Comparison of Two Synthesis Routes to Obtain Gold Nanoparticlesin Polyimide
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ARTICLE
pubs.acs.org/JPCC
Comparison of Two Synthesis Routes to Obtain Gold Nanoparticles
in Polyimide
Katrien Vanherck,† Thierry Verbiest,‡ and Ivo Vankelecom*,†
†
‡
K.U. Leuven, Centre for Surface Chemistry and Catalysis, Kasteelpark Arenberg 23, 3001 Heverlee, Belgium
K.U. Leuven, Molecular and Nanomaterials, Celestijnenlaan 200D, 3001 Heverlee, Belgium
ABSTRACT: Gold nanoparticle containing polymer materials find applications in
catalysis, facilitated transport, sensing, and separations. In this study, two routes to
obtain stable gold nanoparticles in a polymer matrix, namely, in situ chemical reduction
of a gold salt and the use of preformed poly(vinylpyrrolidone) protected gold
nanoparticles, were followed to prepare gold containing polyimide hybrid membranes.
The influence of the synthesis method on the nanoparticle size, dispersion, and surface
plasmon behavior was investigated by transmission electron microscopy, UVvis
spectroscopy, and diffuse reflectance spectroscopy. Significant differences were found
concerning the dispersion and aggregation of the nanoparticles. The influence of the
synthesis method on the membrane structure and performance was also studied by
scanning electron microscopy and in filtrations of dye solutions in ethanol and
isopropanol. The filtrations were repeated while the gold nanoparticles were plasmonically heated by a green Argon ion laser
beam, resulting in localized heating of the membrane and increased fluxes.
’ INTRODUCTION
To obtain stable metal nanoparticles (NP) in a solid polymeric
matrix, two routes are commonly followed. First, the NPs can be
presynthesized in a solvent that is then used to prepare the
polymer matrix. In this case, the NPs are usually protected by a
ligand to avoid their aggregation. Second, the NPs can be formed
in situ, by (photo)chemical reduction inside the solid matrix.
These two methods to prepare NPpolymer composites have
been studied for a variety of polymer matrices and gold nanoparticles (GNPs).117 Overall, the first method has been shown
to allow a better control of the size of the NPs while the second
method strongly reduces the incidence of NP aggregation.4,6
Such problems with aggregation during the incorporation of
preformed nanoparticles into a solid matrix may be avoided by
surface-modifying the nanoparticles with a suitable agent.4,6,15 A
direct comparison of the two methods has so far only been done
by Dammer et al. for GNPs synthesized in poly([2-methoxy5-(2-ethylhexyloxy)-1,4-phenylene]vinylene).13 However, polymer degradation occurring in the case of in situ reduction,
through oxidation by the GNP precursor (H[AuCl4]/tetraoctylammonium bromide/tetraoctylammonium bromide (TOAB)
complex), did not allow for a proper comparison.
Polymeric membranes containing gold nanoparticles have
been prepared for various applications, such as (electro)catalysis,8,1719 facilitated transport,14,20 protein separation,21
and sensing,2224 and have potential applications in other areas
such as drug delivery. When preparing GNPs inside a polymer
membrane matrix, it can be expected that both methods will have
a different influence on the nanoparticle size and dispersion in
the membrane but also on the membrane structure and hence
the membrane performance. To our knowledge, no comparison
r 2011 American Chemical Society
between the two methods has been made for a nanofiltration
membrane.
Solvent resistant nanofiltration (SRNF) involves the separation of an organic mixture down to a molecular level by simply
applying a pressure gradient over a membrane.25 It has some
important advantages compared to other industrial separation
processes, such as its energy and waste efficiency. To turn SRNF
into a viable industrial process, excellent membranes should
become available, combining chemical, mechanical, and thermal
stability with good rejections and sufficiently high fluxes. However, most commercially available membranes for SRNF combine high rejections for low molecular weight (MW) compounds
with low fluxes.
Recently, we have studied the effects of plasmonic heating of
GNPs incorporated into nanofiltration membranes on the membrane performance, showing an overall increase of the membrane
permeability without affecting its rejection of a low MW dye.26,27
Plasmonic heating is a method more commonly employed
in imaging and sensing, drug release, and biomedicine (tumor
destruction).6,2833 In most membrane processes, developing a
membrane with a higher selectivity is coupled to a loss in permeability and visa versa. Photothermal heating of GNP containing
membranes is thus of high interest as a potential route to overcome this traditional flux-selectivity trade-off.
