First-principles Study of the Products of CO2 Dissociation on Nickel-based Alloys: Trends in Energetics with Alloying Element

Oxidation and corrosion of nickel and Ni-based alloys are a problem for many industrial applications, such as power plants that use supercritical CO2 as the working fluid. In supercritical CO2 environments, CO2 dissociates on the surface forming adsorbed CO and O, which can oxidize the surface. The adsorbed CO can further breakdown via direct CO dissociation or via the Boudouard reaction to form adsorbed C, which can in turn carburize the surface. Understanding how the adsorbed species interact with different Ni-based alloys can help guide the design of future alloys. The interactions of adsorbed O, C, and CO on the (100) and (111) facets of pure Ni and Ni individually alloyed with Al, Co, Cr, Cu, Fe, Mn, Mo, Nb, Ti, V, and W are examined using density functional theory. We find that the binding of CO is energetically similar across all alloy surfaces and both facets, while O binding varies strongly with different metals added to nickel and C binding varies between the different facets but only slightly for different metals alloyed to nickel. The binding of O is weaker on pure Ni and Ni alloyed with Cu, Co, Fe, Al, or Mn and stronger on Ni alloyed with Nb, Cr, Mo, Ti, V, or W, while the binding of C is weaker on the (111) facet than the (100) facet. The difference in the binding energies of the adsorbates across the different alloy surfaces is due mainly to the ensemble effect, rather than the ligand effect. The thermodynamics of CO breakdown are also studied and we find that the breakdown of CO via direct CO dissociation is endothermic on the (111) facet and exothermic on the (100) facet, with the alloy surfaces that bind O strongly having the most exothermic reaction energies. The breakdown of CO via the Boudouard reaction has similar reaction energies across the different alloy surfaces of a single facet and is endothermic on both facets, with the (111) facet being most endothermic. This comprehensive study presents a summary of the current literature as well as a well-rounded view of the products of CO2 breakdown on Ni surfaces alloyed with the most common alloying elements used in industrial applications