Benzyl Alcohol Oxidation on Carbon-Supported Pd Nanoparticles: Elucidating the Reaction Mechanism
Benzyl Alcohol Oxidation on Carbon-Supported Pd Nanoparticles: Elucidating the Reaction Mechanism
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DOI：
10.1002/cctc.201402552
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发表时间：
2014-12-01
期刊：
影响因子：
4.5
通讯作者：
Prati, Laura
中科院分区：
文献类型：
--
作者：
Savara, Aditya;Chan-Thaw, Carine E.;Prati, Laura
对苯甲醇在Pd纳米粒子上的液相氧化进行了实验，目的是确定操作的化学反应。实验在间歇式反应器中进行，以对二甲苯作为溶剂并对顶部空间进行连续气体吹扫。改变以下实验参数：初始苯甲醇浓度、顶部空间中的氧分压和反应器温度。从每种产物的浓度分布和综合生产的趋势，确定存在两种主要反应路径：A）导致甲苯、苯甲醛和苄醚的烷氧基路径，和B）导致苯甲酸、苯和苯甲酸苄酯的羰基氧基路径（“中性羧酸酯”）。从阐明的机制，很明显，原子氢，原子氧，和表面羟基的覆盖率必须占实现定量动力学的完整描述。
Experiments were conducted on the liquid-phase oxidation of benzyl alcohol over Pd nanoparticles, with the aim of determining the operative chemical reaction. Experiments were conducted in a batch reactor with para-xylene as the solvent and continuous gas purging of the headspace. The following experimental parameters were varied: the initial benzyl alcohol concentration, the oxygen partial pressure in the headspace, and the reactor temperature. From trends in the concentration profiles and integrated production of each product, it was determined that there are two primary reaction paths: A) an alkoxy pathway leading to toluene, benzaldehyde, and benzyl ether, and B) a carbonyloxyl pathway ("neutral carboxylate") leading to benzoic acid, benzene, and benzyl benzoate. From the mechanism elucidated, it is clear that the coverages of atomic hydrogen, atomic oxygen, and surface hydroxyls must be accounted for to achieve a complete description of the quantitative kinetics.