Tailoring the d-band center in Pt-based catalysts for hydrogen evolution via transition metals incorporation

Platinum-based bimetallic catalysts exhibit superior hydrogen evolution reaction performance compared to single platinum catalysts. Most studies on platinum bimetallic catalysts have focused on changing the metals used, with not much attention on how the d-band theory affects the catalyst's performance. Herein, we investigated the additional of different transition metals alters the d-band center for better hydrogen evolution. A method combining the ultrasound processing and in-situ reduction was designed, resulting in the alloys with different stacking orders. As the d-band of transition metal elements in the alloy shifts upwards, the lower the energy of the alloy's d-band center, the better the stability of the adsorption bonding exhibited by the alloy. The PtCu/C, with a hexagonal-close-packed structure and a d-band center at −1.823 eV, has an 84 mV overpotential at 100 mA cm −2 , lower than PtNi/C (89 mV) and PtCo/C (91 mV). It also has 4.75 times the mass activity of commercial Pt/C. As a cathode catalyst, PtCu/C provides improved water-splitting at 2.31 V vs. 2.55 V for commercial Pt/C (at 1 A cm −2 ). This analytical strategy through the d-band center advances the design of platinum-based bimetallic catalysts and offers a new direction for the optimization and development of hydrogen evolution reaction electrocatalysts.