XPS study of [Ir(COD)Cl]2–L–SiO2 catalytic system

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Аннотация

The X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) spectroscopy were used to study the features of anchoring of the [Ir2(COD)2Cl2] complex on the surface of modified silica gel L–SiO2 (where L is NC5H5–CH2–CH2–, N(CH3)2–CH2–CH2–CH2–, NH2–C3H6–) depending on the nature of the linker and the conditions of preparation of the systems. The catalytic activity was tested in reactions of gas-phase selective hydrogenation of propylene with parahydrogen (p-H2). According to the XPS data, a single-site iridium catalyst is prepared in all cases. Analysis of the XPS spectra indicates the possibility of anchoring the complex through one of the Ir atoms while preserving the dimer. It was shown that at different durations of interaction of the iridium complex solution with modified NH2–C3H6– silica gel approximately the same amount of the complex is anchored, but the nature of the complex coordination changes. For the sample obtained by long-term interaction of the complex solution with the modified support (24 h), a high increase in the NMR signal was observed at 60°C, while in the case of the sample prepared by short-term interaction (1 h), the signal increased with a rise in temperature to 80°C.

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Авторлар туралы

A. Nartova

Boreskov Institute of Catalysis SB RAS

Хат алмасуға жауапты Автор.
Email: nartova@catalysis.ru
Ресей, Acad. Lavrentieva ave., 5, Novosibirsk, 630090

K. Donskikh

Boreskov Institute of Catalysis SB RAS

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

R. Kvon

Boreskov Institute of Catalysis SB RAS

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

L. Kovtunova

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

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

A. Dmitrachkov

Boreskov Institute of Catalysis SB RAS

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

I. Skovpin

International Tomography Center SB RAS

Email: nartova@catalysis.ru
Ресей, Institutskaya str., 3A, Novosibirsk, 630090

I. Koptyug

International Tomography Center SB RAS

Email: nartova@catalysis.ru
Ресей, Institutskaya str., 3A, Novosibirsk, 630090

V. Bukhtiyarov

Boreskov Institute of Catalysis SB RAS

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

Әдебиет тізімі

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2. Fig. 1. Change in the intensity of the Cl2p line during a 12-hour measurement of the NH2-1h sample.

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3. Fig. 2. XPS spectra of the Ir4f region for freshly prepared NH2-1h and NH2-24h samples.

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4. Fig. 3. Possible modes of complex anchoring on the surface of modified SiO2: I – linker coordination through one iridium atom with retention of the dimer [Ir2(COD)2Cl2]; II – coordination of two neighboring linkers through both iridium atoms with retention of the dimer [Ir2(COD)2Cl2]; III – coordination to the linker by a monomer [Ir(COD)Cl] with dimer cleavage.

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5. Fig. 4. NMR signal enhancement (a) and propylene conversion (b) in the gas-phase selective hydrogenation of propylene by parahydrogen for NH2-1h and NH2-24h samples.

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6. Fig. 5. XPS spectra of the Ir4f region for NH2-1h (a) and NH2-24h (b) samples after the gas-phase selective hydrogenation of propylene by parahydrogen.

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