Designing highly active and non-precious-metal single-atom catalysts (SAC) for electrochemical water splitting is of great significance to the development of renewable hydrogen energy in future. SAC have attracted increasing attention in important electrocatalytic reaction such as the oxygen evolution reaction (OER). Due to the local electronic/chemical environment on graphyne (GY) surface, which is significantly influenced and contribute to its improved catalytic performance by doping foreign atoms with different formats. Herein, by means of density functional theory (DFT) simulations coupled with machine learning (ML) technology, we explore the quantitative structure-property relationship (QSPR) and catalytic activity of SAC, where metal is coordinated by B, C, N, P, S-doped graphyne. The distinct OER performance depends on the reaction free energy of *OH, *O and *OOH (G*OH, G*O, G*OOH). The values of G*OH, G*O and G*OOH are accurately predicted via partial least square (PLS) only by using simply structural and elemental feature. The approach is based on combining a complex machine-learning model trained on the dataset which 10 typical transition-metals (TM) single atoms (Sc, Ti, V, Cr, Mn, Pd, Ag, W, Os, Ir) and nonmetal (B, C, N, P, S) decorated graphyne nanosheet (TM@GY, TM@3B-GY, TM@3N-GY, TM@3P-GY, TM@3S-GY) as electrocatalysts for OER by DFT calculation. With the analysis of combined descriptors and the feature importance, the d-band centers is a key factor to influence OER activity of the decorated graphyne. The d-band centers of decorated graphyne is affected with the d-band of transition-metal and the p-band of nonmetal. Thus, we adopt machine-learning approach to identify the activity origin for the OER on graphyne, which input data is partial densities of states (PDOS) and output data is the reaction free energy on OER. Our work not only identifies promising yet unexplored in the experiment, but also provides useful guidelines for the development of novel and highly efficient OER catalysts.

Theoretical investigation of metal-nonmetal co-decorated graphyne for electrocatalytic water splitting by DFT study and CoDOSA model

ACS Fall 2021

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.