Alloying Cu, Fe, and Co in Ni/YSZ Electrodes for High-Temperature CO₂ Electrolysis: Impact on TPB Density, Activity, and Carbon Deposition Resistance

Abstract

Electrochemical CO₂ reduction using solid oxide electrolysis cells (SOECs) directly converts CO₂ into value-added chemicals, mitigating greenhouse-gas emissions. Nickel (Ni) is the conventionally used fuel-electrode electrocatalyst, yet its intrinsic catalytic behavior is underexplored. This study systematically evaluates Ni alloyed with 5 at% Fe, Co, or Cu for changes in microstructure, electrochemical activity, and carbon coking resistance. Model electrodes fabricated by pulsed laser deposition are analyzed by scanning and transmission electron microscopy, X-ray diffraction, and X-ray absorption spectroscopy, which confirm homogeneous alloy formation and show that additive metals modulate active site density by modulating sintering behavior, thereby tuning the triple-phase-boundary density in the order Ni > Ni–Cu > Ni–Co > Ni–Fe. Electrochemical impedance spectroscopy reveals that the apparent activation energy (E_a) related to surface reaction decreases for all samples, accelerating CO₂ electrolysis, while sensitivity to the CO/CO₂ ratio rises when the alloying element is less prone to CO₂ dissociation. Diffuse reflectance Fourier-transform infrared spectroscopy and density functional theory calculations indicate that Co and Fe facilitate CO₂ dissociation, whereas Cu facilitates fast desorption of product species and enhances turnover activity. Cu alloying markedly suppresses carbon coking, whereas Co exacerbates it. Enhanced performance and durability are validated by impedance and Galvano-static measurements. These findings demonstrate that Ni–Cu alloy electrodes offer a practical route to boost SOEC efficiency and mitigate coking with minimal structural change.

Keywords

alloy catalyst / carbon deposition / CO₂ electrolysis / electrochemical CO₂ conversion / solid oxide electrolysis cells

References

[1] Q. Zhu, “Developments on CO₂-Utilization Technologies,” Clean Energy 3, no. 2 (2019): 85–100.

[2] 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.

[3] A. Hauch, R. Küngas, P. Blennow, et al., “Recent Advances in Solid Oxide Cell Technology for Electrolysis,” Science 370, no. 6513 (2020): eaba6118.

[4] L. Wang, Y. Zhang, M. Pérez-Fortes, et al., “Reversible Solid-Oxide Cell Stack Based Power-To-X-To-Power Systems: Comparison of Thermodynamic Performance,” Applied Energy 275 (2020): 115330.

[5] R. Küngas, “Review—Electrochemical CO₂ Reduction for CO Production: Comparison of Low- and High-Temperature Electrolysis Technologies,” Journal of the Electrochemical Society 167, no. 4 (2020): 044508.

[6] K. Ghaib and F.-Z. Ben-Fares, “Power-To-Methane: A State-Of-The-Art Review,” Renewable and Sustainable Energy Reviews 81 (2018): 433–446.

[7] M. S. Khan, Z. Lin, L. Lin, M. Abid, H. M. Ali, and C. Chen, “Techno-Economic Analysis of Solar-Driven Co-Electrolysis for Renewable Methanol Production Using Soec,” Energy Conversion and Management 302 (2024): 118129.

[8] S. Ali, K. Sørensen, and M. P. Nielsen, “Modeling a Novel Combined Solid Oxide Electrolysis Cell (SOEC)-Biomass Gasification Renewable Methanol Production System,” Renewable Energy 154 (2020): 1025–1034.

[9] R. G. Grim, D. Ravikumar, E. C. Tan, et al., “Electrifying the Production of Sustainable Aviation Fuel: The Risks, Economics, and Environmental Benefits of Emerging Pathways Including CO₂,” Energy & Environmental Science 15, no. 11 (2022): 4798–4812.

[10] Y. Zhou, S. Searle, and N. Pavlenko, “Current and Future Cost of e-Kerosene in the United States and Europe. I: International Council on Clean,” Transportation Working Paper. (2022), 14.

[11] R. J. Detz, C. J. Ferchaud, A. J. Kalkman, et al., “Electrochemical CO₂ Conversion Technologies: State-Of-The-Art and Future Perspectives,” Sustainable Energy & Fuels 7, no. 23 (2023): 5445–5472.

[12] C. P. O'Brien, R. K. Miao, A. Shayesteh Zeraati, G. Lee, E. H. Sargent, and D. Sinton, “CO₂ Electrolyzers,” Chemical Reviews 124, no. 7 (2024): 3648–3693.

