TY - JOUR
T1 - The Deposition of Isolated Fe(3+) Species in Mesoporous Silicon for Oxidation of Cyclohexane
AU - Zhai, Liming
AU - Zhang, Bin
AU - Li, Haitao
AU - Jiang, Min
AU - Yang, Xinchun
AU - Li, Zhuo
AU - Zhao, Shichao
AU - Qin, Yong
N1 - Publisher Copyright:
© 2023 Wiley-VCH GmbH.
PY - 2023/12/7
Y1 - 2023/12/7
N2 - The balance of activity and selectivity in liquid alkane oxidation is challenging for the design of supported Fe catalysts. When Fe species leach to the solvent, uncontrolled free radical chain reactions happen. Herein, isolated Fe(3+) species were constructed by forming a strong Fe−O−Si bond for the selective oxidation of cyclohexane to cyclohexanone by H2O2. Compared to the supported FeOx clusters, the strong Fe−O−Si bond between isolated Fe(3+) species and SiO2 prevents the leaching of Fe in strong oxidation (H2O2) reaction conditions and dominates the non-free radical mechanism. The turnover frequency over 10FeOx/SBA-15 reached 15.2 h−1, higher than for reported Fe-based catalysts. High selectivity of cyclohexanone is maintained at different conversions. Moreover, the (SiO)xFe3+(OH)3-x−OOH active species were detected by Raman and FTIR and are generated from the oxidation of isolated Fe species. The strong Fe−O−Si bond and non-free-radical mechanism by (SiO)xFe3+(OH)3-x−OOH active species induce high activity and selectivity for the oxidation of many other alkanes.
AB - The balance of activity and selectivity in liquid alkane oxidation is challenging for the design of supported Fe catalysts. When Fe species leach to the solvent, uncontrolled free radical chain reactions happen. Herein, isolated Fe(3+) species were constructed by forming a strong Fe−O−Si bond for the selective oxidation of cyclohexane to cyclohexanone by H2O2. Compared to the supported FeOx clusters, the strong Fe−O−Si bond between isolated Fe(3+) species and SiO2 prevents the leaching of Fe in strong oxidation (H2O2) reaction conditions and dominates the non-free radical mechanism. The turnover frequency over 10FeOx/SBA-15 reached 15.2 h−1, higher than for reported Fe-based catalysts. High selectivity of cyclohexanone is maintained at different conversions. Moreover, the (SiO)xFe3+(OH)3-x−OOH active species were detected by Raman and FTIR and are generated from the oxidation of isolated Fe species. The strong Fe−O−Si bond and non-free-radical mechanism by (SiO)xFe3+(OH)3-x−OOH active species induce high activity and selectivity for the oxidation of many other alkanes.
KW - Fe−O−Si bond
KW - atomic layer deposition
KW - cyclohexane oxidation
KW - isolated Fe(3+) species
KW - selective cyclohexane oxidation
UR - https://www.scopus.com/pages/publications/85176394103
U2 - 10.1002/cctc.202300887
DO - 10.1002/cctc.202300887
M3 - 文章
AN - SCOPUS:85176394103
SN - 1867-3880
VL - 15
JO - ChemCatChem
JF - ChemCatChem
IS - 23
M1 - e202300887
ER -