Photocatalytic Production of Ethanolamines and Ethylenediamines from Bio‐Polyols over a Cu/TiO2 Catalyst

Abstract Valorization of biomass‐derived polyols into high‐value‐added ethanolamines and ethylenediamines is highly attractive. Herein, we report a one‐step photocatalytic protocol to convert bio‐polyols into a 60 % yield of ethanolamines and ethylenediamines over a multifunctional Cu/TiO 2 catalyst. This catalyst enables a tandem process of photocatalytic polyol C−C bond cleavage and reductive amination in one pot at room temperature, and also allows the selective conversion of various bio‐polyols and amines. Mechanistic studies revealed that photogenerated holes in TiO 2 promote the retro‐aldol C−C bond cleavage or oxidative dehydrogenation of polyols, and photogenerated electrons accumulate on small‐sized Cu clusters, which facilitate the reductive amination via hydrogen transfer and prevent the H 2 generation. This strategy provides new opportunities for the development of non‐noble metal photocatalysts and methods of biomass conversion under mild conditions.