Pseudo-copper Ni–Zn alloy catalysts for carbon dioxide reduction to C₂ products

Abstract

Electrocatalytic CO₂ reduction reaction (CO2RR) to obtain C₂ products has drawn widespread attentions. Copper-based materials are the most reported catalysts for CO₂ reduction to C₂ products. Design of high-efficiency pseudo-copper catalysts according to the key characteristics of copper (Cu) is an important strategy to understand the reaction mechanism of C₂ products. In this work, density function theory (DFT) calculations are used to predict nickel–zinc (NiZn) alloy catalysts with the criteria similar structure and intermediate adsorption property to Cu catalyst. The calculated tops of 3d states of NiZn3(001) catalysts are the same as Cu(100), which is the key parameter affecting the adsorption of intermediate products. As a result, NiZn3(001) exhibits similar adsorption properties with Cu(100) on the crucial intermediates *CO₂, *CO and *H. Moreover, we further studied CO formation, CO hydrogenation and C–C coupling process on Ni–Zn alloys. The free energy profile of C₂ products formation shows that the energy barrier of C₂ products formation on NiZn3(001) is even lower than Cu(100). These results indicate that NiZn3 alloy as pseudo-copper catalyst can exhibit a higher catalytic activity and selectivity of C₂ products during CO₂RR. This work proposes a feasible pseudo-copper catalyst and provides guidance to design high-efficiency catalysts for CO₂RR to C₂ or multi-carbon products.

Graphical abstract

Keywords

pseudo-copper catalysts / surface and electronic structure / adsorption abilities / Ni–Zn alloys / CO₂RR C₂ products / DFT

References

[1] Z. Cui, W. Du, C. Xiao, Q. Li, R. Sa, C. Sun, and Z. Ma, Enhancing hydrogen evolution of MoS₂ Basal planes by combining single-boron catalyst and compressive strain, Front. Phys. 15(6), 63502 (2020)

[2] K. Chen, H. Li, Y. Xu, K. Liu, H. Li, X. Xu, X. Qiu, and M. Liu, Untying thioether bond structures enabled by “voltage-scissors” for stable room temperature sodiumsulfur batteries, Nanoscale 11(13), 5967 (2019)

[3] X. Li, Y. B. Zhao, F. Fan, L. Levina, M. Liu, R. Quintero-Bermudez, X. Gong, L. N. Quan, J. Fan, Z. Yang, S. Hoogland, O. Voznyy, Z. H. Lu, and E. H. Sargent, Bright colloidal quantum dot light-emitting diodes enabled by efficient chlorination, Nat. Photon. 12(3), 159 (2018)

[4] Y. Wei, G. Xing, K. Liu, G. Li, P. Dang, S. Liang, M. Liu, Z. Cheng, D. Jin, and J. Lin, New strategy for designing orangish-red-emitting phosphor via oxygen-vacancyinduced electronic localization, Light Sci. Appl. 8(1), 15 (2019)

[5] K. Chen, W. Fan, C. Huang, and X. Qiu, Enhanced stability and catalytic activity of bismuth nanoparticles by modified with porous silica, J. Phys. Chem. Solids 110, 9 (2017)

[6] Q. Li, S. Qiu, and B. Jia, Theoretical investigation of CoTa₂O₆/graphene heterojunctions for oxygen evolution reaction, Front. Phys. 16(1), 13503 (2021)

[7] Z. Q. Wang, T. Y. Lü, H. Q. Wang, Y. P. Feng, and J. C. Zheng, Review of borophene and its potential applications, Front. Phys. 14(3), 33403 (2019)

[8] Y. H. Lui, B. Zhang, and S. Hu, Rational design of photoelectrodes for photoelectrochemical water splitting and CO₂ reduction, Front. Phys. 14(5), 53402 (2019)

[9] J. Fu, K. Jiang, X. Qiu, J. Yu, and M. Liu, Product selectivity of photocatalytic CO₂ reduction reactions, Mater. Today 32, 222 (2020)

[10] J. Fu, K. Liu, K. Jiang, H. Li, P. An, W. Li, N. Zhang, H. Li, X. Xu, H. Zhou, D. Tang, X. Wang, X. Qiu, and M. Liu, Graphitic carbon nitride with dopant induced charge localization for enhanced photoreduction of CO₂ to CH₄, Adv. Sci. 6(18), 1900796 (2019)