In this paper, two common synthesis routes were used to
obtain composite GNPpolyimide phase inversion membranes
with varying gold content. Polyimide (PI) is a well-known polymer
Received: July 29, 2011
Revised:
November 17, 2011
Published: November 23, 2011
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Table 1. Membrane Compositions (Weight in g in the Casting Solution) for Reference and GNP Containing Membranes
Prepared by Two Methods (PRE and ISR)
HAuCl4 3 3H2O [g]
membrane
method
matrimid [g]
DMA [g]
THF [g]
ISR-0
ISR
2.2
4.5
3.3
0
0
0
ISR-1
ISR-2
ISR
ISR
2.2
2.2
4.5
4.5
3.3
3.3
0.044
0.088
0
0
0
0
ISR-3
ISR
2.2
4.5
3.3
0.132
0
0
ISR-4
ISR
2.2
4.5
3.3
0.176
0
0
PRE-0
PRE
2.2
4.5
3.3
0
0.268
0
PRE-1
PRE
2.2
4.5
3.3
0.044
0.134
0.02
PRE-2
PRE
2.2
4.5
3.3
0.088
0.268
0.04
PRE-3
PRE
2.2
4.5
3.3
0.132
0.45
0.06
PRE-4
PRE
2.2
4.5
3.3
0.176
0.536
0.08
for producing SRNF membranes.25 PI membranes containing
GNPs have been prepared by adding presynthesized PVPprotected GNPs by Mertens et al.,8 but they have never before
been prepared by in situ reduction of the GNPs. It can be
anticipated that the two different NP incorporation strategies
to be studied will also strongly influence the surface plasmon
resonance behavior of the GNPs and thus further change the
membrane performance. The polymer composites were characterized by UVvis spectroscopy and diffuse reflection spectroscopy (DRS), scanning electron microscopy (SEM), and
transmission electron microscopy (TEM). The photothermal
effect of the selected GNPs on the temperature and flux behavior
of the membranes was compared by irradiating the membrane
with continuous green laser light during solvent filtrations.
PVP [g]
NaBH4 [g]
was obtained. The solutions were then allowed to stand until air
bubbles had disappeared and were cast onto a nonwoven support
material that had been saturated with DMA. An automated
casting knife (250 μm slid) was used, and the resulting polymer
films were immediately immersed into a water bath. The reference
membrane was yellow, and the membranes containing GNPs
were light pink to red-brown in color. The membranes were then
stored in an IPA bath for 3 h and transferred to an IPA/glycerol
bath (volume ratio 60:40) for three days, before being dried in
an oven at 60 °C. The membranes will further be referred to as
PRE-0, PRE-1, PRE-2, PRE-3, and PRE-4, respectively corresponding with the membrane containing 0, 1.0, 2.0, 3.0, and 4.0 wt %
GNPs.
For the in situ chemical reduction (ISR) method, based on
Huang et al.,21 HAuCl4 3 3H2O was added to a PI solution prepared in a mixture of DMA and THF to obtain casting solutions
with gold to polymer weight ratios of 1.0, 2.0, 3.0, and 4.0 wt %.
A similar polymer solution PI was prepared without HAuCl4 3 3
H2O, as a reference. The exact membrane compositions are given
in Table 1. The solutions were stirred until homogeneous and
cast onto the nonwoven support material. After a solvent evaporation step (30s), they were immersed into a water coagulation
bath. After the immersion, the membranes were moved immediately into a solution of NaBH4 in water to reduce the gold to
nanoparticles, upon which the membrane color turned from
yellow to dark red. The membranes were further kept in IPA and
IPA:glycerol and then dried as in Method A. The membranes will
further be referred to as ISR-0, ISR-1, ISR-2, ISR-3 and ISR-4,
respectively corresponding with the membrane containing 0, 1.0,
2.0, 3.0, and 4.0 wt % GNPs.
