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XPS Study of the Synthesis of Single-Site Catalysts Based on Ir(I) and Rh(I) Complexes Immobilized on the SiO2 Surface Using a P-Containing Linker

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Abstract

Samples of model single-site catalysts based on iridium and rhodium were synthesized by immobilizing the complexes [Ir(COD)(IMes)Cl] and [Rh(COD)(IMes)Cl] (where COD is 1,5-cyclooctadiene and IMes is 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) on silica, the surface of which was modified with a linker containing a diphenylphosphine group (Ph2P). The supports were silicon plates with a flat surface coated with a layer of natural oxide 1–3 nm thick (Si–SiO2(nat)) or with a specially grown SiO2 film (∼300 nm) (Si–SiO2(ox)). The states of chemical elements in the modified silicon plates and samples of model catalysts were determined by XPS. Based on the results obtained, the nature of the coordination of the immobilized complexes was assumed. Samples of the catalysts were tested in the reaction of gas-phase hydrogenation of propene with parahydrogen.

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ACKNOWLEDGMENTS

The studies were carried out using the equipment of the Center for Collective Use “National Center for the Study of Catalysts” (SPECS X-ray photoelectron spectrometer). The authors thank O.E. Tereshchenko. (Rzhanov Institute of Semiconductor Physics, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia) for providing silicon plates for the studies.

Funding

The synthesis of the catalysts and their study by XPS were supported by the Russian Science Foundation (project no. 19-13-00172-P). The study of catalytic activity was supported by the Ministry of Science and Higher Education of the Russian Federation (basic budget funding from the International Tomography Center, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia, no. AAAA-A21-121012290043-3).

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Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk, Russia

    M. Yu. Smirnov, L. M. Kovtunova, A. V. Kalinkin & V. I. Bukhtiyarov

  2. International Tomography Center, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk, Russia

    I. V. Skovpin & I. V. Koptyug

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  1. M. Yu. Smirnov
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  2. L. M. Kovtunova
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  3. A. V. Kalinkin
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  4. I. V. Skovpin
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  5. I. V. Koptyug
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  6. V. I. Bukhtiyarov
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Correspondence to M. Yu. Smirnov.

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Translated by V. Glyanchenko

Abbreviations and notation: COD, 1,5-cyclooctadiene; IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; XPS, X-ray photoelectron spectroscopy; Eb, binding energy; HOPG, highly oriented pyrolytic graphite; NMR, nuclear magnetic resonance; PHIP, parahydrogen-induced nuclear polarization; SE, NMR signal enhancement; PASADENA, parahydrogen and synthesis allow dramatic enhancement of nuclear alignment.

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Smirnov, M.Y., Kovtunova, L.M., Kalinkin, A.V. et al. XPS Study of the Synthesis of Single-Site Catalysts Based on Ir(I) and Rh(I) Complexes Immobilized on the SiO2 Surface Using a P-Containing Linker. Kinet Catal 64, 895–908 (2023). https://doi.org/10.1134/S0023158423060150

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  • DOI: https://doi.org/10.1134/S0023158423060150

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