Journal of Aerosol Science 76 (2014) 1–12

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Journal of Aerosol Science

journal homepage: www.elsevier.com/locate/jaerosci

Aerosol synthesis of nanoporous silica particles with

controlled pore size distribution
Lintao Zeng n, Alfred P. Weber
Institute of Particle Technology, Technical University of Clausthal, Leibnizstraße 19, D-38678 Clausthal-Zellerfeld, Germany

a r t i c l e i n f o abstract

Article history: Spherical porous silica particles with well-defined mesoscopic pore structures were
Received 25 September 2013 synthesized by spray drying of nanocolloidal SiO2, using polyvinylpyrrolidone (PVP) as
Received in revised form pore template. During droplet drying, the surface tension of the water leads to spherical
11 February 2014
close-packed agglomerates of PVP coated silica nanoparticles. After removal of the PVP by
Accepted 10 May 2014
calcination, well-defined porous particles were obtained which were characterized by
Available online 27 May 2014
SEM, TEM and nitrogen adsorption–desorption isotherms. Pore size distribution and
Keywords: porosity could be tailored by using colloidal nanosuspensions with different silica particle
Aerosol synthesis sizes and by adding different amounts of template (PVP) into the colloidal silica solution.
Tunable pore size distribution
By adding Co3O4 nanoparticles as active phase into the starting suspension, porous
Nanoporous silica particles
catalytic particles were produced by spray drying and calcination. These particles, after
Template
reduction to metallic cobalt, are intended to be used as catalyst for the Fischer–Tropsch
synthesis, where the product selectivity can be adjusted by tuning the pore size
distribution.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction

Porous particles with well-defined pore structures are of interest for applications involving catalysis (Rytter et al., 2007),
chromatography (Wu et al., 2006) and drug delivery (Edwards et al., 1997). Sol–gel chemistry is often used to prepare porous
structures (Lorjai et al., 2009); however, this solution based method is limited regarding the fast and continuous synthesis of
functional particles due to complicated sequences of multiple time-consuming steps (Zuo et al., 2012). In addition, most sol–
gel processes are not easily scalable which limits their throughput (Raab et al., 2011). In contrast, spray processing is a well-
established and versatile technique to produce large amounts of functional particles (Maters, 1979). It is a process in which
particles with controllable size, morphology and composition can be produced (Okuyama & Lenggoro, 2003; Okuyama et al.,
2006; Iskandar et al., 2003). In combination with template techniques spherical porous particles haven been prepared. For
instance, porous particles have been successfully synthesized via spray drying of TEOS precursor solutions containing
polystyrene latex particles or micro emulsion as templates, passing through a heated tube furnace and collecting the
particles on a filter (Fan et al., 2001). In the subsequent off-line calcination porous particles were formed with a silica layer
on the outside. However, the voids resulting from the burn-off of the template particles (polystyrene particles or emulsion)
formed an unconnected pore system inside the particles. Peterson et al. (2010) have prepared porous silica particles with
interconnected pores by spray drying of colloidal silica using simple salts as templates. Since the molten salts were

n
Corresponding author. Tel.: þ49 5323 72 2117; fax: þ 49 5323 72 2830.
E-mail address: zeng@mvt.tu-clausthal.de (L. Zeng).

http://dx.doi.org/10.1016/j.jaerosci.2014.05.003
0021-8502/& 2014 Elsevier Ltd. All rights reserved.
2 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12

inhomogeneously distributed in the particles after drying and tempering, the resulting particles exhibited a broad pore size
distribution. However, for many applications such as the selectivity control in heterogeneous catalysis narrow pore size
distributions are required. As an important example, the Fischer–Tropsch synthesis (FTS) is mentioned here, in which the
educt gases hydrogen and carbon monoxide are transformed over a supported metal catalyst into higher hydrocarbons
(Witoon et al., 2011; Zhang et al., 2010). For cobalt catalyst nanoparticles supported on porous silica Saib et al. (2002) found
that the pore size of the support has a strong influence on activity and selectivity of the catalyst. Silica support with pore
size of about 5–10 nm proved to be most active and selective for the formation of hydrocarbons of at least 5 carbon atoms
(C5 þ) with a minimum production of the undesired methane. Therefore, for the rational design of the liquid fuels produced
by FTS, it is desirable to develop a simple method to synthesize porous particles with controllable narrow pore size
distribution and interconnected pores. In addition, the synthesis process should be easy to control and scalable with cheap,
nontoxic and easily removable template materials.
In this paper, we present an aerosol approach based on spray drying of colloidal silica towards the fast preparation of
well-defined mesoporous silica particles using simple and inexpensive polyvinylpyrrolidone (PVP) as pore template. Pore
size distribution and porosity of the particles after template removal were measured as function of PVP concentration. It will
be shown that this generic approach which may be extended to other colloidal systems, e.g. containing already the catalyst,
allows tailoring pore size and porosity by controlling the amount of polymer template.