Membrane Characterization. Diffuse reflectance spectra
(DRS) were taken of the membrane surfaces by a PerkinElmer
Lambda 40 spectrophotometer with deuterium and wolfram
lamps. A piece of each membrane was redissolved in DMA,
and these GNP solutions were characterized by a PerkinElmer
UVvis spectrophotometer. Membrane pieces were immersed
and broken in liquid nitrogen. The cross sections were studied
with a Philips XL 30 FEG SEM, a semi-in-lens type SEM with a
cold field-emission electron source. All SEM samples were first
coated with a 1.52 nm Au layer to reduce sample charging
under the electron beam using a Cressington HR208 high resultion
sputter coater. To study the size of the GNPs in the membranes, the cross sections were examined by TEM. The membranes were dried and then embedded into Araldite resin. Semithin
sections for light microscopy with a thickness of 5 μm were made
with a Reichert Ultracut E microtome. Finally, cubic samples of
’ EXPERIMENTAL SECTION
Materials. Matrimid9725 PI was obtained from Huntsman
(Switzerland). The polyethylene/polypropylene nonwoven fabric
Novatexx 2471 was kindly provided by Freudenberg (Germany).
Hydrogen tetrachloroaurate(III) trihydrate(HAuCl4 3 3H2O) and
sodium borohydrid (NaBH4, >98.5%) were obtained from SigmaAldrich. Poly(vinylpyrrolidone) (10 000 g mol1), N,N0 -dimethylacetamide (99.5%, DMA), tetrahydrofuran (99.5%, THF), isopropanol (99.5%, IPA), and absolute ethanol (EtOH) were
obtained from Acros. All used water was desionized.
Membrane Synthesis. Membranes were synthesized according to two different methods. For the incorporation of presynthesized GNPs (PRE), PVP-protected GNPs were prepared
in DMA similar to the synthesis methods described by Teranishi
et al.58 and Mertens et al.8 Solutions of HAuCl4 3 3H2O (0.05, 0.1,
and 0.2 mmol) and an amount of PVP (molar ratio monomeric
units of PVP/gold = 12) were prepared in DMA (6 g). Then, a
freshly prepared NaBH4 solution in DMA (2 g) was added under
vigorous stirring (molar ratio NaBH4/gold = 5), and immediately, a color change from yellow to dark red occurred in the
solution, indicating the reduction of gold into nanoparticles. The
solution was characterized by a PerkinElmer UVvis spectrophotometer, and the typical dark red color showed as a large peak
at 530 nm, corresponding to the plasmon absorbance band of the
GNPs.58 PI was added to the GNP solutions in DMA resulting
in four casting solutions with different gold/PI weight ratios
(1.0, 2.0, 3.0, and 4.0%). A similar PVP containing polymer
solution PI in DMA and THF without GNPs was prepared as a
reference. The compositions are given in Table 1. The solutions
were stirred at room temperature until a homogeneous mixture
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Figure 2. Chemical structures of dye rose bengal (1017 Da) and methyl
orange (327 Da).
The irradiation improvement factor (IIF) is calculated as the
percentual increase in permeance or rejection when the membrane is irradiated, as follows:
Figure 1. Schematic representation of a dead-end filtration cell
equipped for laser irradiation of the GNP containing membrane during
separations.
about 1 mm side were obtained. Double stained 70 nm thin sections
were examined in a Zeiss EM900 electron microscope. Chemicals
and procedures for sample treatments were obtained from the
Laboratory for Entomology of the K.U. Leuven, Leuven, Belgium.
The particle size distributions of the GNPs were measured from
the TEM pictures using ImageJ software (Image Processing and
Analysis in Java59).
Dead-End Filtrations. Dead-end membrane filtrations were
carried out in a specially made glass filtration cell (Figure 1). A
transparent glass window was built in the top to allow a laser
beam to pass and illuminate 40% of the active membrane surface
(0.001736 m2). For each filtration, a membrane was mounted in
the cell and sealed off with a Viton O-ring. In some filtrations, a
sealing flat plate was used to reduce the active membrane surface
to equal the illuminated part. Before each filtration, the membranes were immersed in isopropanol for at least one day.
Filtrations were carried out with dilute ethanol and isopropanol
based methyl orange (MO, 327 Da, 35 μM) and rose bengal
solutions (RB, 1017 Da, 17 μM) at 5 bar with and without laser
irradiation. The chemical structures of the dyes are given in
Figure 2.
