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 is recognized as a promising yet challenging synthesis route to produce value-added chemicals. Here, a highly selective catalyst for the transformation of glycerol to the high-value product glycolaldehyde is presented, which is composed of nickel single atoms confined to the surface of titanium dioxide. Driven by light, the catalyst operates under ambient conditions using air as a green oxidant. The optimized catalyst shows a selectivity of over 60% to glycolaldehyde, resulting in 1058 µmol g Cat -1  h -1 production rate, and ≈3 times higher turnover number than NiO x -nanoparticle-decorated TiO 2 photocatalyst. Diverse operando and in situ spectroscopies 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 toward glycolaldehyde over other by-products.