Oxygen Vacancy Shell Coupled Pt Clusters Engineering for Sunlight Driven Selective Decarboxylation of Amino Acids

ABSTRACT Solar‐driven photocatalytic decarboxylation of amino acids is promising for the production of bio‐based amines to address intensive energy consumption and overmuch CO ₂ emissions in conventional thermo‐catalytic process. In this work, we design a new heterogeneous photocatalyst with a rich oxygen vacancy (V _O ) shell and Pt nanoclusters (Pt NCs) in TiO _2. The results unveil a strong interaction between the amorphous V _O ‐shell layer and Pt NCs in the engineered Pt/TiO ₂ @V _O ‐shell catalyst, leading to a prolonged lifetime from 0.79 to 1.12 ns. In the photocatalytic decarboxylation of L‐lysine, Pt/TiO ₂ @V _O ‐shell exhibited a cadaverine selectivity of 70.2% and productivity of 154.5 mM/g, which is 14 and 111 times higher than that of TiO ₂ @V _O ‐shell. Notably, under sunlight irradiation of 1 h, the selectivity further increased to 73.5%. In addition, for other amino acids containing aliphatic side chains, the selectivity toward the corresponding amines exceeded 50%. Mechanistic study shows that positively charged V _O s facilitate the adsorption and activation of L‐lysine via forming a bidentate bridging to produce alkyl radicals, while Pt NCs significantly promote the formation of hydrogen‐rich surface of TiO ₂ to give a high selectivity of cadaverine. This work offers a novel design strategy of catalysts for bridging a sustainable solar energy utilization and high‐valued chemical synthesis.