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Controlled synthesis of nanoparticles with desired geometries can provide a direct approach for the
formation of nanomaterials with tuneable size/shape-dependent characteristics, vastly expanding their
range of applications in catalysis, electronics and optics, biology and medicine. In this report, we
demonstrate the development of a microfluidics-based process for the direct synthesis (without seed-
mediated growth) of silver nanoprisms in a continuous flow format using a flow focusing microreactor,
coupled with UV-Vis-NIR spectroscopy for real time monitoring of optical properties of the produced
nanoprisms. By adjusting microfluidic conditions, the nanomaterial's absorbance spectral position and
peak broadness can be fine-tuned. TEM analysis of the produced nanoparticles quantitatively correlates
Received 11th July 2013
Accepted 23rd September 2013
the characteristics of absorbance spectra with the shape/geometry of nanoparticles. Furthermore, faster
kinetics for the formation of nanoparticles has been observed in the microreactor compared to those in
DOI: 10.1039/c3tc31335b
traditional batch reactors, and the microreactor's capability of synthesising homogenous nanoparticles
www.rsc.org/MaterialsC over a prolonged operation time is demonstrated.
7540 | J. Mater. Chem. C, 2013, 1, 7540–7546 This journal is ª The Royal Society of Chemistry 2013
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faster mixing31,33 and control over heat exchange32,41,42 which peruorooctylsilane were supplied by Sigma-Aldrich (UK). Iso-
lead to the production of highly mono-disperse isotropic propanol and hydrogen peroxide were purchased from Fisher
particles (i.e. spheres). Particle analysis has shown that the Scientic (UK). Sodium borohydride was obtained from Acros
dimensional standard deviation of metal nanoparticles Organic (Belgium). Polydimethylsiloxane (PDMS) monomer
produced with microuidics is reduced by approximately 20% Sylgar 184 and curing agents were purchased from Dow Corning
compared to batch systems.31,33 It has been suggested that more (USA), and SU-8 photoresist was obtained from Chestech (UK).
homogenous diffusion of the reagents obtained inside the
microreactor grants more uniform and efficient nucleation,
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which is crucial for the subsequent growth phase, leading to a 2.2 Microreactor fabrication
narrower distribution in both particle size and shape. A hybrid PDMS-glass microreactor was fabricated for the
However, the production of anisotropic materials represents synthesis of silver nanoparticles. Firstly, an SU-8 mold with the
an additional challenge, which is commonly tackled by the use designed microchannel pattern, consisting of three inlets and
of specic ligands for selectively blocking the growth of some one reaction channel, was prepared following the standard
faces of the growing crystal.42,43 Due to the precise control procedure provided by Microchem.57 Subsequently, the mold
required over nucleation and growth steps, a seed-mediated was covered with a layer of a 10 : 1 (w/w) PDMS precursor and
approach is usually employed in order to bypass the nucleation curing agent mixture and heated for 1 h at 80 C for the polymer
step and to simplify the overall procedure.44,45 Among aniso- to cure. The PDMS sheet with the microchannel architecture
tropic particles studied, triangular prisms46 have recently fabricated on the surface was then removed from the mold and
attracted the interest of researchers in view of their wide range permanently bonded to a glass slide aer oxidizing its surface
of applications (such as surface enhanced Raman scattering or with a plasma treatment. The reaction microchannel had
SERS, and optical lters).47–49 In general, size control in batch dimensions of 150 mm 50 mm 3 cm (width depth
synthesis can be achieved by photo-irradiation mediated length). The angle between the lateral feeding channels and the
assembly,50 through changing the concentration of the reducing central channel was 30 , as illustrated in Fig. 1.
agent NaBH4 whilst keeping the concentrations of the other Following the bonding of the PDMS sheet to the glass layer,
reagents constant,51 or by adding halide ions (Cl and Br) to the channel wall was functionalized with a solution of tri-
nely tune their size and shape.52 Alternatively, a seed-mediated chloro(1H,1H,2H,2H)-peruorooctylsilane (5% v/v in dime-
approach can be used to exert control over the nal absorption thylformamide) to make the channel surface hydrophobic in
of silver nanoprisms; by changing the concentration of the seed order to reduce the interaction between silver cations and
different sizes of prisms can be achieved.53 This approach has hydroxyl groups on the glass surface. Notably, other protocols
been successfully implemented with ow reactors54,55 where usually employed to reduce fouling,33 such as increasing the
effects similar to those observed in the batch synthesis on the
optical properties of silver nanoprisms can be achieved.
Although the seed mediated approach is the most widely used
to prepare silver nanoprisms in microreactors, the combination
of microstructured reactors and efficient LED illumination has
also been successfully applied for synthesising nanoprisms of
enhanced homogeneity.56
Here we demonstrate the development of a microuidics-
based process for the direct synthesis (i.e. without seed-medi-
ated growth) of silver nanoprisms in a continuous ow format
using a ow focusing microreactor, coupled with UV-Vis-NIR
spectroscopy for real time monitoring of optical properties of
the produced nanoprisms. The spectral position of the
maximum absorbance peak (lmax) and the full width at half
maximum (FWHM) of the in-plane dipole surface plasmon
resonance can be tuned by varying major microuidic param-
eters only, namely the ow rate ratio (R) and total ow rate (Vtot).
