Computational screening toward transition metal doped vanadium carbides in different crystal planes for efficient hydrogen evolution: a first-principles study

In the present work, we evaluated the hydrogen evolution reaction (HER) performance of transition metal (Co, Fe, Ni, Mn, and Mo) doped vanadium carbides (VC). In addition, the doping atoms were screened separately on the (100), (110) and (111) crystal planes to analyze the differences in HER activities. Among all the calculated models, Mn-VC(100) exhibited the best catalytic hydrogen evolution performance with a Gibbs free energy for hydrogen adsorption (ΔGH*) of 0.0012 eV. Doping Mn greatly improved the HER performance of VC(100) by enhancing the adsorption of hydrogen on the catalyst surface. The analysis of the electronic density of states and charge transfer confirmed that doping transition metal atoms into the surfaces of the VC model successfully optimized the electronic structure and promoted catalytic reaction kinetics. Besides, the relationship between the catalytic activity and pH value of different models was considered, and doping Co atoms on the (100) crystal plane could effectively modify the pH value range applicable for the efficient HER. Interestingly, even if the same metal atoms were doped, various active sites of VC models exhibited different catalytic performances due to disparate exposed crystal planes and pH values. This indicates that the main exposed crystal surfaces and the pH range of application need to be considered when selecting the appropriate doping element for the catalyst.