Sodium hydroxide (NaOH) has been an indispensable additive in the selective aerobic oxidation of alcohols/polyols in water for ketone and carboxylic acid syntheses over supported metal catalysts, including Au, though the exact function of NaOH remains far from clear. We disclose here that NaOH alone can independently serve as a homogeneous catalyst for the oxidation reactions. This conclusion is supported by rigorous investigations of the effects of NaOH alone (without the presence of any metal catalyst) on the reactivity of aqueous glycerol, ethylene glycol, 2-propanol, and ethanol and their product distribution. Computational results based on density functional theory are also provided to explain the experimentally measured reactivity order of the various alcohols and to generate insight into the molecular mechanisms for the oxidation reactions. Besides challenging existing knowledge about the function of NaOH in alcohol oxidation reactions, this study opens a new avenue for catalytic alcohol/polyol upgrading.

氢氧化钠（NaOH）在水中的醇/多元醇选择性好氧氧化过程中，是在包括Au在内的负载型金属催化剂上进行酮和羧酸合成的必不可少的添加剂，尽管NaOH的确切功能尚不清楚。我们在这里公开了单独的NaOH可以独立地用作氧化反应的均相催化剂。严格研究氢氧化钠（不存在任何金属催化剂）对甘油，乙二醇，2-丙醇和乙醇的反应性及其产物分布的影响，对此结论提供了支持。还提供了基于密度泛函理论的计算结果，以解释各种醇在实验上测得的反应顺序，并深入了解氧化反应的分子机理。