Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University , Wuhan 430079, China.
J Am Chem Soc. 2016 Aug 17;138(32):10128-31. doi: 10.1021/jacs.6b06860. Epub 2016 Aug 4.
Splitting of alcohols into hydrogen and corresponding carbonyl compounds has potential applications in hydrogen production and chemical industry. Herein, we report that a heterogeneous photocatalyst (Ni-modified CdS nanoparticles) could efficiently split alcohols into hydrogen and corresponding aldehydes or ketones in a stoichiometric manner under visible light irradiation. Optimized apparent quantum yields of 38%, 46%, and 48% were obtained at 447 nm for dehydrogenation of methanol, ethanol, and 2-propanol, respectively. In the case of dehydrogenation of 2-propanol, a turnover number of greater than 44 000 was achieved. To our knowledge, these are unprecedented values for photocatalytic splitting of liquid alcohols under visible light to date. Besides, the current catalyst system functions well with other aliphatic and aromatic alcohols, affording the corresponding carbonyl compounds with good to excellent conversion and outstanding selectivity. Moreover, mechanistic investigations suggest that an interface between Ni nanocrystal and CdS plays a key role in the reaction mechanism of the photocatalytic splitting of alcohol.
醇的氢解和相应的羰基化合物的分裂在制氢和化学工业中有潜在的应用。在此，我们报告了一种多相光催化剂（Ni 修饰的 CdS 纳米粒子）可以在可见光照射下以化学计量的方式有效地将醇分解为氢气和相应的醛或酮。在 447nm 下，甲醇、乙醇和 2-丙醇脱氢的优化表观量子产率分别为 38%、46%和 48%。在 2-丙醇脱氢的情况下，周转数超过 44000。据我们所知，这是迄今为止可见光下光催化分解液体醇的前所未有的数值。此外，该催化剂体系还能很好地作用于其他脂肪族和芳香族醇，得到相应的羰基化合物，转化率好，选择性高。此外，机理研究表明，Ni 纳米晶和 CdS 之间的界面在光催化醇分解反应机制中起着关键作用。