The single device setup is greatly simplifying the synthesis of
silver nanoprisms with controlled optical properties without
changing the concentrations of the feed solutions.
2 Experimental section
2.1 Reagents
Fig. 1 (a) Schematic of the experimental setup showing the microreactor layout
All chemicals were of analytical grade and were used as received and the process monitoring systems. (b) Microphotograph of the microreactor
from their respective suppliers. Trisodium citrate dihydrate, flow focusing configuration with three co-flowing streams. Liquid–liquid inter-
silver nitrate, dimethylformamide and trichloro(1H,1H,2H,2H)- faces due to different fluid optical properties can be seen.
This journal is ª The Royal Society of Chemistry 2013 J. Mater. Chem. C, 2013, 1, 7540–7546 | 7541
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total ow rate (Vtot) or increasing the pH of the solution, proved 400 mesh grids), and imaging at an acceleration potential of
to be ineffective for our systems. 120 kV.
was rapidly injected into a water solution of AgNO3, trisodium solution of AgNO3 (36 mM), TSCD (6.5 mM) and H2O2 (76 mM)
citrate dihydrate (TSCD, capping agent) and H2O2 (oxidizing was injected into C1 at a selected volumetric ow rate V1, while
agent), resulting in the production of triangular nanoprisms. NaBH4 (3.6 mM) was injected through C3 at a ow rate V3. Water
For the microuidic system, a basic isopropanolic solution of owing in the central channel at a ow rate V2 was anked by
NaBH4 was employed as a reducing agent instead of the the inorganic precursor (AgNO3) on one side and the reducing
conventional aqueous solution in order to reduce H2 develop- agent (NaBH4) on the other side (as detailed in the Experimental
ment in solution due to spontaneous degradation of NaBH4 section). The total inlet ow rate (Vtot ¼ V1 + V2 + V3) was
in H2O. operated in the range of 2.41–3.41 mL h1. With this setting, it
The protocol for solution preparation followed that was observed that a stable ow focusing was achieved within the
described by Shalom et al.58 Briey, 1 mL of a 0.01 M solution of main reaction channel, and the use of water as the central
sodium borohydride (prepared by dissolving 0.038 g of NaBH4 “spacer” stream effectively avoided the immediate clogging of
in 70 mL of MilliQ H2O and 30 mL of 1 M NaOH) was added to the channel (Fig. 1b). By varying the lateral inlet ow, the
32 mL of a 0.1 M isopropanolic solution of NaBH4. The pH of chemical composition of the reaction system was adjusted as
the solution was adjusted by varying the amount of NaOH used desired.
for the NaBH4 solution. Notably, a higher pH resulted in the Fig. 2a shows the absorbance spectra of the silver nano-
production of solely nanospheres or a complete impairment of prisms obtained with the inline UV-Vis-NIR spectrophotometer
the nanoprecipitation process (i.e., no particles formed in this under different ow conditions, with R ranging from 0.41 to
case, see ESI†). Solutions were freshly prepared before each 0.58; R represents the ow rate ratio of the central ow over the
experiment. total ow rate (V2/Vtot), with a constant central ow rate (V2) at
In the microuidic reactor system, the two solutions were 1.41 mL h1. These ow conditions were selected for the
injected through the lateral channels (inlet C1 for AgNO3, TSCD concentration of reagents inside the microreactor to reect the
and H2O2, and inlet C3 for NaBH4, Fig. 1) by means of syringe chemical conditions employed in the batch experiments by
pumps. Additionally, MilliQ H2O was injected through inlet C2 Mirkin et al.51 As can be seen from Fig. 2a, all six spectra show a
in order to (a) dilute the two solutions from C1 and C3 to the single maximum absorbance peak which shis from 690 nm to
desired concentration level, and (b) act as a spacer between the 796 nm, with increasing R from 0.41 to 0.54. It should be noted
two solution streams containing the reactants as they would that a small peak at an identical position of 340 nm appears in
otherwise react rapidly at the focused interface resulting in all spectra, which may be attributed to the out-of-plane
clogging or fouling at the channel junction. PTFE tubes with an quadruple resonance effect which is signicantly weaker than
internal diameter of 750 mm were used for connecting the the main absorbance band due to the in-plane dipole surface
feeding syringes to the reactor inlets, and for transferring the plasmon resonance.59
product colloid from the reactor outlet to a ow cell for inline Previous studies have suggested that the in-plane dipole
absorbance measurements. resonance is a good indicator of general nanoprism geometries.
The microreactor was placed on an inverted microscope Its redshi, particularly, is correlated with increased edge
(Olympus IX70) stage with a CCD camera (QICAM Fast, Qimage, length.51,60 The results shown in Fig. 2 suggest that, by adjusting
Canada) coupled to the microscope (Fig. 1). This allowed a the ow conditions, different sizes of nanoprisms can be
direct in situ monitoring of the uidic behavior within micro-
channels, especially if clogging and/or fouling of the channel
occurred. Both microuidic and batch experiments were per-
formed at room temperature and in the dark to avoid sponta-
neous photo reduction of AgNO3.
