Activating HfX 2 (X = S, Se and Te) for the hydrogen evolution reaction by introducing defects: a first-principles study.

An ideal catalyst should have a relative hydrogen adsorption Gibbs free energy (Δ G H ) close to zero [J. K. Nørskov, et al., J. Electrochem. Soc. , 2005, 152 , J23]. However, most of the known catalysts cannot reach this standard. Based on first-principles calculations, we studied the hydrogen evolution reaction (HER) catalytic performance of pristine and defect (including vacancy and heteroatom doping) structures in terms of its Δ G H . We found that the Δ G H values of Co-doped HfS 2 and P-doped HfSe 2 are extremely close to zero, even closer than that of Pt (111), indicating that they are excellent catalysts. Moreover, we found that the source of the HER catalytic performance of Co-doped HfS 2 is the reduction of electron accumulation of the active site S atom. Our work provides two potential ideal catalysts and provides guidance for the experimental group to search for suitable catalysts.