Establishing an orbital-level understanding of active origins of heteroatom-coordinated single-atom catalysts : The case of N2 reduction

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

8 Scopus Citations
View graph of relations

Detail(s)

Original languageEnglish
Pages (from-to)961-971
Journal / PublicationJournal of Colloid and Interface Science
Volume650
Issue numberPart A
Online published9 Jul 2023
Publication statusPublished - 15 Nov 2023

Abstract

Heteroatom-coordinated single-atom catalysts (SACs) supported by porous graphene exhibit high activity in electrochemical reduction reactions. However, the underlying active origins are complex and puzzling, hindering the development of efficient catalysts. Herein, we investigate the active origins of heteroatom-coordinated Fe-XmYn SACs (X, Y = B, C, N, O, m + n = 4) toward nitrogen reduction reaction (NRR) as a model reaction, through comprehensive analysis of structural, energetic, and electronic parameters. Specifically, the number and arrangement of heteroatoms are found to significantly affect the degree of d-orbital splitting and magnetic moment of the Fe center. Moreover, d-orbital splitting energy (dSE), rather than the conventional d-band theory, explains the adsorption behavior of intermediates in multi-step electron–proton coupling (EPC) reactions. In addition, both s- and d-orbitals of Fe are found to be important for Fe–N bonding, which promotes charge transfer (CT) and N2 activation. Importantly, CT is thought to influence the Pauli repulsion and orbital interaction. Correspondingly, relationships are unveiled between limiting potential (limit) and adsorption energy Δ(*NNH), dSE, CT, Fe–N bond. In all, this work provides orbital-level insights into the active origins of Fe-XmYn SACs, contributing to the understanding of intrinsic mechanism and the design of electrocatalysts for multi-step EPC reactions. © 2023 Elsevier Inc. All rights reserved.

Research Area(s)

  • Active origin, d-orbital, DFT, Nitrogen reduction, Single-atom catalysts

Citation Format(s)

Establishing an orbital-level understanding of active origins of heteroatom-coordinated single-atom catalysts: The case of N2 reduction. / Zhang, Yaqin; Wang, Yuhang; Ma, Ninggui et al.
In: Journal of Colloid and Interface Science, Vol. 650, No. Part A, 15.11.2023, p. 961-971.

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review