Efficient aerobic oxidation of alcohols to esters by acidified carbon nitride photocatalysts

• Published in: Journal of catalysis Vol. 393; pp. 116 - 125
• Main Authors: Wang, Chong, Wan, Qiang, Cheng, Jiajia, Lin, Sen, Savateev, Aleksandr, Antonietti, Markus, Wang, Xinchen
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.01.2021
• Subjects: Alcohol; Carbon nitride; Esterification; Photocatalysis; Selective oxidation; Selective oxidation; Alcohol; Photocatalysis; Esterification; Carbon nitride
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2020.11.021

[Display omitted] •Surface acidic sites were imparted onto the carbon nitride photocatalysts.•The adsorption and activation of the intermediate aldehyde is significantly enhanced.•Tuning the surface acidic sites could greatly change the photocatalytic activity.•Excellent conversion of alcohols to esters with up to 99% selectivity was achieved.•A scalable continuous flow systemexhibits high efficiency and stability. Photocatalytic aerobic oxidation of alcohols for the direct synthesis of esters has received significant attention in recent years, but the relatively low efficiency and selectivity under visible light irradiation is the main challenge for their practical applications. Here, surface acidic sites were imparted onto metal-free heterogeneous photocatalysts by the protonation of carbon nitride (HMCN) to promote the activity for the esterification reaction through further adsorption and activation of the intermediate aldehyde. The activation of the substrate could be remarkably modulated through tuning the acidic sites on the surface of the photocatalyst, leading to a controllable reactivity of the catalytic reaction. The one-pot process for the direct aerobic oxidative esterification of alcohol exhibits high efficiency and selectivity under mild and additive-free conditions and the apparent quantum yield (AQY) of the photocatalytic esterification reaction is 0.41% at 420 nm. Moreover, a scalable photocatalytic process by the merging of a continuous flow system with the heterogeneous HMCN photocatalyst is demonstrated, combining high catalytic efficiency and stability at ambient temperatures and being promising for larger-scale applications.