Engineering Platinum–Oxygen Dual Catalytic Sites via Charge Transfer towards Highly Efficient Hydrogen Evolution

A dual-site catalyst allows for a synergetic reaction in the close proximity to enhance catalysis. It is highly desirable to create dual-site interfaces in single-atom system to maximize the effect. Herein, we report a cation-deficient electrostatic anchorage route to fabricate an atomically dispersed platinum-titania catalyst (Pt1 O1 /Ti1-x O2 ), which shows greatly enhanced hydrogen evolution activity, surpassing that of the commercial Pt/C catalyst in mass by a factor of 53.2. Operando techniques and density functional calculations reveal that Pt1 O1 /Ti1-x O2 experiences a Pt-O dual-site catalytic pathway, where the inherent charge transfer within the dual sites encourages the jointly coupling protons and plays the key role during the Volmer-Tafel process. There is almost no decay in the activity of Pt1 O1 /Ti1-x O2 over 300 000 cycles, meaning 30 times of enhancement in stability compared to the commercial Pt/C catalysts (10 000 cycles).