4.8 Article

Formation of Catalytic Active Sites in Hydrothermally Obtained Binary Ceria-Iron Oxides: Composition and Preparation Effects

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 13, Issue 1, Pages 1838-1852

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.0c16326

Keywords

cerium-iron binary oxides; effect of Fe/Ce ratio; effect of preparation conditions; methanol decomposition; ethyl acetate oxidation

Funding

  1. BIKE project from European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant [813748, BG05M2OP001-1.002-0019]
  2. INFRAMAT (Research Infrastructure from National roadmap of Bulgaria) [D01-284/17.12.2019]
  3. Bulgarian Ministry of Education and Science
  4. Research Infrastructure NanoEnviCZ - Ministry of Education, Youth, and Sports of Czech Republic [LM2018124]
  5. Bulgarian Scientific Fund [KP06-H-29/2]
  6. Marie Curie Actions (MSCA) [813748] Funding Source: Marie Curie Actions (MSCA)

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A series of mesoporous cerium-iron binary oxides were prepared using CTAB as a template via a hydrothermal technique. The influence of Fe/Ce ratio and variations in preparation techniques on the properties of the materials were studied extensively. The shared Ce-O-Fe structures played a key role in the catalytic behavior, which could be controlled by the Fe/Ce ratio and the hydrothermal synthesis procedure.
A series of mesoporous cerium-iron binary oxides was prepared by a hydrothermal technique using CTAB as a template. The influence of the Fe/Ce ratio and the variations in the preparation techniques such as the type of solvent and the precipitation agent, the approach of the template release, and the temperature of calcination on the phase composition, textural, structural, surface, and redox properties of the obtained materials was studied in details by XRD, nitrogen physisorption, TPR, FTIR, UV-vis, XPS, Raman, and Moessbauer spectroscopies. The materials were tested as catalysts in methanol decomposition and total oxidation of ethyl acetate. It was assumed that the binary materials represented a complex mixture of differently substituted ceria- and hematite-like phases. Critical assessment of their formation on the base of a common mechanism scheme was proposed. This scheme declares the key role of the formation of shared Ce-O-Fe structures by insertion of Fe3+ in the ceria lattice and further competitive compensation of the lattice charge balance by the existing in the system ions, which could be controlled by the Fe/Ce ratio and the hydrothermal synthesis procedure used. This mechanism provides proper understanding and regulation of the catalytic behavior of cerium-iron oxide composites in methanol decomposition with a potential for hydrogen production and total oxidation of ethyl acetate as a model of VOCs.

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