Effect of synthesis conditions on porous structure, luminescence

and absorption properties of dye-loaded silica xerogels

J. Krause
a
, Ch. Schrage
b
, A. Schuy
a
, Th. Woike
a
, E. Kockrick
b
, S. Kaskel
b
, D. Schaniel
c,
a
I. Physikalisches Institut, Universitt zu Kln, Zlpicher Str. 77, 50937 Kln, Germany
b
Institut fr Anorganische Chemie, Technische Universitt Dresden, Helmholtzstr. 10, 01069 Dresden, Germany
c
CRM2, Institut Jean Barriol, Nancy Universit, BP 70239 Bvd. des Aiguillettes, 54506 Vandoeuvre-les-Nancy, France
a r t i c l e i n f o
Article history:
Received 4 July 2010
Received in revised form 23 October 2010
Accepted 7 December 2010
Available online 13 December 2010
Keywords:
Xerogels
Luminescence
SAXS
pH value
a b s t r a c t
Silica xerogels were prepared at different pH values in the range 0.8 to 1.2 and loaded with Rhodam-
in6G (Rh6G) dyes using the solgel technique and by variation of the HCl/TEOS and H
2
O/TEOS ratios.
The luminescence properties such as the spectral range of emission and the photostability of the laser
dyes remain unchanged as a function of pH value at which the xerogels are prepared, although the porous
structure of the xerogels is signicantly changed. Inclusion of the dyes after gelation results in similar
luminescence spectra as during-synthesis admixture of the dye. A detailed structural study using small
angle X-ray scattering and nitrogen adsorption reveals that the dyes embedded by the postloading pro-
cedure occupy mainly micropores, while the dyes added during the solgel process are located mainly in
mesopores. This is reected in the position of the absorption maximum of the Rh6G dye, which is found
at 506516 nm for dyes in micropores and at 530540 nm for dyes in mesopores.
2010 Elsevier Inc. All rights reserved.
1. Introduction
The embedding of dye molecules into solid host matrices via the
solgel technique has attracted considerable interest in the last
two decades due to the potential applications such as solid-state
dye lasers (see e.g. [17]). Advantages of the solgel technique
are the low-temperature processing, which allows a destruction-
free embedding of guest molecules, as well as the high variability
of compositions, ranging from pure silica gels to hybrid organic-
inorganic nanocomposites, which allows to inuence the proper-
ties of the embedded guest molecule. With respect to dye-loaded
gels two properties are of major interest: the spectral emission
range of the dye and its photostability [8]. Tunable properties of
the gel are porosity, polarity, pore sizes and shapes. Factorial de-
sign has been applied [9,10] in order to understand the inuence
of single tuning parameters such as pH, ethanol:TEOS ratio, water:-
TEOS ratio, and synthesis temperature on gelation time and struc-
tural properties of empty xerogels. The pH value of the starting
composition was varied in the range 810 [10] and between 2.5
and 4.5 [9]. It was found that xerogels prepared at pH 2.5 were
microporous while higher ethanol:TEOS ratios yielded xerogels
with higher specic surface area, lower pore volume and pore size.
Systematic studies of xerogels loaded with organic dyes and pre-
pared at pH values between 0.2 and 9 were performed earlier
[20] without drawing a direct correlation between pore sizes and
physical properties of the dyes. The absorption maximum of Rhod-
amin6G (Rh6G) was found at 530 nm for xerogels prepared at pH
between 9 and 1 and increased to 545 nm for xerogels prepared
at pH 0.2. This shift of the absorption maximum at low pH values
was explained by the inuence of surface charges on the silica, that
interact with the encapsulated dye molecules. Additionally a dete-
rioration of the Rh6G dye molecules at pH values below 1 was
observed.
