Component-Controlled Synthesis of Necklace-Like Hollow NiXRuy Nanoalloys as Electrocatalysts for Hydrogen Evolution Reaction.

Developing highly efficient and long-durable nanoalloy electrocatalysts toward the hydrogen evolution reaction (HER) are highly desirable for implementation of the water-splitting technique to prepare clean fuels. Though great progress has been achieved, controllable synthesis of hollow NixRuy nanoalloys with a wide component ratio range remains a challenge and their applications for HER have not been explored. Here, a series of necklace-like hollow NixRuy nanoalloys (Ni72Ru28, Ni63Ru37, Ni43Ru57, and Ni29Ru71) are prepared using the galvanic replacement reaction between the Ni nanochains and RuCl3·3H2O and the hollowing process based on the Kirkendall effect. Electrochemical tests reveal that those NixRuy nanoalloys can efficiently catalyze HER in acidic media. Among them, the Ni43Ru57 nanoalloy exhibits the highest catalytic activity with an overpotential of 41 mV to attain a current density of -10 mA cm-2, outperforming other NixRuy nanoalloys and close to commercial Pt/C. Additionally, its current density will exceed Pt/C catalyst as the overpotential surpasses 102 mV. Moreover, such Ni43Ru57 nanoalloy also shows an exceptional durability that can continuously work for 8 h only with a little loss of activity. Deduced from some featured spectroscopic and electrochemical analysis, the excellent catalytic performance of Ni43Ru57 nanoalloy is attributed to the proper component ratio and effective electronic coupling of Ni and Ru, causing the faster interfacial electron transfer kinetics and more available active sites on it compared with other NixRuy nanoalloy ones.