[13] P. Su-Ungkavatin, L. Tiruta-Barna, and L. Hamelin, “Biofuels, Electrofuels, Electric or Hydrogen?: A Review of Current and Emerging Sustainable Aviation Systems,” Progress in Energy and Combustion Science 96 (2023): 101073.

[14] T. L. Skafte, P. Blennow, J. Hjelm, and C. Graves, “Carbon Deposition and Sulfur Poisoning During CO₂ Electrolysis in Nickel-Based Solid Oxide Cell Electrodes,” Journal of Power Sources 373 (2018): 54–60.

[15] A. K. Clausen, M. Traulsen, P. V. Hendriksen, X. Sun, and A. Hauch, “CGO-Infiltrated Ni/YSZ SOEC Fuel Electrodes for Increased Carbon Tolerance During CO₂ Electrolysis,” ECS Transactions 103, no. 1 (2021): 1945–1954.

[16] H. Wang, F. Jiang, X. Wang, L. Ye, and K. Xie, “Enhanced CO₂ Electrolysis With the Modification of Ni–YSZ Cathodes by SDC in Microtubular Solid Oxide Electrolysis Cells,” Energy & Fuels 36, no. 21 (2022): 13195–13202.

[17] S. A. Barnett, B.-K. Park, and R. Scipioni, “Effect of Infiltration on Performance of Ni-YSZ Fuel Electrodes,” ECS Transactions 91, no. 1 (2019): 1791–1797.

[18] B.-K. Park, R. Scipioni, D. Cox, and S. A. Barnett, “Enhancement of Ni–(Y₂O₃)_0.08(ZrO₂)_0.92 Fuel Electrode Performance by Infiltration of Ce_0.8Gd_0.2O_2−δ Nanoparticles,” Journal of Materials Chemistry A 8, no. 7 (2020): 4099–4106.

[19] P. J. Gasper, Y. Lu, A. Y. Nikiforov, S. N. Basu, S. Gopalan, and U. B. Pal, “Detailed Electrochemical Performance and Microstructural Characterization of Nickel–Yttria Stabilized Zirconia Cermet Anodes Infiltrated With Nickel, Gadolinium Doped Ceria, and Nickel–Gadolinium Doped Ceria Nanoparticles,” Journal of Power Sources 447 (2020): 227357.

[20] S.-W. Kim, M. Park, H. Kim, et al., “Catalytic Effect of Pd-Ni Bimetallic Catalysts on High-Temperature Co-Electrolysis of Steam/CO₂ Mixtures,” Journal of the Electrochemical Society 163, no. 11 (2016): F3171–F3178.

[21] P. Błaszczak, M. Zając, A. Ducka, et al., “High-Temperature Co-Electrolysis of CO₂/H₂O and Direct Methanation Over Co-Impregnated SOEC. Bimetallic Synergy Between Co and Ni,” International Journal of Hydrogen Energy 47, no. 82 (2022): 35017–35037.

[22] H. Y. Jeong, S. W. Kim, Y. Bae, K. J. Yoon, J. H. Lee, and J. Hong, “Effect of Fe Infiltration to Ni/YSZ Solid-Oxide-Cell Fuel Electrode on Steam/CO₂ Co-Electrolysis,” International Journal of Energy Research 43, no. 9 (2019): 4949–4958.

[23] C. M. Grgicak, M. M. Pakulska, J. S. O'Brien, and J. B. Giorgi, “Synergistic Effects of Ni_1−xCo_x-YSZ and Ni_1−xCu_x-YSZ Alloyed Cermet SOFC Anodes for Oxidation of Hydrogen and Methane Fuels Containing H₂S,” Journal of Power Sources 183, no. 1 (2008): 26–33.

[24] D. Chen, J. Zhang, M. Barreau, et al., “Ni-Doped CeO₂ Nanoparticles to Promote and Restore the Performance of Ni/YSZ Cathodes for CO₂ Electroreduction,” Applied Surface Science 611 (2023): 155767.

[25] M. Zheng, S. Wang, Y. Yang, and C. Xia, “Barium Carbonate as a Synergistic Catalyst for the H₂O/CO₂ Reduction Reaction at Ni–Yttria Stabilized Zirconia Cathodes for Solid Oxide Electrolysis Cells,” Journal of Materials Chemistry A 6, no. 6 (2018): 2721–2729.

[26] Y. Song, Z. Zhou, X. Zhang, et al., “Pure CO₂ Electrolysis Over an Ni/YSZ Cathode in a Solid Oxide Electrolysis Cell,” Journal of Materials Chemistry A 6, no. 28 (2018): 13661–13667.

