Towards Mesoporous Titania Microspheres by
Master’s Thesis in Engineering Nanoscience
Martin A. Olsson
Department of Materials Chemistry
SE-581 83 Lund, Sweden
Lunds tekniska högskola
581 83 Lund
Towards Mesoporous Titania Microspheres by
Master’s Degree Project in Materials Chemistry
at the Ångström Laboratory
Martin A. Olsson
Dr. Alfonso E. Garcia-Bennett
Nanotechnology and Functional Materials,
dept. Engineering Sciences, Uppsala University.
Nanologica AB, Uppsala Science Park
Prof. Reine Wallenberg
Dept. Materials Chemistry, Lund Institute of Technology
Prof. Staﬀan Hansen
Dept. Materials Chemistry, Lund Institute of Technology
Lund, August 26th, 2009
Division for Chemical Engineering
Department of Materials Chemistry
SE-581 83 Lund, Sweden
2 Övrig rapport
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Porös Titandioxid genom Supramolekylär Självorganisering
Towards Mesoporous Titania Microspheres by Supramolecular Self-assembly
Författare Martin A. Olsson
The increasing demand for electricity with a larger population of our planet forces
solutions to ensure a future energy source for humanity. The climate change demands that this energy source is renewable. Such an energy source is the sunlight
that hits our planet every day, which exceeds the present world consumption of
energy per year. Dye-sensitized solar cells (DSSCs) are attractive light-harvesting
devices since their design is suitable for large-scale mass production compared
to all other present solar cell devices. DSSCs would be highly suitable as rooftop solar collectors if their conversion eﬃciency was increased. However, there is
room for improvement of the power conversion eﬃciency of dye-sensitized solar
cells. The high accessible surface area to sensitize titania is a viable route to improvement in the conversion eﬃciency of DSSCs. Employing the sol-gel method
of producing titanium dioxide causes an inexpensive method for producing nanostructured titania nanomaterials with high surface area. The results in this thesis
show that the sol-gel method with supramolecular self-assembly templating is a
plausible approach of generating high surface area TiO2 , since there is an evident
templating eﬀect in titania. Decreasing the pore size has been investigated for
the self-assembly of folate molecules in solution to achieve mesoporous titania by
lower reaction rates. The results from this thesis show that formation of microspheres of titania by spray-drying increases the surface area by a factor of two. In
this thesis the titania does not reach the goals for application in dye-sensitized
solar cells due to constraints on a pH > 7 which causes too high reaction rates
and low crystallinity. The main conclusion is that acidic conditions for titania
synthesis is essential to the anatase crystallization and therefore the methods employed except chelation will improve the titanium dioxide and hence the eﬃciency
of dye-sensitized solar cells. Materials prepared towards the end of this thesis,
show that the relationship between surface area, crystallinity and dye adsorption
capacity is not evident. High dye adsorption capacities were achieved by materials
prepared by an atrane route which shows 28% of the dye adsorption capacity of
the commercial titania P-25.
Sol-Gel, Mesoporous, Titania, Chelation, Atrane, Acetylacetone, Folic acid, DSSC
The increasing demand for electricity with a larger population of our planet forces
solutions to ensure a future energy source for humanity. The climate change demands
that this energy source is renewable. Such an energy source is the sunlight that hits
our planet every day, which exceeds the present world consumption of energy per
year. Dye-sensitized solar cells (DSSCs) are attractive light-harvesting devices since
their design is suitable for large-scale mass production compared to all other present
solar cell devices. DSSCs would be highly suitable as roof-top solar collectors if
their conversion eﬃciency was increased. However, there is room for improvement
of the power conversion eﬃciency of dye-sensitized solar cells. The high accessible
surface area to sensitize titania is a viable route to improvement in the conversion
eﬃciency of DSSCs. Employing the sol-gel method of producing titanium dioxide
causes an inexpensive method for producing nanostructured titania nanomaterials
with high surface area. The results in this thesis show that the sol-gel method with
supramolecular self-assembly templating is a plausible approach of generating high
surface area TiO2 , since there is an evident templating eﬀect in titania. Decreasing
the pore size has been investigated for the self-assembly of folate molecules in
solution to achieve mesoporous titania by lower reaction rates. The results from this
thesis show that formation of microspheres of titania by spray-drying increases the
surface area by a factor of two. In this thesis the titania does not reach the goals
for application in dye-sensitized solar cells due to constraints on a pH > 7 which
causes too high reaction rates and low crystallinity. The main conclusion is that
acidic conditions for titania synthesis is essential to the anatase crystallization and
therefore the methods employed except chelation will improve the titanium dioxide
and hence the eﬃciency of dye-sensitized solar cells. Materials prepared towards
the end of this thesis, show that the relationship between surface area, crystallinity
and dye adsorption capacity is not evident. High dye adsorption capacities were
achieved by materials prepared by an atrane route which shows 28% of the dye
adsorption capacity of the commercial titania P-25.
This master’s thesis project has been ﬁnanced by Nanologica AB. I want to thank
Dr. Alfonso Garcia-Bennett in particular for giving me this opportunity to work in
a state of the art research environment in the ﬁeld of mesoporous materials and for
for his advice. I want to thank Prof. Reine Wallenberg for his supervision. I want
to acknowledge the generous advice for UV-vis spectroscopy by the Nanologica
employee Dr. Roberto Hanoi. I want to thank Ph.D.-student Rambabu Atluri
for sharing his oﬃce with me at the division for Nanotechnology and Functional
Materials at the Ångström Laboratory.
List of Abbreviations
DSSC : Dye Sensitized Solar Cell
SEM : Scanning Electron Microscopy
FA : Folic acid
APES : (3-aminopropyl)triethoxysilane
TTIP : Titanium(IV) isopropoxide
CSDA : Co-Structuring Directing Agent
FWHM : Full Width at Half Maximum
XEDS : X-ray energy dispersive spectrometry
TG : Thermogravimetric measurements
TEAH3 : triethanolamine (2,2’,2”-nitriloethanol)
NFM-2 : Titania prepared by folate route
TG : Thermogravimetric measurement
SE : Secondary electron
AT : Atrane route
AC : Acetylacetone route
SD : Spray-drying route
There has been a long search for a low-cost solar cell since the early 90s [1–5] that
can replace and compete with solid state solar cell devices based on silicon. Plant
cells and bacteria uses photosynthesis to harvest light energy. Using light-harvesting
molecules for making solar cells was ﬁrstly developed by Michael Grätzel et al.  .
A DSSC uses light-harvesting molecules to make a semiconductor sensitive towards
light i.e. dye-sensitization of the semiconductor. Titanium dioxide is one of the most
studied materials for DSSCs as the sensitized semiconductor.  The high amount
of research on titania as a suitable electrode material is due to its wide band gap
and electron transfer properties of one of its crystal structures, namely anatase  .
A detailed description of a DSSC will be given in the following chapter. DSSCs has
the advantage of low-cost processing compared to other solar cell devices  . The
demand for electrical grade silicon for the electronics industry is undoubtedly high.
The largest cost of the conventional pn-junction solar cells comes from processing.
For the DSSCs, the largest part of the cost comes from the dyes which roughly costs
about $750 per gram. The drawback of DSSCs is that the manufacturing process
has not yet really been improved much since the original design. The highest power
conversion eﬃciency that has been achieved is 11% for non-transparent DSSCs. 
