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Selective Oxidation of Alcohols to Carbonyl Compounds over Small Size Colloidal Ru Nanoparticles

机译:小尺寸胶体Ru纳米粒子的选择性氧化醇和羰基化合物

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摘要

The selective oxidation of alcohols to corresponding aldehydes is one of the most challenging problems in modern chemistry due to over-oxidation of these products further into corresponding acids and esters. Herein, we report an efficient and eco-friendly method for selective oxidation of aliphatic, unsaturated and aromatic alcohols to aldehydes (>90 %) using small size (2 nm) non-supported colloidal Ru nanoparticles. The selectivity rapidly decreases with increase of the size of nanoparticles (from 2 to 10 nm) or after their deposition over support. X-ray photoelectron spectroscopy suggests that this catalytic performance can be attributed to high content Ru-O species on the surface of small size Ru nanoparticles, which undergo reduction with formation of water and aldehyde and easy oxidation cycles during the reaction according to the Mars-van Krevelen mechanism. The presence of surface oxide layer over small size Ru nanoparticles suppresses over-oxidation of aldehydes to acids.
机译:对应于相应醛的选择性氧化是现代化学中最具挑战性的问题之一,由于这些产品的过度氧化进一步进入相应的酸和酯。 在此,我们报告了使用小尺寸(2nM)非负载型胶体Ru纳米颗粒选择性氧化脂族,不饱和和芳族醇的脂族,不饱和和芳族醇和醛(> 90%)的高效且生态友好的方法。 选择性随着纳米颗粒的尺寸(从2至10nm)的增加而迅速降低,或者在它们上沉积后沉积。 X射线光电子能谱表明,这种催化性能可归因于小尺寸Ru纳米粒子表面上的高含量Ru-O物种,其在反应过程中易于形成水和醛和易氧化循环,根据MARS- 范克维特伦机制。 在小尺寸Ru纳米颗粒上存在表面氧化物层抑制醛的过度氧化至酸。

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