[27] Y. Chen, J. Bunch, C. Jin, C. Yang, and F. Chen, “Performance Enhancement of Ni-YSZ Electrode by Impregnation of Mo_0.1Ce_0.9O_2+δ,” Journal of Power Sources 204 (2012): 40–45.

[28] S. Liu, Q. Liu, and J.-L. Luo, “CO₂-to-Co Conversion on Layered Perovskite With In Situ Exsolved Co–Fe Alloy Nanoparticles: An Active and Stable Cathode for Solid Oxide Electrolysis Cells,” Journal of Materials Chemistry A 4, no. 44 (2016): 17521–17528.

[29] S. W. Lee, T. H. Nam, M. Kim, et al., “Enhancing CO₂ Electrolysis Performance With Various Metal Additives (Co, Fe, Ni, and Ru)–Decorating the La(Sr)Fe(Mn)O₃ Cathode In Solid Oxide Electrolysis Cells,” Inorganic Chemistry Frontiers 10, no. 12 (2023): 3536–3543.

[30] M. Li, J. Hou, Y. Fan, X. Xi, X.-Z. Fu, and J.-L. Luo, “Interface Modification of Ru-CeO₂ Co-Infiltrated SFM Electrode and Construction of SDC/YSZ Bilayer Electrolyte for Direct CO₂ Electrolysis,” Electrochimica Acta 426 (2022): 140771.

[31] W. Wang, H. Li, C. Y. Regalado Vera, et al., “Improving the Performance for Direct Electrolysis of CO₂ in Solid Oxide Electrolysis Cells With a Sr_1.9Fe_1.5Mo_0.5O_6−δ Electrode via Infiltration of Pr₆O₁₁ Nanoparticles,” Journal of Materials Chemistry A 11, no. 16 (2023): 9039–9048.

[32] J. K. Nørskov, F. Studt, F. Abild-Pedersen, and T. Bligaard, Fundamental Concepts in Heterogeneous Catalysis (John Wiley & Sons, 2014).

[33] A. Logadottir, T. H. Rod, J. K. Nørskov, B. Hammer, S. Dahl, and C. J. H. Jacobsen, “The Brønsted–Evans–Polanyi Relation and the Volcano Plot for Ammonia Synthesis Over Transition Metal Catalysts,” Journal of Catalysis 197, no. 2 (2001): 229–231.

[34] I. E. L. Stephens, A. S. Bondarenko, F. J. Perez-Alonso, et al., “Tuning the Activity of Pt (111) for Oxygen Electroreduction by Subsurface Alloying,” Journal of the American Chemical Society 133, no. 14 (2011): 5485–5491.

[35] M. Escudero-Escribano, P. Malacrida, M. H. Hansen, et al., “Tuning the Activity of Pt Alloy Electrocatalysts by Means of the Lanthanide Contraction,” Science 352, no. 6281 (2016): 73–76.

[36] F. Calle-Vallejo, J. Tymoczko, V. Colic, et al., “Finding Optimal Surface Sites on Heterogeneous Catalysts by Counting Nearest Neighbors,” Science 350, no. 6257 (2015): 185–189.

[37] B. Hammer and J. K. Norskov, “Why Gold Is the Noblest of All the Metals,” Nature 376, no. 6537 (1995): 238–240.

[38] J. Greeley and J. K. Nørskov, “A General Scheme for the Estimation of Oxygen Binding Energies on Binary Transition Metal Surface Alloys,” Surface Science 592, no. 1–3 (2005): 104–111.

[39] T. Adit Maark and B. R. K. Nanda, “Enhancing CO₂ Electroreduction by Tailoring Strain and Ligand Effects in Bimetallic Copper–Rhodium and Copper–Nickel Heterostructures,” Journal of Physical Chemistry C 121, no. 8 (2017): 4496–4504.

[40] H. Thirumalai and J. R. Kitchin, “Investigating the Reactivity of Single Atom Alloys Using Density Functional Theory,” Topics in Catalysis 61 (2018): 462–474.

[41] A. Cho, J. Ko, B.-K. Kim, and J. W. Han, “Electrocatalysts With Increased Activity for Coelectrolysis of Steam and Carbon Dioxide in Solid Oxide Electrolyzer Cells,” ACS Catalysis 9, no. 2 (2018): 967–976.

[42] X.-K. Gu, J. S. Carneiro, and E. Nikolla, “First-Principles Study of High Temperature CO₂ Electrolysis on Transition Metal Electrocatalysts,” Industrial & Engineering Chemistry Research 56, no. 21 (2017): 6155–6163.

