Исследование микроструктуры синтезированных in situ медь-цинковых катализаторов гидродеоксигенации глицерина до 1,2-пропандиола

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Abstract

Исследованы структурные особенности синтезированных in situ в условиях жидкофазного гидрогенолиза глицерина до 1,2-пропандиола медь-цинковых катализаторов с различным содержанием меди (от 6.25 до 100 мас%). Установлено, что проведение процесса формирования катализатора в реакционной среде в диапазоне концентраций 12.5–25 мас% Cu обеспечивает как достижение минимальных размеров Cu-зерен (50–150 нм), устойчивый анизотропный рост ZnO (длина 80–230 нм), так и формирование тонкой оксидной оболочки на поверхности частиц Cu. Результатом является максимальная каталитическая активность и селективность формирующейся in situ каталитической системы.

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About the authors

К. И. Чернышев

НИЦ «Курчатовский институт»

Author for correspondence.
Email: a.vasiliev56@gmail.com
ORCID iD: 0009-0005-4770-5096

к.ф.-м.н.

Russian Federation, 123182, г. Москва, пл. Академика Курчатова, д. 1

Ю. И. Порукова

Институт нефтехимического синтеза им. А. В. Топчиева РАН

Email: a.vasiliev56@gmail.com
ORCID iD: 0000-0003-3452-8009

к.х.н.

Russian Federation, 119991, ГСП-1, г. Москва, Ленинский пр., д. 29

A. Л. Максимов

Институт нефтехимического синтеза им. А. В. Топчиева РАН

Email: a.vasiliev56@gmail.com
ORCID iD: 0000-0001-9297-4950

д.х.н., акад. РАН

Russian Federation, 119991, ГСП-1, г. Москва, Ленинский пр., д. 29

A. Л. Васильев

НИЦ «Курчатовский институт»; Московский физико-технический институт (национальный исследовательский университет)

Email: a.vasiliev56@gmail.com
ORCID iD: 0000-0001-7884-4180
Russian Federation, 123182, г. Москва, пл. Академика Курчатова, д. 1; 141701, Московская обл., г. Долгопрудный, Институтский пер., д. 9

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Supplementary files

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2. Fig. 1. Cu–ZnO sample with 6.25% Cu content. a — bright-field TEM image; b — results of elemental EDX mapping; c — HRTEM image of a ZnO particle; d — electron diffraction pattern of the particle conglomerate shown in a.

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3. Fig. 2. Histograms of particle size distribution.

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4. Fig. 3. X-ray images of samples.

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5. Fig. 4. Cu–ZnO sample with 12.5% ​​Cu content. a — bright-field TEM image, b — results of elemental EDX mapping.

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6. Fig. 5. a — HRTEM image of a Cu particle with a Cu2O shell; b — EDX map of a section of the copper particle highlighted in red and the shell — in turquoise; c — two-dimensional Fourier spectrum obtained from the shell region highlighted by the square in a; g — image of a section of the crystal lattice after Fourier filtering.

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7. Fig. 6. Cu–ZnO sample with 25% Cu content. a — bright-field TEM image, b — EDX mapping results.

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8. Fig. 7. HRTEM image of a group of ZnO particles. The upper inset shows an enlarged image of the crystal lattice, and below is a two-dimensional Fourier spectrum obtained from this region.

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9. Fig. 8. Sample with 25% Cu. a — HRTEM image of a particle, twins in the Cu core are clearly visible, the CuO shell is indicated by an arrow; b — element distribution map obtained by the EDX method; c — HRTEM image of the Cu particle surface with c-CuO ​​and m-CuO layers, the red square highlights the region enlarged by d, with a crystallite (in the yellow square), from which a two-dimensional Fourier spectrum was obtained — d; f — Cu particle surface with an inclined Cu–CuO boundary, squares highlight the regions of the crystal lattice analysis; g — two-dimensional Fourier spectrum of an m-CuO particle; h — two-dimensional Fourier spectrum of a c-CuO ​​particle.

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10. Fig. 9. Cu–ZnO sample with 25% Cu content (ex situ). a — bright-field STEM image, b — EDX mapping.

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11. Fig. 10. HRTEM image of a ZnO particle with zone axis B = [2110], inset – two-dimensional Fourier spectrum from the region highlighted by the red square.

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12. Fig. 11. a — HRTEM image of a ZnO particle and a Cu2O particle; corresponding two-dimensional Fourier spectra: b — from a ZnO particle, zone axis B = [2110]; c — Cu2O particle, zone axis B = [101]; d — enlarged image of the crystal lattice of a Cu2O particle after Fourier filtering.

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13. Fig. 12. Cu–ZnO sample with 50% Cu content. a — bright-field TEM image, b — EDX mapping.

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14. Fig. 13. Cu–ZnO sample (repeat) with 50% Cu content. a — TEM image, b — EDX mapping.

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15. Fig. 14. Sample with 75% Cu precursor. a — bright-field TEM image of a group of sample particles; b — EDX map of element distribution; c — enlarged image of a Cu particle, arrows indicate an island of m-CuO, squares indicate regions of Fourier analysis: region 1 — c-CuO, region 2 — m-CuO; g — two-dimensional Fourier spectrum of region 1, corresponding to the zone axis B = [011] fcc-CuO; d — image of the crystal lattice of region 1 after Fourier filtering; e — two-dimensional Fourier spectrum of region 2, corresponding to the zone axis B = [112] m-CuO; g — image of the crystal lattice of region 2 after Fourier filtering, a high density of defects is noted.

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16. Fig. 15. Cu2O particle in the sample. a — HRTEM image, arrows indicate c-CuO ​​islands with the zone axis B = [101]; b — the corresponding two-dimensional Fourier spectrum obtained from the particle region; c — HRTEM image of a c-CuO ​​island on the surface of a Cu2O particle after Fourier filtration; d — the corresponding two-dimensional Fourier spectrum, zone axis B = [101].

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17. Fig. 16. HRTEM image of ZnO nanoparticle.

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18. Fig. 17. Sample with 100% Cu precursor. a — bright-field STEM image of one of the sample particles; b — enlarged image of the particle demonstrating the edge morphology; c — EDX map of the element distribution, the CuOx oxide shell is visible; d — HRTEM image of the oxide shell, the m-CuO island is highlighted by a square, the inset is a two-dimensional Fourier spectrum of the highlighted region, corresponding to the zone axis B = [011] m-CuO.

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