Prediction of HER electrocatalyst with enhanced performance based on atoms-doped black phosphorene: A first-principles study

Black phosphorene (BP), with great potential as electrocatalyst material, has been paid much attention around the world due to its unique structural and electronic properties. And doping of atoms has been regarded as an efficient method to boost their electrocatalytic performance. Herein, we investigated the structural characteristics and hydrogen evolution reaction (HER) performance of atoms-doped BP based on density functional theory (DFT) calculations. The results show that the doping of metal atoms can readjust the Bader charge distribution and density of state (DOS), improving their electronic properties. In addition, among the systems doped with eight kinds of elements (e.g. Fe, Co, Ni, Cu, Ru, Rh, Pd, and Ag), the Fe-doped BP (Fe/BP) presents most nearly neutral hydrogen adsorption free energies (ΔGH*, 0.034 eV), the highest charge exchange between Fe and P through the Fe-P bond, the highest charge exchange between H and Fe/BP model, and its d-band center is most nearly the Femi level as compared with the other systems. The results mentioned above can verify that the doping of metal atoms, especially the doping of Fe atoms can improve the HER performance obviously. This work can provide theoretical significance for the design of high-efficiency HER electrocatalyst.