The conversion eﬃciency is determined by several parameters e.g. the thickness of
the titania electrode  , surface area of the titania  and the dye absorbance spectra
amongst others  , the surface morphology  and the amount of inter-particle
connections  that causes increased conductivity. Synthesis of titania is achieved
at low temperature with weak dissociative acids or bases. Sol-gel chemistry occurs
via nucleophilic attack during acidic, neutral and basic  conditions for salts and
transition metal alkoxides. [13;14] Titania has been recognized for its potential as an
electrode material due to its photoinduced electronic transfer properties associated
with the anatase phase.  Other applications of the anatase are in catalysis [15;16] ,
lithium-ion batteries  and cosmetics  . Therefore the titania has been intensely
studied the past years for applications such as: DSSCs, self-cleaning coatings  ,
antibacterial tooth implants  , sensors  and depolluting layers  . This master’s
thesis is concerned with the design of titania for DSSCs with the use of folic acid as
nanoscale pore forming agents. Previously, mesoporous titania has been prepared
for DSSCs giving mixed results in eﬃciency in similar cell designs e.g. mesoporous
titania by surfactant routes has given 5%  and 8%  . When mesoporous titania is
sintered during processing the mesopores are blocked and the surface area decreases.
This thesis will describe a novel route to slow down hydrolysis under basic conditions
for titanium alkoxides. The thesis elaborates upon titania materials obtained during
this thesis work. The thesis starts oﬀ in the application of titanium dioxide in
DSSCs as a motivation for an in-depth sol-gel chemistry review. This is followed by
a brief general extension of sol-gel chemistry to mesoporous materials. Self-assembly
and its application for synthesis of mesoporous materials is described. The literature
review of the thesis covers mostly synthesis but also processing of the material.
The characterization with the procedures used are presented as well, since some of
the techniques are not conventional in nanoscience. Detailed procedures are not
intended to be exhaustive but merely increase the reproducibility of the work.
Aims of the thesis
• To investigate a novel self-assembly synthesis route for making a new titania
• Investigation of the pore size control in titania by supramolecular self-assembly.
• To investigate an industrial drying processing method of the titania material
by laboratory bench-scale method for obtaining solid spherical microparticles
of titania for use as electrode material in DSSCs.
• To compare the dye adsorption of standard commercial available titania
powder used for DSSCs (Degussa P-25) [22;23] and the synthesized titania
There are several scientiﬁc reports available on the sol-gel synthesis of mesoporous
titania.  However, since there are a lot of patents on the use of surfactant routes
it has become diﬃcult to commercialize those routes further [24;25] . Since sol-gel
chemistry is a broad ﬁeld with a lot of diﬀerent precursors, a general treatment is
not the scope for a master’s thesis project. A full treatment of sol-gel chemistry
is covered by Brinker (1990)  . Transition metal oxides are covered by Livage
et al. (1988)  . Since the synthesis conditions are very important in the case of
sol-gel chemistry, two diﬀerent materials are not often comparable with the same
synthesis conditions. The work in this thesis is based on the recent synthetic results
of self-assembly templating by Garcia-Bennett et al. (2009). The following chapter
is a brief review based on and around this literature.
Dye-Sensitized Solar Cells
A DSSC is an electrochemical cell. The cell design is depicted in Figure 2.1(a). The
principle of a DSSC is a sandwich structure that consists of two transparent glass
layers each coated with an electrode material. The whole cell is denoted as F-doped
ITO//nc-TiO2 //N719//electrolyte//Pt//F-doped ITO, where nc-TiO2 is referred
to as nanocrystalline titania. One of the electrodes is a titania layer and the other
is a transparent conducting oxide (TCO), usually Indium Tin Oxide, ITO. The
titania electrode is soaked in a dye (Figure 2.1(b)) during processing causing the
dye to chemisorb to the surface of the titania by carboxylate linkages. Between the
two electrodes there is an electrolyte usually I – /I3 which serves as a redox pair.
The dye adsorbs UV-light and causes a charge separation  of electrons and holes
in the ground and excited redox states. The electrons are injected to the titania
conduction band through the carboxylate-titanium linkage. The injected electrons
from the dye is replaced by electrons from the oxidation of the electrolyte redox
molecule iodide. The electrons are transported through the titania network to a
back contact and performs work in an external circuit. The electrons return to the
counter electrode and take place in the reduction of triiodide. There is a decreasing
energy path through the cell, hence it is thermodynamically possible. In general the
eﬃciency reaches 10% when sintered nanocrystalline TiO2 is used. Novel designs for
the electrode material are TiO2 -nanotubes  , ZnO nanowires [28;29] with conversion
eﬃciency 0.5-1.5 %  and microspheres of nanocrystalline ZnO  with conversion
eﬃciency 5.4%  . The latter design will be further elaborated upon for titania in
this master’s thesis.
Figure 2.1: (a) The principle of a dye-sensitized solar cell. (b) The most widely used dye for
DSSCs, namely N719.
The oxidation and reduction reactions taking place in the DSSC are
Oxidation: 3 I− − 2 e− → I−
Reduction: I− + 2 e− → 3 I−
Crystal structure of titania
Titania is a wide band gap semiconductor with three polymorphs  . The three
crystal structures are rutile, brookite and anatase. Since brookite is not relevant to
this master’s thesis it is excluded from this description. The rutile crystal structure
is shown in 2.2(a)-(b) whereas the anatase crystal structure is depicted in Figures
2.2(c)-(d). Both rutile and anatase are tetragonal minerals. Rutile can be viewed as
removing every other row of octahedra from an NiAs crystal structure. Compared
to the NiAs crystal structure which is ionic, the TiO2 is covalently bonded. The
structure has a Ti:O coordination of 6:3 and is nearly close-packed.  The titanium
atom is coordinated by six oxygen in a slightly distorted octahedron. Viewing the
structure from the perspective of the oxygen, one oxygen atom is surrounded by
three planar titanium atoms at the corners of a triangle. The structure can also
be viewed in terms of chains of octahedra sharing corners and opposite edges  .
Anatase is body centred. The crystal structure also has a glide plane along the
c-axis in the ab-plane. The TiO6 octahedra are corner sharing in the plane in an
alternating pattern. The space group for rutile is the tetragonal P 42 /mnm where
P means a primitive lattice, 42 describes how the elements are screwed along a
four-fold axis 90◦ with translation half of the lattice vector, the m and n indices are
mirror plane and a n-glide plane , respectively. An n-glide plane is a translation
half the lattice vector and mirroring of a diagonal of a face for the unit cell. For
anatase the space group is I41 /amd, where I means a body centred lattice, 41
2.3 Sol-gel chemistry
means a screw axis where a rotational symmetry occurs by 90◦ with four-fold
symmetry and translation one fourth of the lattice vector. [6;32] The letters a and
d are glide planes where a is a translation 1/2 of the lattice vector along only the
a-axis and d is a glide plane along a fourth of a space diagonal or face of the unit cell.
Figure 2.2: (a) The rutile structure (b) The rutile structure in the -projection. (c) The
anatase crystal structure viewed from the -projection. (d) The anatase crystal structure
viewed from the -projection. The titanium atoms are illustrated with the larger spheres and
the polyhedra. Oxygen atoms are represented with the smaller spheres. [33;34]
Preparing titanium dioxide in the simplest possible manner by the sol-gel method
is straightforward and comprises adding a highly reactive titanium alkoxide to
water, which causes a white precipitate. Templating titanium dioxide on the
nanoscale by supramolecular self-assembly is however not as straightforward. In
order to control the reactions occurring, a deeper understanding is appropriate.
