Mapping hydrogen evolution activity trends of V-based A15 superconducting alloys.

[Display omitted] • A series of V-based Si-group intermetallic compounds were successfully synthesized. • The excellent HER activity of V 3 Si in V-based Si-group intermetallic compounds. • High electronic conductivity and a suitable d -band center contributed to an excellent performance by HER. • Providing the fundamental guidance of rational design of desirable silicide electrocatalysts. Exploring high-efficiency and low-cost electrocatalysts is valuable for water-splitting technologies. Recently, Si-group compounds have attracted increasing attention in electrocatalysis, considering the abundant Si-group elements on Earth. However, Si-group compounds for HER electrocatalysis have not been systematically studied. In this study, we unveil the activity trends of non-noble metal catalyst A15-type V 3 M (i.e. , V 3 Si, V 3 Ge, and V 3 Sn) superconductors and show that V 3 Si is the most efficient HER catalyst because of the high electronic conductivity and suitable d -band center. Among them, the V 3 Si only requires 33.4 mV to reach 10 mA cm−2, and only 57.6 mV and 114.6 mV are required to attain a high current density of 100 mA cm−2 and 500 mA cm−2, respectively. These low overpotentials are close to the 34.3 mV at 10 mA cm−2 of state-of-art Pt/C (20 %) but superior to 168.5 mV of Pt/C (20 %) at 100 mA cm−2. Furthermore, the V 3 Si illustrates exceptional durability with no obvious decay in the 120 h at the different current densities (i.e. , 10–250 mA cm−2). The excellent HER activity of V 3 Si alloy can be ascribed to the synergies of superior electronic conductivity and suitable d -band center. Moreover, DFT calculations reveal that |ΔG H* | is decreased after introducing the V to Si. Beyond offering a stable and high-performance electrocatalyst in an acidic medium, this work inspires the rational design of desirable silicide electrocatalysts. [ABSTRACT FROM AUTHOR]