Tunable Hydrogen Doping of Metal Oxide Semiconductors with Acid–Metal Treatment at Ambient Conditions

Hydrogen doping of metal oxide semiconductors is promising for manipulation of their properties toward various applications. Yet it is quite challenging because it requires harsh reaction conditions and expensive metal catalysts. Meanwhile, acids as a cheap source of protons have long been unappreciated. Here, we develop a sophisticated acid-metal treatment for tunable hydrogenation of metal oxides at ambient conditions. Using first-principles simulations, we first show that, with proper work function difference between the metal and metal oxide, H-diffusion into negatively charged metal oxide can be well controlled, resulting in tunable H-doping of metal oxides with quasi-metal characteristics. This has been verified by proof-of-concept experiments that achieved the controllable hydrogenation of WO₃ using Cu and hydrochloric acid at ambient conditions. Further, H-doping of other metal oxides (TiO₂/Nb₂O₅/MoO₃) has been achieved by metal-acid treatment and induced a change in properties. Our work provides a promising way to tailor metal oxides via tunable H-doping.