Direct Electrochemical Protonation of Metal Oxide Particles

Metal oxides with surface protonation exhibit versatile physical and chemical properties suitable for use in many fields. Here, we develop an electrochemical route to directly protonize the physically assembled oxide particles, such as TiO₂, Nb₂O₅, and WO₃, in a Na₂SO₄ neutral electrolyte, which is a result of electrochemically induced oxygen vacancies reacting with water molecules. With no need of electric connection among particles or between particles and conductive substrate, the electrochemical protonation follows a bottom-up particle-by-particle surface protonation mechanism due to the fact that the protonation inducing high surface conductivity creates an efficient electron transfer pathway among particles. Our results show that electrochemical protonation of particles provides a chance to finely functionalize the surface of a single particle by only adjusting electrode potentials. Such a facile, cost-efficient, and green route is easy to run for a large-scale production and unlocks the potential of semiconductor oxides for various applications.