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19b ph. It is evident that in some cases there is the superpo-
sition of some components due to the frequency closeness of
the different species. In particular, for instance, for some
modes the perturbation induced by Lewis sites is definitely
smaller and these bands are, therefore, superimposed to those
of hydrogen-bonded species. The identification of Lewis
moieties is supported by comparison with IR experiments of
pyridine dosed on c-Al2O3 (a solid characterized by strong
Lewis acid sites), where four bands, respectively at 1620 (8a),
1578 (8b), 1492 (19a), and 1450 (19b) cm-1, are observed
[38, 39]. Sn-beta zeolite is known as a Sn-based Lewis acid,
catalyzing a variety of green chemical reactions [40, 41]. We
tested a reference Sn-beta zeolite under the same reaction
conditions as Sn–EOF and observed a black colouring. The
Sn-beta zeolite was inactive with an oleic acid conversion of
4 % only after 20 h, even below the conversion in absence of
catalyst (20 %).
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4 Conclusions
Selective esterification of oleic acid with glycerol to
monoglyceride is a demanding reaction. The catalytic
activity of MOFs including HPW/Cu3(BTC)2, HSiW/
Cu3(BTC)2, Al-MIL-53-NH2, In-MIL-68-NH2, UiO-66,
UiO-66-NH2 and ZnF(TAZ-NH2) hardly exceeds the
autocatalytic activity of the fatty acid. On top of limited
activity, there is a MOF stability issue, oleic acid being
responsible for the degradation of MOFs. Solvents in
which both glycerol and oleic acid can be dissolved in high
quantity were identified: tert-butanol, DMF, DMSO and-
monoolein. tert-Butanol was identified as the optimum
solvent. In this solvent MOF catalysts and especially Sn–
EOF are catalytically active. In a catalytic experiment
using Sn–EOF catalyst departing from a mixture with
molar ratio of oleic acid to glycerol of 0.1:1 in tert-butanol
solvent, Sn–EOF was most effective and showed limited
tin leaching. The use of tert-butanol solvent and reaction
conditions with low concentration of oleic acid are rec-
ommended for further MOF catalyst screening programs.
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Acknowledgments The authors gratefully acknowledge financial
support from the EU FP-7 Framework NANOMOF project under
grant agreement CP-IP 228604-2. JAM acknowledges the Flemish
government for long-term structural funding (Methusalem).
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