The two types of reactions that take place for sol-gel chemistry are hydrolysis
and condensation. Polycondensation causes formation of colloids which readily
polymerize to precipitates in solution if the hydrolysis rate is too fast.  It is the
initial hydrolysis step that is the rate determining step in gel formation and the
gelation rates is increased by the addition of spectator solvent.  Sol-gel chemistry is
a subﬁeld of inorganic and materials chemistry. Sol-gel chemistry has been recently
re-visited due to the discovery of mesoporous materials. The sol-gel chemistry uses
precursor molecules that usually are in the form of alkoxides but halogen derivatives
are also common but even more reactive  . Some typical precursor alkoxides are
depicted in Figure 2.3. Precipitation occurs by the same theory as proposed by
Flory [13;14] on the general polymerization, extending the deﬁnition from organic
polymers to inorganic. Even if the inorganic framework is polymerizing it is not this
fact that causes gelling, but the polymerization of colloids. The meaning of a colloid
in the sense of sol-gel chemistry is strictly an oligomeric entity. The transition metal
alkoxides are very reactive due to the electronegative alkoxide groups. This makes
the titanium alkoxides highly unstable to nucleophilic attack which is the main
reaction for the alkoxide chemistry. Therefore titanium dioxide readily precipitates
upon contact with merely water.  The general diﬀerences for silica precursors
and titania precursors can be summarized as:
• Silica has been the most studied material system, but the sol-gel chemistry of
silica is somewhat diﬀerent from titania. The titanium atom, in the precursor
alkoxides, is more electropositive than the silicon atom. 
• Titanium alkoxides exhibit various stable coordinations. When the alkoxide
is coordination unsaturated i.e. has a stable coordination diﬀerent from the
oxidation number, it is able to undergo coordination expansion by olation and
Figure 2.3: (a) Tetraethylorthosilicate (b) Titanium(IV) ethoxide (c) Titanium(IV) isopropoxide.
The alkoxy group OR where R is alkyl or an aryl-group, is an electron donating group and stabilizes the highest oxidation state of the titanium atom in the
molecule. A silicon atom (14 Si) has the orbital structure 1s2 2s2 2p6 3s2 3p2 whereas
a titanium atom (22 Ti) is described by an orbital structure 1s2 2s2 2p6 3s2 3p6 4s2 3d2 .
The lone d-electron pair of the titanium causes a very high reactivity in comparison to the p-electrons of silicon. The consequence is that titanium alkoxides are
much more reactive than its corresponding silicon alkoxides. Titania therefore
precipitates by hydrolysis and condensation of titanium alkoxides. The mechanism for hydrolysis and condensation is nucleophilic substitution. The hydrolysis
takes place by nucleophilic addition of a water molecule to the titanium alkoxide
at neutral conditions. This leads to a transition state with an intermediate with
coordination number ﬁve  , and produces a good leaving group shown in Figure 2.4.
The leaving group can be deduced by a partial charge model. In the non-catalyzed
reaction a proton transfer is essential to take place in the transition state. A
proton is transferred from the incoming water molecule to the leaving alkoxy-group
producing the parent alcohol as the leaving group in the neutral reaction mechanism
shown in Figure 2.4.  The meaning of ’parent’ in this sense is the corresponding
alcohol to the alkoxy-groups. The molecular species with the largest negative
partial charge is the nucleophile. The partial charge of a molecular species is
2.3 Sol-gel chemistry
Figure 2.4: The reaction formulas under neutral conditions pH=7. [13;14;36] .
related to its reactivity. When two atoms combine in a reaction a charge transfer
occurs. The electronegativity is linear with the atom charge. The charge transfer
stops when the electronegativities of the moleuclar species becomes equal to the
mean electronegativity. This is the principle of electronegativity equalization and
corresponds to the electronic corresponding principle of chemical equilibrium in
thermodynamics.  . In the absence of a catalyst, hydrolysis and condensation is
taking place by a SN -mechanism according to nucleophilic addition and a consecutive
proton transfer in the transition state and the production of a leaving group which
receives the proton as depicted in Figure 2.4. The reactions depend on the strength
of the nucleophile, the electrophilicity of the metal atom and the partial charge of of
the leaving group, δ(molecule) . The general reaction is that an alkoxy-group where
the partial charge is negative, attacks the metal atom where the partial charge
is positive. Silicon alkoxides are not very reactive with water (pH=7) compared
to the transition metal alkoxides which causes highly exothermic reactions. The
partial charge of the titanium metal atom in Ti(OEt)4 is +0.63 and for Si in
Si(OEt)4 it is +0.32. A minimum value of the rate of hydrolysis can be estimated to
k = 1 mmoldm−3 s−1 at pH=7 for Si(OR)4 which is ﬁve orders of magnitudes less
than for Ti(OR)4 .  Acid or base catalysts can inﬂuence both the hydrolysis and
condensation rates, but also the structure of the condensed product.  Acids serve
to protonate nucleophilic alkoxide groups in the reaction mechanism, enhancing
the reaction kinetics by producing good leaving groups and eliminate the need for
proton transfer in the transition state. Therefore hydrolysis goes to completion if
suﬃcient water is added. 
Under basic conditions the hydroxyl ion acts as a nucleophile towards titanium
alkoxides and no proton transfer is needed in the transition states  . For example
Figure 2.5: The reaction mechanisms under acidic conditions. The acidic hydrolysis is related
to a SN 2-reaction and the condensation is a SN 1-type of reaction.
the hydrolysis of titanium isopropoxide is not generating any isopropanol leaving
molecules under basic conditions compared to acidic conditions. Increasing the
synthesis temperature causes a faster hydrolysis and condensation, in general, due
to lowering of the energy barrier for the reaction. In general under a large pH range
for acidic conditions the hydrolysis is fast and the condensation is slow. Under
basic conditions the hydrolysis is slow and condensation is fast. By dissolving
the transition metal alkoxide in diﬀerent media, diﬀerent nucleophilic interactions
occurs due to the polarity of the solvent. For example, the titanium(IV) ethoxide
takes the form of an oligomer in non-polar solvents. This is due to the coordination
number of 5-6. This type of alkoxy bridges are is stable to hydrolysis and therefore
slows down the hydrolysis rate, but causes the formation of unwanted gels instead.
When dissolving titanium ethoxide in ethanol the alkoxide is instead monomeric
due to solvent interaction instead. Metal alkoxides are often dissolved in organic
solvent before hydrolysis is performed. As a general rule, dilution should lead to
lower alkoxy association but the polarity of the solvent has to be taken into account
e.g. Ti(OEt)4 remains trimeric in non-polar solvent such as hexane, but the same
is not true for using polar solvent such as ethanol. This is due to the nucleophilicity
of the polar solvent causing solvation of the oligomer. The polar solvent is thus
expected to be associated with the alkoxide instead.
The eﬀect of synthesis parameters
The changes upon pH of the sol-gel chemistry of titania under acidic and basic conditions is explained by adsorption and desorption of hydronium ions or hydroxide ions
respectively at titanium and oxygen-sites.  The time for reaching the equilibrium
of adsorption of hydroxide ions to Ti(OH)4 is a few hours at room temperature
and is accelerated at higher temperatures.  Neutral electrolytes also can enhance
the anatase transformation due to shielding the eﬀect of the attractive forces from
titanium-atoms to hydroxide ions under basic conditions. Increasing the adsorption
of hydroxide ions to TiO2 nuclei is the reason for the declining nucleation rate of
anatase TiO2 with basic pH.  The synthesis temperature determines the phase
transformation temperature during calcination. For a lower water-to-alkoxide ratio,
organic components are easier to eliminate and the grain size is smaller explained
by less degree of polymerization. 
Figure 2.6: The reaction mechanisms under basic conditions.
The discovery of the ﬁrst synthetic zeolite ZSM-5 was done by what today is the
Exxon Mobil Corporation. But it was not until the discovery of the ﬁrst mesoporous
silica MCM-41 that the wide research into the mesoscale porosity (2-50 nm) begun in
1992  . If the pores are below 2 nanometres they are called micropores and above
50 nanometres they are called macropores. It was mesoporous silica with the use of
cationic surfactants that was ﬁrstly discovered in  . An alkaline route renders the
silica negatively charged, whereas the surfactant is positively charged. This leads to
a charge interaction between a micellar phase above a critical micelle concentration.
