Nano Research ( IF 9.9 ) Pub Date : 2020-03-13 , DOI: 10.1007/s12274-020-2651-x Songwei Zhang , Jerry Pui Ho Li , Jingpeng Zhao , Dan Wu , Biao Yuan , Willinton Yesid Hernández , Wen-Juan Zhou , Tao He , Yi Yu , Yong Yang , Vitaly Ordomsky , Tao Li
The aerobic oxidation of monoalcohols and diols to acetals is an important academic and industrial challenge for the production of fine chemicals and intermediates. The existing methods usually rely on a two-step process in which alcohols are first oxidized to aldehydes over metal catalysts (Ru, Pt, Pd) and then acetalized using acids. Due to the instability of aldehydes, how to avoid over-oxidation to their respective carboxylic acids and esters is a long-standing challenge. For this reason, certain non-conjugated dialdehydes have never been successfully produced from diol oxidation. Hereby we report a Ru@metal-organic framework (MOF) tandem catalyst containing ultra-fine Ru nanoparticles (< 2 nm) for direct alcohol to acetal conversion of monoalcohol and diols with no formation of carboxylic acids. Mechanistic study reveals that the presence of Lewis acid sites in the MOF work in concert with Ru active sites to promptly convert aldehydes to acetals thereby effectively suppressing the formation of over-oxidation byproducts.
中文翻译:
使用串联Ru @ MOF催化剂将一元醇和二醇直接好氧氧化为缩醛
一元醇和二醇的好氧氧化为缩醛是生产精细化学品和中间体的重要学术和工业挑战。现有方法通常依赖于两步过程,其中首先在金属催化剂(Ru,Pt,Pd)上将醇氧化为醛,然后使用酸将其缩醛化。由于醛的不稳定性,如何避免过氧化成它们各自的羧酸和酯是一个长期的挑战。因此,从未成功地从二醇氧化中制备某些非共轭二醛。据此,我们报告了一种Ru @ metal-organic framework(MOF)串联催化剂,其中包含超细Ru纳米颗粒(<2 nm),用于将单醇和二醇直接醇转化为缩醛,而不会形成羧酸。