Computational screening of two-dimensional metal-benzenehexathial for the oxygen reduction reaction

Abstract

Two-dimensional (2D) conductive coordination nanosheets have attracted extensive attention in facilitating the oxygen reduction reaction (ORR) due to their unique structural properties. Herein, a systematic investigation of the ORR catalyzed by conductive coordination M-BHT monolayers (M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu; BHT = benzenehexathiol) is conducted based on first-principles and constant-potential calculations. The monolayers exhibit dense single-metal-atom sites, favorable conductivity, and excellent stability, which are beneficial to electrocatalysis. A rapid screening of their ORR reactivity shows that Ni-BHT and Pt-BHT monolayers exhibit substantial activity and four-electron selectivity. Constant-potential simulation and microkinetic modeling further demonstrate the superior ORR performance of the two monolayers, and in particular, the Ni-BHT monolayer displays a theoretical half-wave potential of 0.90 V at pH = 1, which outperforms that of the Pt catalyst. This work provides essential insight into the development of conductive coordination nanosheet-based catalysts and highlights the explicit considerations of electrode potential and pH effects in electrocatalysis modeling.