Boosting Benzene Oxidation with a Spin‐State‐Controlled Nuclearity Effect on Iron Sub‐Nanocatalysts. (13th December 2022)

• Record Type: Journal Article
• Authors: Bu, Fanle; Chen, Chaoqiu; Yu, Yu; Hao, Wentao; Zhao, Shichao; Hu, Yongfeng; Qin, Yong
• Is Part Of: Angewandte Chemie. Volume 135:Number 3(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-12-13
• Subjects: Benzene Oxidation -- Coordination Environment -- Fe Sub-Nanocatalysts -- Nuclearity Effect -- Spin Configuration; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202216062
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A fundamental understanding of the nature of nuclearity effects is important for the rational design of superior sub‐nanocatalysts with low nuclearity, but remains a long‐standing challenge. Using atomic layer deposition, we precisely synthesized Fe sub‐nanocatalysts with tunable nuclearity (Fe1 –Fe4 ) anchored on N, O‐co‐doped carbon nanorods (NOC). The electronic properties and spin configuration of the Fe sub‐nanocatalysts were nuclearity dependent and dominated the H2 O2 activation modes and adsorption strength of active O species on Fe sites toward C−H oxidation. The Fe1 ‐NOC single atom catalyst exhibits state‐of‐the‐art activity for benzene oxidation to phenol, which is ascribed to its unique coordination environment (Fe1 N2 O3 ) and medium spin state ( t2g 4 eg 1 ); turnover frequencies of 407 h −1 at 25 °C and 1869 h −1 at 60 °C were obtained, which is 3.4, 5.7, and 13.6 times higher than those of Fe dimer, trimer, and tetramer catalysts, respectively. Abstract : An atomic layer deposition approach precisely tunes the nuclearity of Fe sub‐nanocatalysts anchored on N, O‐doped carbon nanorods. The electronic properties and spin configuration of the sub‐nanocatalysts are nuclearity dependent and dominate H2 O2 activation modes and the adsorption strength of active O species on Fe sites during C−H oxidation. The single‐atom catalyst, Fe1 ‐NOC, achieves state‐of‐the‐art activity for benzene oxidation.