The study of the pore structure is usually done using adsorption
measurements [11,12] which works well for empty xerogels,
although care has to be taken for micro- and ultramicroporous
materials. Small-angle X-ray scattering (SAXS) is another powerful
tool to structurally characterize xerogels and aerogels as demon-
strated by comparitive SAXS and adsorption studies [13,14]. Espe-
cially in the case, where part of the pores are blocked by embedded
species such as dye molecules, we would expect additional insight
by SAXS measurements. We therefore studied in detail the struc-
ture of xerogels prepared at different pH value using both SAXS
and nitrogen adsorption measurements in order to determine the
inuence of the structural environment on the emission and
absorption properties of embedded dye molecules (Rhodamin6G,
Rh6G). In the range of pH values 0.8 to 1.2 we observe that
although the xerogel structure is inuenced by the pH value the
spectral emission properties of Rh6G are hardly changed. On the
other hand the absorption properties of the dye clearly reect
the structural environment.
1387-1811/$ - see front matter 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2010.12.007

Corresponding author. Tel.: +33 383684889.

E-mail address: dominik.schaniel@crm2.uhp-nancy.fr (D. Schaniel).
Microporous and Mesoporous Materials 142 (2011) 245250
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2. Experimental
2.1. Synthesis
Nineteen microgram of Rhodamin6G (Rh6G) were added to a
solution of 3.5 ml ethanol (Merck), double distilled water, hydro-
chloric acid 32% (Merck) and 2.240ml Tetraethoxyorthosilicate
(Alfa Aesar). The amount of HCl and water was varied as indicated
in Table 1 in order to adjust the pH value of the mixture. The mix-
ture was stirred and allowed to gelate. The samples were dried
over ve days at 50 C and subsequently evacuated over night to
remove the remaining solvent molecules. For comparison the xero-
gels with different pH value have been prepared in the same way
by a postloading procedure. Hereby a solution of 19 lg Rh6G in
1ml ethanol was deposited after gelation on the solidied but still
wet gel. The dye was then adsorbed into the gel.
2.2. SAXS
Small angle X-ray scattering (SAXS) experiments were per-
formed on a Bruker Nanostar (Cu Ka; k = 1.51406 ) with a position
sensitive HiStar detector. The sample to detector distance was
25 cm and 105 cm, respectively to cover a q-range from 0.03 to
0:84
1
q 4psinh=k.
The scattering data obtained from monolithic xerogel samples
was corrected according to sample transmission and background
scattering. Assuming a random pore system surrounded by a dense
silica matrix the scattering intensity results from the electron den-
sity contrast between matrix and empty (or lled) pore. An inverse
Fourier transformation of scattering data according to Eq. (1) offers
a distance distribution function revealing information about the
shape and size of the pore [15]. The data evaluation was performed
using the program GNOM [16]
Pr
1
2p
2
Z
1
0
Iqqr sinqrdr 1
Spherical pore shapes would give symmetric distance distribution
functions while elongated cylindrical or disc like pores would lead
to a more asymmetric function. The slope of the linear regime in
a double-logarithmic plot of the scattering intensity versus the scat-
tering vector reveals the fractal dimension and hence information
about the surface structure of a porous disordered material. The
scattering intensity of fractal objects can be described with a
power-law function [17,18]:
Iq I
0
q
n
: 2
For an ideal smooth surface n would be 4 (Porod behavior) while the
exponent decreases when aspherities and inhomogeneities are
present. In principle one can distinguish between mass and surface
fractals according to their scattering behavior at larger q values.
Mass and surface fractal dimensions D
m
and D
s
allow to describe
and quantify fractal properties of the porous material. For mass
fractals 1 < n < 3 the fractal dimension is equal to the slope
D
m
n; 1 < D
m
< 3 whereas for surface fractals n 6 D
s
3 < n < 4; 2 < D
s
< 4. For mass fractals a higher fractal dimen-
sions indicates spatially denser and more ramied aggregates while
for surface fractals a higher fractal dimension indicates more irreg-
ular and nearly space lling surface structures [18].
