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In-situ X-ray absorption spectroscopy study on the formation of superoxides on CuxSny composite catalysts enables the direct synthesis of catechol

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Abstract

This work proposes the activated mechanical alloyed composite catalysts by in-situ O2 heat treatment (CuxSn100−xO2HT). The catalytic activity of catalysts is improved tremendously for the phenol hydroxylation by superoxide (O2−). The conversion is almost 100% and selective to 94% catechol (CAT). To understand the formation of superoxide, in situ time-resolved Cu K-edge and Sn L3-edge X-ray absorption spectroscopy explain the contribution of an oxygen atom to the CuxSny composites. Meanwhile, in-situ XAS with O2 heat treatment depicts how superoxide bonded on CuxSny composites. Quantitatively, H2-TPR and curve fitting ATR-FTIR determine the total amount of superoxide on MAed CuxSn100−xO2HT and distinguish the numbers of O2− on Cu and Sn sites in CuxSn100−xO2HT. EPR explains that the hybridization of d-orbitals of Cu2+ and p-d orbitals of Sn4+ shifted the g-factor of a free electron in superoxide. XPS depth profiling of O 1s reveals identical superoxide on the composite CuxSnyO2HT catalysts. After optimizing the Sn contents, Cu30Sn70O2HT exhibits the highest catalytic activity and a number of superoxides, giving the CAT 183 μmol in conjunction with reducing tar contents. Extended X-ray absorption fine structure (EXAFS) illustrates the present compressive strain of Cu–O distance and is essential in increasing the quantity of CAT. The work presents how mechanical alloying can be a potential free-solvent catalyst synthesis.

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Acknowledgements

The authors gratefully acknowledge the mutual support or partial scholarship from The Petroleum and Petrochemical college; Ratchadaphiseksompote Endowment Fund, Chulalongkorn University; Thailand Research Fund (Senior Research Scholar); and Powder Metallurgy Research and Development Unit (PM_RDU) of the National Metal and Materials Technology Center (MTEC). The authors also would like to thank Dr. Robert Butcher for proofreading the paper.

Funding

Funding was provided by National Metal and Materials Technology Center and Petroleum and Petrochemical College, Chulalongkorn University.

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Authors and Affiliations

  1. The Petroleum and Petrochemical College, Chulalongkorn University, 254 Soi Chulalongkorn 12, Wangmai, Pathumwan, Bangkok, 10330, Thailand

    Sakollapath Pithakratanayothin, Sirawit Numbenjapon, Thanyalak Chaisuwan & Daikwan Bunyaviroch

  2. National Metal and Materials Technology Center, 114 Thailand Science Park (TSP), Phahonyothin Road, Khlong Nueng, Khlong Luang, Pathum Thani, 12120, Thailand

    Ruangdaj Tongsri

  3. National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), 114 Thailand Science Park (TSP), Phahonyothin Road, Khlong Nueng, Khlong Luang, Pathum Thani, 12120, Thailand

    Phongtanawat Khemthong

  4. School of Agro-Industry, Mae Fah Luang University, 333 Moo 1, Thasud, Muang, Chiang Rai, 57100, Thailand

    Sujitra Wongkasemjit

  5. Clean Fuel Technology and Advanced Chemistry Research Team, Low Carbon Energy Research Group, National Energy Technology Center, 114 Thailand Science Park (TSP), Phahonyothin Road, Khlong Nueng, Khlong Luang, Pathum Thani, 12120, Thailand

    Eumporn Buarod

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Contributions

SP: Conceptualization; methodology; validation; writing—original draft; writing—review and editing, supervision, project administration. SN: Writing—original draft, visualization, methodology, software. RT: Funding acquisition. TC: Validation, funding acquisition; writing—review and editing. PK: Funding acquisition. SW: Validation, funding acquisition; writing—review and editing. DB: Visualization. EB: Visualization, validation, investigation.

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Pithakratanayothin, S., Numbenjapon, S., Tongsri, R. et al. In-situ X-ray absorption spectroscopy study on the formation of superoxides on CuxSny composite catalysts enables the direct synthesis of catechol. Reac Kinet Mech Cat 136, 3079–3104 (2023). https://doi.org/10.1007/s11144-023-02518-5

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