[43] C. Liu, T. R. Cundari, and A. K. Wilson, “CO₂ Reduction on Transition Metal (Fe, Co, Ni, and Cu) Surfaces: In Comparison With Homogeneous Catalysis,” Journal of Physical Chemistry C 116, no. 9 (2012): 5681–5688.

[44] J. Carneiro, X.-K. Gu, E. Tezel, and E. Nikolla, “Electrochemical Reduction of CO₂ on Metal-Based Cathode Electrocatalysts of Solid Oxide Electrolysis Cells,” Industrial & Engineering Chemistry Research 59, no. 36 (2020): 15884–15893.

[45] X. Gao, L. Ye, and K. Xie, “In-Situ Exsolved Ni-Cu Alloy Nanoparticles for Optimization of Perovskite Electrodes in Solid Oxide Electrolysis Cell,” Fuel 371 (2024): 131959.

[46] W. Cui, X. Yang, M. Ma, et al., “Boosting Catalytic and CO₂ Adsorption Ability by In Situ Cu Nanoparticle Exsolution for Solid Oxide Electrolysis Cell Cathode,” Ceramics International 49, no. 16 (2023): 27214–27221.

[47] W. An, D. Gatewood, B. Dunlap, and C. H. Turner, “Catalytic Activity of Bimetallic Nickel Alloys for Solid-Oxide Fuel Cell Anode Reactions From Density-Functional Theory,” Journal of Power Sources 196, no. 10 (2011): 4724–4728.

[48] S. Kim, C. Kim, J. H. Lee, J. Shin, T.-H. Lim, and G. Kim, “Tailoring Ni-Based Catalyst by Alloying With Transition Metals (M= Ni, Co, Cu, and Fe) for Direct Hydrocarbon Utilization of Energy Conversion Devices,” Electrochimica Acta 225 (2017): 399–406.

[49] N. Galea, D. Knapp, and T. Ziegler, “Density Functional Theory Studies of Methane Dissociation on Anode Catalysts in Solid-Oxide Fuel Cells: Suggestions for Coke Reduction,” Journal of Catalysis 247, no. 1 (2007): 20–33.

[50] L. Zhu and A. E. DePristo, “Microstructures of Bimetallic Clusters: Bond Order Metal Simulator for Disordered Alloys,” Journal of Catalysis 167, no. 2 (1997): 400–407.

[51] A. A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, and J. K. Nørskov, “How Copper Catalyzes the Electroreduction of Carbon Dioxide Into Hydrocarbon Fuels,” Energy & Environmental Science 3, no. 9 (2010): 1311–1315.

[52] J. Horlyck, C. Lawrey, E. C. Lovell, R. Amal, and J. Scott, “Elucidating the Impact of Ni and Co Loading on the Selectivity of Bimetallic NiCo Catalysts for Dry Reforming of Methane,” Chemical Engineering Journal 352 (2018): 572–580.

[53] E. Ruckenstein and H. Y. Wang, “Carbon Deposition and Catalytic Deactivation During CO₂ Reforming of CH₄ Over Co/γ-Al₂O₃ Catalysts,” Journal of Catalysis 205, no. 2 (2002): 289–293.

[54] J. Estephane, S. Aouad, S. Hany, et al., “CO₂ Reforming of Methane Over Ni–Co/ZSM5 Catalysts. Aging and Carbon Deposition Study,” International Journal of Hydrogen Energy 40, no. 30 (2015): 9201–9208.

[55] S. A. Theofanidis, V. V. Galvita, H. Poelman, and G. B. Marin, “Enhanced Carbon-Resistant Dry Reforming Fe-Ni Catalyst: Role of Fe,” ACS Catalysis 5, no. 5 (2015): 3028–3039.

[56] E. Pippel, J. Woltersdorf, and H. J. Grabke, “Microprocesses of Metal Dusting on Iron-Nickel Alloys and Their Dependence on the Alloy Composition,” Materials and Corrosion 54, no. 10 (2003): 747–751.

[57] M. Shahid, C. He, S. Sankarasubramanian, V. K. Ramani, and S. Basu, “Co₃O₄-Impregnated NiO–YSZ: An Efficient Catalyst for Direct Methane Electrooxidation,” ACS Applied Materials & Interfaces 12, no. 29 (2020): 32578–32590.

[58] O. Costa-Nunes, R. J. Gorte, and J. M. Vohs, “Comparison of the Performance of Cu–CeO₂–YSZ and Ni–YSZ Composite SOFC Anodes With H₂, CO, and Syngas,” Journal of Power Sources 141, no. 2 (2005): 241–249.

[59] E. W. Park, H. Moon, M. Park, and S. H. Hyun, “Fabrication and Characterization of Cu–Ni–YSZ SOFC Anodes for Direct Use of Methane via Cu-Electroplating,” International Journal of Hydrogen Energy 34, no. 13 (2009): 5537–5545.