2.3. Adsorption
The N
2
adsorption isotherms of ball milled samples were taken
on a Quantachrome Quadrasorp. Specic surfaces were determined
using multi-point BET analysis in the p=p
0
range of 0.050.2. The
total pore volume was examined using p=p
0
of 0.9 and the mi-
cro-pore volume was calculated using p=p
0
of 0.2 considering only
pores with a radius smaller than 1 nm. Pore size distributions (PSD)
were calculated using the adsorption branch with the BarretJoy-
nerHalenda (BJH) theory. Fractal analysis of the adsorption iso-
therms were applied using the FrenkelHalseyHill (FHH) model
[19]. The surface fractal dimension is accessible through a regres-
sion of the linear range in a lnN=N
m
versus lnlnp=p
0
plot,
where N is the number of moles of nitrogen adsorbed at a certain
p=p
0
and N
m
is the number of moles of nitrogen in a monolayer
Table 1
Classication and characteristic structural parameters of the prepared xerogels with different pH-value. 1.0 ml of Rh6G were added to a solution of 2.5 ml ethanol (Merck), double
distilled water, hydrochloric acid (32% or 25%) and 2.240 ml TEOS. Postloaded samples are marked as PL.
No. pH HCl H
2
O V
HCl
=V
TEOS
R
G
n=Ds D S
BET
V
micro
V
total
Max PSD
ml ml nm (FHH) m
2
=g cm
3
=g cm
3
=g nm
A-287 0.625 3.0 0.0 1.34 1.2 3.52/2.48 2.37 718 0.31 0.49 1.22
A-288 0.546 2.5 0.5 1.12 1.3 3.47/2.53 2.37 819 0.35 0.58 1.36
A-289 0.449 2.0 1.0 0.89 0.9 3.68/2.32 2.26 817 0.35 0.46 1.22
A-290 0.324 1.5 1.5 0.67 1.22 3.26/2.74 2.36 670 0.30 0.61 1.22
A-291 0.148 1.0 2.0 0.45 1.19 3.45/2.55 2.42 763 0.33 0.5 1.38
A-292 0.153 0.5 2.5 0.22 1.22 3.50/2.50 2.38 718 0.32 0.49 1.23
D-293 0.044 0.1 2.0 0.045 1.19 3.70/2.30 2.35 737 0.32 0.51 1.22
D-294 0.345 0:5

2.5 0.22 1.09 3.67/2.33 2.37 817 0.35 0.55 1.22

D-295 0.500 0:35

2.65 0.16 1.01 3.69/2.31 2.35 793 0.34 0.54 1.23

D-296 0.308 0.35 2.65 0.16
B-298 0.561 0.2 3.0 0.089 0.98 3.74/2.26 2.36 728 0.32 0.49 1.23
B-299 0.684 0.15 3.0 0.067 0.85 3.53/2.47 2.45 687 0.30 0.43 1.09
B-300 0.857 0.1 3.0 0.045 0.78 3.44/2.56 2.58 644 0.33 0.37 0.97
B-301 1.15 0.05 3.0 0.022 0.67 3.25/2.75 2.72 568 0.28 0.31 0.85
C-310 0.537 2.24 0.0 1.00 1.62 2.98/3.02 2.61 687 0.30 0.41 1.23
C-311 0.625 3.0 0.0 1.34 1.18 3.48/2.52 2.4 797 0.35 0.53 1.09
C-312 0.757 5.0 0.0 2.23 1.35 3.64/2.36 2.07 701 0.33 0.66 1.91
PL-288 2.7 3.28/2.72 2.41 557 0.24 0.78 3.0
PL-289 2.87 3.39/2.61 2.31 548 0.21 0.79 2.6
PL-290 2.7 3.47/2.53 2.41 595 0.26 0.91 3.1
PL-291 2.5 3.75/2.25 2.43 597 0.26 0.96 3.6
PL-292 2.2 3.65/2.35 2.42 576 0.25 0.73 2.8
PL-296 2.1 3.55/2.45 2.44 598 0.26 0.68 2.4
PL-310 2.4 3.32/2.68 2.01 600 0.26 0.85 3.1
246 J. Krause et al. / Microporous and Mesoporous Materials 142 (2011) 245250
ln
N
N
m

DFHH 3 ln ln
p
p
0

: 3
2.4. Absorption- and luminescence spectroscopy
Absorption measurements were performed with a Shimadzu
5300 UV/Vis two-beam-spectrophotometer in the range 200
900 nm with a resolution of 5 nm. The solid monolithic samples
of thickness 0.30.5 mm were glued on a sample holder with a
2 mm slit. Luminescence spectra were recorded in reection geom-
etry using a M266 spectrograph from SOLAR laser systems with a
TCD1304AP CCD-detector and a resolution of 0.1 nm. Excitation
was performed with an Argon-Ion Laser (line at 476 nm) at an inci-
dent intensity of 10 mW=cm
2
. The beam was focussed on a spot
size of 0:785 cm
2
resulting in an intensity of 12:73 mW=cm
2
. The
laser line was blocked with a Semrock Razor Edge Filter at
488 nm, which was mounted in front of the entrance slit of the
monochromator. The dye xerogels were measured directly after
synthesis and drying (2 weeks) and remeasured after one year of
storage at ambient conditions.
