Low-Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation

Low-Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation

© 2024 Wiley‐VCH GmbH.

Bibliographische Detailangaben
Veröffentlicht in:Advanced materials (Deerfield Beach, Fla.). - 1998. - 36(2024), 52 vom: 02. Dez., Seite e2412598
1. Verfasser: Wang, Yihao (VerfasserIn)
Weitere Verfasser: Li, Shanqing, Hou, Xu, Cui, Tingting, Zhuang, Zechao, Zhao, Yunhe, Wang, Haozhi, Wei, Wei, Xu, Ming, Fu, Qiang, Chen, Chunxia, Wang, Dingsheng
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2024
Zugriff auf das übergeordnete Werk:Advanced materials (Deerfield Beach, Fla.)
Schlagworte:Journal Article defect engineering layered double hydroxides low‐spin Fe3+ spin state regulation water oxidation
Beschreibung
Zusammenfassung:© 2024 Wiley‐VCH GmbH.
Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin-state manipulation holds great promise to break through this bottleneck. Low-spin Fe3+ (LS, t2g 5eg 0) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe3+ in NiFe-layered double hydroxide (NiFe-LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their d orbital splitting energy. The as-obtained catalyst exhibits extraordinary OER performance with an ultra-low overpotential of 244 mV at the industrially required current density of 500 mA cm-2, which is 110 mV lower than that of the conventional NiFe-LDH with high-spin Fe3+ (HS, t2g 3eg 2) and superior to most previously reported NiFe-based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe3+ configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate-determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin-dependent electrocatalysts for OER and beyond
Beschreibung:Date Revised 28.12.2024
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:1521-4095
DOI:10.1002/adma.202412598