Regulating local polarization in hollow multi-shelled nanospheres for efficient atomic site activation towards selective aerobic oxidation of aromatic alcohols

Abstract

Light-driven selective organic synthesis presents a promising means to sustainable production of value-added fine chemicals. Nonetheless, the photocatalytic efficiency is obstructed by low charge transfer efficiency and few uncoordinated electrons. Herein, hollow multi-shelled PbBiOBr nanospheres with atomically thin shells and richly local polarization sites were initially synthesized to effectively tackle these issues. The ultrathin hollow multi-shelled geometry facilitates charge separation and offers spatially distributed catalytic sites for redox reactions. The local polarization induced by oxygen vacancies can afford abundant coordination-unsaturated sites, effectively facilitate the activation of O and benzyl alcohol, significantly lower free energy barrier through the formation of stable Pb−O−Bi intermediate. Consequently, the richly polarized PbBiOBr hollow multi-shelled nanospheres exhibit excellent catalytic activity (96 % conversion and 99 % selectivity) and superior adaptability for selective oxidation of aromatic alcohols to aldehydes. The results can motivate the study on hollow multi-shelled geometry with local polarization for fine chemicals photosynthesis.