[11] J. Fu, S. Wang, Z. Wang, K. Liu, H. Li, H. Liu, J. Hu, X. Xu, H. Li, and M. Liu, Graphitic carbon nitride based single-atom photocatalysts, Front. Phys. 15(3), 33201 (2020)

[12] R. Kas, R. Kortlever, H. Yilmaz, M. T. M. Koper, and G. Mul, Manipulating the hydrocarbon selectivity of copper nanoparticles in CO₂ electroreduction by process conditions, ChemElectroChem 2(3), 354 (2015)

[13] M. Zhong, K. Tran, Y. Min, C. Wang, Z. Wang, C. T. Dinh, P. De Luna, Z. Yu, A. S. Rasouli, P. Brodersen, S. Sun, O. Voznyy, C. S. Tan, M. Askerka, F. Che, M. Liu, A. Seifitokaldani, Y. Pang, S. C. Lo, A. Ip, Z. Ulissi, and E. H. Sargent, Accelerated discovery of CO₂ electrocatalysts using active machine learning, Nature 581(7807), 178 (2020)

[14] R. Reske, M. Duca, M. Oezaslan, K. J. P. Schouten, M. T. M. Koper, and P. Strassert, Controlling catalytic selectivities during CO₂ electroreduction on thin Cu metal overlayers, J. Phys. Chem. Lett. 4(15), 2410 (2013)

[15] F. Calle-Vallejo and M. T. Koper, Theoretical considerations on the electroreduction of CO to C₂ species on Cu(100) electrodes, Angew. Chem. Int. Ed. 52(28), 7282 (2013)

[16] X. Wang, Z. Wang, F. P. García de Arquer, C. T. Dinh, A. Ozden, Y. C. Li, D. H. Nam, J. Li, Y. S. Liu, J. Wicks, Z. Chen, M. Chi, B. Chen, Y. Wang, J. Tam, J. Y. Howe, A. Proppe, P. Todorović, F. Li, T. T. Zhuang, C. M. Gabardo, A. R. Kirmani, C. McCallum, S. F. Hung, Y. Lum, M. Luo, Y. Min, A. Xu, C. P. O’Brien, B. Stephen, B. Sun, A. H. Ip, L. J. Richter, S. O. Kelley, D. Sinton, and E. H. Sargent, Efficient electrically powered CO₂-to-ethanol via suppression of deoxygenation, Nat. Energy 5(6), 478 (2020)

[17] P. An, L. Wei, H. Li, B. Yang, K. Liu, J. Fu, H. Li, H. Liu, J. Hu, Y. R. Lu, H. Pan, T. S. Chan, N. Zhang, and M. Liu, Enhancing CO₂ reduction by suppressing hydrogen evolution with polytetrafluoroethylene protected copper nanoneedles, J. Mater. Chem. A 8(31), 15936 (2020)

[18] H. Zhou, K. Liu, H. Li, M. Cao, J. Fu, X. Gao, J. Hu, W. Li, H. Pan, J. Zhan, Q. Li, X. Qiu, and M. Liu, Recent advances in different-dimension electrocatalysts for carbon dioxide reduction, J. Colloid Interface Sci. 550, 17 (2019)

[19] Y. Zhou, F. Che, M. Liu, C. Zou, Z. Liang, P. De Luna, H. Yuan, J. Li, Z. Wang, H. Xie, H. Li, P. Chen, E. Bladt, R. Quintero-Bermudez, T. K. Sham, S. Bals, J. Hofkens, D. Sinton, G. Chen, and E. H. Sargent, Dopant-induced electron localization drives CO₂ reduction to C2 hydrocarbons, Nat. Chem. 10(9), 974 (2018)

[20] S. Nitopi, E. Bertheussen, S. B. Scott, X. Liu, A. K. Engstfeld, S. Horch, B. Seger, I. E. L. Stephens, K. Chan, C. Hahn, J. K. Norskov, T. F. Jaramillo, and I. Chorkendorff, Progress and perspectives of electrochemical CO₂ reduction on copper in aqueous electrolyte, Chem. Rev. 119(12), 7610 (2019)

[21] 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, Nat. Energy 4(9), 732 (2019)

