Rhodium electronic state in catalysts based on Rh/НZSM-5 for oxidative carbonylation of methane into acetic acid: effect of copper and zinc doping

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Abstract

Diffuse reflectance infrared Fourier transform spectroscopy of adsorbed carbon monoxide is used along with X-ray absorption spectroscopy to study the effect a second alloying metal (Zn, Cu) has on the electronic state and local structure of rhodium on the surfaces of Rh/HZSM-5 zeolite catalyst. It is established that introducing copper and zinc helps improve the stability of rhodium toward aggregation (the formation of clusters) under conditions of the oxidative carbonylation of methane into acetic acid. Compared to monometallic catalyst Rh/HZSM-5, where single atom rodium sites are partially aggregated into clusters, the proportion of Rh° is halved in the case of Rh–Zn/HZSM-5, and Rh clustering does not occur in the case of Rh‒Cu/HZSM-5. The stabilizing effect of Cu is due to the interaction between copper and rhodium cations on the surface of zeolite.

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About the authors

M. I. Shilina

Lomonosov Moscow State University

Email: batova.ti@ips.ac.ru

Faculty of Chemistry

Russian Federation, Moscow, 119991

E. V. Khramov

National Research Center Kurchatov Institute

Email: batova.ti@ips.ac.ru
Russian Federation, Moscow, 123098

T. I. Batova

Topchiev Institute of Petrochemical Synthesis

Author for correspondence.
Email: batova.ti@ips.ac.ru
Russian Federation, Moscow, 119991

N. V. Kolesnichenko

Topchiev Institute of Petrochemical Synthesis

Email: batova.ti@ips.ac.ru
Russian Federation, Moscow, 119991

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Supplementary files

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2. Fig. 1. XANES (a) and EXAFS spectra (b) at the Rh K-edge of the initial and spent rhodium-containing catalysts: Rh/НZ, Rh-Cu/HZ and Rh-Zn/HZ.

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3. Fig. 2. XANES (a) and EXAFS spectra (b) at the K-edge of Zn for the initial and spent bimetallic catalysts Rh-Zn/HZ.

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4. Fig. 3. XANES (a) and EXAFS spectra (b) at the Cu K-edge for the initial and spent bimetallic catalysts Rh-Cu/HZ.

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5. Fig. 4. IR spectra of adsorbed CO on zinc and rhodium containing samples: Zn/HZ (1) and Rh-Zn/HZ (2), Rh/HZ (3) and unmodified HZ (4) at an equilibrium pressure of 3 Torr, 298K; k is the wave number, ε is the absorption.

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6. Fig. 5. IR spectra of DO of adsorbed CO on copper- and rhodium-containing samples: Cu/HZ (1) and Rh-Cu/HZ (2), Rh/HZ (3) and unmodified HZ (4) at a pressure of 3 Torr; k is the wave number, ε is the absorption.

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7. Fig. 6. IR spectra of DO of adsorbed CO on copper- and rhodium-containing samples: Cu/HZ (1) and Rh-Cu/HZ (2), Rh/HZ (3) with adsorption of 5 μmol/g CO (a). Spectra 3 and 2 shown on an enlarged scale, and their difference spectrum (b).

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