It is owing to this charge interaction that there is a pore formation. The framework
condenses around an already formed surfactant liquid crystalline phase. Several different mesoporous titania routes have been reported since then such as the use of the
anionic surfactant Dodecyl sulphate  , the neutral surfactant Dodecylamine  ,
the cationic surfactant Cetyltrimethylammonium bromide  , the neutral poly-
meric surfactant P123  and a non-surfactant β-cyclodextrin/urea-mixture  .
The use of derivatives of nucleotides as templates has only been reported in silica  .
Figure 2.7: (a) Folic acid molecule. (b) Tetrameric self-assembly unit of folate molecules  .
Figure 2.8: The sequence of self-assembly with stacking into columns and into an hexagonal
phase with p6mm symmetry.
Supramolecular self-assembly is deﬁned as the process by which a molecular species
forms spontaneously from its monomer molecules. Common interactions are aromatic interactions, van der Waals forces and hydrogen bonding. It is possible to
analyze the interactions based on combined perpendicular T-geometry, face-to-face
interactions and oﬀset interactions of π − π-stacked systems [47;48] . Net favourable
π − π interactions are not due to attractive π − π interactions but occur due to
attractive interactions between π-electrons and the σ-framework i.e. π − σ interactions that are larger than the repulsion of the π − π interactions.  . Garcia-Bennett
et al. showed that folic acid, see Figure 2.7(a), self-assemble and can be utilized
for pore formation with a silica framework, using (3-aminopropyl)triethoxysilane
for inducing the self-assembly  . The fact that folic acid derivatives self-assemble
in salt solution has been reported previously [50;51] . The self-assembly with ions
are best with potassium ions for guanosine derivatives and sodium ions for folic
acid which utilizes cation-pi interactions [52–54] . The self-assembly used in sol-gel by
Garcia et al.  of folate is somewhat diﬀerent from the surfactant self-assembly
since no hexagonal phase exists but is formed in-situ. The self-assembly rely on the
hydrogen-bonding of one of the tautomers of the pterin-group. The pterin-group is
the nucleotide-derivative of guanine. Four folate pterin-groups with two hydrogen
bonds per group arrange the folate molecules into tetramers, shown in Figure 2.7(b).
The tetramers stack themselves as face-to-face [46;55] in a beautiful way as chiral
columns with the glutamate groups of the folic acid sticking out from the columns,
see Figure 2.8. The distance between tetramers in the stacks is 0.33-0.34 nm for
sodium folates. The sodium is thought to be present between the tetramers stabilizing the structure. Both carboxylates of folate molecules interact with APES. The
co-structure directing agent (3-aminopropyl)triethoxysilane is depicted in Figure
2.11. It acts as a base causing production of OH – catalysing hydrolysis of the
alkoxide. But it also associates with its protonated positive amine-group to the
negative deprotonated carboxylic group of the folate-stacks. The alkoxy groups of
(3-aminopropyl)triethoxysilane can then contribute in hydrolysis and condensation
of an inorganic network. The tetrameric stacks produce a hexagonal phase within
a framework. The stacks formed by the discoid tetramers are depicted in Figure
2.8. The APES is critical to the pore condensation as it will cause condensation to
occur at the surface of the folate-stacks. The pore condensation is depicted for a
single folate molecule of a tetramer in Figure 2.9(a) and a corresponding pore is
sketched in Figure 2.9(b).
Figure 2.9: (a) Condensation of a mesopore under basic conditions. The titania has a negatively
charged surface.(b) The Figure is a sketch of a plausible pore caused by one tetramer of a
folate-stack. When the as-synthesized titania is calcined the organic is burned.
Figure 2.10: The relationship of the pH to the self-assembly process at room temperature. Note
the neutral amine-group of the folate above pKa = 8.3. Below the pH of 3.5 the amine-group of
the folic acid is positively charged and both carboxylic groups of the glutamic acid moiety are not
deprotonated. Below the pH of 5 the α-carboxylate is formed. Below the pH of 8.3 the γ-carboxylic
group is deprotonated. Above the pH of 8.3 the amine of the pterin-group is deprotonated. The
neutral amine group of the pterin moiety is critical to the Hoogsten-type hydrogen bonding for the
formation of tetramers.
Folate forms at a pH above 3.5.  Above the pH of the pKa = 8.3, the amine on
the pterin-group of folate is deprotonated. [46;57] The amine takes part in Hoogstentype hydrogen bonding  causing the formation of the tetrameric unit. Below
the pKa = 9.8 of the base APES the amine of (3-aminopropyl)triethoxysilane is
protonated  . The synthesis conditions are therefore in the approximate pH range
of 8.3 < pH < 9.8. The reason for using a CSDA is that the titania is negatively
charged under basic conditions. The folate is also negatively charged hence an electrostatic interaction causes the possibility to condense a framework surrounding the
folate stacks. The relationship with pH of the folate is similar to the titration curve
of glutamic acid. The scheme with relation to the pKa -values is shown in Figure 2.10.
Figure 2.11: (3-aminopropyl)triethoxysilane. The co-structuring agent (CSDA).
2.6 Hydrolysis retardation
The crystal structure of titania that is obtained by synthesis is determined primarily
by the preparation. The crystallite size of anatase can be controlled by adjusting
the aging time of the dry gel. The rutile content can be controlled by the wet gel
aging time. Moreover, the surface structure also contributes to the nucleation of
Figure 2.12: Organic reaction mechanism of 1-isopropoxytitanatrane.
Selecting the proper solvent for the reaction can determine the precipitation of a stable colloid. [13;14;20] Sol-gel reactions of TTIP has all led to immediate precipitation
in water and organic solvent. This is not the case if a chelating agent is used. 
As was stated in section 2.3 the hydrolysis rate of titanium alkoxides are very high.
The reaction rate can be decreased by lowering the functionality i.e. the amount of
available alkoxy-groups that can be hydrolysed can be decreased by addition of a
chelating agent.  Increasing the coordination number, causes a higher stability to
nucleophilic substitution. [13;14] Displacing the equilibrium can be made with the
parent alcohol in excess in the synthesis solution under acidic conditions.  In terms
of the available theory on sol-gel chemistry the most straightforward way to obtain
a lower hydrolysis rate would be to decrease the partial charge of the titanium atom
in the precursor.  The partial charge of titanium isopropoxide was emphasized
in section 2.3 where it was compared to the silica precursor tetraethylorthosilicate.
The decrease of only the functionality can be obtained with acetylacetone. Acetylacetone has been shown to stabilize the anatase crystal structure and prevent rutile
formation up to 1000◦ C.  The replacing ligands are however not larger than e.g.
isopropoxide groups, hence not blocking coordination sites.  The sol-gel reaction
of acetylacetone modiﬁed titanium alkoxides causes acetylacetone to remain bound
to titania even when hydrolysis is performed with excess of water.  Lowering the
partial charge and the functionality can be obtained by the use of an atrane complex.
Triethanolamine has been used to slow down the hydrolysis rate of titanium dioxide
Industrial drying of powders
This section will deal with an industrial method for large-scale drying of titania
powders. Spray-drying is a drying method that has been considered as a bottom-
Figure 2.13: Spray-dryer setup. The droplets produced is in the micron range. (a) feed solution
(b) peristaltic pump (c) nozzle column (d) nozzle (e) spray cylinder (f) outlet (g) cyclone (h)
vessel (i) ﬁlter
up approach since it causes the possibility of designing functional materials with
nanoscale properties of architectures in the size of microns from nanoparticles. 