[22] W. Luo, X. Nie, M. J. Janik, and A. Asthagiri, Facet dependence of CO₂ reduction paths on Cu electrodes, ACS Catal. 6(1), 219 (2016)

[23] H. Li, F. Calle-Vallejo, M. J. Kolb, Y. Kwon, Y. Li, and M. T. Koper, Why (1 0 0) terraces break and make bonds: Oxidation of dimethyl ether on platinum single-crystal electrodes, J. Am. Chem. Soc. 135(38), 14329 (2013)

[24] M. T. Koper, Structure sensitivity and nanoscale effects in electrocatalysis, Nanoscale 3(5), 2054 (2011)

[25] X. G. Zhang, S. Feng, C. Zhan, D. Y. Wu, Y. Zhao, and Z. Q. Tian, Electroreduction reaction mechanism of carbon dioxide to C₂ products via Cu/Au bimetallic catalysis: A theoretical prediction, J. Phys. Chem. Lett. 11(16), 6593 (2020)

[26] Z. X. Chen, K. M. Neyman, A. B. Gordienko, and N. Rösch, Surface structure and stability of PdZn and PtZn alloys: Density-functional slab model studies, Phys. Rev. B 68(7), 075417 (2003)

[27] D. Kim, J. Resasco, Y. Yu, A. M. Asiri, and P. Yang, Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold-copper bimetallic nanoparticles, Nat. Commun. 5(1), 4948 (2014)

[28] A. Nilsson, L. G. M. Pettersson, B. Hammer, T. Bligaard, C. H. Christensen, and J. K. Nørskov, The electronic structure effect in heterogeneous catalysis, Catal. Lett. 100(3–4), 111 (2005)

[29] J. K. Norskov, F. Abild-Pedersen, F. Studt, and T. Bligaard, Density functional theory in surface chemistry and catalysis, Proc. Natl. Acad. Sci. USA 108(3), 937 (2011)

[30] M. Luo, Z. Wang, Y. C.Li, J. Li, F. Li, Y. Lum, D. H. Nam, B. Chen, J. Wicks, A. Xu, T. Zhuang, W. R. Leow, X. Wang, C. T. Dinh, Y. Wang, Y. Wang, D. Sinton, and E. H. Sargent, Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen, Nat. Commun. 10(1), 5814 (2019)

[31] A. Bagger, W. Ju, A. S. Varela, P. Strasser, and J. Rossmeisl, Electrochemical CO₂ reduction: A classification problem, ChemPhysChem 18(22), 3266 (2017)

[32] 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, J. Am. Chem. Soc. 141(19), 7646 (2019)

[33] Z. Zhao and G. Lu, Computational screening of nearsurface alloys for CO₂ electroreduction, ACS Catal. 8(5), 3885 (2018)

[34] S. Lee, G. Park, and J. Lee, Importance of Ag–Cu biphasic boundaries for selective electrochemical reduction of CO₂ to ethanol, ACS Catal. 7(12), 8594 (2017)

[35] X. Lv, L. Shang, S. Zhou, S. Li, Y. Wang, Z. Wang, T. K. Sham, C. Peng, and G. Zheng, Electron-deficient Cu sites on Cu₃Ag1 catalyst promoting CO₂ electroreduction to alcohols, Adv. Energy Mater. 10(37), 2001987 (2020)

[36] D. Ren, B. S. H. Ang, and B. S. Yeo, Tuning the selectivity of carbon dioxide electroreduction toward ethanol on oxide-derived CuxZn catalysts, ACS Catal. 6(12), 8239 (2016)

[37] H. S. Jeon, J. Timoshenko, F. Scholten, I. Sinev, A. Herzog, F. T. Haase, and B. R. Cuenya, Operando insight into the correlation between the structure and composition of CuZn nanoparticles and their selectivity for the electrochemical CO₂ reduction, J. Am. Chem. Soc. 141(50), 19879 (2019)

[38] A. R. Paris and A. B. Bocarsly, Ni–Al films on glassy carbon electrodes generate an array of oxygenated organics from CO₂, ACS Catal. 7(10), 6815 (2017)

[39] A. R. Paris and A. B. Bocarsly, Mechanistic insights into C2 and C₃ product generation using Ni₃Al and Ni₃Ga electrocatalysts for CO₂ reduction, Faraday Discuss. 215, 192 (2019)