A continuous green argon laser beam (514 nm) was used to
illuminate the membrane. The laser intensity was measured as
the laser power divided by the illuminated surface, also calculating the minor loss of intensity in the laser pathway. The laser was
set at an intensity of 0.2 W/cm2. Permeances were calculated as
the amount of solvent (V) that passed through the membrane per
unit of time (t), membrane surface (A), and applied pressure
(ΔP) so that
Permeance ¼ V 3 t 1 3 A1 3 P1
1ị
3ị
IIFR ẳ 100 3 RL RC Þ 3 RC 1
ð4Þ
where PC and RC are the conventual permeance and rejection
(measured without laser irradiation) and PL and RL are the permeance and rejection measured when the membrane is irradiated.
’ RESULTS AND DISCUSSION
Since the size, distribution, aggregation, and dielectric environment all have a strong influence on the surface plasmon
resonance behavior of the GNPs,29,3440 the GNPs inside the PI
membranes were thoroughly characterized. In the ISRmembranes, the GNPs are formed inside the solid membrane
matrix by chemical reduction of a gold salt, wherein the membrane polymer itself acts as a stabilizer. In the PRE-membranes,
PVP-stabilized GNPs are present in the polymer solution before
the membrane is cast and solidified by phase inversion. The
preformed GNPs may have an influence on the membrane
structure, as it has been previously shown that adding (nano)particles to a polymer solution can cause significant changes in
the resulting phase inversion membrane structure.4145 However, the addition of salt to a membrane casting solution may also
influence the membrane morphology. For example, Park et al.
have shown that polyetherimide (PEI) membranes containing
ZnCl2 have thicker and denser top layers.46 It has been shown
for lithium salts in poly(vinylidene fluoride) (PVDF) that the
addition of the salts increases the viscosity of the casting solution
and affects the phase inversion process.4749 Similar effects may
be found for the addition of HAuCl4 3 3H2O, where the salt will
later be reduced to GNPs.
Influence of Gold Content and Synthesis Method on the
Polyimide Membrane Morphology. The cross sections of
where V is the collected permeate volume in a time t, A is the
active membrane surface area, and ΔP is the applied pressure.
Rejections were calculated as the percentage of the feed concentration that was retained:
Rejection ẳ 100ẵ1 Cp 3 Cf 1 ị
IIFP ẳ 100 3 PL PC Þ 3 PC 1
the upper part of the reference membranes PRE-0 and ISR-0 are
given in Figure 3. Both membranes have an asymmetric structure
and show a densification of the matrix toward the upper part of
the cross section, which is typical for an asymmetric membrane
prepared by phase inversion. Larger pores are visible in the substructure of PRE-0, probably due to the presence of PVP in the
membrane casting solution. PVP increases the viscosity of a polymer solution, and it can generally be used as a pore former.5055
Since the PVP-protected GNPs are synthesized in a DMA solution
containing an excess amount of PVP to ensure the NP stability,
ð2Þ
where Cp is the permeate concentration and Cf is the feed
concentration of the dye. All permeances and rejections shown
are averages of three measurements with a standard deviation
below 10%. When necessary, measurements were repeated more
than three times, to obtain a standard deviation below 10%.
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Figure 3. SEM pictures of ISR-0 and PRE-0 cross sections, magnified at 20000.
Figure 4. SEM pictures magnified at 20000 of the cross sections of membranes ISR-1, ISR-2, ISR-3, and ISR-4.
it can be expected that a similar porous structure will be found in
the other PRE-membranes (see further below).
SEM Pictures for ISR-Membranes. The cross sections of ISR-1
to ISR-4 are given in Figure 4. The membranes containing
increasing weight percent of GNPs have rather similar structures
as the reference membrane, although the roughness of the cross
section increases. Some effects of salt addition to the casting
solution on the membrane morphology have been reported in
literature for PEI and PVDF membranes.46,49 For these ISR
membranes, there seems to have been no large influence of the
addition of the chloroauric acid to the polymer solution on the
membrane morphology. However, the resolution of SEM is not
high enough to fully characterize the structure.
SEM Pictures for PRE-Membranes. The PRE-membranes
(Figure 5), cast from a solution containing PVP-protected GNPs,
have a structure that is clearly different from the ISR-membranes.
