Mapping Hydrogen Evolution Activity Trends of V-based A15 Superconducting Alloys

TL;DR

This study systematically investigates V-based A15 superconducting alloys as efficient, durable, and low-cost electrocatalysts for hydrogen evolution, highlighting V3Si's superior performance and providing insights for designing silicide catalysts.

Contribution

It uncovers the HER activity trends of V3M alloys, identifies V3Si as a highly efficient catalyst, and offers a rational design approach for silicide electrocatalysts based on electronic structure insights.

Findings

V3Si requires only 33.4 mV at 10 mA cm-2

V3Si shows durability over 120 hours at various current densities

V3Si's HER activity is comparable or superior to Pt/C catalysts

Abstract

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 V3M (i.e., V3Si, V3Ge, and V3Sn) superconductors and show that V3Si is the most efficient HER catalyst because of the high electronic conductivity and suitable d-band center. Among them, the V3Si 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 V3Si 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 V3Si alloy can be ascribed to the synergies of superior electronic conductivity and suitable d-band center. Moreover, DFT calculations reveal that the absolute hydrogen adsorption Gibbs free energy 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.