4.6 Article

Crystalline Microporous MoVBiO Polyoxometalates for Indirect Oxidation of Methanol to Methyl Formate: Effects of Organic Additives on Crystals Size and Catalytic Performance

Journal

CHEMCATCHEM
Volume 14, Issue 19, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.202200528

Keywords

methanol; methyl formate; MoVBiO; polyoxometalate; size effect

Funding

  1. National Natural Science Foundation of China [21908246, 21975285, 22175200]
  2. Recruitment Program of High-end Foreign Experts [G2022152005L]
  3. International Research Network (IRN) Zeolites

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Crystalline porous Mo-V-Bi oxides were prepared by hydrothermal synthesis, and the effects of organic additives on morphology and particle size were investigated. The 30 nm MoVBiO crystals showed high performance in the oxidation of methanol to methyl formate.
Crystalline porous Mo-V-Bi oxides (MoVBiO) were prepared by hydrothermal synthesis approach. The effects of organic additives (methanol and tartaric acid) on the morphology and particle size of the MoVBiO crystals were investigated. The size of MoVBiO crystals was tuned in the range of 30-300 nm. It was found that methanol accelerated the formation of crystal nuclei resulting in the crystallization of small particles (30 nm), while tartaric acid inhibited the nucleation thus resulting in MoVBiO crystals with a size of 300 nm. The as-synthesized MoVBiO samples were used in the indirect oxidation of methanol to methyl formate. The MoVBiO crystals with a size of 30 nm, synthesized with methanol, showed a high methyl nitrite conversion of 92 % and methyl formate selectivity of 94 % at 140 degrees C. The catalyst exhibited a relatively slow but almost constant deactivation over 50 h due to deposition of reaction species. The small MoVBiO crystals (30 nm) with more surface active sites and accessibility showed high performance in the oxidation of methanol to methyl formate in contrast to the big crystals (300 nm).

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