2. Experimental

2.1. Materials

All chemicals were used as received for the synthesis. Aqueous colloidal silica suspensions of 20 nm nanoparticles
(Köstrosols2040AS, 40 wt%) and of 8 nm nanoparticles (Köstrosols0830AS, 30 wt%), respectively, which were stabilized electro-
statically by salt ions, were obtained from CWK Chemiewerk Bad Köstritz GmbH. The polymer stabilizer polyvinylpyrrolidone (PVP)
with an average molecular weight of 10,000 was purchased from Sigma-Aldrich. Deionized water was used in all synthesis steps.

2.2. Particle synthesis

Colloidal silica solution was diluted with deionized water under stirring. A certain amount of PVP (0–15.52 g) was then
added to the aqueous colloidal silica solution to give a desired PVP-to-SiO2 weight ratio. The solutions were sonicated in an
ultrasonic bath for 10 min. For example, 7.37 g PVP and 20 ml colloidal silica (20 nm) were added to 100 ml deionized water
to form a solution with 5.54 wt% PVP and a PVP-to-SiO2 weight ratio of 0.72 (Table 1).
The silica/PVP suspension was then employed in the aerosol setup consisting mainly of an aerosol nebulizer (Atomizer
ATM 220, Topas), a tube furnace and a particle filter (Fig. 1). PVP containing silica aerosols were generated with the atomizer
operated by compressed air with flow rates ranging from 120 to 150 l/h. A silica gel dryer was used to adsorb the moisture
from the airflow. The droplets were dried in a tube furnace at 500 1C. The dry particles were collected on a filter (Cellulose
Nitrate Membrane Filter, pore size 1.2 mm, Sartorius) in a rig. The collected particles were heat treated in a muffle oven at
500 1C for 6 h to remove remaining PVP.

2.3. Particle characterization

The size distribution of the dried particles was measured with a Scanning Mobility Particle Sizer (SMPS, Model 5.403,
Grimm). After calcination the products were characterized by Transmission Electron Microscopy (TEM), Scanning Electron
Microscopy (SEM) and nitrogen adsorption. TEM was performed with a JEOL JEM2100 operated at 160 kV, while SEM was
carried out with a Zeiss DSM Gemini 982 operated at 10 kV. Nitrogen adsorption–desorption isotherms were recorded with
an ASAP2020 from micromeritics to determine the specific surface area (SSA) and the pore size distribution. Prior to
adsorption measurements all samples were degassed for 2 h at 300 1C.

Table 1
Silica/PVP suspensions used for synthesis.

PVP (g) Colloidal silica (ml) Primary particle size (nm) Water (ml) PVP concentration (wt%) PVP-SiO2 weight
ratio (dimensionless)

0 20 20 100 0 0
1 20 20 100 0.79 0.10
3.18 20 20 100 2.47 0.31
7.37 20 20 100 5.54 0.72
15.52 20 20 100 10.99 1.52
0 7.4 8 23 0 0
0.8 7.4 8 23 2.46 0.31
1.84 7.4 8 23 5.51 0.72
3.88 7.4 8 23 10.94 1.51
 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12 3

Fig. 1. Experimental setup consisting of atomizer, drying furnace and particle separation unit as well as characterization (SMPS: Scanning Mobility Particle
Sizer (Grimm), ASAP: Accelerated Surface Area and Porosimetry System (micromeritics), TGA: Thermogravimetric Analysis (Netzsch)).

