Insights Into Nitrogen Adsorption and Dinitrogen Dissociation on C n P Clusters: A First‐Principles Density Functional Theory Study

Abstract This theoretical study employs first‐principles density functional calculations to investigate the adsorption mechanisms of dinitrogen on C n P clusters ( n ≤ 3), comparing them with pure carbon clusters under identical conditions. Surprisingly, the adsorption energy of nitrogen on C n P clusters is generally lower than that on pure carbon clusters, which contradicts conventional expectations based solely on carbon. Intriguingly, instances occur where the adsorption energy on C n P clusters exceeds that on pure carbon clusters. Notably, the study reveals that even a pure carbon dimer can completely dissociate dinitrogen, suggesting its potential as a catalyst. Examining various cluster sizes, including dimers, trimers, and tetramers, the research elucidates that how configurations and orientations of adsorbed nitrogen molecules significantly impact adsorption properties. These insights underscore the potential of C n P clusters as the efficient catalysts for breaking the strong triple bond of dinitrogen. This research delivers unexpected findings that contribute significantly to the field of cluster catalysis and offers a novel perspective on nitrogen fixation processes. The observed variations in adsorption energy highlight the intricate interplay between cluster size, nitrogen orientation, and adsorption behavior. Our work advances the fundamental understanding of nitrogen adsorption on C n P clusters, demonstrating their promising role in developing energy‐efficient nitrogen fixation processes.