[60] S. Liu, Q. Liu, and J.-L. Luo, “Highly Stable and Efficient Catalyst With In Situ Exsolved Fe–Ni Alloy Nanospheres Socketed on an Oxygen Deficient Perovskite for Direct CO₂ Electrolysis,” ACS Catalysis 6, no. 9 (2016): 6219–6228.

[61] P. J. Schilling, J. H. He, R. C. Tittsworth, and E. Ma, “Two-Phase Coexistence Region in Mechanically Alloyed Cu–Fe: An X-Ray Absorption Near-Edge Structure Study,” Acta Materialia 47, no. 8 (1999): 2525–2537.

[62] D. J. Sprouster and M. C. Ridgway, “Ion Beam Formation and Modification of Cobalt Nanoparticles,” Applied Sciences 2, no. 2 (2012): 396–442.

[63] J. L. Alfke, A. Müller, A. H. Clark, et al., “BCC-Cu Nanoparticles: From a Transient to a Stable Allotrope by Tuning Size and Reaction Conditions,” Physical Chemistry Chemical Physics 24, no. 39 (2022): 24429–24438.

[64] S. Olvera, J. Sánchez-Marcos, F. J. Palomares, E. Salas, E. M. Arce, and P. Herrasti, “Characterization and Corrosion Behaviour of CoNi Alloys Obtained by Mechanical Alloying,” Materials Characterization 93 (2014): 79–86.

[65] H. Wu, H. Liu, W. Yang, and D. He, “Synergetic Effect of Ni and Co in Ni–Co/SBA-15-Cd Catalysts and Their Catalytic Performance in Carbon Dioxide Reforming of Methane to Syngas,” Catalysis Science & Technology 6, no. 14 (2016): 5631–5646.

[66] X. Yao, Q. Cheng, Y. Attada, et al., “Atypical Stability of Exsolved Ni– Fe Alloy Nanoparticles on Double Layered Perovskite for CO₂ Dry Reforming of Methane,” Applied Catalysis, B: Environmental 328 (2023): 122479.

[67] L. R. Winter, E. Gomez, B. Yan, S. Yao, and J. G. Chen, “Tuning Ni-Catalyzed CO₂ Hydrogenation Selectivity via Ni-Ceria Support Interactions and Ni– Fe Bimetallic Formation,” Applied Catalysis, B: Environmental 224 (2018): 442–450.

[68] A. J. Flegler, T. E. Burye, Q. Yang, and J. D. Nicholas, “Cubic Yttria Stabilized Zirconia Sintering Additive Impacts: A Comparative Study,” Ceramics International 40, no. 10 (2014): 16323–16335.

[69] A. Hauch and A. Georg, “Diffusion in the Electrolyte and Charge-Transfer Reaction at the Platinum Electrode in Dye-Sensitized Solar Cells,” Electrochimica Acta 46, no. 22 (2001): 3457–3466.

[70] T. Kawashima, S. Miyoshi, Y. Shibuta, and S. Yamaguchi, “Particle Size Dependence of Polarization of Ni/YSZ Cermet Anodes for Solid Oxide Fuel Cells,” Journal of Power Sources 234 (2013): 147–153.

[71] T. Abe, H. Fukuda, Y. Iriyama, and Z. Ogumi, “Solvated Li-Ion Transfer at Interface Between Graphite and Electrolyte,” Journal of the Electrochemical Society 151, no. 8 (2004): A1120.

[72] H. Lv, L. Lin, X. Zhang, et al., “In Situ Investigation of Reversible Exsolution/Dissolution of CoFe Alloy Nanoparticles in a Co-Doped Sr₂Fe_1.5Mo_0.5O_6−δ Cathode for CO₂ Electrolysis,” Advanced Materials 32, no. 6 (2020): 1906193.

[73] H. Seo, S. Jang, W. Lee, et al., “Highly Efficient, Coke-Free Electrolysis of Dry CO₂ in Solid Oxide Electrolysis Cells,” Chemical Engineering Journal 481 (2024): 148532.

[74] P. Caliandro, A. Nakajo, S. Diethelm, and J. Van herle, “Model-Assisted Identification of Solid Oxide Cell Elementary Processes by Electrochemical Impedance Spectroscopy Measurements,” Journal of Power Sources 436 (2019): 226838.

[75] Q. Jiang, Z. Chen, J. Tong, M. Yang, Z. Jiang, and C. Li, “Direct Thermolysis of CO₂ Into CO and O₂,” Chemical Communications 53, no. 6 (2017): 1188–1191.

