Theoretical investigation of HER/OER/ORR catalytic activity of single atom-decorated graphyne by DFT and comparative DOS analyses

• Published in: Applied surface science 2022-08, Vol.592, p.153237, Article 153237
• Main Authors: Guo, Mingming, Ji, Mingjuan, Cui, Wei
• Format: Article
• Language: English
• Subjects: CoDOSA; DFT calculation; Graphyne; Multifunctional electrocatalyst; Single-atom catalyst
• ISSN: 0169-4332; 1873-5584
• DOI: 10.1016/j.apsusc.2022.153237

[Display omitted] •Using density functional theory (DFT) simulations to identify a suitable series of metal-nonmetal co-decorated graphyne materials.•Co@GY and Ni@3B-GY would be highly promising multifunctional electrocatalysts for HER/OER/ORR.•The d-band shape of the active center is affected by the coordination environment and plays a key role in determining the surface catalytic activity.•Built quantitative structure–property relationship (QSPR) between electronic density of states (DOS) structure and catalytic performance using comparative DOS analysis (CoDOSA). Multifunctional catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) play a key role in the development of electrochemical energy systems. Moreover, single metal atoms embedded in a two-dimensional material substrate have emerged as outstanding catalysts. Owing to its large surface area and novel electronic properties, graphyne (GY) is a promising substrate for the fabrication of single-atom catalysts (SACs). By doping foreign atoms of different types on GY, their local electronic/chemical environment and catalytic performance would be improved. Based on recent experimental advances, we used density functional theory (DFT) simulations to identify a suitable series of co-decorated GY materials, with boron-, nitrogen-, phosphorus-, and sulfur-doped GY (3B-GY, 3N-GY, 3P-GY, 3S-GY) as the two-dimensional substrate, and transition metal (TM) atoms (Sc to Zn) as the single-atom centers. Our screening process showed that Co@GY and Ni@3B-GY would be highly promising multifunctional electrocatalysts for HER/OER/ORR. Then, we built quantitative structure–property relationship (QSPR) between electronic density of states (DOS) structure and catalytic performance using comparative DOS analysis (CoDOSA). The present results further support the development and application of d-band center theory. Our work identifies promising co-decorated GY for HER/OER/ORR and provides quantitative information on their DOS.