XPS study of the stability variations of [M(COD)Cl]2 (M = Ir, Rh) complexes anchored on modified silica in reactions of spin-selective hydrogenation of unsaturated hydrocarbons by parahydrogen

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Resumo

Changes in the composition of anchored [M(COD)Cl]2–NH2–C3H6–SiO2 and [M(COD)Cl]2–P(Ph)2–C2H4–SiO2 (where M = Ir, Rh) catalysts in reactions of gas-phase selective hydrogenation of propene, propyne and 1,3-butadiene with parahydrogen (p-H2) were studied using XPS. The atomic ratio M/Cl has been proposed as an indicator of the stability of the structure of the anchored complex, both at the stage of sample preparation and in the reaction. Based on a comparison of XPS data and the results of catalytic testing using parahydrogen-induced polarization, it is shown that the stability of the anchored {[M(COD)Cl]2–Linker–SiO2} complex during hydrogen activation is a key factor in the catalytic behavior of systems. Such stability is influenced not only by the chosen metal and linker, but also by the nature of the hydrogenated substrate.

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Sobre autores

A. Nartova

Boreskov Institute of Catalysis SB RAS

Autor responsável pela correspondência
Email: nartova@catalysis.ru
Rússia, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

R. Kvon

Boreskov Institute of Catalysis SB RAS

Email: nartova@catalysis.ru
Rússia, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

L. Kovtunova

Boreskov Institute of Catalysis SB RAS

Email: nartova@catalysis.ru
Rússia, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

A. Dmitrachkov

Boreskov Institute of Catalysis SB RAS

Email: nartova@catalysis.ru
Rússia, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

I. Skovpin

Boreskov Institute of Catalysis SB RAS; International Tomography Center SB RAS

Email: nartova@catalysis.ru
Rússia, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090; st. Institutskaya, 3A, Novosibirsk, 630090

V. Bukhtiyarov

Boreskov Institute of Catalysis SB RAS

Email: nartova@catalysis.ru
Rússia, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

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2. Fig. 1. Data on the enhancement of the NMR signal (a) and conversion (b) in the reaction of hydrogenation of 1,3-butadiene with parahydrogen in the presence of the studied catalysts.

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3. Fig. 2. Change in the atomic ratio Cl/Ir during long-term recording of XPS spectra of crystals of the [Ir(COD)Cl]2 complex under UHV conditions.

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4. Fig. 3. P2s + Cl2p region of the XPS spectrum for the Rh–P sample depending on the reaction conditions and after reduction in the cell.

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