Tuning regioselective oxidation toward phenol via atomically dispersed iron sites on carbon

Yuxiao Ding; Pengfei Zhang; Hailong Xiong; Xiaoyan Sun; Alexander Klyushin; Bingsen Zhang; Zigeng Liu; Jinshui Zhang; Huiyuan Zhu; Zhen-An Qiao; Saskia Heumann; Sheng Dai

doi:10.1039/D0GC01717E

Tuning regioselective oxidation toward phenol via atomically dispersed iron sites on carbon†

Yuxiao Ding,^ab Pengfei Zhang,

^b Hailong Xiong,^c Xiaoyan Sun,^ad Alexander Klyushin,

^e Bingsen Zhang,

^f Zigeng Liu,

^g Jinshui Zhang,

^b Huiyuan Zhu,

^b Zhen-An Qiao,

*^c Saskia Heumann

*^a and Sheng Dai

*^b

Author affiliations

* Corresponding authors

^a Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 43-36, Mülheim an der Ruhr 45470, Germany
E-mail: saskia.heumann@cec.mpg.de

^b Chemical Science Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
E-mail: dais@ornl.gov

^c State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China
E-mail: qiaozhenan@jlu.edu.cn

^d Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, Berlin 10623, Germany

^e Fritz-Haber-Institut der Max-Planck Gesellschaft, Faradayweg 4-6, Berlin 14195, Germany

^f Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

^g Institute of Energy and Climate Research, Forschungzentrum Jülich GmbH, Ostring O10, Jülich 52425, Germany

Abstract

The development of environmentally benign catalysts for highly regioselective hydroxylation of phenol remains an unsolved challenge in both industry and academia because the electrophilic substitution of phenol simultaneously occurs on both ortho- and para-positions. Herein, we report a designed atomically dispersed iron-based heterogeneous catalyst, in which the iron species is coordinated by a functionalized ionic liquid monolayer on carbon nanotubes. The catalyst exhibits an unprecedented level of regioselectivity (>99%) towards the hydroxylation of phenol and displays a much better activity (TOF towards catechol productivity, 1.79 s⁻¹) compared to the homogeneous free ion system (TOF towards catechol productivity, 0.44 s⁻¹). Both experimental and theoretical investigations confirm that the catalytic oxidation with hydroperoxide undergoes a non-radical addition process and substitutes only the ortho-positions of phenol. This finding provides not only a quite active and selective catalyst for industrially very important reactions, but also a promising methodology of designing biomimetic iron-based heterogeneous catalysts at the atomic level.

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Tuning regioselective oxidation toward phenol via atomically dispersed iron sites on carbon†

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