Mechanistic Insights Into Selective Hydrogenation of Naphthalene on NiMo Alloys: A DFT‐Based Study for Catalytic Optimization

Abstract The selective hydrogenation of naphthalene to tetralin (TL) represents a pivotal process in petroleum refining. However, achieving high activity while mitigating excessive hydrogenation presents a considerable challenge. In this study, density functional theory (DFT) is used to systematically evaluate the catalytic performance of nickel–molybdenum (NiMo) alloys with varying stoichiometric ratios. By establishing a thermodynamic stability criterion, the hydrogenation pathway on the surface of the catalyst is elucidated. Mechanistic analysis reveals that Mo doping enhances catalytic efficacy through dual electronic modulation: 1) a downshifted Ni d‐band center facilitates hydrogen desorption, and 2) intensified π‐d orbital interactions between naphthalene molecules and metallic surfaces promote its activation. The Ni 3 Mo 2 catalyst, recognized as the most effective, exhibits superior hydrogenation activity, with a rate constant of 1.76 × 10 6 s −1 , and high TL selectivity, indicated by an adsorption energy difference of 1.03 eV between naphthalene and TL. These values markedly exceed those of pure Ni (rate constant: 4.15 × 10 4 s −1 ; adsorption energy difference: 0.62 eV). These findings establish key theoretical foundations for designing efficient transition metal catalysts and understanding of aromatic hydrogenation mechanisms, thereby providing guidance for the development of industrial catalysts.