D-band center modulation of supported Ru on phosphorous doped black TiO2 for efficient hydrogen generation

Metal oxide has been considered as promising support to regulate the active microenvironment of noble metals to promote the catalytic performance, but they suffer from unsatisfactory electrical resistance and poor stability. Herein, ultrafast quasi-solid microwave (60 s) is employed to achieve phosphorous-doped black TiO2 supported Ru (Ru/P-TiO2) with d-band center modulation to optimize the reaction kinetics of hydrogen evolution reaction (HER). The as-synthesized Ru/P-TiO2 exhibits extraordinary HER activities in alkaline fresehwater/seawater electrolytes with overpotential of 43 mV to reach 10 mA cm−2 coupled with satisfactory stability. Experiment and density functional theory (DFT) calculation clarify that the achieved Ru/P-TiO2 owns optimal d-band center for H* adsorption. Moreover, the phosphorous doping enhanced the electronic interactions between Ru and oxygen vacancy-enriched TiO2 to optimize the reaction kinetics and enhance the stability. This work provides promising strategy to modulate the metal oxide matrix for designing novel catalysts on energy conversion and storage applications.