3. Results and discussion

After atomization, the evaporation of the water in the droplets induced a self-assembly process, leading to spherical
aerosol particles consisting of primary silica particles. When using PVP templates the removal of the PVP by calcination
resulted also in well-defined porous particles. Examples of porous silica particles produced by spray drying a solution with a
PVP-to-SiO2 weight ratio of 0.31 and a PVP content of 2.47 wt%, respectively are shown in Fig. 2. The spherical raspberry-like
particles consist of small primary silica particles with an average diameter of 20 nm.
In the following the characteristics of spraying and calcination process, the influence of PVP content on the pore size
distribution and the agglomerate restructuring during calcination will be discussed.

3.1. Spraying and drying characteristics of pure silica suspensions

In the first experiments silica particles were produced by spray drying of silica suspension of different silica
concentrations but without PVP templates. As shown in Fig. 3, the experimental results indicate that the particle size
depends on the suspension concentration and the atomization air flow rate. The particle size increases with increasing silica
concentration and with decreasing air flow rate.
Assuming that one droplet formed one raspberry-like particle during the drying process, a mass balance yields the
following relation between droplet diameter dd and particle size dp (Elversson et al., 2003):
!1=3
ρsus
dp ¼ dd C ð1Þ
ρp

where ρsus and ρp are the density of suspension and particles, respectively, and C is the silica concentration in the
suspension.
When the atomizer is operated at constant air flow rate and the silica concentration is varied within a limited range so
that the suspension properties such as surface tension, density and viscosity do not change significantly, the resulting
droplet size can be considered as constant. The SEM and TEM micrographs of the particles synthesized with different silica
concentration showed uniform close packing of the primary nanoparticles. Therefore, the density of the particles can also be
considered as constant. Then the particle size scales with the silica concentration to the power of 1/3. As indicated in Fig. 3
(left), the measured particle sizes follow the fit curve closely.
Besides the silica concentration, also the air flow rate can affect the particle size. Atomization studies of Elversson et al.
(2003) and Thybo et al. (2008) with two-fluid nozzles show that the droplet size decreases as the air flow rate increases.
Since at constant silica concentration the particle size scales with the droplet size (see Eq. (1)), an increase of air flow rate
results in a decrease of particle size (Fig. 3, right). However, in the atomizer used here (ATM 220 Topas) the generated
droplet jet impinges on the wall of the suspension container (see Fig. 1). Larger particles with sufficient inertia cannot follow
the flow bending towards the exit, hit the wall and drip back into the container. Only the smaller droplets can exit with the
gas flow. Since this classification process is superimposed onto the atomization process, existing models for mere
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Fig. 2. SEM (left) and TEM micrographs (right) of porous particles (2.47 wt% PVP and 20 nm silica primary particles) after calcination for 6 h at 500 1C.

Fig. 3. Measured particle size as function of suspension concentration (at an air flow rate of 150 l/h, solid line is a fitting according to function (1), left) and
atomization air flow rate (at a constant silica concentration of 1.75 wt%, solid line as guide to the eye, right). The silica suspensions did not contain PVP
template.

atomization, e.g. Nukiyama & Tanasawa (1939) do not apply here. Therefore, only a line as guide to the eye is shown in Fig. 3
(right) together with the measured particle sizes.

3.2. Characterization of the PVP/SiO2 solutions

Regarding the interaction of PVP with silica particles in suspension, it is well known that PVP strongly adsorbs on the
silica surface in form of trains, loops and tails, depending on the PVP concentration (Stuart et al., 1982; Nelson et al., 2002).
To deduce the layer thickness of adsorbed PVP on silica, particle sizes in suspensions were measured with photon
correlation spectroscopy (PCS, Nanophox, Sympatec) for different PVP concentrations (from 0 to 10.99 wt%). The
suspensions were prepared in the same way as the suspensions for spray drying. The results show that the layer thickness
of adsorbed PVP on silica particles increases with the added amount of PVP per unit silica surface area before reaching a
plateau (Fig. 4). This result is qualitatively consistent with the observation of Cattoz et al. (2011), as indicated in Fig. 4. The
initially low values for the layer thickness at low PVP concentrations are due to the special adsorption geometry of the PVP
molecules which are lying flatly on the silica surface (so called train-like configuration). With increasing PVP concentration,
the train layer becomes saturated and a new configuration is established (loops and tails) which increases significantly the
layer thickness (Fig. 5) (Stuart et al., 1982; Cattoz et al., 2011). However, also this configuration becomes saturated at a
critical concentration of about 1.7 mg/m2 and a further increase of PVP concentration has no more influence on the layer
thickness. This behavior has been observed here independently of the primary particle size (as shown for 8 nm and 20 nm
silica particles in Fig. 4). Compared to the measurement of Cattoz et al. (triangles in Fig. 4), the layers in our experiments are
thicker. This is probably due to the different types of PVP which have been used. While PVP K15 was employed in our
experiments, PVP K40 was used by Cattoz et al.. These two types of PVP differ in average molecular weight and in chain
length, which may affect the layer thickness during the adsorption process in the suspension.
 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12 5