[76] J. Liang and M. Han, “Different Performance and Mechanisms of CO₂ Electrolysis With CO and H₂ as Protective Gases in Solid Oxide Electrolysis Cell,” International Journal of Hydrogen Energy 47, no. 43 (2022): 18606–18618.

[77] J. Hong, A. Bhardwaj, H. Bae, I. Kim, and S.-J. Song, “Electrochemical Impedance Analysis of SOFC With Transmission Line Model Using Distribution of Relaxation Times (DRT),” Journal of the Electrochemical Society 167, no. 11 (2020): 114504.

[78] H. Sumi, H. Shimada, Y. Yamaguchi, T. Yamaguchi, and Y. Fujishiro, “Degradation Evaluation by Distribution of Relaxation Times Analysis for Microtubular Solid Oxide Fuel Cells,” Electrochimica Acta 339 (2020): 135913.

[79] S. Singhal, High Temperature SolidOxide Fuel Cells: Fundamentals, Design and Applications (Elsevier, 2003).

[80] L. Lu, W. Liu, J. Wang, et al., “Long-Term Stability of Carbon Dioxide Electrolysis in a Large-Scale Flat-Tube Solid Oxide Electrolysis Cell Based on Double-Sided Air Electrodes,” Applied Energy 259 (2020): 114130.

[81] B. Zhang, S. Zhang, Z. Zhang, K. Tang, and C. Xia, “Metal-Supported Solid Oxide Electrolysis Cell for Direct CO₂ Electrolysis Using Stainless Steel Based Cathode,” Journal of Power Sources 556 (2023): 232467.

[82] Y. Nishiyama, K. Moriguchi, N. Otsuka, and T. Kudo, “Improving Metal Dusting Resistance of Transition-Metals and Ni-Cu Alloys,” Materials and Corrosion 56, no. 11 (2005): 806–813.

[83] G. Ertl, H. Knözinger, and J. Weitkamp, Handbook of Heterogeneous Catalysis (VCH Weinheim, 1997), 2.

[84] P. I. Zámostný and J. W. Chorkendorff, “Niemantsverdriet: Concepts of Modern Catalysis and Kinetics,” Chemické listy 98, no. 5 (2004): 268.

[85] J. Cai, Y. Han, S. Chen, et al., “CO₂ Activation on Ni (111) and Ni (100) Surfaces in the Presence of H₂O: An Ambient-Pressure X-Ray Photoelectron Spectroscopy Study,” Journal of Physical Chemistry C 123, no. 19 (2019): 12176–12182.

[86] S. E. Collins, M. A. Baltanás, and A. L. Bonivardi, “Infrared Spectroscopic Study of the Carbon Dioxide Adsorption on the Surface of Ga₂O₃ Polymorphs,” Journal of Physical Chemistry B 110, no. 11 (2006): 5498–5507.

[87] A. Solis-Garcia, J. F. Louvier-Hernandez, A. Almendarez-Camarillo, and J. C. Fierro-Gonzalez, “Participation of Surface Bicarbonate, Formate and Methoxy Species in the Carbon Dioxide Methanation Catalyzed by ZrO₂-Supported Ni,” Applied Catalysis, B: Environmental 218 (2017): 611–620.

[88] H. L. Huynh, J. Zhu, G. Zhang, et al., “Promoting Effect of Fe on Supported Ni Catalysts in CO₂ Methanation by In Situ Drifts and DFT Study,” Journal of Catalysis 392 (2020): 266–277.

[89] H.-J. Freund and R. P. Messmer, “On the Bonding and Reactivity of CO₂ on Metal Surfaces,” Surface Science 172, no. 1 (1986): 1–30.

[90] D. Shen, M. Huo, L. Li, et al., “Effects of Alumina Morphology on Dry Reforming of Methane over Ni/Al₂O₃ Catalysts,” Catalysis Science & Technology 10, no. 2 (2020): 510–516.

[91] O. Pozdnyakova, D. Teschner, A. Wootsch, et al., “Preferential CO Oxidation in Hydrogen (PROX) on Ceria-Supported Catalysts, Part I: Oxidation State and Surface Species on Pt/CeO₂ Under Reaction Conditions,” Journal of Catalysis 237, no. 1 (2006): 1–16.

[92] R. B. David, A. R. Head, S. Lin, A. B. Yaacov, M. A. Andres, and B. Eren, “Molecular-Level Insights into CO₂ Activation on Ni (111) From In Situ Infrared Spectroscopy,” Cell Reports Physical Science 5, no. 4 (2024): 101890, https://doi.org/10.1016/j.xcrp.2024.101890.

