Intermetallic compounds with high hydrogen evolution reaction performance: a case study of a MCo2 (M = Ti, Zr, Hf and Sc) series†
Noble metals (e.g., Ru, Ir and Pt) or their derivatives exhibit very appealing activity toward the hydrogen evolution reaction (HER), but their high price and low reserves impede their wide use. Herein, we propose a strategy in which, through the manipulation of crystal and electronic structure, one can convert a common metal to have a Pt-like performance for HER. To achieve this goal, a series of MCo2 (M = Ti, Zr, Hf and Sc) has been synthesized by using a rapid arc-melting method. TiCo2 exhibits comparable HER activity to that of Pt/C, for which it requires only −70 mV (V vs. RHE) to reach 10 mA cm−2 with a Tafel slope of 33 mV decade−1 in 1.0 M KOH. Moreover, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) indicate that the lower adsorption energy (ΔGH*) of H on the Co atom in TiCo2, due to the change in Co electronic state, is another key factor to account for its high HER activity. This case study offers a good illustration of how to transform a non-noble metal so it behaves like a noble metal toward HER and can potentially be applied under other conditions.