TY - JOUR
T1 - Boosting Benzene Oxidation with a Spin-State-Controlled Nuclearity Effect on Iron Sub-Nanocatalysts
AU - Bu, Fanle
AU - Chen, Chaoqiu
AU - Yu, Yu
AU - Hao, Wentao
AU - Zhao, Shichao
AU - Hu, Yongfeng
AU - Qin, Yong
N1 - Publisher Copyright:
© 2022 Wiley-VCH GmbH.
PY - 2023/1/16
Y1 - 2023/1/16
N2 - 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 H2O2 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 (Fe1N2O3) and medium spin state (t2g4eg1); 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.
AB - 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 H2O2 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 (Fe1N2O3) and medium spin state (t2g4eg1); 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.
KW - Benzene Oxidation
KW - Coordination Environment
KW - Fe Sub-Nanocatalysts
KW - Nuclearity Effect
KW - Spin Configuration
UR - http://www.scopus.com/inward/record.url?scp=85143791336&partnerID=8YFLogxK
U2 - 10.1002/anie.202216062
DO - 10.1002/anie.202216062
M3 - 文章
C2 - 36412226
AN - SCOPUS:85143791336
SN - 1433-7851
VL - 62
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 3
M1 - e202216062
ER -