Universal band center model for the HER activity of non-metal site

TL;DR

This study uses first principles calculations and machine learning to identify key electronic factors influencing HER activity at non-metal sites in MX2 transition metal dichalcogenides, proposing a universal predictive model.

Contribution

It introduces a universal band center model based on pz band center, bandgap, and period effects for predicting HER activity of non-metal sites, validated across various catalysts.

Findings

pz band center, bandgap, and period are key HER activity factors

The non-scaling law is due to bandgap-induced state shifts

The descriptor applies broadly to different catalysts

Abstract

In this work, the hydrogen evolution reaction activities of non-metal sites in the transition metal dichalcogenides with the stoichiometry of MX2 are investigated using the first principles calculations. The trained machine learning model demonstrates that the pz band center, bandgap, and period effect are the key factors influencing the HER activity of MX2. Furthermore, it also reveals that the observed non-scaling law between the pz band center and HER activity in the semiconductor-like materials originates from the bandgap-induced downshift of bonding and antibonding states. In addition to the bandgap, the intrinsic p orbital energy level of the non-metal atoms also contributes to the periodic variation of pz band center. Extended calculations indicate that the descriptor is equally applicable to the other catalysts, suggesting its universality in predicting the HER activity of non-metal sites.