Ordered PtNiTiZrHf nanoparticles on carbon nanotubes catalyze hydrogen evolution reaction with high activity and durability

With the scarcity of the earth's natural resources, hydrogen production from electrolyzing water is seen as an alternative energy source. Although platinum (Pt) is an advanced catalyst for hydrogen evolution reaction (HER), its application is limited by high cost and limited electrocatalytic performance. In this article, the five-element alloy nanoparticles are successfully synthesized on carbon nanotubes (CNT) by employing liquid-phase reduction and gas-phase sintering to reduce Pt utilization and improve catalytic performance. For comparison, a series of ordered and disordered (PtNi)x(TiZrHf)100-x/CNT catalysts are obtained. Results show that the ordered samples have more excellent HER catalytic performance and stability than disordered samples in 0.5 M H2SO4 and 1 M KOH electrolytes. In particular, when the electrolyte is acidic, the overpotentials of ordered (PtNi)55(TiZrHf)45/CNT at 10 and 100 mA cm-2 are 11 and 52 mV, with low Tafel slope of 37.73 mV dec- 1. At 10 mA cm-2, the stabilization time can reach 58 h, which is much better than commercial Pt/C (20 wt.%). Density functional theory (DFT) calculation shows that ordered (PtNi)55(TiZrHf)45/CNT has lower hydrogen adsorption energy and activated water adsorption energy than disordered one, indicating better performance in both acidic and alkaline electrolytes. It is mainly attributed to the electronic coupling effect after ordering that makes the overall D-band center decrease. This work presents a cost-effective approach to optimize the structural design for acid-base HER electrocatalysts.