The pictures of PRE-1 and PRE-2 show a porous substructure
similar to the reference membrane PRE-0. For PRE-3 and PRE-4,
the pores reach almost to the very top of the membrane. Since the
GNP content of PRE-3 and PRE-4 is higher, the excess amount of
PVP will be higher as well, which can explain these more porous
structures. PVP is known to increase the membrane porosity, as it
may leach from the membrane during its immersion in water, the
final step in the phase inversion synthesis process. The cross sections
are a lot smoother than those obtained for the ISR membranes.
Since the resolution of SEM is not high enough, TEM pictures
were made of the top layer and substructure of the cross sections
to gain information on the size and dispersion of the GNPs in the
membranes.
Influence of the Synthesis Method on the GNP Properties.
An important parameter of GNPs for purposes such as sensing
and photothermal heating is the surface plasmon resonance
wavelength. A surface plasmon is a collective movement of the
outer band electrons circling a GNP. This electron gas moves
at a certain wavelength, and when light of this same wavelength
is aimed at the nanoparticle, it is strongly absorbed and turned
into thermal energy. The wavelength at which surface plasmon
resonance occurs is strongly dependent on the size and shape of
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Figure 5. SEM pictures magnified at 20000 of the cross sections of membranes PRE-1, PRE-2, PRE-3, and PRE-4.
This indicated that, regardless the gold concentration, the size
and dispersion of GNPs in the membrane top layer were similar.
The wavelength found by UVvis spectroscopy increased from
1 to 3 wt % gold and stabilized further. A higher SPR wavelength
may indicate a larger GNP size. Alternatively, since the GNPs
were formed in a solid membrane matrix, the rise in gold concentration may have resulted in a stronger aggregation of the
GNPs. For the PRE membranes, both the DRS and the UVvis
wavelength are clearly increasing for increasing gold concentration. This indicates that, both in the top and sublayer, larger GNPs
may have been formed at higher gold concentrations. It may also
indicate that the GNPs have been insufficiently stabilized at the
higher concentrations in the DMA solution during the membrane
synthesis. This would lead to an aggregation of GNPs already in
the membrane casting solution. Since the DRS and UVvis data
are purely indicative and provide no real data on the size and
dispersion of the GNPs in the PI membranes, the membrane
cross sections were also investigated by TEM.
Transmission Electron Microscopy. The TEM pictures of the
cross sections of the skin layers and the porous substructures
of the membranes are given in Figures 69. In Figures 6 and 8,
the top of the membrane is shown, with the skin layer slowly
blending into the substructure toward the bottom of the photo.
For both methods, the mean particle size is around 35 nm,
depending on the gold content of the membrane. There is one
clear difference between the IRS and PRE membranes, namely, in
the aggregation of the GNPs. In the ISR membranes, hardly any
aggregation of GNPs is visible neither in the top layer nor in the
substructure, at any concentration of gold. In the PRE membranes, clustering of GNPs occurs both in the skin layer and the
substructure. The aggregation is moderate at the lowest GNP
Table 2. Maximum Absorption Wavelengths Obtained in
DRS and UVVis Spectroscopy for GNP Containing PI
Membranes Prepared by PRE and ISR Methods
membrane
DRS wavelength [nm]
UVvis wavelength [nm]
ISR-1
556
556
ISR-2
556
556
ISR-3
555
555
ISR-4
562
562
PRE-1
533
533
PRE-2
545
545
PRE-3
552
552
PRE-4
558
558
the GNPs and on the dielectric environment.29,3537,56,57 For
GNPs, the resonance wavelength will generally be at 520 nm or
higher. The two preparation methods have a different influence
on the GNP size and dispersion in the membrane and will thus
affect the SPR behavior differently.
Spectroscopy Measurements. To estimate the dispersion and
aggregation of the GNPs in the membrane, DRS and UVvis
spectra were obtained. Since DRS is a surface characterization
technique, these measurements will give information solely on
the GNPs found in the top layer of the membrane, near the
surface. To obtain information on the GNPs found in the entire
membrane, a piece of each membrane was redissolved in DMA
and analyzed by UVvis spectroscopy. The wavelength where
the maximal absorbance is found is given in Table 2.
For the ISR membranes, the SPR wavelength found by DRS
was stable for 13 wt % gold and increased slightly for 4 wt % gold.