Fig. 4. The layer thickness of adsorbed PVP on silica particles as function of amount of added PVP (open squares for 8 nm silica particles, filled circles for
20 nm silica particles, filled triangles for the measurement of Cattoz et al. (2011)).

Fig. 5. Schematic representation of the adsorption of PVP at the silica interface.

The thickness of the PVP layer as measured with PCS does not provide information on the amount of adsorbed PVP.
However, for silica particles of nearly the same size (21 nm) as used here (20 nm) van der Beer and Stuart (1991) extracted
the amount of adsorbed PVP from relaxation measurements using NMR. At the same time, they measured the amount of
free PVP molecules in the solution. Using these and our data, an exponential approach of PVP adsorbed on silica
nanoparticles towards a saturation value was obtained with increasing PVP concentration in the solution (Fig. 6).
By assuming an average density of 0.13 g/cm3 our experimental results fit nicely to the curve obtained from van der Beer
and Stuart (1991). This value is much lower than the typical bulk density of PVP of 1.2 g/cm3, indicating a very porous
arrangement of the PVP molecules in the shell. However, in the suspension this pore system is filled with water which will
evaporate during drying leading to densification of the PVP shell as further discussed below.

3.3. Calcination of the spray dried PVP/SiO2 particles

3.3.1. Mass loss during calcination

To remove the PVP template, the spray dried particles were collected on a filter and calcinated in air either in a muffle
oven or in a TGA apparatus. As an example, the TGA curve of spray dried particles prepared from a silica suspension with
5.54 wt% PVP (PVP-to-SiO2 weight ratio 0.72) is shown in Fig. 7. The sample was heated in air from room temperature to
500 1C with a heating rate of 10 K/min and then kept at 500 1C for 360 min. The evaporation of the residual water contained
in particles lead to a slight mass loss of about 3%. A further substantial mass loss was observed starting at about 300 1C due
to the decomposition of the PVP contained in the particles. No further mass loss was observed when the particles were
tempered at 500 1C for 3 h, which indicates the complete removal of PVP. The sample had a residual mass of about 61.5%
after calcination (Fig. 7, curve PVPþ SiO2). To investigate the thermal decomposition characteristics of PVP in more detail, a
TGA analysis of particles synthesized by spray drying a pure PVP (5.54 wt%) solution was carried out under the same
experimental conditions. After calcination in the TGA, the residual weight of PVP is 5.9% (Fig. 6, curve pure PVP). This is in
agreement with the results of Du et al. (2006). An energy dispersive X-ray analysis (EDX) of the rest of PVP after
decomposition showed that it consists mainly of Si, O, Al and Na, which are considered to be impurities of the PVP. Based on
the two thermogravimetric analyses, the PVP-to-SiO2 weight ratio in the synthesized PVP coated silica particles was
calculated to be 0.64, which is slightly lower than the PVP-to-SiO2 weight ratio in the feed suspension (0.72). Figure 7 shows
that PVP begins to decompose at 300 1C. Therefore, the disagreement of the PVP-to-silica weight ratios between feed stock
and after spray drying may be explained by the partial decomposition of the PVP during the drying process in the tube
6 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12

Fig. 6. The layer thickness of adsorbed PVP as function of PVP concentration in the solution (filled circles for our measurement, open squares for the
measurement of van der Beer and Stuart (1991) assuming an effective density of 0.13 g/cm3).

