Isobutane Dehydrogenation on CrO  x  /Al 2 O 3  Nanoparticles, Prepared by Laser Synthesis in Various Gases

M. G. Baronskiy; Баронский М. Г.; N. A. Zaitseva; Зайцева Н. А.; A. I. Kostyukov; Костюков А. И.; A. V. Zhuzhgov; Жужгов А. В.; V. N. Snytnikov; Снытников В. Н.

doi:10.31857/S0453881123050015

Isobutane Dehydrogenation on CrO_x/Al₂O₃ Nanoparticles, Prepared by Laser Synthesis in Various Gases

Authors: Baronskiy M.G.¹, Zaitseva N.A.¹, Kostyukov A.I.¹, Zhuzhgov A.V.¹, Snytnikov V.N.¹
Affiliations:
1. Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Science
Issue: Vol 64, No 5 (2023)
Pages: 620-630
Section: ARTICLES
URL: https://journal-vniispk.ru/0453-8811/article/view/140952
DOI: https://doi.org/10.31857/S0453881123050015
EDN: https://elibrary.ru/TTXFPY
ID: 140952

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Abstract

The catalytic properties of nCrO_x/Al₂O₃ nanoparticles (n = 4.8 ± 0.05 wt %) tested in the isobutane dehydrogenation reaction which were obtained by laser synthesis in various gases are studied in detail for the first time. Laser synthesis of 4.8% CrO_x/Al₂O₃ nanopowders was carried out by the vaporization of 5.0% Cr : α-Al₂O₃ ceramic targets using cw CO₂ laser irradiation in an inert, oxidizing and reducing gaseous environment in a vaporization chamber: in an Ar medium; Ar with addition of O₂, H₂ and CH₄ at concentrations of 20, 30, and 13 vol. %, respectively. The role of the gas medium during the synthesis of 4.8% CrO_x/Al₂O₃ nanopowders in their catalytic properties (activity, selectivity, conversion, and stability in the reaction) was determined. A comprehensive study of the physicochemical properties of the obtained nanocatalysts was carried out using XRD, TEM, UV-Vis DRS, and Raman techniques. According to XRD data the phase composition is predominantly consists of γ-Al₂O₃ with the beginning of the transition to δ-Al₂O₃. According to the TEM results, the shape of nanoparticles is spherically symmetric with an average particle size d_m = 15 nm. Using the UV-Vis DRS method, charge states of Cr^q+ (q = 3, 6) in different coordination (Cr⁶⁺(T_d) and Cr³⁺(O_h)) and its different ratios depending on the gas atmosphere used in the process of laser vaporization were revealed in the obtained 4.8% CrO_x/Al₂O₃ nanopowders. Nanosized 4.8% CrO_x/Al₂O₃ catalyst prepared in an atmosphere (Ar + H₂) demonstrated the highest values of isobutane conversion (39%) and isobutylene selectivity (90.7%); the lowest corresponding values of conversion (18.8%) and selectivity (85.6%) were typical for the sample obtained in the atmosphere (Ar + CH₄). Thus, the most active and selective in the isobutane dehydrogenation reaction was the 4.8% CrO_x/Al₂O₃ nanocatalyst synthesized in the (Ar + H₂) medium, and the presence of methane during vaporization led to the initial surface carbonization, which prevents the access of reacting molecules to it.

Keywords

CrO_x/Al₂O₃, nanoparticles, Cr₂O₃ nanoclusters, isobutane dehydrogenation, isobutylene, active sites, laser vaporization, gas phase, hydrogen, CO₂ laser

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