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Figure 6. TEM pictures and particle size distributions of the GNPs in
the skin layer of ISR membranes containing 14 wt % GNPs.
Figure 7. TEM pictures and particle size distributions of the GNPs in
the porous substructure of ISR membranes containing 14 wt % GNPs.
concentration but aggregates at the higher concentrations. In
membranes PRE-3 and PRE-4, the GNP clusters are dominant,
and there are hardly any well-dispersed particles visible. These
results are in accordance with literature, also indicating that the
in situ synthesis methods often lead to a better dispersion and less
aggregation of the GNPs compared to the use of presynthesized
GNPs.4,6
For the ISR membranes, the amount of GNPs in the top layer
was higher than in the substructure. This is probably due to
size restrictions in the denser top layer, where the GNPs would
remain smaller and did not have the chance to grow closely together. In the more porous substructure, the GNPs have room to
grow larger. Since gold nanoparticles are visibly present in the
entire cross section of the membrane, it may be assumed that the
NaBH4 reducing agent was able to penetrate into the entire bulk
of the membrane.
These TEM data provide an explanation for the spectroscopic
data mentioned above. In the skin layer of ISR membranes, the
mean particle diameter is 3 nm for ISR-1 to ISR-3, rising to 5 nm
in ISR-4. The DRS data, giving information on the membrane
surface and thus mostly on the skin layer, clearly reflect this; the
SPR wavelengths remains stable for ISR-1 to ISR-3, slightly rising
for ISR-4. In the substructure of ISR membranes, the 3 nm
particles are still present, but many larger particles are also visible.
Since the UVvis data were taken for redissolved membranes,
these larger particles are also taken into account. The amount of
larger particles rises at higher gold concentration, and this is
reflected in the rise of the SPR wavelength for the higher gold
concentrations. The systematically higher wavelengths observed
in DRS compared to the UVvis data may be due to the difference in environment: the solid PI versus the DMA solution.
The UVvis data seem to better reflect the size range of the
GNPs, since 35 nm GNPs in solution have been indicated to
have wavelengths around 530 nm.18,58
SPR wavelengths obtained for membranes containing increasing gold concentrations are higher, especially for PRE-3 and
PRE-4. This is caused by the increasing aggregation of the GNPs
that is abundantly clear on the TEM pictures. The TEM pictures
also indicate that the lower DRS wavelengths obtained for PRE
compared to ISR membranes may not be interpreted as an indication of smaller GNPs, since the mean particle size is 3 nm in
both cases. However, this difference in wavelength more probably reflects the difference in immediate environment of the
GNPs, that are protected by PVP in the PRE membranes and by
PI in the ISR membranes.
Overall, the TEM pictures prove that higher gold contents in
the membranes lead to broader particle size distributions but that
the mean particle size remains constant up to 3 wt % gold, regardless the incorporation method. It also shows that the presynthesized GNPs are more prone to aggregation, as was expected
from literature.4,6 During the PRE membrane synthesis, there
are many steps in which this aggregation may occur, for example,
while adding the polymer to the GNP solution, or during the
casting and solidification of the membrane. These TEM images
indicate that, even though PVP blends well with PI, it did not improve the dispersion of GNPs in the PI membranes. It is possible
that, while the PI was added to the GNP solution, the increasing
viscosity resulted in an entanglement of the GNPs between the
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(520 nm) visible in the top 500 nm of the membrane PRE-1
and larger pores (50100 nm) in PRE-2 to PRE-4. In the ISR
membranes, a denser top layer is seen, which may partially be a
result of the higher viscosity in the casting solution, induced by
the addition of the gold salt. A higher viscosity in the casting
solution will generally lead to a denser membrane top layer due
to a delayed demixing in the phase inversion synthesis process.46
Influence of Gold on Membrane Filtration Performance.
Due to the changes in membrane morphology, the gold content
should also have an influence on the membrane performance,
even in absence of laser irradiation. This was studied by carrying
out IPA and ethanol filtrations with dyes rose bengal (1017 Da)
and methyl orange (324 Da). The permeance and rejection
for the ISR membranes and the PRE membranes are given in
Figure 10.
