Enhanced Photocatalytic Hydrogen Evolution with TiO₂–TiN Nanoparticle Composites

Metal nitrides have potential in energy applications because of their physical and optical properties. Nanoparticle composites of titanium nitride (TiN) and titanium dioxide (TiO2) were investigated for their photocatalytic hydrogen (H2) evolution activity via methanol reformation. Physical mixing of the nanoparticulate TiO2 and TiN was employed to prevent the oxy-nitride formation and particle aggregation observed in thermal preparations. This convenient combination of TiO2 and TiN demonstrated a substantial synergistic effect with enhanced activity (9.4 μmol/h TiO2–TiN vs 1.8 μmol/h TiO2) under combined UV/vis light. Irradiation under only UV light resulted in a similar enhancement factor compared to using combined UV/vis light, demonstrating that the enhanced activity of the composites occurs essentially for UV-driven photocatalysis. No activity/enhancement was observed with only visible light irradiation; however, minor enhancement was observed when switching between UV and UV/vis irradiation, suggesting a contribution from the TiN plasmon. We propose that the plasmonic contribution is dependent on the band gap excitation of TiO2, which reduces the degree of band bending at the TiO2/TiN interface. This promotes the migration of hot electrons from TiN away from the TiO2/TiN interface to be used for H2 evolution