Study of Deactivation in Suzuki Reaction of Polymer-Stabilized Pd Nanocatalysts

Linda Nikoshvili; Elena S. Bakhvalova; Alexey V. Bykov; Alexander I. Sidorov; Alexander L. Vasiliev; Valentina G. Matveeva; Mikhail G. Sulman; Valentin N. Sapunov; Lioubov Kiwi-Minsker

LAPSE

Living Archive for Process Systems Engineering

LAPSE:2021.0659

Published Article

LAPSE:2021.0659

Study of Deactivation in Suzuki Reaction of Polymer-Stabilized Pd Nanocatalysts

Linda Nikoshvili, Elena S. Bakhvalova, Alexey V. Bykov, Alexander I. Sidorov, Alexander L. Vasiliev, Valentina G. Matveeva, Mikhail G. Sulman, Valentin N. Sapunov, Lioubov Kiwi-Minsker

July 29, 2021

This work is addressed to the phenomenon of catalyst deactivation taking place during the repeated uses in the reaction of Suzuki-Miyaura (S-M) cross-coupling, which is widely applied in industry for C-C bond formation. Ligandless catalysts based on Pd(0) NPs supported on hyper-cross-linked polystyrene (HPS) of two types (non-functionalized and bearing tertiary amino groups) were studied in a model S-M reaction between 4-bromoanisole and phenylboronic acid. Synthesized catalysts were shown to be highly active under mild reaction conditions. HPS allows stabilization of Pd(0) NPs and prevents their agglomeration and detectable Pd leaching. However, the loss of catalytic activity was observed during recycling. The deactivation issue was assigned to the hydrophobic nature of non-functionalized HPS, which allowed a strong adsorption of cross-coupling product during the catalyst separation procedure. A thorough washing of Pd/HPS catalyst by hydrophobic solvent was found to improve to the big extent the observed catalytic activity, while the replacement of non-functionalized HPS by a one containing amino groups increased the catalyst stability at the expense of their activity.

Record ID

LAPSE:2021.0659

Keywords

catalyst stability, hyper-cross-linked polystyrene, palladium nanoparticles, Suzuki cross-coupling

Subject

Reaction Engineering

Suggested Citation

Nikoshvili L, Bakhvalova ES, Bykov AV, Sidorov AI, Vasiliev AL, Matveeva VG, Sulman MG, Sapunov VN, Kiwi-Minsker L. Study of Deactivation in Suzuki Reaction of Polymer-Stabilized Pd Nanocatalysts. (2021). LAPSE:2021.0659

Author Affiliations

Nikoshvili L: Department of Biotechnology, Chemistry and Standardization, Tver State Technical University, A. Nikitina str., 22, 170026 Tver, Russia [ORCID]
Bakhvalova ES: Regional Technological Centre, Tver State University, Zhelyabova str., 33, 170100 Tver, Russia
Bykov AV: Department of Biotechnology, Chemistry and Standardization, Tver State Technical University, A. Nikitina str., 22, 170026 Tver, Russia
Sidorov AI: Department of Biotechnology, Chemistry and Standardization, Tver State Technical University, A. Nikitina str., 22, 170026 Tver, Russia
Vasiliev AL: National Research Centre “Kurchatov Institute”, 123182 Moscow, Russia
Matveeva VG: Department of Biotechnology, Chemistry and Standardization, Tver State Technical University, A. Nikitina str., 22, 170026 Tver, Russia; Regional Technological Centre, Tver State University, Zhelyabova str., 33, 170100 Tver, Russia
Sulman MG: Department of Biotechnology, Chemistry and Standardization, Tver State Technical University, A. Nikitina str., 22, 170026 Tver, Russia
Sapunov VN: Department of Chemical Technology of Basic Organic and Petrochemical Synthesis, D. Mendeleev University of Chemical Technology of Russia, Miusskaya pl., 9, 125047 Moscow, Russia [ORCID]
Kiwi-Minsker L: Regional Technological Centre, Tver State University, Zhelyabova str., 33, 170100 Tver, Russia; Ecole Polytechnique Fédérale de Lausanne, GGRC-ISIC-EPFL, CH-1015 Lausanne, Switzerland

Journal Name

Processes

Volume

8

Issue

12

Article Number

E1653

Year

2020

Publication Date

2020-12-15