For the ISR membranes, an overall slight increase in membrane permeance was found for higher gold contents. In IPA, the
rejection of both dyes was higher than 95%, and the rejection did
not depend on the gold content of the membrane. In ethanol,
however, the permeances were higher than in IPA and the rejection lowered somewhat. For the PRE membranes, the permeance
depends strongly on the gold content in the membrane, showing
an overall decrease at increasing gold content. This seems to
contradict the increasing porosity clearly seen on the TEM
pictures in the top layer. An explanation may be that the very
thin (∼nm) skin layer of these membranes is still very dense, thus
resulting in such a low permeance. It is commonly supposed that
this skin layer has the largest influence on the membrane separation performance. However, it is expected to be only a couple
of nanometers thick and cannot be differentiated on the SEM
or TEM pictures. Similar to the ISR membranes, there was no
strong influence on the rejection in the case of the isopropanol
filtrations for the PRE membranes.
At the lower gold content, the permeance was higher for PRE
membranes than for ISR membranes, which is in accordance with
the TEM pictures showing a higher porosity in the skin layer
for the PRE membranes. At the higher gold contents, ISR-3 and
ISR-4 had higher permeances compared to PRE-3 and PRE-4,
which again seems to contradict the very high porosity seen on
TEM pictures for the latter. For both methods, it is clear that the
incorporation of GNPs and the method used to do so has a strong
influence on the membrane structure and performance. The
method of incorporation also has a clear effect on the GNP
size and dispersion in the membrane matrix and on their SPR
wavelength.
Effect of Light-Induced Local Photothermal Heating of
Membrane on Filtration Behavior. The effect of plasmonic
heating of the GNPs in the membranes on the membrane performance was finally tested as a possible application for these
membranes.
Dead-end filtrations of methyl orange in ethanol were repeated for the PRE and ISR membranes under laser irradiation.
The laser irradiation of the GNPs induces plasmonic heating
inside the membrane matrix. As our previous studies has indicated, this local heating of the membrane can have a positive
effect on the membrane permeance without affecting the membrane selectivity.26,27 The performance under laser irradiation
was compared to the original performance of the membranes in
Figure 11.
For both the ISR and the PRE membranes, the IRR in permeance induced by plasmonic heating increased at higher gold
contents. The absolute differences in permeance are similar for
Figure 8. TEM pictures and particle size distributions of the GNPs in
the skin layers of PRE membranes containing 14 wt % GNPs.
Figure 9. TEM pictures of the porous substructure of PRE membranes
containing 14 wt % GNPs. No accurate size distributions of the GNPs
could be measured due to the strong aggregation.
PI chains, preventing a good dispersion of the GNPs in the
casting solution.
The effect of PVP as a pore-former on the membrane structure
was also visualized on the TEM pictures. There are small pores
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Figure 10. Isopropanol and ethanol permeance and rejection of dyes rose bengal and methyl orange for membranes prepared by ISR (A) and PRE (B).
Figure 12. Temperature increase upon laser irradiation for a PI
reference membrane and GNP containing ISR and PRE PI membranes
wetted by ethanol (ambient temperature 20 °C).
Figure 11. Irradiation improvement factors for permeance and rejection of ethanol + methyl orange mixtures obtained by laser irradiation for
PRE and ISR membranes.
followed by the increasing percentual difference in permeance.
However, for both methods, the temperature stabilizes at 3 wt %
of gold, which is not reflected in the filtration results. Higher
temperatures are obtained for the ISR membranes compared to
the PRE membranes, which is probably due to the problems with
aggregation in the PRE membranes, diminishing the photothermal effect of the GNPs. However, this difference in temperature
is not reflected in the filtration data. It should be kept in mind that
the heating experiments were carried out in a static system, while
during the filtrations there is heat dissipation to a flowing solvent stream involved, leading to a more complicated mass and
heat transfer process. During filtrations, the heat produced by the
both methods. The rejection is in neither case affected by the
laser irradiation, and the differences fall within the expected
experimental error. This also indicates that there was no unwanted influence of the laser heating on the membrane material,
such as melting. In previous works, it was already shown that no
defects were induced by heating the GNP containing membranes
at low laser intensities, since the membrane performance returned to the original state after turning off the laser.26,27
When these data are compared to the measured temperature
increase in the ethanol-wetted membrane under laser irradiation (Figure 12), it is clear that the rising temperature trend is
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Figure 13. Combined data taken from this study ()), reference 26 () and reference 60 (() comparing the conventional and laser-irradiated
permeance and rejection for different GNP containing membranes in filtrations of IPA and ethanol dye solutions.
