Highly dispersed Pd nanoparticles deposited on Sibunite by laser electrodispertion in Suzuki-Miyaura catalytic reaction

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Resumo

The paper presents the results of the study of the Suzuki-Miyaura reaction catalysis with aryl bromides using palladium catalyst precursors with a low metal content (10-2–10-1 wt %), deposited by laser electrodispersion of palladium on the surface of a carbon support (Sibunite). The analysis of the patterns of activity and stability of the synthesized catalysts, as well as their differential selectivity, along with an analysis of the changes in the state of the catalysts before the catalytic reaction and after its completion, allowed us to conclude that catalysis occurs with the participation of palladium nanoparticles and single atoms located on the surface of the carbon support.

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Sobre autores

A. Schmidt

Irkutsk State University

Autor responsável pela correspondência
Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, K. Marx Str.,1, Irkutsk, 664003

A. Kurokhtina

Irkutsk State University

Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, K. Marx Str.,1, Irkutsk, 664003

E. Larina

Irkutsk State University

Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, K. Marx Str.,1, Irkutsk, 664003

N. Lagoda

Irkutsk State University

Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, K. Marx Str.,1, Irkutsk, 664003

T. Grigorieva

Irkutsk State University

Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, K. Marx Str.,1, Irkutsk, 664003

I. Krotova

Lomonosov Moscow State University

Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, Leninskie Gory 1 build 3., GSP-1, Moscow, 119991

K. Maslakov

Lomonosov Moscow State University

Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, Leninskie Gory 1 build 3., GSP-1, Moscow, 119991

S. Nikolaev

Lomonosov Moscow State University

Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, Leninskie Gory 1 build 3., GSP-1, Moscow, 119991

S. Gurevich

Ioffe Institute of the Russian Academy of Sciences

Email: aschmidt@chem.isu.ru
Rússia, Polytekhnicheskaya st., 26, St. Petersburg, 194021

D. Yavsin

Ioffe Institute of the Russian Academy of Sciences

Email: aschmidt@chem.isu.ru
Rússia, Polytekhnicheskaya st., 26, St. Petersburg, 194021

T. Rostovshchikova

Lomonosov Moscow State University

Email: aschmidt@chem.isu.ru

Chemical Department

Rússia, Leninskie Gory 1 build 3., GSP-1, Moscow, 119991

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2. Fig. 1. TEM micrographs of different resolutions (a–g) of the 0.08Pd/C-0.5 sample.

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3. Fig. 2. TEM micrographs of the 0.08Pd/C-0.5 sample (a, b); EDA spectrum (c) of the region highlighted in the image (a); Pd distribution map (d) in the image (b); histograms of Pd particle size distributions (d) and distances between the nearest particles (e).

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4. Fig. 3. TEM micrographs of samples 0.04Pd/C-1 (a, b); 0.007Pd/C-2 (c, d); 0.04Pd/C-2 (d, e).

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5. Fig. 4. TEM micrographs of the 4Pd/C comparison sample obtained by the impregnation method (a–d) and a histogram of the particle size distribution in it (e).

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6. Fig. 5. TEM micrograph (a), EDA spectra (b–d) of marked locations 1, 2 and 3, image and TEM-EDA map of Pd distribution (d–f) for the 4Pd/C sample obtained by the impregnation method.

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7. Fig. 6. XPS spectra of Pd3d samples 0.007Pd/C-2, 0.08Pd/C-0.5 and 4Pd/C.

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8. Fig. 7. TOF (a) and TON (b) values ​​calculated for the Suzuki-Miyaura reaction (Scheme 1) in the presence of a number of Pd/C samples obtained by the LED method, as well as a reference sample prepared by the impregnation method (in the figure in the red frame).

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9. Fig. 8. Phase trajectories of the Suzuki-Miyaura reaction with phenylboronic acid (Scheme 1), plotted in the coordinates of the concentrations of biaryls formed from competing 4-bromoacetophenone and bromobenzene, in the presence of Pd/C samples obtained by the LED method, as well as a comparison sample prepared by the impregnation method (in the figure in the red frame).

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10. Fig. 9. TEM micrographs of different resolutions (a–g) of the 0.08Pd/C-0.5 sample isolated from the reaction mixture after completion of the catalytic reaction.

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11. Fig. 10. TEM micrographs (a, b) of the 0.08Pd/C-0.5 sample isolated from the reaction mixture after the completion of the catalytic reaction; EDA spectrum (c) from the region highlighted in the image (a); Pd distribution map (d) in the image (b).

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12. Scheme 1. Suzuki-Miyaura reaction under conditions of competition between a pair of aryl bromides.

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13. Scheme 2. Mutual transformations of different forms of palladium in catalytic systems of the Suzuki–Miyaura reaction.

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