Highly selective transformation of biomass derivatives to valuable chemicals by single-atom photocatalyst Ni/TiO 2 .

Selective C-C cleavage of the biomass derivative glycerol under mild conditions has been recognised as a promising yet challenging synthesis route to produce value-added chemicals. Here, a highly selective catalyst is presented for the transformation of glycerol to the high-value product glycolaldehyde, which is composed of nickel single atoms confined to the titanium dioxide surface. Driven by light, the catalyst operates under ambient conditions using air as a green oxidant. The optimised catalyst shows a selectivity of over 60% to glycolaldehyde, resulting in 1058 μmol·g Cat -1 ·h -1 production rate, and nearly 3 times higher turnover number than NiO x nanoparticle-decorated TiO 2 photocatalyst. Diverse operando and in-situ spectroscopies (including operando XANES, in-situ XPS, O 2 -TPD, EXAFS, etc.) unveil the unique function of the Ni single atom, which can significantly promote oxygen adsorption, work as an electron sink and accelerate the production of superoxide radicals, thereby improving the selectivity towards glycolaldehyde over other by-products. This article is protected by copyright. All rights reserved.