3. Results and discussion
3.1. Structure
As indicated by the variations in the adsorptiondesorption
characteristics (Fig. 1), the structural formation of the xerogel is
signicantly affected by the amount of HCl, H
2
O and TEOS used.
According to the ratios of starting materials (see Table 1) xerogel
samples were classied in four sample classes. Isotherms of class
B (water excess) and class C (hydrochloric acid excess) reveal an
increasing pore size with higher HCl/TEOS ratio, which is reected
by more pronounced hysteresis loops. On the other hand, the
adsorptiondesorption characteristics of class A and D is only
slightly affected by varying the starting composition and no spe-
cic trends were observed. Post-loading (PL) of dried samples
causes a different adsorptiondesorption characteristic. The hys-
teresis loops are shifted to higher relative pressures and are more
pronounced in comparison to dye loaded xerogels prepared by
in situ integration. Hence, post-loading of Rh6G leads to xerogels
with a higher contribution of mesopores reected also by the pro-
portion of micro-pore volume to total pore volume found in Table 1
(for calculated pore size distributions, scattering curves, and nor-
malized distance distribution functions see Supporting informa-
tion Figs. S5S7). SAXS investigations were carried out in order
to obtain a conrmation of the physisorption results and to receive
additional information concerning the structural properties of the
prepared xerogel samples. Due to the fractal structure of the silica
surface the exponent n in Eq. (2) differs from 4 leading to smaller
values in the range 33.8. These values indicate a rough silica sur-
face with fractal dimensions of 2.33, which is conrmed also by
the independent evaluation according to the FHH theory. While
the radius of gyration shows systematic changes with a varying
starting composition for some classes, it seems hardly affected by
Fig. 1. Adsorptiondesorption isotherms of prepared xerogels. Labels AD denote classes of xerogels as dened in Table 1.
J. Krause et al. / Microporous and Mesoporous Materials 142 (2011) 245250 247
the integration method of the dye. Additionally the surface proper-
ties reected by the fractal exponents show no drastic changes.
Hence, the dye integration method has no signicant effect on
the structure-formation (gelling) of the xerogel. Table 1 summa-
rises the results of SAXS and N
2
physisorption experiments.
In contrast to SAXS evaluations different physisorption charac-
teristics and as a result different pore sizes and pore volumes were
obtained for in situ loaded and postloaded xerogels, respectively.
These results can be explained by an incomplete inltration of
the dye into the pore system when the post-loading method is ap-
plied. While the incorporated dye should cause only minor differ-
ences in electron density contrast and as a result in scattering data,
the pore-accessibility of nitrogen molecules is strongly dependent
on the presence of the dye. The higher micro-pore contribution
indicated by the larger ratio of V
micro
=V
total
for in situ integration
leads to the conclusion that the dye is located predominantly in
the mesopores while the post-integration leads to a preferred ll-
ing of the micropores. This is reected also by the lower specic
surface area and the lower micro-pore volume of post-loaded sam-
ples. In the following the experimental results are discussed in de-
tail according to the sample class.
