Interfacial modification of titanium dioxide to enhance photocatalytic efficiency towards H₂ production

Strong demand for affordable clean energy to support applications ranging from conventional energy supply to space propulsion places spotlight on advanced energy generation using photovoltaic and wind power. Yet, the intermittent nature of solar and wind sources drives the search for energy storage solutions that would permit the needed level of resilience and support further growth in the use of renewable sources of power. Hydrogen generation using sunlight is a promising pathway to decouple demand from supply. Herein, we show how exposure to reactive Ar-H₂, Ar-H₂-N₂, and Ar-O₂ plasma environments can notably enhance surface properties of photocatalytic TiO₂ nanosheets used in advanced energy generation systems. Treatment using Ar-H₂ plasmas produced highly hydrogenated, surface-disordered TiO₂ nanosheets with oxygen vacancies, whereas exposure to Ar-H₂-N₂ plasmas resulted in N doping. Surprisingly, Ar-O₂ plasma treatment did not change surface properties of TiO₂. Optical emission spectroscopy was used to monitor transient species to further understand surface modification in plasma. Direct measurements demonstrated that among thus-produced samples, hydrogenated TiO₂ nanosheets exhibit the highest photocatalytic H₂-generation activity under visible-light irradiation, which is also greater than the activity of pure, untreated nanosheets. The mechanism of enhancing the visible-light photocatalytic H₂-generation activity on hydrogenated TiO₂ nanosheets is also proposed. The level of surface disorder and oxygen vacancies plays an important role in enhancing visible-light absorption and reducing the recombination of photogenerated electrons and holes.