Fig. 7. Thermogravimetric analysis of particles prepared by spray drying a silica suspension with 5.54 wt% PVP (PVP-to-SiO2 weight ratio 0.72) and
particles synthesized by spray drying a pure PVP solution (5.54 wt% PVP, without SiO2 particles).

furnace. This hypothesis is further supported by the observed color changes. While without decomposition of PVP, the silica/
PVP particles are light yellow, the spray dried particles appear dark brown. Therefore, it is likely that the PVP containing
particles experienced partial removal of PVP during the drying at 500 1C for several seconds.

3.3.2. Particle size change during calcination

To investigate the particles size change during calcination, particles produced by spray drying a 5.54 wt% PVP silica
suspension (without calcination) were exposed in a TEM heating stage to 550 1C for 20 min. TEM micrographs were taken
befrore and after this calcination step (Fig. 8). The particle sizes were analysized with ImageJ and the shrinkage of the
particles was calculated. The particle size was reduced by about 9% on average after calcination. The shrinkage of the
particles during calcination is due to the thermal removal of PVP and the restructuring of the silica nanoparticles which will
be discussed later in more detail (cf. chap. 3.5.1).

3.4. Pore size distribution after calcination

To investigate the influence of the amount of PVP added to the suspension on the resulting pore size distribution after
calcination, the collected particles were exposed to 500 1C in a muffle furnace for 6 h under air atmosphere prior to nitrogen
adsorption–desorption measurements. Figure 9 shows the pore size distributions obtained from Barrett–Joyner–Halenda
(BJH) analysis of samples with different amounts of PVP (the amount of silica in the suspension was kept constant). In the
BJH analysis the adsorption–desorption isotherm is evaluated by assuming cylindrical pores (Allen, 1997). Without PVP
template, the particles are raspberry-like structures with an average pore size of 3–4 nm. Iskandar et al. (2007) showed that
the maximal size of a ball to pass the pores of close-packed monodisperse particles of diameter d is equal to 0.155 d.
Assuming the primary silica particles to be monodisperse with a diameter of 20 nm, the maximum ball size for the
measurements presented here is 3.1 nm which is within the range of the pore diameters obtained from the BJH analysis
 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12 7

Fig. 8. TEM micrographs of PVP containing particles before (left) and after (right) calcination in vacuum at 550 1C for 20 min with a heating stage.

Fig. 9. Pore size distribution as function of added amount of PVP (20 nm silica primary particles).

(Fig. 9). By adding 0.79 wt% PVP the mean pore size was already enlarged to 5 nm. The further increase of the PVP
concentration to 10.99 wt% resulted in a pore size of about 9 nm, which is close to the optimal size for FTS catalyst support.
During drying the droplets transform into spherical particles consisting of primary silica particles coated with PVP (as
discussed in more detail below). After decomposition of PVP by calcination pores were formed between silica particles.
Therefore, an increase of PVP concentration results in an increase of the PVP-coating thickness which leads to larger pores
after thermal decomposition (Fig. 10).
However, to the best of our knowledge, no validated model has been presented so far to reveal the relationship between
PVP concentration and the pore size enlargement. During droplet drying the spatial distribution of the free PVP molecules
could change in two limiting ways, i.e. a further attachment of free PVP to the existing shells or a filling up of the pores
between the silica particles.
In addition, the restructuring of the silica nanoparticles during calcination also affects the pore size distribution after
calcination. Regarding the complexity of these mechanisms, a quantitative model of the restructuring process is beyond the
scope of this work. However, the relationship between the pore size enlargement and the PVP layer thickness can be
deduced from the data shown in Fig. 10. Using the same functional dependence on the amount of PVP added per unit silica
surface area for both quantities, it turns out that about 70% of the layer thickness in the suspension is recovered in the
enlargement of the average pore size. In this way, a simple tool is provided to predict the average pore size enlargement of
spray dried and calcinated particles from PVP/SiO2 suspensions using PCS measurements of the feed stock. The general
validity of this hypothesis needs to be explored with respect to silica size and PVP concentration, especially towards very
high PVP concentrations. However, the results for the 8 nm silica particles are also included in Fig. 10 (open triangle) and at
least the one available point for pore size enlargement (Fig. 10) fits into the proposed relationship.
Besides the PVP concentration, the size of the primary silica particles may also influence the pore sizes. Figure 11 shows
the pore size distributions of porous particles for two primary particle sizes, each with and without PVP templates. When no
PVP was added, the average pore size of the building blocks made of 8 nm primary particles was about 4 nm. For a dense
8 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12

Fig. 10. PVP layer thickness (open square for 8 nm silica particles and filled circles for 20 nm silica particles) and pore size enlargement (open triangle for
8 nm silica particles and open stars for 20 nm silica particles) as function of PVP added per unit silica surface area.

