Ma. Natal-santiago et al., Studies of the adsorption of acetaldehyde, methyl acetate, ethyl acetate, and methyl trifluoroacetate on silica, J MOL CAT A, 140(2), 1999, pp. 199-214
Microcalorimetric, infrared spectroscopic, and temperature-programmed-desor
ption studies are combined with quantum-chemical calculations based on dens
ity-functional theory (DFT) to study the adsorption of acetaldehyde, methyl
acetate, ethyl acetate, and methyl trifluoroacetate on amorphous silica. A
dsorption of these molecules on silica proceeds primarily through formation
of two hydrogen bonds per adsorbate, involving the donation of electron de
nsity from the lone-pair orbital on the carbonyl oxygen to hydrogen atoms i
n surface hydroxyl groups. The formation of these hydrogen bonds causes shi
fts to lower wavenumbers of infrared bands associated with the stretching o
f C=O and O-H bonds. On the basis of microcalorimetric and thermal-desorpti
on measurements, hydrogen bonds are estimated to have an average energy of
34 +/- 4 kJ/mol for methyl or ethyl acetate adsorption, and an energy of 27
+/- 4 kJ/mol per bond for the adsorption of acetaldehyde or methyl trifluo
roacetate. The initial heats of adsorption of methyl acetate, ethyl acetate
, and methyl trifluoroacetate are 95, 96, and 92 (+/-5) kT/mol, respectivel
y. These high heats of adsorption at low coverages are assigned, based on D
FT calculations and spectroscopic measurements, to the formation of more th
an two hydrogen bonds with the oxide surface, thereby involving the alkoxy
oxygen of the esters. The high initial heat of acetaldehyde adsorption (86
kT/mol) may be caused by oligomerization processes. (C) 1999 Elsevier Scien
ce B.V. All rights reserved.