Spray-drying is an already used method of preparing large amounts of dried powders
for the food industry [63;64] e.g. as dairy powders [63;64] , for the chemical industry 
and the pharmaceutical industry [64–68] . The method has been increasingly used
for preparation of materials for controlled release of drugs in drug-delivery. [69;70]
This is even the method for making instant coﬀee.  Spray-drying has shown to
produce micron-sized particles which are collapsed  , donought-shaped, dispersed
spherical shells [63;72;73] , dispersed [73;74] and agglomerated  spherical solids in
silica. Spray-drying has also been used to spray-dry mesoporous silica successfully
into microspheres using surfactant  . Moreover, collapsed  , spherical shells [75;76]
and solid spheres  have been reported for titanium dioxide. Nanocrystalline
titania microspheres of an approximate size of 10 µm has shown to have a surface
area of 560 m2 /g even without any template for mesoporosity.  Even mesoporous
titania microspheres of size 8.3 µm that are solid have been reported but with
a low surface area of 50.1 m2 /g and smooth surface texture  . It is therefore
desirable to investigate spray-drying of nanocrystalline titania but also to investigate
if mesoporosity can give higher surface area.
The synthetic conditions contributes to high temperatures due to the water content
i.e. outlet temperatures needed is at least 100◦ C at (d) in Figure 2.13. A lower
temperature is expected to improve the morphology of the particles. A donought
shape form due to higher evaporation rates in the centre of the droplet, which is
due to the higher temperature in the droplet centre. The formation of a crust in
the beginning of the drying and the migration of dispersant to the surface causes
the crust formation that results in particle shells.
The spray-dryer used is depicted in Figure 2.13 with letters corresponding to the
diﬀerent parts of the equipment. The gas supply is attached to the N2 -inlet and
is heated up by an electric heater. The feed solution (a) is pumped with a simple
2.8 Characterization techniques
peristaltic pump (b). The feed solution is heated up in the nozzle tube (c) by the
hot gas. The sprayed solution leaves the nozzle at (d) and travels through the spray
cylinder (e). The aerosols travel to a cyclone (g) to separate from the gas stream
and the product is obtained in a vessel(h). The outgoing air is ﬁltered and an
aspirator pumps air through the system.  Solvent circulates in a closed loop. The
inert gas with solvent vapour is cooled hence the solvent condenses into a bottle. 
The cleaned gas stream is pre-heated and ﬂows back into the spray dryer.  In
general, hollow microspheres are produced from well-dispersed sols whereas if the
sols are partially aggregated they produce solid particles  .
Scanning electron microscopy
Characterization of the material morphology is performed with scanning electron
microscopy (SEM). A scanning electron microscope uses electrons instead of photons
to produce an image. To produce electrons an electron gun is used. For high
resolution SEM ﬁeld emission sources are used exclusionary. The lenses used to
focus the electron beam are magnetic and therefore has hysteresis built in which
causes astigmatism. Bombarding a conducting sample with high energy electrons,
can be used to produce signals that contain morphological information. Secondary
electrons (SEs) that are knocked out from core electron shells have a low kinetic
energy and can be collected with a detector that attracts the electrons with a
positive potential. This way of detecting the SEs causes an artiﬁcial light in the
images. Also due to the bombarding of electrons, X-rays are produced from the
excited volume when electrons fall back from their respective excited states. X-ray
energy dispersive spectroscopy can be used to analyse the characteristic X-rays
Figure 2.14: The image shows a LEO1550 scanning electron microscope equipped with a high
resolution SE-detector called InLens within the pole piece.(a) N2 -liquid dewar (b) Secondary
electron detector (c) Column of lenses (d) IR-camera (e) XEDS detector that can be inserted in
to the chamber.
X-ray diﬀraction (XRD)
Characterization of the crystal structure is performed with the use of X-ray radiation.
The X-rays have wavelengths in the order of atomic distances in crystal structures
i.e. in the order of 0.1 nm. X-ray diﬀraction is described by the Bragg law
nλ = dhkl sin θhkl
Figure 2.15: Image of a Bragg-Bretano Siemens D5000 X-ray diﬀractometer geometry in locked
coupled mode; the x-ray tube and detector are aligned at the same angle. The order of the X-ray
pathway is (a) X-ray tube (b) divergence slit (c) illuminated spot (d) anti-scattering slit (e) ﬁlter
slit for calibration of the equipment (f) detector slit (g) detector. In (h) a sample holder is shown
and in (i) a sample holder lid. In (j) a titania specimen prepared by capillarity eﬀects is shown.
where dhkl is the spacing between sets of crystal planes with indices hkl, θhkl is half
the angle between the incoming light beam and the outgoing ray. This law describes
the constructive and destructive interference of the radiation when incident on
the set of crystal planes. The crystallite size is described by the Scherer equation
which is equation 2.2. This equation states qualitatively that the crystallite size
decreases with a broad Full-Width-at-Half-Maximum (FWHM). The larger FWHM,
the smaller crystallite size. The opposite is also true i.e. that for a high intensity
with a small FWHM has a large crystallite size.
βhkl cos θhkl
The value n in equation 2.1 is an integer and λ is the wavelength of incoming rays.
The Dhkl is the crystallite thickness, the K-factor takes a value between 0.94 and
0.98 for perfect cubic and perfect spherical crystallites, respectively. All angles are
in radians as well as the peak width βhkl and in θ(◦ ). For anatase the crystallite size
is calculated from the 101 peak since it has the highest abundance in the crystallites.
Reﬂections at low-angles < 6◦ are equivalent to order at distances corresponding to
mesoscale order. Low-angle XRD cannot measure mesoporosity, only the quality of
the mesoporosity in terms of the orderity. The diﬃculties with measurements at
low angles is that the background noise from the sample holder increases, it is also
possible that artefacts from the detector appear. Zero noise silicon wafer sample
holders are preferred for these measurements.
2.8 Characterization techniques
A typical equipment for measuring surface area and pore size is shown in Figure
2.16. For a mesoporous material, ﬁlling the pores with N2 -gas will primarily lead to
monolayer coverage. The next layer will then be physisorbed to the ﬁrst layer at a
higher pressure. At a high enough pressure the pores will be ﬁlled with gaseous
N2 that condenses to liquid N2 . When lowering the pressure isothermally, it takes
more energy to ﬁll the pore than to evaporate the liquid N2 .  This can be seen
as a relative pressure drop in desorption and hence hysteresis in the sorption data.
Figure 2.16: A Micromeritics ASAP 2020 equipment for N2 -sorption measurements.(a) degas
stations (b) reference tubes with thermos ﬁlled with liquid nitrogen (c) analysis station with
thermos ﬁlled with nitrogen (d) glass balloon for N2 -sorption measurements (e) isothermal jacket.
A thermogravimetric analyser is depicted in Figure 2.17(a). The thermogravimetric
analysis (TG) is used to measure weight-loss of a sample by heating at a constant
rate inside a furnace (b). The furnace contains a delicate balance (c) which is
able to record the weight of the sample. For porous materials the weight-loss from
burning the organic template can be deduced from the change in weight within the
corresponding temperature interval where the organic phase is burned.
Chromophores have the ability to absorb light. This is owing to the potential wells
formed by the delocalization of electrons. The electrons can therefore be excited
to higher energy levels. The electronic states can be divided into singlet states
and triplet states. When electrons fall back from excited singlet states it causes
ﬂuorescence for singlet state transitions and phosphorescence for electrons falling
back to triplet states. Ultraviolet-visible spectroscopy is the opposite of measuring
the ﬂuorescence i.e. measuring the transmittance of light and hence the absorption
by excitation in the ultraviolet-visible region. The UV-vis spectroscopy has been
used to measure the light absorbance as a function of adsorption of dye to titanium
Figure 2.17: The ﬁgure shows a thermogravimetric analyser to measure weight loss upon heating
a sample. (a) A thermogravimetric analyser (b) a furnace (in cavity) (c) a delicate balance inside
the furnace (d) air ﬂow meter (e) N2 -ﬂow meter.
Figure 2.18: The ﬁgure shows the box that is a UV-vis spectrometer.