[93] N. Colthup, Introduction to Infrared and Raman Spectroscopy (Elsevier, 2012).

[94] J. Mascetti and M. Tranquille, “Fourier Transform Infrared Studies of Atomic Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel and Copper Reactions With Carbon Dioxide in Low-Temperature Matrices,” Journal of Physical Chemistry 92, no. 8 (1988): 2177–2184.

[95] E. Nikolla, J. Schwank, and S. Linic, “Promotion of the Long-Term Stability of Reforming Ni Catalysts by Surface Alloying,” Journal of Catalysis 250, no. 1 (2007): 85–93.

[96] I. Gavrielatos, V. Drakopoulos, and S. Neophytides, “Carbon Tolerant Ni–Au SOFC Electrodes Operating Under Internal Steam Reforming Conditions,” Journal of Catalysis 259, no. 1 (2008): 75–84.

[97] M. Boder and R. Dittmeyer, “Catalytic Modification of Conventional SOFC Anodes With a View to Reducing Their Activity for Direct Internal Reforming of Natural Gas,” Journal of Power Sources 155, no. 1 (2006): 13–22.

[98] T. Margossian, K. Larmier, S. M. Kim, F. Krumeich, C. Müller, and C. Copéret, “Supported Bimetallic NiFe Nanoparticles Through Colloid Synthesis for Improved Dry Reforming Performance,” ACS Catalysis 7, no. 10 (2017): 6942–6948.

[99] M. Koike, D. Li, Y. Nakagawa, and K. Tomishige, “A Highly Active and Coke-Resistant Steam Reforming Catalyst Comprising Uniform Nickel-Iron Alloy Nanoparticles,” Chemsuschem 5, no. 12 (2012): 2312–2314.

[100] S. M. Kim, P. M. Abdala, T. Margossian, et al., “Cooperativity and Dynamics Increase the Performance of NiFe Dry Reforming Catalysts,” Journal of the American Chemical Society 139, no. 5 (2017): 1937–1949.

[101] X. Gao, Z. Tan, K. Hidajat, and S. Kawi, “Highly Reactive Ni-Co/SiO₂ Bimetallic Catalyst via Complexation With Oleylamine/Oleic Acid Organic Pair for Dry Reforming of Methane,” Catalysis Today 281 (2017): 250–258.

[102] I. V. Zagaynov, “Active Components of Catalysts of Methane Conversion to Synthesis Gas: Brief Perspectives,” Energy & Fuels 35, no. 11 (2021): 9124–9136.

[103] D. L. Trimm, “The Formation and Removal of Coke From Nickel Catalyst,” Catalysis Reviews 16, no. 1 (1977): 155–189.

[104] H. Dai, A. G. Rinzler, P. Nikolaev, A. Thess, D. T. Colbert, and R. E. Smalley, “Single-Wall Nanotubes Produced by Metal-Catalyzed Disproportionation of Carbon Monoxide,” Chemical Physics Letters 260, no. 3–4 (1996): 471–475.

[105] K. Girona, J. Laurencin, J. Fouletier, and F. Lefebvre-Joud, “Carbon Deposition in CH₄/CO₂ Operated SOFC: Simulation and Experimentation Studies,” Journal of Power Sources 210 (2012): 381–391.

[106] A. Utz, A. Leonide, A. Weber, and E. Ivers-Tiffée, “Studying the CO–CO₂ Characteristics of SOFC Anodes by Means of Patterned Ni Anodes,” Journal of Power Sources 196, no. 17 (2011): 7217–7224.

[107] M. Torimoto and Y. Sekine, “Effects of Alloying for Steam or Dry Reforming of Methane: A Review of Recent Studies,” Catalysis Science & Technology 12, no. 11 (2022): 3387–3411.

[108] F. Besenbacher, I. Chorkendorff, B. S. Clausen, et al., “Design of a Surface Alloy Catalyst for Steam Reforming,” Science 279, no. 5358 (1998): 1913–1915.

[109] A. Chatla, M. M. Ghouri, O. W. El Hassan, N. Mohamed, A. V. Prakash, and N. O. Elbashir, “An Experimental and First Principles DFT Investigation on the Effect of Cu Addition to Ni/Al₂O₃ Catalyst for the Dry Reforming of Methane,” Applied Catalysis, A: General 602 (2020): 117699.

[110] B. Li, W. Gao, and Q. Jiang, “Electronic and Geometric Determinants of Adsorption: Fundamentals and Applications,” Journal of Physics: Energy 3, no. 2 (2021): 022001.

[111] S. McIntosh and R. J. Gorte, “Direct Hydrocarbon Solid Oxide Fuel Cells,” Chemical Reviews 104, no. 10 (2004): 4845–4866.