[40] D. A. Torelli, S. A. Francis, J. C. Crompton, A. Javier, J. R. Thompson, B. S. Brunschwig, M. P. Soriaga, and N. S. Lewis, Nickel–gallium-catalyzed electrochemical reduction of CO₂ to highly reduced products at low overpotentials, ACS Catal. 6(3), 2100 (2016)

[41] R. Kortlever, I. Peters, C. Balemans, R. Kas, Y. Kwon, G. Mul, and M. T. Koper, Palladium-gold catalyst for the electrochemical reduction of CO₂ to C1–C₅ hydrocarbons, Chem. Commun. (Camb.) 52(67), 10229 (2016)

[42] K. J. P. Schouten, E. Pérez Gallent, and M. T. M. Koper, Structure sensitivity of the electrochemical reduction of carbon monoxide on copper single crystals, ACS Catal. 3(6), 1292 (2013)

[43] H. A. Hansen, C. Shi, A. C. Lausche, A. A. Peterson, and J. K. Norskov, Bifunctional alloys for the electroreduction of CO₂ and CO, Phys. Chem. Chem. Phys. 18(13), 9194 (2016)

[44] M. J. Cheng, E. L. Clark, H. H. Pham, A. T. Bell, and M. Head-Gordon, Quantum mechanical screening of singleatom bimetallic alloys for the selective reduction of CO₂ to C1 hydrocarbons, ACS Catal. 6(11), 7769 (2016)

[45] A. Vasileff, C. Xu, Y. Jiao, Y. Zheng, and S. Z. Qiao, Surface and interface engineering in copper-based bimetallic materials for selective CO₂ electroreduction, Chem 4(8), 1809 (2018)

[46] M. Karamad, V. Tripkovic, and J. Rossmeisl, Intermetallic alloys as CO electroreduction catalysts — Role of isolated active sites, ACS Catal. 4(7), 2268 (2014)

[47] Y. Cai and X. Luo, First-principles investigation of carbon dioxide adsorption on MN₄ doped graphene, AIP Adv. 10(12), 125013 (2020)

[48] A. C. Hegde, K. Venkatakrishna, and N. Eliaz, Electrodeposition of Zn–Ni, Zn–Fe and Zn–Ni–Fe alloys, Surf. Coat. Tech. 205(7), 2031 (2010)

[49] G. Kresse and J. Hafner, Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium, Phys. Rev. B 49(20), 14251 (1994)

[50] G. Kresse and J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54(16), 11169 (1996)

[51] G. Kresses and J. Hafner, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6(1), 15 (1996)

[52] J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation, Phys. Rev. B 46(11), 6671 (1992)

[53] K. Liu, J. Fu, L. Zhu, X. Zhang, H. Li, H. Liu, J. Hu, and M. Liu, Single-atom transition metals supported on black phosphorene for electrochemical nitrogen reduction, Nanoscale 12(8), 4903 (2020)

[54] J. K. Nörskov, T. Bligaard, J. Rossmeisl, and C. H. Christensen, Towards the computational design of solid catalysts, Nat. Chem. 1(1), 37 (2009)

[55] J. Li, Z. Wang, C. McCallum, Y. Xu, F. Li, Y. Wang, C. M. Gabardo, C. T. Dinh, T. T. Zhuang, L. Wang, J. Y. Howe, Y. Ren, E. H. Sargent, and D. Sinton, Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction, Nat. Catal. 2(12), 1124 (2019)

[56] T. K. Todorova, M. W. Schreiber, and M. Fontecave, Mechanistic understanding of CO₂ reduction reaction (CO₂RR) toward multicarbon products by heterogeneous copper-based catalysts, ACS Catal. 10(3), 1754 (2020)

[57] D. D. Zhu, J. L. Liu, and S. Z. Qiao, Recent advances in inorganic heterogeneous electrocatalysts for reduction of carbon dioxide, Adv. Mater. 28(18), 3423 (2016)

[58] S. Hanselman, M. T. M. Koper, and F. Calle-Vallejo, Computational comparison of late transition metal (100) surfaces for the electrocatalytic reduction of CO to C₂ species, ACS Energy Lett. 3(5), 1062 (2018)

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