The method to achieve the aims of this thesis have been synthesis of titanium dioxide
by the sol-gel method and characterization thereof. There are several diﬀerent
available pathways including chemical vapour deposition, inert gas condensation  ,
oxidation-hydrothermal synthesis of metallic titanium, non-hydrolytic  sol-gel
synthesis of anatase at low temperature and hydrolytic  synthesis of titania
from titanium alkoxides and titanium chlorides  . The reason for choosing the
hydrolytic synthesis lies in the aﬀordability  of the method for up-scaling with
widely researched titania precursors. The fact that this master’s thesis has the
intention of investigating an extension of a silica route for Nanologica AB to the
synthesis of mesoporous titania has come with certain challenges. The largest
challenges is the basic conditions of the folate route  that comes from the use of
the folic acid as a template. This comprises a narrow pH range that is essential
to have a templating eﬀect.  Moreover, the reasons for using π − πstacking for
preparing mesoporous titania is that a hierarchical supramolecular self-assembly
route has not yet been reported for titania in the literature. In addition, folic
acid have interesting electronic properties  . The semiconducting properties of
guanine-based nanowires has been reported to conduct charge  . A general method
can be extended to a range of transition metal oxides that are interesting as supports
in heterogeneous catalysis. A novel folate route  with potential is investigated for
obtaining control of mesoporosity. Characterization has been made of crystallinity,
morphology, organic weight-loss, surface area and adsorption.
In chapter 2, the reasons for synthesizing titania was stated for the use as a
dye-sensitized electrode. Several precursors can be used for the preparation of
titanium dioxide. Common precursors used are Ti(OR)4 where R=ethyl  , isopropyl [12;38;89;90] and butyl [39;91] . In this thesis, titanium isopropoxide was chosen
because it is a ﬂuid at room temperature compared e.g. titanium ethoxide. Titanium ethoxide is decisive because one might think that this precursor will behave
as tetraethylorthosilicate (TEOS), which has become a standard in the literature
for synthesis of mesoporous silica  . As was stated in section 2.3 the titanium
isopropoxide has more chemical similarities with TEOS owing to the fact that the coordination number equals the oxidation state. APES can be used as a co-structuring
agent and as the base.  The basic conditions are needed for the charge-interaction
of APES and folate. The recipes used is similar to and modiﬁcations of a folate route
proposed by Garcia-Bennett et al.  using TEOS as precursor. In the synthesis,
the reacted solution is unstirred overnight. Keeping the solution unstirred was a
suitable way for storage in oven, at synthesis temperature, decreasing the batch time
in oil-bath. That means a higher quantity of batches can be made consecutively. In
the following chapter the synthesis of titanium dioxide will be described.
There are a couple of ways to consider for lowering the hydrolysis rate in the
synthesis. By capping the titanium with a nitrogen atom the nucleophilicity is
lowered under basic conditions.  Since titanatranes have a high viscosity, an
1-isoporpoxytitanatrane was diluted in polar solvent to make it possible to pipette
from a stock solution according with section 2.3. The following folate route was
prepared at room temperature with the use of the 1-isopropoxytitanatrane in
ethanolic solution as precursor. Addition of solvent causes dilution of the alkoxide
prior to mixing which causes a slower reaction  . A lower water content also lowers
the hydrolysis rate of titanium alkoxides.  In order to commercialize a mesoporous
titania powder a spray-drying technique that causes smaller monodispersed particles
is needed for use in DSSCs. Spray-drying has been reported to be a viable route to
obtaining spherical shaped particles from slurry and was described in section 2.7.
Synthesis of TiO2 by folate route (NFM-2)
All synthesis of NFM-2 materials was carried out by the author. Titanium(IV)
isopropoxide (TTIP) was used as a precursor. The (3-aminopropyl)triethoxysilane
(APES) was used as the base. The templating agent was folic acid (FA). All chemicals
were purchased from Sigma-Aldrich and used as received. Safety precautions were
taken due to the high reactivity of the base and the TTIP. The chemicals were
prepared in the molar ratio of 0.13 FA/ 1 TTIP/0.33 APES/ 230.5 H2 O  . An
amount of 1.21 g of folic acid was added to 87.6 ml distilled water in a plastic
bottle. The aqueous folic acid yellow solution was stirred in a closed ﬂask vigorously
at 60◦ C on a Heidolph MR3002 heater/stirrer. The base APES was added at
once using a pipette. The colour change upon addition of APES was from dark
yellow to bright yellow. The precursor TTIP was added in a shot of 6.0 mL.
The (3-aminopropyl)triethoxysilane was added ﬁrstly and then the titanium(IV)
isopropoxide within 15 seconds. A rule of thumb was to add the precursor when
the solution changed colour. The synthesis was heated and stirred for about 20 min
and was then left unstirred for 18 h. The reacted solution was vacuum ﬁltered and
washed with about 30 ml of distilled water.
Slowing down the hydrolysis rate
Slowing down the hydrolysis rate was investigated through preparing chelated
titanium(IV) isopropoxide with acetylacetone and triethanolamine for use in the
synthesis of NFM-2-AC and NFM-2-AT, respectively.
Acetylacetone route (NFM-2-AC)
The recipe was only changed by increasing the complexity by preparing the precursor.
Instead of adding the TTIP precursor directly to the synthesis it was chelated with
acetylacetone. An amount of 6 mL acetylacetone was stirred together with TTIP
for 10 minutes. The solution turned colour from being transparent to being bright
Atrane route (NFM-2-AT)
Folic acid was added to a plastic bottle and was dissolved in distilled water. The
prepared titanatrane was added in a shot. The solution was stirred at room
temperature for about 5 minutes. The solution was clear yellow with no precipitation
occurring. The ﬂask with the containing solution was placed in the oven at the
synthesis temperature 60 ◦ C. A phase separation of solvent and the wet powder
could be seen after aging in the oven. The powder was a paste and the water
content was high even after ﬁltering. The paste was dried in the oven at 40◦ C.
An 1-isopropoxytitanatrane was prepared by organic synthesis with the reaction
depicted in Figure 3.1. Preparation was ﬁrstly investigated by rotoevaporation at
40◦ C to collect the isopropanol formed. It was found that this is an expensive way,
since a large amount is evaporated in the vacuum line. Instead isopropanol was
smelled during evaporation without vacuum in fume cupboard and then a vacuum
line attached. The preparation of the titanatrane used 30 mL TTIP added to a
Figure 3.1: The reaction scheme for the synthesis of 1-isopropoxytitanatrane.
Figure 3.2: Setup for organic synthesis of 1-isopropoxytitanatrane. A vacuum line is used for
evaporation of isopropanol.
Figure 3.3: A Nabertherm B150 oven used for calcination. The oven can heat up to 2000◦ C.
The procedure used for calcination was cleaning ceramic boats with ethanol and
which were dried in oven at 100◦ C. A temperature ramp of 10 h for reaching 550◦ C
was used. Samples were heated isothermally for 6 h. The calcination was performed
with a Nabertherm B150 oven. The synthesis temperature was chosen to 60◦ C to
enhance anatase transformation during calcination.
A Büchi Mini Spray-Dryer B-290 was used. The glassware of the spray-dryer was
cleaned thoroughly for prevention of possible contamination of processed powder.
A feed solution was prepared by normal synthesis as described in section 3.1. The
spray-dryer was started-up and the aspirator was set to 50 %. The N2 -carrier gas
was switched on and the oxygen sensor was controlled so that the apparatus was
evacuated with air and ﬁlled with N2 -ﬂow. The ﬂow was controlled with respect to
a pressure of 20 bar. The inlet temperature was typically set to around 200◦ C to
reach an outlet temperature of 100◦ C. During spray-drying with the pumping rate
set too high the outlet temperature dropped.
N2 -ﬂow (%)
inlet (◦ C)
outlet (◦ C)
Table 3.1: Spray-drying conditions as described in section 2.7. The speciﬁc conditions are only
relevant to the Büchi Mini Spray-Dryer B-290 and the corresponding industrial spray-dryer.
