Boosting Benzene Oxidation with a Spin‐State‐Controlled Nuclearity Effect on Iron Sub‐Nanocatalysts
Fanle Bu, Chaoqiu Chen, Yu Yu, Wentao Hao, Shichao Zhao, Yongfeng Hu, Yong Qin
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 (Fe 1 –Fe 4 ) 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 H 2 O 2 activation modes and adsorption strength of active O species on Fe sites toward C−H oxidation. The Fe 1 ‐NOC single atom catalyst exhibits state‐of‐the‐art activity for benzene oxidation to phenol, which is ascribed to its unique coordination environment (Fe 1 N 2 O 3 ) and medium spin state ( t 2g 4 e g 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.