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Dynamic evolution of nitrogen and oxygen dual-coordinated single atomic copper catalyst during partial oxidation of benzene to phenol

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Abstract

Single atom catalysts (SACs) with metal1-Nx sites have shown promising activity and selectivity in direct catalytic oxidation of benzene to phenol. The reaction pathway is considered to be involving two steps, including a H2O2 molecule dissociated on the metal single site to form the (metal1-Nx)=O active site, and followed by the dissociation of another H2O2 on the other side of metal atom to form O=(metal1-Nx)=O intermediate center, which is active for the adsorption of benzene molecule via the formation of a C-O bond to form phenol. In this manuscript, we report a Cu SAC with nitrogen and oxygen dual-coordination (Cu1-N3O1 moiety) that doesn’t need the first H2O2 activation process, as verified by both experimental and density function theory (DFT) calculations results. Compared with the counterpart nitrogen-coordinated Cu SAC (denoted as Cu1/NC), Cu SAC with nitrogen and oxygen dual-coordination (denoted as Cu1/NOC) exhibits 2.5 times higher turnover frequency (TOF) and 1.6 times higher utilization efficiency of H2O2. Particularly, the coordination number (CN) of Cu atom in Cu1/NOC maintains four even after H2O2 treatment and reaction. Combining DFT calculations, the dynamic evolution of single atomic Cu with nitrogen and oxygen dual-coordination in hydroxylation of benzene is proposed. These findings provide an efficient route to improve the catalytic performance through regulating the coordination environments of SACs and demonstrate a new reaction mechanism in hydroxylation of benzene to phenol reaction.

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Acknowledgements

We thank the National Key R&D Program of China (Nos. 2018YFA0703503 and 2018YFA0208504), the National Natural Science Foundation of China (No. 21932006) and the Youth Innovation Promotion Association of CAS (No. 2017049) for financial support. We thank the beamline 1W1B station in Beijing Synchrotron Radiation Facility (BSRF) and Dr. Lirong Zheng for help in XAFS characterization.

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Laboratory of Molecular Nanostructures and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Weiming Chen, Hongqiang Jin, Changyan Cao & Weiguo Song

  2. Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Feng He

  3. School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China

    Weiming Chen, Hongqiang Jin, Changyan Cao & Weiguo Song

  4. Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing, 210008, China

    Peixin Cui

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Dynamic evolution of nitrogen and oxygen dual-coordinated single atomic copper catalyst during partial oxidation of benzene to phenol

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Chen, W., Jin, H., He, F. et al. Dynamic evolution of nitrogen and oxygen dual-coordinated single atomic copper catalyst during partial oxidation of benzene to phenol. Nano Res. 15, 3017–3025 (2022). https://doi.org/10.1007/s12274-021-3936-4

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