GNPs inside the membrane is dissipated in the medium, including the permeating solvent. It was shown previously that the
permeating solvent may have a cooling effect, the extent of which
depends on the intrinsic permeability of the membrane.27 Since
the ISR membranes at the higher gold contents have a higher
intrinsic ethanol flux than the PRE membranes (see Figure 10),
the solvent cooling effect will be stronger. If the solvent cooling
effect is large enough, it may result in a lower IIF (Figure 11) even
though these membranes reached higher temperatures under static
conditions. To fully comprehend the mechanism involving the flux
increase by plasmonic heating, more data should still be collected.
The continuous green argon laser beam used in these experiments emits light at wavelength of 514 nm, which is lower than
the actual surface plasmon wavelength of the GNPs (see Table 1)
but close enough to expect a heating effect. Also, the illuminated
membrane surface was only 40% of the active membrane surface.
Due to both these parameters, the experiments were carried out
at a suboptimal level, and even stronger increases in permeance
can be expected when the laser is at the exact SPR wavelength
and when the membrane is illuminated entirely. Also, some
losses in laser intensity are expected when the laser beam travels
through the dye feeds, for example, due to reflection by impurities. In upscaled filtration units, the light should be transferred
to the membrane more efficiently, for example, by use of optical
fibers incorporated into the membrane support.
In Figure 13, the new data are combined with the previously
obtained data.26,27 The added dashed line indicates the 1:1 data,
where the irradiated permeance and rejection are equal to the
nonirradiated results. It is clear that, while the rejection data fluctuate
around this 1:1 line, the permeance data are consistently above this
line. This confirms that overall rejections are not significantly influenced by the irradiation while permeances are always increased. To
increase fluxes of a given membrane without lowering its selectivity
is a highly desired but rarely found effect in membrane technology.27
’ CONCLUSIONS
Two methods to prepare GNP containing polymeric solids
were compared, namely, the incorporation of preformed PVPprotected GNPs into a PI membrane and the in situ synthesis
of GNPs inside a PI membrane matrix. In both cases, GNPs
are obtained with an average size of 3 nm in the top layer of the
membrane. However, there is a clear difference in the membrane
behavior and the GNP distribution. When preformed GNPs are
used, the excess of PVP in the casting solution induces a higher
porosity in the membrane, and the GNPs are more prone to
aggregation. It is possible that PVP is not the optimal GNP
stabilizer during the specific PI membrane synthesis procedure
reported here. When the GNPs are synthesized in situ, the GNPs
are dispersed very well, with smaller nanoparticles formed in the
dense top layer of the membrane and larger nanoparticles in the
porous sub layer, where more space is available. The better
dispersion also resulted in a stronger heating of the composite
material upon laser irradiation.
The permeance of GNP containing PI membranes in SRNF
could thus be increased by plasmonic heating of the GNPs in the
membrane by means of a green argon ion laser. Higher IIFs were
found for higher gold contents, regardless the synthesis method.
The aggregation of the preformed PVP-protected GNPs in the
membrane unexpectedly did not have a large influence on the
photothermal filtration behavior of the membranes. These data
further confirm that localized photothermal heating of a membrane during a filtration process can significantly enhance the
separation, by inducing an increased permeance without lowering rejections, a most remarkable combination. The GNP containing PI membranes may also be used for other applications,
such as combined catalysis and membrane separation processes.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: ; fax: 32 1632 1998;
phone: 32 1632 1549.
’ ACKNOWLEDGMENT
K.V. acknowledges the Fund of Scientific Research Flanders
(FWO-Vlaanderen) for financial support as a research assistant.
This research was done in the framework of an I.A.P.-PAI grant
(IAP 6/27) sponsored by the Belgian Federal Government,
of a GOA grant from K.U. Leuven and of long-term structural
fundingMethusalem funding by the Flemish Government.
Professor J. Billen of the Laboratory for Entomology of K.U.
Leuven, Leuven, Belgium, is kindly acknowledged for assisting
with TEM measurements.
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