Aerobic oxidation of cyclohexane, propane, ethane, and methane to the corresponding alcohols was investigated over an Au55 gold nanoparticle with icosahedron symmetry using density functional theory. Reaction mechanisms were elucidated and activation barriers for catalytic CH bond cleavage and corresponding alcohols’ formation were estimated. Furthermore, on the basis of the reaction rate constants calculated for realistic reaction temperatures, the relative reaction rates for each alkane hydroxylation were discussed. The catalyst selectivity was investigated for the formation of primary and secondary alcohols. All reaction mechanisms for alkane hydroxylation are compared with the catalytic dissociation of dioxygen molecule over gold nanoparticle surface, which is an important precursor reaction for aerobic oxidation. We have further investigated overoxidation reaction mechanisms leading to formation of ketones. Our results are compared with experimental findings to provide important guidelines for the tuning of catalytic reactions towards the desired products and reaction conditions.

利用密度泛函理论在具有二十面体对称性的Au55金纳米颗粒上研究了环己烷，丙烷，乙烷和甲烷的好氧氧化成相应的醇。阐明了反应机理和催化C的活化障碍估计氢键裂解和相应的醇的形成。此外，基于针对实际反应温度计算的反应速率常数，讨论了每种烷烃羟基化反应的相对反应速率。研究了形成伯醇和仲醇的催化剂选择性。将烷烃羟基化的所有反应机理与双氧分子在金纳米颗粒表面上的催化离解进行了比较，这是有氧氧化的重要前体反应。我们进一步研究了导致酮形成的过氧化反应机理。我们的结果与实验结果进行了比较，为针对所需的产物和反应条件调节催化反应提供了重要的指导。