter the Reaction Pathway of the Electrochemical CO₂ Reduction Reaction,” ACS Omega 7, no. 47 (2022): 42655–42663.

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