Ordered Mesoporous TiO₂ Gyroids: Effects of Pore Architecture and Nb‐Doping on Photocatalytic Hydrogen Evolution under UV and Visible Irradiation

Abstract

Abstract Pure and Nb‐doped TiO 2 photocatalysts with highly ordered alternating gyroid architecture and well‐controllable mesopore size of 15 nm via co‐assembly of a poly(isoprene)‐ block ‐poly(styrene)‐ block ‐poly(ethylene oxide) block copolymer are synthesized. A combined effort by electron microscopy, X‐ray scattering, photoluminescence, X‐ray photoelectron spectroscopy, Raman spectroscopy, and density functional theory simulations reveals that the addition of small amounts of Nb results in the substitution of Ti 4+ with isolated Nb 5+ species that introduces inter‐bandgap states, while at high concentrations, Nb prefers to cluster forming shallow trap states within the conduction band minimum of TiO 2 . The gyroidal photocatalysts are remarkably active toward hydrogen evolution under UV and visible light due to the open 3D network, where large mesopores ensure efficient pore diffusion and high photon harvesting. The gyroids yield unprecedented high evolution rates beyond 1000 µmol h −1 (per 10 mg catalyst), outperforming even the benchmark P25‐TiO 2 more than fivefold. Under UV light, the Nb‐doping reduces the activity due to the introduction of charge recombination centers, while the activity in the visible triple upon incorporation is owed to a more efficient absorption due to inter‐bandgap states. This unique pore architecture may further offer hitherto undiscovered optical benefits to photocatalysis, related to chiral and metamaterial‐like behavior, which will stimulate further studies focusing on novel light–matter interactions.