Fig. 11. Pore size distribution as function of primary silica particle size (left for 8 nm, right for 20 nm) in both cases without PVP (open squares) and with
5.5% PVP (filled circles).

packing, the model by Iskandar et al. would predict a maximum ball size of 1.7 nm. While for building blocks of 20 nm the
maximum ball size model agrees well with the measured pore size distribution, there is a significant deviation for building
blocks of 8 nm. This is probably due to a reduced reordering ability of the 8 nm particles compared to the 20 nm particles.
Okuyama & Lenggoro (2003) found that the ordering ability of nanoparticles during an evaporation induced self-assembling
process increases with increasing particle size. Furthermore, due to the reduced ordering of the primary particles, the mass
specific pore volume of the building blocks made of 8 nm particles (0.44 cm3 pore volume/g silica) is higher than the mass
specific pore volume of the building blocks made of 20 nm particles (0.30 cm3 pore volume/g silica) for the same PVP
concentration.
However, the pore enlargement effect of the PVP template is stronger for the building blocks of 20 nm primary particles
than for the building blocks of 8 nm primary particles. For the same PVP concentration of 5.5%, the mass of PVP added per
unit area of silica particles is higher for building blocks of 20 nm silica particles (about 1.38 mg/m2) than for building blocks
of 20 nm silica particles (0.55 mg/m2). As discussed above, these different values of the PVP surface loading lead to different
pore size enlargements (Fig. 11).
The mesoporous silica particles prepared with our method can be used as catalyst support for FTS. Some research groups
have investigated the potential of mesoporous silica as supports for co-catalysts for FTS. Their results shown that porous
structures with average pore size of 6–10 nm displayed higher C5þselectivity (Saib et al., 2002; Song & Li, 2006). The
catalytic behavior of the FT catalyst, especially the product selectivity, is determined by a complex interplay among diffusion,
reactions at active sites, and secondary reactions. The pore size of the support has not only effect on the diffusion of products
and reactants but also on the probability of secondary reactions through α-olefin readsorption in a confined nanospace
 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12 9

(Zhang et al., 2010). The porous particles synthesized with our method show interconnected pores with narrow distribution
in range of 2–10 nm. This property makes it especially suitable as catalyst support for FTS.
Iskandar et al. (2003) have shown that the morphology of the particles prepared by spray drying of nanoparticles sol can
be controlled by varying droplet size, gas flow rate, surface tension of sol and drying temperature etc. The building blocks
observed in the presented experiments showed all spherical shape due to strong surface tension and small droplet sizes
(leading to low Bond numbers). The morphological stability of the building blocks found here is not expected for much
larger droplets.
Lee et al. (2010) observed distortions in the symmetry of the colloidal silica packing spheres made up of 13 primary
particles. The disordering of the spheres increases with increasing number of primary particles. In the presented
experiments, the building blocks consisted of at least 75 primary particles (corresponding to 100 nm cluster of 20 nm
primary particles), which suggests a significant number of distortions. However, when no PVP was added to the feedstock, a
porosity of 0.26 was measured indicating that the primary particles are arranged in a dense packing.
Mesoporous silica particles were synthesized in many way for instance by using discrete template materials (PSL
particles) (Gradoń et al., 2004; Iskandar et al., 2009; Lee et al., 2009). In that case, the pore size and porosity of the particles
can be independently controlled by the size of PSL template particles and their concentration. However, the PSL particles
tended to the outer part of the droplet during the drying process. Therefore, the pores formed by PSL particles were
distributed on the surface of the particles being rather poorly interconnected. Compared to discrete template materials, the
continuous template material PVP was more homogenously distributed throughout the whole spherical agglomerate. Owing
to the homogenous distribution of PVP, interconnected pores with narrow distribution can be achieved after removal of the
template materials. With this method porous structures with interconnected pores in narrow range of 2–10 nm can be
fabricated. However, pores larger than 12 nm can hardly be achieved this continuous template technique, as the pore size
enlargement effect is limited. Another limitation of the presented method is that the pore size and porosity cannot be tuned
independently.
Fan et al. (2001) have successfully prepared nice porous structures in a rapid aerosol process using TEOS as precursor.
However, the particles produced with their method shown many hollow voids isolated by relative dense silica skin.
To improve the interconnectivity of the pores extra surfactants should be added. In our method colloidal silica was used as
precursor. Compared to the continuous TEOS is colloidal silica a discrete precursor, which makes it much easier to form
interconnected pores in the self-assembly process. Furthermore, instead of discrete template materials (emulsion or PS
particles) a continuous material such as PVP was used. In the suspension, the PVP builds a polymer shell around the primary
silica particles which determines the pore enlargement according to the PVP concentration as shown in Fig. 10, leading to a
narrow pore size distribution and an interconnected pore system.