The characterization techniques used were brieﬂy described in chapter 2. These are
low-angle XRD, TG, high-angle XRD, SEM, XEDS, N2-sorption, SEM and UV-vis
spectroscopy. All characterization has been performed by the author.
For a typical specimen preparation the powder sample was crushed to a ﬁner powder
by using a mortar and pestle. The sample was placed in a plastic holder with a
cavity for the sample. The amount of sample was approx 1 g. Powder samples were
prepared by making the powder smooth in the plastic sample holder by pressing
with a glass piece. A Bragg-Bretano Siemens D5000 diﬀractometer was used for
both high-angle and low-angle investigations. The scanning-routine used was locked
coupled. The diﬀractometer was set up by increasing the voltage manually to 45
kV working voltage and the working current to 40 mA. For low-angle XRD, the
divergence and receiving slits were set to 1.0 mm and the detector slit used was 0.2
mm. For high-angle XRD the divergence and receiving slits was 1.0 mm whereas
the detector slit used was 0.6 mm. The samples were typically scanned with 2.5
sec/step with an increment of 0.03◦ (2θ) for 1 h runs, with 3.4 sec/step with an
increment of 0.02◦ (2θ) for 2 h runs and with step size 0.014◦ (2θ) and 10 sec/step
for night runs. The magnetic specimen holder was inserted into the diﬀractometer.
A LEO1550 was used. Samples were prepared with low amount of powder for the
SEM by mounting conducting carbon ﬁlms on the specimen holders. The SEM
was set up to start at an intermediate voltage typically 7-10 kV. Depending on
the sample, typically a lower accelerating voltage of 2 kV was later required. An
improved secondary electron detector was typically used called InLens. The InLens
detector was used for higher resolutions at a low working distance about 2-3 mm
and the normal secondary electron detector was used higher resolution than the
InLens detector at higher working distance. A typical alignment of the column
was made by ﬁrst choosing the voltage and aperture to use. A standard 30 µm
aperture was used. The aperture alignment was followed by stigmation at high
magniﬁcations. This was done repeatedly several times at a higher magniﬁcations
for improvement of the resolution. An Oxford Instruments INCA system was used
for XEDS. XEDS measurements were performed with a voltage higher than the
electronic transitions between the electron shells in titanium, silicon and oxygen
where the highest voltage needed is above the Kβ peak of titanium. The working
distance was set to 15 mm. The XEDS detector with ultra-thin window was inserted
into the chamber pointing towards the specimen. The conditions used in the INCA
software was an acquisition rate of 0.5 kcps, dead time of 7% and acquisition time
of 100 seconds.
The isotherm-equipment, Micromeritics ASAP 2020, was ﬁlled up with liquid
nitrogen. Glass balloons were ﬂushed with acetone which was evaporated in an
oven at 60◦ C. The glass balloons were weighed ﬁrstly without sample, secondly
with sample and thirdly with frit. Samples were degassed for 18 h at 120◦ C to
remove any residual moisture. The degassed samples were weighed again to obtain
the dry weight. After the dry weight measurement the sample was inserted in the
instrument again to obtain the isotherm with the sample weight as input in the
Thermogravimetric measurements were performed on a Mettler-Toledo TGA
/SDTA851e . A small crucible sample holder was used and cleaned in a prepared
HCl bath. The crucibles were handled with pincette. The crucible was dried in
an oven at 60◦ C for a couple of minutes and the apparatus was tared with the
sample holder inside. A small amount of sample was placed in the crucible which
was placed in the furnace. The software was set up to run the measurements.
Absorbance tests were done using a SHIMADZU UV-1650PC spectrometer and the
software UVProbe 2.21 from SHIMADZU. A dilute dye stock solution was prepared
with 1·10−4 M of the dye N719. The dye was bought from DyeSol, Australia and used
as received. An amount of 0.1 g titania was added directly to prepared solution of
20 mL stock-solution in glass-vials. Samples were tested normally after calcination.
The stock-solution was prepared with tertiary butanol/acetonitrile in 1:1 volume
ratio. The tertiary butanol/acetonitrile was also used as a blank. Solutions with
analyte were heated at 40◦ C for 1 h before ﬁltering and measurements. Scans were
taken from 190 - 450 nm with 0.2 nm sampling interval. The analyte was prepared by
stirring the titania in stock solution for 24 hours before ﬁltration and measurements.
The following chapter describes the results obtained from the characterization of
titanium dioxide obtained from the synthetic routes and processing.
Results and discussion
The yellow powder obtained from NFM-2 synthesis varied in colour very much
when changing the synthetic conditions, such as temperature and pH. Below room
temperature and at 45◦ C, large precipitates formed whereas at 80◦ C a paste was
obtained. SEM micrographs of NFM-2 are shown in Figures 4.4(a)-(d). From Figure
4.4(a) it can be seen that NFM-2 powders consists of large particles, which have
large-scale porosity and smaller porosity like channels and random large scale pores
in the micron range. The Figure 4.4(b) shows that the porosity is macroporous.
The largest pores are approximately 2-3 µm. The Figure 4.4(c) shows pore walls
have small particles on the surface. The Figure 4.4(d) shows that the nanoparticles
on the pore walls have a surface texture below 50 nm that is not attributed to
nanocrystallinity due to the amorphous nature of the samples.
The composition of NFM-2 was determined from XEDS-spectrometry and the
average composition was 63.7 at% oxygen, 32.2% titanium and 4.1 at% silicon. The
XEDS-spectra is shown in Figure 4.1. The composition was therefore concluded to
be 88.6 % TiO2 and 11.4% SiO2 .
Figure 4.2 shows low-angle XRD patterns of the diﬀerent NFM-2 derivatives. The
curve (a) is a reference curve for NFM-1 which is the mesoporous silica by the folate
route. The curve (b) shows only a broad peak. Curve (c) shows a typical peak of no
order at lower angles obtained for the materials NFM-2, NFM-2-AT and NFM-2-SD.
The Figure 4.3 shows six X-ray diﬀraction patterns that are shifted in relative
intensity. The curve (a) in Figure 4.3 shows the high crystallinity of P-25. The curve
(b) in Figure 4.3 shows a high intensity 101 reﬂection at 25.4◦ . A superposition
of 103, 004 and 112 reﬂections can be seen at 37.7◦ . At 48.1◦ the 200 reﬂection
is present as a single peak and the peak 54.7◦ is a superposition of the 105 and
the 211 peaks. The 101 reﬂection has the highest intensity and therefore has the
highest abundance in the crystallites. Curve (e) has only a large broad peak which
Results and discussion
Figure 4.1: XEDS measurement on NFM-2-AC. Inset shows the site of interest for the measurement using a SE-detector at a working distance of 15 mm.
Figure 4.2: Low-angle XRD patterns. (a) NFM-1 (b) NFM-2-AC (c) NFM-2-AT and NFM-2
4.1 Designed materials
Figure 4.3: XRD patterns of calcined NFM-2 with synthesis temperature at 60◦ C (a) P-25
(b) NFM-2-d, pH=8.3 (c) NFM-2-a, pH=8.6 (d) NFM-2-c, pH=9.0 (e) NFM-2-b, pH=9.6 (f)
means that the powder is completely amorphous. Since 4.3(b) shows low degree of
order, the crystallinity is indeed low. In Figure 4.3 diﬀraction patterns are shown
of NFM-2 with curves (b)-(e) in the order of increasing pH. It can be seen that the
crystallinity increases in the reverse order (e),(d),(c) and (b). Therefore it can be
deduced that the crystallinity increases with decreasing pH. This can be explained
by the adsorption and desorption of hydroxide ions to titanium-sites at basic pH
that blocks condensation and prevents the formation of anatase with agreement
with Sugimoto et al.  described in section 2.3. Therefore a low pH in the available
range for pi-pi-stacking to occur, is highly favourable. The curve (f) shows the
diﬀraction pattern from the NFM-2-AT material which shows no large diﬀerence in
crystallinity compared to NFM-2.
