Intrinsically Activated SrTiO3: Photocatalytic H2 Evolution from Neutral Aqueous Methanol Solution in the Absence of Any Noble Metal Cocatalyst

Noble metal cocatalysts are conventionally a crucial factor in oxide-semiconductor-based photocatalytic hydrogen generation. In the present work, we show that optimized high-temperature hydrogenation of commercially available strontium titanate (SrTiO 3 ) powder can be used to engineer an intrinsic cocatalytic shell around nanoparticles that can create a photocatalyst that is highly effective without the use of any additional cocatalyst for hydrogen generation from neutral aqueous methanol solutions. This intrinsic activation effect can also be observed for SrTiO 3 [100] single crystal as well as Nb-doped SrTiO 3 [100] single crystal. For all types of SrTiO 3 samples (nanopowders and either of the single crystals), hydrogenation under optimum conditions leads to a surface-hydroxylated layer together with lattice defects visible by transmission electron microscopy, electron paramagnetic resonance (EPR), and photoluminescence (PL). Active samples provide specific defects identified by EPR, PL, and electron-energy loss spectroscopy as Ti 3+ states in a defective matrix—this is in contrast to the inactive defects formed in other reductive atmospheres. In aqueous media, active SrTiO 3 samples show a significant negative shift of the flatband potential (in photoelectrochemical as well as in capacitance data) and a lower charge-transfer resistance for photoexcited electrons. We therefore ascribe the remarkable cocatalyst-free activation of the material to a synergy between thermodynamics (altered interface energetics induced by hydroxylation) and kinetics (charge transfer mediation by suitable Ti 3+ states).