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Effects of preparation mode and doping on the genesis and properties of Ni/Ce1-xMxOy nanocrystallites (M = Gd, La, Mg) for catalytic applications

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Abstract

To create the catalytically active ceria-based nanocrystallites with the superior anti-sintering and anti-coking behavior, the peculiarity of genesis and properties of Ni/Ce1-xMxOy nanocrystallites (M = Gd, La, Mg; x = 0–0.5; 1.5 ≤ y ≤ 2.0) were studied by thermal analysis, N2 adsorption, X-ray diffraction, transmission, and scanning electron microscopy. The control of nanocrystallite characteristics was achieved by tuning of metal-support interaction through the application of different synthesis method (polymerizable complex method, sol–gel template method), doping, and conditions of thermal treatment (300-800 °C, oxidizing and reducing atmospheres). From undoped CeO2, the mesoporous nanosized Ce1-xMxOy solid solutions are distinguished by higher surface area (95 vs. 155 m2/g), smaller crystallite size (15 vs. 5 nm), and advanced thermal stability. The supported Ce1-xMxOy material Ni species of different dispersion and reducibility were prepared through regulation of composition and crystallite sizes of CexM1-xOy.The Ni dispersion increases upon a decrease of support crystallite sizes, with an increase of mole fraction of M and in the following row of doping cations: Gd ˂ Mg ˂ La. The presence of La or Mg in the nanocrystallite composition promotes the stability against sintering while small particle size provides the anti-coking resistance. The developed Ni/Ce1-xMxOy nanocrystallites were remarkable for their performance in autothermal conversion of ethanol and stability against carbonaceous deposits.

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Abbreviations

BET:

Brunauer–Emmett–Teller

CSR:

Coherent scattering region

DTA:

Differential thermal analysis

EDS:

Energy-dispersive spectroscopy

HRTEM:

High-resolution transmission electron microscopy

HAADF-STEM:

High-angle annular dark-field imaging scanning transmission electron microscopy

OSC:

Oxygen storage capacity

SEM:

Scanning electron microscopy

TGA:

Thermogravimetric analyses

XRD:

X-ray diffraction

XRF:

X-ray fluorescence spectroscopy

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Acknowledgments

The authors are grateful to G.S. Litvak, T.Ya. Efimenko, Dr. E.Y. Gerasimov, Serkova A.N., and Dr. V.A. Ushakov for their assistance with catalyst characterization. This work was conducted within the framework of the budget project No. АААА-А17-117041710090-3 for Boreskov Institute of Catalysis.

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Matus, E.V., Okhlopkova, L.B., Sukhova, O.B. et al. Effects of preparation mode and doping on the genesis and properties of Ni/Ce1-xMxOy nanocrystallites (M = Gd, La, Mg) for catalytic applications. J Nanopart Res 21, 11 (2019). https://doi.org/10.1007/s11051-018-4454-5

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