Electronic-State Manipulation of Surface Titanium Activates Dephosphorylation Over TiO₂ Near Room Temperature

Dephosphorylation that removes a phosphate group from substrates is an important reaction for living organisms and environmental protection. Although CeO₂ has been shown to catalyze this reaction, cerium is low in natural abundance and has a narrow global distribution (>90 % of these reserves are located within six countries). It is thus imperative to find another element/material with high worldwide abundance that can also efficiently extract the phosphate out of agricultural waste for phosphorus recycle. Using para-nitrophenyl phosphate (p-NPP) as a model compound, we demonstrate that TiO₂ with a F-modified (001) surface can activate p-NPP dephosphorylation at temperatures as low as 40 °C. By probe-assisted nuclear magnetic resonance (NMR), it was revealed that the strong electron-withdrawing effect of fluorine makes Ti atoms (the active sites) on the (001) surface very acidic. The bidentate adsorption of p-NPP on this surface further promotes its subsequent activation with a barrier ≈20 kJ mol^-1 lower than that of the pristine (001) and (101) surfaces, allowing the activation of this reaction near room temperature (from >80 °C).