Boosting Hydrogen Evolution Reaction by Phase Engineering and Phosphorus Doping on Ru/P-TiO2

Synergistic optimization of the elementary steps of water dissociation and hydrogen desorption for the hydrogen evolution reaction (HER) in alkaline media is a challenge. Herein, the Ru cluster anchored on a trace P-doped defective TiO2 substrate (Ru/P-TiO2) was synthesized as an electrocatalyst for the HER; it exhibited a commercial Pt/C-like geometric activity and an excellent mass activity of 9984.3 mA mg(Ru)(-1) at -0.05 V vs. RHE, which is 34.3 and 18.7 times higher than that of Pt/C and Ru/TiO2, respectively. Experimental and theoretical studies indicated that using a rutile-TiO2-crystal-phase substrate enhanced the HER activity more than the anatase phase. Rich surface oxygen vacancies on rutile-TiO2 facilitated the adsorption and dissociation of water, while the partial substitution of Ti4+ with P5+ enhanced H-2 generation by facilitating hydrogen spillover from the Ru site to the surface P site, synergistically enhancing the HER activity.

Automated summary

In this study, a Ru cluster anchored on a trace P-doped defective TiO2 substrate (Ru/P-TiO2) was synthesized as an electrocatalyst for the hydrogen evolution reaction (HER) in alkaline media. The Ru/P-TiO2 exhibited superior activity compared to commercial Pt/C and Ru/TiO2 materials. Experimental and theoretical studies revealed that the rutile-TiO2 crystal phase substrate with rich surface oxygen vacancies facilitated water adsorption and dissociation, while P substitution enhanced hydrogen generation by promoting hydrogen spillover, synergistically enhancing the HER activity.