3.5. Restructuring and final porosity of building blocks

Restructuring of nanoparticle agglomerates is an activated process (Weber & Friedlander, 1997) induced by thermal
treatment (Seipenbusch et al., 2003) or by impaction (Seipenbusch et al., 2010). A restructuring process occurs also during
the template removal by calcination. The extent of restructuring is confined by the limiting cases of complete and vanishing
rearrangement of the silica nanoparticles. To the best of our knowledge, there is no information available on the internal
structure of the PVP containing building blocks after drying but before calcination. Therefore, the effective density of such
building blocks was determined with Archimedes method. From the known PVP-to-SiO2 fraction of 0.64 (cf. chap. 3.3.1) and
the measured effective density of the composite building blocks of 1.5 g/cm3 an additional pore volume of 0.13 cm3/g
(i.e. 0.13 cm3 void volume per g SiO2) is attributed to the uncalcinated building blocks. This means that after the drying
process the silica nanoparticles are not embedded in a dense PVP matrix but the building blocks exhibit internal pores
between PVP coated silica particles, as shown schematically in Fig. 12. The pore volume of 0.13 cm3/g translates into porosity
of 0.23, which is nearly the value for close-packed structures (0.26). To calculate the porosity of the building blocks after
drying in the absence of restructuring, it was assumed that PVP is completely consumed in the silica coatings and that these

Fig. 12. Schematic diagram of the restructuring process during calcination.

10 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12

core–shell particles are arranged in close-packed structures. Then, after calcination, the porosity of the building blocks
increases with PVP concentration as shown in Fig. 13. As expected, the porosity extracted from the measured density of the
uncalcinated building blocks is close to the model described above (open circle in Fig. 13). In contrast, the porosities after
calcination are much lower indicating partial restructuring. In particular, the porosities extracted from the ASAP
measurements agree quite well with the porosity obtained from TEM heating stage analysis. However, no complete
restructuring into close-packed structures is obtained after calcination (indicated by dashed line in Fig. 13).

