Well-Dispersed Ruthenium in Mesoporous Crystal TiO as an Advanced Electrocatalyst for Hydrogen Evolution Reaction.

TiO mesoporous crystal has been prepared by one-step corroding process via an oriented attachment (OA) mechanism with SrTiO as precursor. High resolution transmission electron microscopy (HRTEM) and nitrogen adsorption-desorption isotherms confirm its mesoporous crystal structure. Well-dispersed ruthenium (Ru) in the mesoporous nanocrystal TiO can be attained by the same process using Ru-doped precursor SrTiRu O. Ru is doped into lattice of TiO, which is identified by HRTEM and super energy dispersive spectrometer (super-EDS) elemental mapping. X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance spectroscopy (EPR) suggest the pentavalent Ru but not tetravalent, while partial Ti in TiO accept an electron from Ru and become Ti, which is observed for the first time. This Ru-doped TiO performs high activity for electrocatalytic hydrogen evolution reaction (HER) in alkaline solution. First-principles calculations simulate the HER process and prove TiO:Ru with Ru and Ti holds high HER activity with appropriate hydrogen-adsorption Gibbs free energies (Δ G).