3.1.1. Class A and class D
Within these two classes the changes in pore size, volume and
fractal surface characteristics show no tendency with changing
HCl/TEOS ratio. The pore radii obtained from SAXS vary from
1.6 nm to 2.2 nm while N
2
-physisorption yields smaller pore radii
from 1.2 nm to 1.4 nm. The surface area is in the range of 670
820 m
2
/g for class A and 740820 m
2
/g for class D samples. In con-
trast to the other sample classes the distance distribution functions
are in general asymmetric for this class indicating a more elon-
gated pore shape. The silica surface has a moderate roughness with
D
s
values around 2.5 and 2.3 for class A and D, respectively.
3.1.2. Class B
Xerogel samples of this class show successive change from a
predominantly microporous structure (B-301) to a higher amount
of larger pores with increasing V
HCl
=V
TEOS
. A growing pore size
(for pore size distribution see Supporting information) is reected
by the characteristics of the radius of gyration also. The increasing
specic surface area together with the total pore volume and the
constant micro-pore volume suggests that the contribution of lar-
ger pores is increased drastically. Interestingly the fractal dimen-
sion follows the trend of the pore size in a reciprocal way
decreasing down to 2.26 D
s
and 2.44 (D(FHH)) revealing a
smoothing of the silica surface with larger pores. According to
the distance distribution functions the pore shape changes from
spherical to slightly elongated for higher V
HCl
=V
TEOS
ratios. Class-
B samples do not show a discrepancy between pore radii obtained
from SAXS and physisorption measurements offering very similar
results. The weak colouration in comparison with all other samples
suggests a failed integration of the dye perhaps due to the smaller
pore size. However, the absence of the dye within these sample
class leads to similar pore sizes obtained from SAXS and N
2
-phys-
isorption while the presence of the dye within the other sample
classes causes pore blocking and hence the discrepancy between
SAXS and physisorption results.
3.1.3. Class C
Evaluation of SAXS and adsorption data reveals a drastic change
in pore size and inner structure. The total pore volume decreases
with decreasing HCl/TEOS ratio while the specic surface increases
to reach a maximum of 797 m
2
/g with V
HCl
=V
TEOS
1:34. A larger
amount of smaller pores with a rougher surface structure, reected
by a higher D
s
value would explain this result. Additionally the
smaller R
G
conrms smaller pore sizes. The last sample of this class
(C-310 V
HCl
=V
TEOS
1:0) cannot be treated as surface fractal struc-
ture due to a slope of 3 in the fractal regime. A D
m
value of 3.02
reects a dense package of silica aggregates with a certain distance
leading to micro-porosity. This result is conrmed through the
change in hysteresis loop type according to IUPAC classication
from H
2
to H
4
type. H
2
type hysteresis loops usually found in these
examinations are characteristic for porous materials with broad
pore size distributions while H
4
type is typical for aggregates of
particles forming slit shaped micropores [19]. Following this con-
sideration the calculated distance distribution function and R
G
va-
lue of this sample would rather describe the aggregates forming
the porous structure than the pores themselves.
3.1.4. Postloaded samples
As mentioned above the post-loaded samples are characterized
by a mesoporous structure with pore radii varying from 2.2 to
2.9 nm (SAXS) and 2.4 to 3.6 nm (physisorption). Because of the
lled micropores the micro-pore volume is decreased to approxi-
mately 0.25 cm
3
/g and in comparison with the in situ integrated
samples the surface area is lower (557600 m
2
/g). The SAXS results
are in agreement with in situ loaded xerogels revealing radii of
gyration of 2.12.8 nm and fractal dimensions of about 2.32.7.
Adsorptiondesorption isotherms, pore sized distributions, scatter-
ing curves, and normalized distance distribution functions for
postloaded samples are shown in Fig. S8 in the Supporting
information.