3.6. Aerosol synthesis of nanostructured Co3O4/SiO2 catalyst particles

Finally, it was investigated how the catalytic cobalt component can be incorporated into the SiO2 building blocks. To take
advantage of the product selectivity due to the pore size distribution discussed above, the catalytic nanoparticles need to be
inside the building blocks. However, experiments using incipient wetness impregnation with liquid cobalt precursors
(Cobalt nitrate, Co(NO3)2  6H2O) lead to disappointing results. After the decomposition of the precursor into Co3O4 and the
reduction of Co3O4 into Co, the active component Co was poorly dispersed with large catalyst particles (mostly with
diameters above 40 nm) located on the outside of the building blocks. Therefore, the direct addition of the Co3O4 catalyst
particles into the starting colloidal silica solution before spray drying was investigated. A typical TEM micrograph of the
spray dried Co3O4/SiO2/PVP suspension is shown in Fig. 14. The results show that the Co3O4 particles (smaller darker dots)
are homogenously dispersed inside the building blocks (Fig. 14A). TEM tomography was used to investigate the distribution
of Co3O4 particles in the SiO2-agglomerate. One of the prepared agglomerates was rotated from  601 to 601 and TEM
tomograms of the sample were taken under different angles. TEM tomograms taken under 01, 531 and  591 are shown in
Fig. 14(B–D). The tomograms displayed that the morphology of the Co3O4/SiO2-agglomerate were almost the same
indicating a homogenous distribution of the Co3O4 particles in the SiO2-agglomerates. However, from the TEM micrographs
it was hard to distinguish cobalt particles on the surface from interior ones. Therefore, the surface charge of the two particle
ensembles has been measured to get further evidence for the internal particle arrangement. While the zeta potential of the
SiO2 particles in the PVP solution was slightly negative (ca. 13 mV) for the pH value of 9 used in the experiments, the
Co3O4 particles were nearly neutral in the PVP solution at pH value of 9. From the evaluation of TEM micrographs the size
range of the Co3O4 particles was 10–15 nm which compares closely with the SiO2 particles. Substantial separation of
colloidal mixtures of SiO2 and PSL particles was observed when there was (i) a significant difference in size (Iskandar et al.,
2003) or (ii) particles exhibited similar surface charge (Lee et al., 2010). Since neither of these two conditions was fulfilled in
the present study, it seems to be unlikely that a pronounced separation of SiO2 and Co3O4 particles should occur during
drying.
The catalytic performance of FTS catalysts strongly depends on the loading of the catalyst and the size of cobalt particles.
The size of the cobalt particles in the FTS catalysts prepared via incipient wetness impregnation using cobalt salt is
influenced by the pore size of the support (Chu et al., 2007). An increase of pore size of the support increases the particle
size of the catalyst (Saib et al., 2002; Borg et al., 2007). Another drawback of the incipient wetness impregnation is that the
maximum loading of the catalyst on the support is limited by the solubility of the precursor in the solution. Compared to the
classical incipient wetness impregnation, our method provides a novel way to prepare two-component (catalyst and
support) particles with tunable pore size. The loading of catalyst in the two-component particles can be arbitrarily (0–100%)
controlled by varying the chemical components in the initial suspension. Furthermore, the size of the catalyst particles can
be controlled independently of the pore size of support. Since the specific surface area of the catalyst depends on the loading
of the catalyst and the particles size of the catalyst, which can be well controlled with our method, the specific surface area

Fig. 13. Porosity as function of PVP concentration in the suspension for a constant SiO2 concentration (based on ASAP and TEM measurements). As limiting
cases complete restructuring (dashed line) and no restructuring (dash-dotted line) are also shown.
 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12 11

Fig. 14. TEM micrographs (A) and TEM tomograms (B–D) of a spray dried silica building block containing Co3O4 nanoparticles (smaller darker dots).

of the catalyst can be optimized in our synthesis process. In addition, the colloidal silica in the suspension may be replaced
by mesoporous silica or zeolites to further increase the surface area and probably to influence the catalyst support
interaction (Girardon et al., 2007; Hong et al., 2010).
To check the accessibility of the catalyst surface, BET measurements of two component particles (15–20 nm Cobalt
particles incorporated within 8 nm silica particles) were carried out. For Co3O4 to SiO2 ratio of 20%, the two-component
particles showed a specific surface area of 220 m2/g. This value is higher than calculated from the single components which
have specific surface areas of 56 m2/g (Co3O4) and 270 m2/g (SiO2), respectively. This indicates that as a consequence of
calcination either only a part of the original surface is still accessible (may be due to coalescence in the contact points
between the particles) or especially the Co3O4 particles have sintered to larger sizes. Although the last hypothesis seems to
be supported by TEM micrographs, this issue needs to be confirmed by further investigations.

4. Conclusions

Spherical porous silica particles with well-defined pore structures were synthesized by an aerosol-based process, using
PVP as pore template. The pore size can be tailored by using colloidal nanosuspensions with different particles sizes and by
addition of different amounts of polymer templates into the colloidal silica solution. This aerosol synthesis process can be
extended for preparation of catalyst containing particles by co-spray drying of a silica suspension containing catalyst
nanoparticles. In future work, the effect of the pore size distribution on the Fischer–Tropsch synthesis and in particular on
the selectivity will be investigated.
12 L. Zeng, A.P. Weber / Journal of Aerosol Science 76 (2014) 1–12

Acknowledgment

The financial support of this work by the German Research Foundation (DFG) under the Grant WE 2331/13-1/2 is highly
appreciated. The authors would like to thank CWK Chemiewerk Bad Köstritz GmbH for providing colloidal silica. The
authors also would like to thank Mr. Henning Becker from Institute of Chemical Process Engineering TU Clausthal for the
nitrogen adsorption measurements.

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