Channels were found in most samples to be pores in a random pattern. Large
scale aggregation seems to occur upon drying. Based on the fact that the size of
a folate-stack is about 3 nm, the stacks should self-assemble into larger columns.
A hypothesis was established that pore control may be achieved with hydrolysis
rate. Therefore the acetylacetone route and atrane routes were designed by means
of using a chelating agent. The Figure 4.8 shows SEM micrographs of NMF-2-AC
samples. The Figures 4.5(a)-(d) shows SEM micrographs of NFM-AT samples.
From Figure 4.5(a)-(b) it can be seen that the particle morphology is monolithic.
Results and discussion
Figure 4.4: Representative SEM micrographs of NFM-2 obtained from the folate route.
From 4.5(c)-(d) it can be deduced that there is no obvious templating eﬀect.
The Figures 4.6(a)-(d) show images from SEM imaging of NFM-SD with in-situ
spray-dried titania. The Figure 4.6(a) shows almost spherical shaped particles in
a range of approximate sizes of 1-15 µm. The Figure 4.6(a) also shows cracks in
the particles that makes it possible to conclude that the spherical particles are
hollow  and not solid throughout. The Figure 4.6(b) shows that the spherical
particles are dispersed and are somewhat donought shaped, which can be spotted
with the change in contrast on the large particles. In Figure 4.6(c) the donought
shape of the particles has increased in comparison to 4.6(a). This fact is even more
evident at higher magniﬁcation as shown in Figure 4.6(d). The spray-dried samples
depicted in Figure 4.6(a)-(d) are thought to have the same particle size distribution
owing to the droplet sizes produced by the spray-dryer nozzle.
The Figure 4.7(a)-(d) shows images from the NFM-2-SD material obtained from
as-synthesized slurry compared to the NFM-2-SD in-situ spray-dried material depicted in Figure 4.6. In Figure 4.7(a) several spherical titania particles can be seen
together with some non-spherical particles. The particles have a large distribution
in sizes. In Figures 4.7(b)-(d) images at high magniﬁcation are shown on three
diﬀerent spherical particles. The Figures 4.7(b) and 4.7(c) shows particles of similar
size of 4 µm. The Figure 4.7(d) shows a spherical particle of smaller size of 1.7 µm
4.1 Designed materials
Figure 4.5: SEM micrographs of the NFM-2-AT material obtained from the atrane route.
Figure 4.6: SEM imaging of morphology obtained from spray-drying. (a) NFM-2-SDA1 (b)
NFM-2-SDA1 (c) NFM-2-SDA2 (d) NFM-2-SDA2 .
Results and discussion
Figure 4.7: The spherical titania aggregates of NFM-2-SD obtained from spray-drying.(a)
NFM-2-SD1 (b) NFM-2-SD2 (c) NFM-2-SD3 (d) NFM-2-SD4.
In Figure 4.8(a)-(d) SEM micrographs from the NFM-2-AC material obtained from
the acetylacetone route is depicted. The Figure 4.8(a) shows a monolithic particle
without macroporosity. The particles have a rough surface. The Figure 4.8(b)
shows that some particles are smaller and that the monolithic particles are in fact
aggregated from smaller entities which also is veriﬁed from Figure 4.8(a) that shows
a range of aggregate sizes 1-10 µm that are aggregated to a monolith. The Figure
4.8(d) shows smaller entities of approximately 1 µm and a ﬂake that has a texture
perpendicular to the plane of the ﬂake. The ﬂake surface has at least one smooth
surface compared to the rough entities in close proximity. The channelled texture
is thought to origin from folate-stack templating.
To obtain further information about the folic acid inside the the as-synthesized
titania material, thermogravimetric measurements were performed. The Table 4.2
shows no trend in the weight loss of folic acid and the surface area or pH.
It was realized that the pKa of the alcohol matters in the sense of retarding hydrolysis and condensation. The alkaline mechanism was described in section 2.3. The
formation of RO – does not promote hydrolysis since the reaction is catalysed by
OH – . The base that catalyses the condensation is also OH – . Thus, if the amount
of RO – increases in the solution, the hydrolysis rate will not increase. Instead it
will decrease due to displacement of the equilibrium of hydrolysis and condensation.
The needed displacement is thought to be 5 orders of magnitudes in the reaction rate.
4.1 Designed materials
Figure 4.8: SEM imaging from acetylacetone route prepared NFM-2-AC materials.
Figure 4.9: Thermogravimetric measurements of percentage weight-loss of NFM-2 and its
Results and discussion
Figure 4.10: The ﬁrst derivative of weight-loss obtained from NFM-2 and its derivatives.
Figure 4.11: N2 -sorption curves of the diﬀerent NFM-2 materials.
4.1 Designed materials
BET (m2 /g)
Org. w.-l. (%)
Table 4.1: Summary of characterization of all the materials.
Figure 4.12: Absorbance of light with concentration. Adsorption of dye to titanium dioxide.
(a) N719 dye stock solution (b) NFM-2 (c) NFM-2-AT (d) P-25. The P-25 titania has a good
dye-adsorption attributed to super-hydrophilicity with wetting angles lower than 3◦ . Since it is
the carboxylic groups of the dye that links to the titania a hydrophilic interaction is critical to the
adsorption of dye. 
The data in Figure 4.12 shows ﬂattened peaks that are due to the ﬁltering of titania
in the preparation but has no direct inﬂuence on the evaluation. The Figure 4.12
shows absorbance curves (b) and (c) corresponding to the developed materials with
the dye stock solution in curve (a) as the absolute reference. The absorbance for
P-25 is also used for comparison depicted as curve (d). The higher amount of
adsorption to titania, the lower is the absorbance with respect to the dye stock
Results and discussion
BET (m2 /g)
Table 4.2: Summary of adsorption results.
solution. The curve (c) describes the absorbance with after exposure to NFM-1-AT
which shows a considerable drop in absorbance at a wavelength of 313 nm. The
peak at 313 nm corresponds to 4d − π ∗ metal-to-ligand absorbance. Both the
peaks at 222 nm and 266 nm correspond to π − π ∗ ligand-centred absorbance. In
comparison to the 4d − π ∗ of the curves (a)-(d) the P-25 samples have the same
peak inverted. Note that NFM-2-AC was not tested due to the time frame.The only
NFM-2 material that compares to P-25 is the NFM-2-AT which has an adsorption
of 28%, with reference to the used stock solution.
From the results in this thesis it can be deduced that the synthesis of titanium
dioxide with folate-stacks as template has inherent limitations. The thesis has been
carried out with respect to the aims of the project description from Nanologica
AB. Using alkaline conditions is not the way for obtaining highly nanocrystalline
anatase compared to acidic conditions. The use of alkaline conditions for synthesis
of titanium dioxide should be avoided, since those conditions will render the material
nearly amorphous. Spray-drying was shown to produce spherical particles. The
largest impact on smaller spheres was using a low weight-fraction of as-synthesized
titania powder in the feed solution.
Future research should focus on the advantages of the acidic conditions of the
sol-gel chemistry of titanium alkoxides that would cause nanocrystalline anatase
at low calcination temperatures. Guanosine-monophosfate is the ﬁrst choice of a
π − π-stacked template for a similar approach as in this thesis because it will stack
under acidic conditions.  More research on controlling the mechanism of forming
π − π-stacks of aromatic molecules with respect to sol-gel chemistry is needed. Also
research on the in-situ mechanism of phase formation for π − π-stacks in comparison
to surfactant self-assembly is needed.
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