3.2. Absorption and luminescence
The absorption spectra of the dye loaded xerogels show in gen-
eral no signicant shifts with respect to the pH values or the HCl/
TEOS ratio (see Fig. 2) in agreement with literature [20]. The
absorption maxima k
max
are found between 530 and 540 (3) nm
for class A and D samples as well as for sample C-310. The samples
C-311 and C-312 however exhibit a signicant shift to the blue,
with maxima at about 510nm. Additionally a shoulder is visible
on the blue side at about 500nm and a further absorption band
around 400nm is observed, which might be due to aggregate for-
mation [2123]. Thus increasing V
HCl
=V
TEOS
above 1.34 leads to a
signicant shift in the absorption of the dye. Class B samples could
not be measured since the dyes are destroyed/bleached during the
xerogel synthesis and only exhibit a weak colouring. Interestingly
the postloaded Rh6G-xerogels exhibit the absorption maximum
in the range 506516 nm (empty squares in Fig. 2), thus at the
same position as the two dye xerogels C-311 and C-312 with the
highest V
HCl
=V
TEOS
value and smaller pore sizes. This result is in
accordance with the observation that in the postloaded samples
the dyes occupy mainly the micropores. This indicates that embed-
ding the dyes in micropores leads to a blue-shift of the absorption
maximum. This observation is in contrast to an earlier report of
Kim et al. [24], where a higher HCl:TEOS ratio (up to 0.5) resulted
in a blue shift of the absorption maximum, which was interpreted
as originating mainly from dimer formation of the Rh6G molecules.
Fig. 3a shows the spectral distribution of the luminescence after
excitation with 476 nm (Argon laser) for xerogels synthesised at
different pH values. Emission ranges from 500 to 660 nm for all
samples. The samples which were prepared by admixture of the
Rh6G solution during gelling exhibit luminescence maxima be-
tween 543 and 553 nm. Sample C-310 is an exception with its
strongly redshifted luminescence maximum at 572 nm. Fig. 3b
shows the comparison between postloaded (open squares) and
as-synthesised dye xerogels as a function of the ratio V
HCl
=V
TEOS
(compare Table 1). It can be seen that the postloaded xerogels ex-
hibit luminescence maxima between 541 and 544 nm independent
of the pH value. Compared to the as-synthesised xerogels the lumi-
nescence maximum is slightly blue shifted (6 nm), but there is no
248 J. Krause et al. / Microporous and Mesoporous Materials 142 (2011) 245250
detectable trend. Note that the apparent multiple maxima in the
luminescence spectrum are an artefact of the used detector due
to internal multiple reections.
Summarising the absorption and luminescence observations we
nd two interesting features: rst, the luminescence and absorp-
tion of C-311 and C-312 is very similar to those of the postloaded
samples. Second, the absorption maximum of the A, C, and D class
samples is found at signicantly higher wavelength than that of
the postloaded samples resulting in a very small Stokes shift of
only a few nanometers, while the Stokes shift in the postloaded
samples and C-311 and C-312 is of the order of 40 nm.
In order to shine more light on this observed difference in the
Stokes shift between as-synthesised and postloaded dye xerogels
we measured the luminescence and absorption spectra after one
year of storage of the xerogels. We nd that the luminescence
spectra are hardly changed, while the absorption maxima of the
as-synthesised dye xerogels shift towards the blue and are found
between 515 and 525 nm. The postloaded xeorgels exhibit their
maxima still at 510 nm. Thus ageing of the dye xerogels leads in
the case of the as-synthesised xerogels to a signicant change in
the absorption properties. This might be due to continued evapora-
tion of solvent molecules which could still be present even in the
dried xerogels (few weeks to months old). This could also explain
the observation in the two samples C-311 and C-312 with a HCl ex-
cess, as gelling and drying proceeds faster. In any case there is no
systematic trend as a function of pH value or V
HCl
=V
TEOS
ratio. Con-
trary to earlier reports [20] no general deteroriation of the dyes at
pH < 1 was observed, only synthesis in class B samples with pH in
the range 0.5611.15 lead to a destruction or bleaching of the Rh6G
dye. However, note that in this class the V
HCl
=V
TEOS
ratio is the low-
est (in the range 0.0220.089) and the gelation time is the longest.
