First-row transition metal embedded pyrazine-based graphynes as high-performance single atom catalysts for the CO2 reduction reaction. Issue 16 (25th March 2022)

• Record Type: Journal Article
• Authors: Wang, Maohuai; Kong, Lingyan; Lu, Xiaoqing; Lawrence Wu, Chi-Man
• Is Part Of: Journal of materials chemistry. Volume 10:Issue 16(2022)
• Page Start: 9048
• Page End: 9058
• Publication Date: 2022-03-25
• Subjects: Materials -- Research -- Periodicals; Chemistry, Analytic -- Periodicals; Environmental sciences -- Research -- Periodicals; 543.0284
• DOI: 10.1039/d2ta00654e
• Languages: English
• ISSNs: 2050-7488

Abstract

Abstract : First-row transition metal embedded pyrazine-based graphynes (TM-pyGYs), especially Mn/Fe/Co/Ni-pyGYs are promising single atom catalysts for the CO2 reduction reaction. Abstract : Single atom catalysts (SACs) have displayed unprecedented activity and selectivity toward the electrochemical CO2 reduction reaction (CO2 RR). Herein, first-row transition metal embedded pyrazine-based graphynes (TM-pyGYs) were evaluated as potential SACs for the CO2 RR by using density functional theory. The computational results showed that TM-pyGYs exhibited large cohesive energies ranging from 6.67 to 6.78 eV per atom and metal binding energies ranging from 0.79 to 5.48 eV. Electronic structure analyses demonstrated the strong covalent bond, large charge transfer, and distinct orbital overlap between the TM atoms and pyGY, which proved the high stability of TM-pyGYs in the CO2 RR. Most TM-pyGYs exhibited preferred CO2 RR selectivity over the hydrogen evolution reaction. The most favorable reaction pathways of the CO2 RR to CO, HCOOH, CH3 OH, and CH4 on TM-pyGYs were systematically explored. Among all the TM-pyGYs, Mn/Fe/Ni-pyGYs were determined to be outstanding electrocatalysts in the CO2 RR for producing HCOOH with low limiting potentials of −0.21 to −0.36 V, and Co-pyGY exhibited high-performance CO2 RR to CH4 with a low limiting potential of −0.35 V, which surpassed the performance of the vast majority of electrocatalysts. With applied potential, Fe/Co/Ni-pyGYs exhibited great advantages in the CO2 RR to CH4 . The results of this work highlighted TM-pyGYs as ideal SACs for the electrochemical CO2 RR.