Transition metal loaded carbon penta-belt SACs for hydrogen and oxygen evolution reactions and identification of systematic DFT method to characterize the main interacting orbital for non-periodic system

Abstract

In the pursuit of efficient hydrogen and oxygen production via water electrolysis, the deployment of single atom catalysts (SACs) plays a pivotal role in reducing the overpotential of this process on a large scale. Hence, the quest for suitable support materials remains imperative for the design of superior SACs. In this study, we explored the potential of the recently proposed penta-belt structure as a support matrix for anchoring late first-row transition metals (Fe - Zn). The catalytic prowess of these engineered SACs in facilitating water electrolysis is assessed through density functional theory (DFT) calculations. Remarkably, the Cu@Penta-belt SACs exhibits the highest catalytic activity for the hydrogen evolution reaction (HER), with a remarkably low ΔGH value of 0.17 eV. Additionally, Ni@Penta-belt demonstrates a competitively moderate overpotential of 0.72 V for the oxygen evolution reaction (OER). To deepen our comprehension of the bonding interactions between the metal atoms and the support structure, we introduce and apply a systematic approach for identifying and analyzing the primary binding molecular orbital. This innovative methodology can be extended to diverse doping investigations that necessitate non-periodic DFT calculations.