Thus we might argue that a long exposure to acidic conditions is
unfavorable for the Rh6G dye.
As mentioned earlier a further important parameter in solid-
state dyes is the photostability, i.e. the stability against bleaching
during laser irradiation. Fig. 4 shows the luminescence intensity
against irradiation time measured at 550 nm (excitation wave-
length 532 nm, 10 mW) for dye-loaded xerogels with different
pH of class A and D, exemplarily. For all samples the photobleach-
ing behavior can be described with a double exponential decay
Fig. 2. (a) Absorption spectra of dye loaded xerogels of class C, normalized to the value at the maximum of the dye absorption band around 540 nm. Class A and D xerogels
show spectra as C-310 with a single absorption band (and possibly a small shoulder on the blue side) around 540 nm. (b) Position of the absorption maximum kmax for dye
loaded xerogels of class A, C, and D (full symbols) and postloaded xerogels (empty symbols). (For interpretation of the references in colour in this gure legend, the reader is
referred to the web version of this article.)
Fig. 3. (a) Luminescence of dye loaded xerogels for different pH values (of gel solution). (b) Position of luminescence maximum kmax as a function of ratio V
HCl
=VTEOS (cf. Table
1). Full circles denote xerogels where the dye was admixed to the gelling solution, open squares denote postloaded xerogels.
J. Krause et al. / Microporous and Mesoporous Materials 142 (2011) 245250 249
with time constants s
1
6510 s and s
2
67050 s. The inten-
sity is reduced by about 80% after 10 min of irradiation. Thus we
observe a rather fast photobleaching in agreement with photoble-
aching studies of Rh6G in PVA [25].
Overall we observe only very small changes of the luminescence
properties as a function of the pH values of the xerogels, although
the specic surface and mean pore size change. The only signicant
change in luminescence was found for sample C-310 which exhib-
its a shift of about 30 nm in the luminescence maximum and has a
different inner structure. Furthermore we note that the ratio
V
HCl
=V
TEOS
is a better measure for classication of the dye xerogels
than the pH-value. For example, samples with similar pH value
such as C-310 and A-288 can have a quite different porous struc-
ture due to the differences in the gelation process.
4. Conclusion
Silica xerogels with different pH values in the range 0.8 to 1.2
and loaded with Rh6G dyes were investigated with respect to
luminescence properties and pore structure. We nd that the spec-
tral emission range and the photostability of Rh6G remains almost
unaffected by the pH value at which the xerogel is prepared. Post-
loading of the xerogels with dyes was successfully performed and
allows for the preparation of dye xerogels with similar lumines-
cence properties. As an advantage this postloading procedure al-
lows for the preparation of dye xerogels, which under normal
synthesis conditions lead to a destruction of the dye molecule.
The SAXS analysis allows for a precise determination of pore sizes
and xerogel structure in the case of loaded xerogels, while the BET
analysis encounters problems due to pore blocking by the embed-
ded molecules. However, the combined SAXS and N
2
-adsorption
study of the xerogels shows that the Rh6G dyes occupy the microp-
ores when using the postloading procedure while they mainly oc-
cupy mesopores when adding them during the solgel process.
Accordingly the absorption spectra of dyes located in micropores
exhibit a blue-shifted absorption maximum in the range 506
516 nm, while absorption maxima of dyes located in mesopores
are found between 530 and 540 nm. Thus the position of the
absorption maximum might be used as an indicator for pore sizes.
From a structural point of view the classication of the prepared
xerogels is better done on the basis of the ratio V
HCl
=V
TEOS
instead
of the pH-value, since the structure of the xerogel depends strongly
on the gelation process, which is signicantly inuenced by the ra-
tio of starting materials.
Acknowledgement
Financial support by the BMBF (FKZ 03X5510) is gratefully
acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.micromeso.2010.12.007.
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D-293
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Fig. 4. Photostability of dye-loaded xerogels with different pH values.
250 J. Krause et al. / Microporous and Mesoporous Materials 142 (2011) 245250