| Summary: | PhD thesis -
Faculty of Science === The main aim of this thesis has been to study the way in which Fe(III) and Co(II)
incorporation into Si-MCM-41 synthesis gels affects the properties of the unmodified
material. Another aim was to investigate the influence of these hetero-atoms
on the dispersion and particle size distribution as well as the catalytic activity of
supported Au nanoparticles in the CO oxidation reaction.
Si-MCM-41 has been successfully synthesized in this work using mixtures containing
CTAB as a structure-directing agent (SDA) and water-glass as a SiO2
source. Replacement of water-glass with pre-calcined Si-MCM-41 for SiO2 source
in the secondary synthesis step has produced Si-MCM-41 with improved structural
properties (XRD, HRTEM and Raman spectroscopy), including restructured
and more crystalline pore walls (Raman spectroscopy).
The conventional shortcomings of Si-MCM-41 as a support for catalyticallyactive
(transition) metal components such as low hydrothermal stability, low PZC,
lack of cation exchange capacity and no reducibility have been partially addressed
by modification with Fe(III) and Co(II). The premodification was achieved both
during framework synthesis and after synthesis by the incipient wetness impregnation
(IWI) method. As opposed to the one-pot synthesis of metal-containing
derivatives, the IWI method gave materials with high metal loadings and maximal
retention of the properties of pristine Si-MCM-41. On the other hand, metal
incorporation during synthesis to a loading of ~8.8 wt% using aqueous solutions
of metal precursors showed some collapse of the mesostructure. Consequently
methods were sought to incorporate this amount of metal (and up to double, i.e.,
16 wt%) with maximal retention of the MCM-41 characteristics. These methods
included (i) using Si-MCM-41 as a SiO2 source, (ii) dissolving the metal precursors
in an acid solution before inclusion into the synthesis gel, and (iii) using
freshly precipitated alkali slurries of the metal precursors. The first method
produced a highly ordered 16wt% Fe-MCM-41 material with excellent reducibility
(TPR showed three well-resolved peaks) and pore-wall structure (Raman spectroscopy). Like the aqueous route, the acid-mediated metal incorporation route
did not produce ordered materials at metal contents of ~16 wt%. The base precipitate
route produced highly ordered composite materials up to 16 wt% metal
content, with characteristics similar to those of Si-MCM-41 (XRD, BET and
HRTEM), although some metal phases were observed as a separate phase on the
SiO2 surface. Thus, metal-containing MCM-41 materials could be obtained with
conservation of MCM-41 mesoporosity. Raman spectroscopic studies have shown
that the effect of transition metal incorporation in MCM-41-type materials is to
strengthen the pore walls (shift of Si-O-Si peaks to higher frequencies), while
TPR studies revealed that the essentially neutral framework of Si-MCM-41 could
be rendered reducible by transition metal incorporation.
Gold-containing mesoporous nanocomposites were prepared by both direct synthesis
and post-synthetically. Catalysts prepared by direct hydrothermal synthesis
were always accompanied by formation of large Au particles because of the need
to calcine the materials at 500 oC in order to remove the occluded surfactant
template. The presence of transition metal components in Me-MCM-41 (Me = Fe
and Co) has been found to play a significant role in the particle size distribution
and also the dispersion of Au nanoparticles when these materials were used as
supports. In general, a base metal-containing support was found to produce
smaller Au nanoparticles than the corresponding siliceous support. It has been
proposed that the transition metal components serve as anchoring or nucleation
sites for the Au nanoparticles, which are likely to sinter during calcination. The
anchoring sites thus retard the surface mobility of Au at calcination temperatures
above their TTammann.
The use of the Au/Me-MCM-41 materials as catalysts in the CO oxidation
reaction has led to the following observations: (i) catalyst on metal-containing
supports showed better activity than those on Si-MCM-41, probably due to the
induced reducibility in metal-MCM-41, (ii) catalysts prepared by direct synthesis
showed inferior activity owing to large Au particles, (iii) increasing Au content
improves the catalytic performance, (iv) increasing the Fe content of the support at constant Au improves the catalytic performance, and (v) changing the base
metal component of the support from Fe to Co led to a significant improvement in
catalytic activity. The similarity of the apparent activation energies (Ea) for the 5
wt% Au-containing 5 wt% Fe- and 5 wt% Co-MCM-41 suggested that the
difference in catalytic activity is associated with the number of active sites
possessed by each catalyst system. The observed order of catalytic activity of
these 5 wt% Au-containing systems in terms of the support type is: Co-MCM-41
> Fe-MCM-41 > Si-MCM-41. This was further supported by the average Au
particle size, which, in terms of the support, followed the order Co-MCM-41 <
Fe-MCM-41 < Si-MCM-41. Thus, metal-support interactions between Au and
MCM-41 have been enhanced by introducing Fe(III) and Co(II), which also
induced framework charge, ion exchange capacity (IEC) and reducibility in the
neutral siliceous support.
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