Thermocatalytic CO2 dissociation over Ni-based single atom alloys: a first-principles investigation

Abstract

Mitigating CO₂ emissions is critical to advancing sustainable climate strategies, with CO₂ reduction emerging as a promising approach for converting CO₂ into value-added fuels and chemicals. At the same time, high-temperature thermocatalytic routes such as CO₂ dissociation are equally essential for processes like dry reforming of methane (DRM). However, its efficiency relies on the design of high-performance catalysts, emphasizing the importance of dopant incorporation and surface engineering. In this study, density functional theory calculations were employed to investigate the pathways and activation energies associated with CO₂ dissociation on nickel-based single-atom alloys (SAAs) doped with a range of elements (3d-metals from Sc to Zn, Al, Pt, Pd, Rh, and Ru). The adsorption behavior of intermediates was systematically investigated, and results indicated that the CO and O species prefer hexagonal close-packed and face-centered cubic hollow sites, respectively, on both pristine and doped Ni(111) surfaces. Additionally, transition state and activation energy calculations were performed using the climbing image nudged elastic band and improved dimer method. Results identified V as a particularly effective dopant in enhancing catalytic performance. Specifically, V doping reduced the reaction barrier by approximately 60% relative to the undoped Ni(111) surface, underscoring its potential to significantly improve the thermocatalytic CO₂ dissociation efficiency. Further electronic structure analyses revealed the mechanisms underlying the observed enhancements, offering insight into the interaction between dopant properties and catalytic performance. These findings suggest that V-doped Ni(111) SAAs are promising candidates for scalable CO₂ reduction technologies, offering an effective approach to greenhouse gas mitigation and sustainable carbon management.