Model bimetallic Pd-Co/HOPG catalysts: preparation and XPS/STM study

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Regularities of formation of bimetallic Pd–Co nanoparticles supported on the highly oriented pyrolytic graphite (HOPG) have been studied by a combination of STM and XPS techniques. Cobalt deposition on monometallic Pd/HOPG sample was determined to lead to formation of the bimetallic Pdcore–Coshell nanoparticles which then transformed into alloyed Pd–Co nanoparticles with homogeneous metal distribution resulting from sample heating at 400—500°C in ultrahigh vacuum. Heating of the Pd–Co/HOPG catalysts at temperatures higher than 500°C in ultrahigh vacuum was revealed to result in sintering of the nanoparticles. Under carbon monoxide environment in a range of temperatures 25—250°C, adsorption-induced segregation of palladium atoms on the surface of the bimetallic nanoparticles was shown to take place, with latter having volcano-shape temperature dependence with a maximum at 200°C. It was established that bimetallic Pd–Co nanoparticles in the model catalysts were stable against sintering up to 250°C in CO atmosphere.

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作者简介

M. Panafidin

Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis

编辑信件的主要联系方式.
Email: mpanafidin@catalysis.ru
俄罗斯联邦, Nikolsky Prosp., 1, Kol’tsovo, 630559

A. Bukhtiyarov

Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis

Email: mpanafidin@catalysis.ru
俄罗斯联邦, Nikolsky Prosp., 1, Kol’tsovo, 630559

A. Martyanov

Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis

Email: mpanafidin@catalysis.ru
俄罗斯联邦, Nikolsky Prosp., 1, Kol’tsovo, 630559

A. Fedorov

Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis

Email: mpanafidin@catalysis.ru
俄罗斯联邦, Nikolsky Prosp., 1, Kol’tsovo, 630559

I. Prosvirin

Boreskov Institute of Catalysis

Email: mpanafidin@catalysis.ru
俄罗斯联邦, Lavrentiev Ave., 5, Novosibirsk, 630090

V. Bukhtiyarov

Boreskov Institute of Catalysis

Email: mpanafidin@catalysis.ru
俄罗斯联邦, Lavrentiev Ave., 5, Novosibirsk, 630090

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2. Fig. 1. STM images (100 × 100 nm²), particle size distribution histograms, and their average sizes for monometallic Pd/VGCF (a), initial bimetallic PdCo/VGCF-1 (b), and bimetallic PdCo/VGCF-2 after vacuum annealing at 620°C for 1 h (c).

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3. Fig. 2. XPS spectra of Pd3d (a) and Co2p3/2 (b) of the PdCo/VGCF-2 sample annealed at different temperatures under ultrahigh vacuum.

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4. Fig. 3. Surface atomic ratios calculated from XPS spectra of Pd3d, Co2p, and C1s for PdCo/VGCF-2 annealed at different temperatures under ultrahigh vacuum.

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5. Fig. 4. Pd/Co atomic ratio and intensity ratios Pd MNN/Pd3d and Co LMM/Co2p calculated from Pd3d, Co2p, Pd MNN, and Co LMM spectra for PdCo/VGCF-3 under different experimental conditions.

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6. Fig. 5. STM image (100 × 100 nm²) and average particle size for bimetallic PdCo/VGCF-1 after CO treatment (a), and particle size distribution histograms for the initial sample and after CO treatment (b).

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7. Fig. 6. XPS spectra of Pd3d (a) and Co2p3/2 (b), and Pd/Co atomic ratios derived from these spectra (c), for the PdCo/VGCF-1 sample after annealing at 500°C in ultrahigh vacuum, CO treatment at various temperatures, and final annealing at 500°C in ultrahigh vacuum.

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