[112] J. Sinfelt, “Catalytic Hydrogenolysis and Dehydrogenation Over Copper-Nickel Alloys,” Journal of Catalysis 24, no. 2 (1972): 283–296.

[113] M. T. Tavares, I. Alstrup, and C. A. A. Bernardo, “Coking and Decoking During Methanation and Methane Decomposition on Ni-Cu Supported Catalysts,” Materials and Corrosion 50, no. 12 (1999): 681–685.

[114] H. Kim, C. Lu, W. L. Worrell, J. M. Vohs, and R. J. Gorte, “Cu-Ni Cermet Anodes for Direct Oxidation of Methane in Solid-Oxide Fuel Cells,” Journal of the Electrochemical Society 149, no. 3 (2002): A247.

[115] S.-I. Lee, J. M. Vohs, and R. J. Gorte, “A Study of SOFC Anodes Based on Cu-Ni and Cu-Co Bimetallics in CeO₂-YSZ,” Journal of the Electrochemical Society 151, no. 9 (2004): A1319.

[116] J. H. Park, S. Oh, B. C. Yang, et al., “Pushing the Envelope of Physical Vapor Deposited Thin-Film Based Solid Oxide Fuel Cells for 500°C Operation: Securing 1 W cm⁻² Performance, 1000 h Stability, Scale Up to 15 W Power, and Associated Limitations,” Chemical Engineering Journal 515 (2025): 163441.

[117] W. Lee, M. Lang, R. Costa, I.-S. Lee, Y.-S. Lee, and J. Hong, “Enhancing Uniformity and Performance in Solid Oxide Fuel Cells With Double Symmetry Interconnect Design,” Applied Energy 381 (2025): 125178.

[118] I. Ohnuma, S. Shimenouchi, T. Omori, K. Ishida, and R. Kainuma, “Experimental Determination and Thermodynamic Evaluation of Low-Temperature Phase Equilibria in the Fe–Ni Binary System,” Calphad 67 (2019): 101677.

[119] T. O. Menteş, N. Stojić, E. Vescovo, J. M. Ablett, M. A. Niño, and A. Locatelli, “Vacancy-Mediated Fcc/Bcc Phase Separation in Fe_1−xNi_x Ultrathin Films,” Physical Review B 94, no. 8 (2016): 085402.

[120] M. Miyake, S. Matsumoto, M. Iwami, S. Nishimoto, and Y. Kameshima, “Electrochemical Performances of Ni_1−xCu_x/SDC Cermet Anodes for Intermediate-Temperature SOFCs Using Syngas Fuel,” International Journal of Hydrogen Energy 41, no. 31 (2016): 13625–13631.

[121] H. Kan and H. Lee, “Enhanced Stability of Ni-Fe/GDC Solid Oxide Fuel Cell Anodes for Dry Methane Fuel,” Catalysis Communications 12, no. 1 (2010): 36–39.

[122] Y. Ishibashi, K. Matsumoto, S. Futamura, et al., “Improved Redox Cycling Durability in Alternative Ni Alloy-Based SOFC Anodes,” Journal of the Electrochemical Society 167, no. 12 (2020): 124517.

[123] M. Kateb, J. T. Gudmundsson, and S. Ingvarsson, “Effect of Atomic Ordering on the Magnetic Anisotropy of Single Crystal Ni₈₀Fe₂₀,” AIP Advances 9, no. 3 (2019): 035308, https://doi.org/10.1063/1.5088602.

[124] H.-S. Noh, J.-W. Son, H. Lee, H.-I. Ji, J.-H. Lee, and H.-W. Lee, “Suppression of Ni Agglomeration in PLD Fabricated Ni-YSZ Composite for Surface Modification of SOFC Anode,” Journal of the European Ceramic Society 30, no. 16 (2010): 3415–3423.

[125] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B 54, no. 16 (1996): 11169–11186.

[126] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 77, no. 18 (1996): 3865–3868.

[127] S. Grimme, S. Ehrlich, and L. Goerigk, “Effect of the Damping Function in Dispersion Corrected Density Functional Theory,” Journal of Computational Chemistry 32, no. 7 (2011): 1456–1465.

[128] H. J. Monkhorst and J. D. Pack, “Special Points for Brillouin-Zone Integrations,” Physical Review B 13, no. 12 (1976): 5188–5192.

[129] G. Henkelman, B. P. Uberuaga, and H. Jónsson, “A Climbing Image Nudged Elastic Band Method for Finding Saddle Points and Minimum Energy Paths,” Journal of Chemical Physics 113, no. 22 (2000): 9901–9904.

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