7542 | J. Mater. Chem. C, 2013, 1, 7540–7546 This journal is ª The Royal Society of Chemistry 2013
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obtained. Fig. 2b shows an example TEM image of nano- response is in good agreement with that observed by Shuford
particles obtained through the microreactor synthesis, showing et al.,63 who found that the absorbance band position of
equilateral triangular platelets with rounded tips. nanoprisms is proportional to the prism edge length (d) and
It is generally understood that the process of silver nano- inversely proportional to the prism thickness (T), as represented
prism formation involves two steps including (i) the reduction by eqn (1).63
of AgNO3 by NaBH4 to form and grow silver seeds in the pres-
d
ence of the stabilizing agent TSCD, and (ii) the chemical lmax ¼ 33:8 þ 418 (1)
T
oxidation of Ag(0) induced by hydrogen peroxide to etch the
Published on 25 September 2013. Downloaded by North Dakota State University on 22/10/2014 00:25:30.
silver nanoparticles formed. With the selective adsorption of Using eqn (1) with the prism edge lengths obtained (Fig. 3a),
citrate ions on the (111) surface of Ag seeds, the most stable the prism thickness was calculated. It was found that the
shape of prisms (or triangular platelets) in solution is ach- minimum average thickness of prisms was 2.3 nm when d ¼ 18
ieved,51,61,62 which is largely attributed to the kinetic factors of nm, and the maximum was 3.6 nm when d ¼ 46 nm. This
the fast growth along the planar twinning defects.53 Previous suggests that the shi of the spectral position shown in Fig. 2a
studies with a traditional batch synthesis method showed that is largely due to the increase in prism edge length (156% max
the growth phase took approximately 30 min or 5 min in the increase) with smaller changes in their thickness (56.5% max
presence or absence of the stabilizer poly(vinylpyrrolidone), increase).
respectively.51 In our microuidic approach, the residence time Fig. 3b shows the percentage of nanoprisms in whole
of reagents within the reaction channel was in the range of samples and their absorbance band FWHM at different ow
0.23–0.34 s under the ow conditions described above, indi- rate ratios (R). It shows that both the percentage of nano-
cating a signicant increase in the reaction kinetics due to prisms and FWHM are signicantly inuenced by the ow
faster mixing compared to bulk reactions.29,36 conditions. In the operational R range, the percentage of
nanoprisms initially increases with increasing R, reaching a
3.2 TEM image analysis maximal percentage of 92% at R ¼ 0.47, and then decreases
when R > 0.47. At the same time, the change in absorbance
To identify and quantify the type of silver nanoprism produced
band FWHM shows an opposite trend, initially decreasing with
under ow conditions described above, analysis of TEM images
increasing R, reaching a minimum FWHM of 360 nm at R ¼
was carried out by using an in house developed Matlab program
0.47, and then increasing when R > 0.47. As the absorbance
for quantitative geometry characterisation in order to further
spectral position and its broadness depend on the size and
correlate the NPs' geometries with the exhibited optical char-
shape distribution of the nanoparticles, the results demon-
acteristics. Specically, by discriminating particles by their
strate the capability of the microreactor for the controllable
shape, the edge length of triangular prisms and their
production of nanomaterials by adjusting microuidic opera-
percentage in the whole particle sample were calculated, as
tional parameters.
detailed in the Experimental section. Representative TEM
As described above, the results shown in Fig. 2 were obtained
images are shown in Fig. 2b and S5 (ESI†). Image analysis
at variable ow rate ratios. R was varied by changing the ow
results are illustrated in Fig. 3 for nanoprisms' average edge
rates of two lateral streams while keeping the central ow rate
length (Fig. 3a) and percentage (Fig. 3b) at different ow rate
constant. This resulted in both the ow rate ratio R and total
ratios; the percentage is related to the overall particle compo-
ow rate Vtot change simultaneously; the higher R, the lower
sition including spheres and other geometries. The corre-
Vtot. Within the continuous ow reaction channel, the change of
sponding absorbance band position and FWHM at different
R altered the width of ow streams and consequently the
ow rate ratios are also plotted for correlation.
chemical composition in the microenvironment where nano-
Fig. 3a shows a growth of the prism edge length from 18 nm
particles formed and grew. At the same time, Vtot determined
to 46 nm with increasing R from 0.41 to 0.58, following an
the overall residence time (RT) of reactants passing through the
approximately linear relationship. Notably, the absorbance
whole reaction channel volume (V), RT ¼ V/Vtot. In the micro-
band position shis following a similar linear trend. This
uidic reactor system, both mixing and reagents' concentration
correlation of nanoprisms' geometries with their optical
proles are dynamic, and the synergistic effect of R and Vtot add
extra dimensions to the complexity of the system. Therefore, it
was necessary to further examine the effect of individual uidic
parameters.
This journal is ª The Royal Society of Chemistry 2013 J. Mater. Chem. C, 2013, 1, 7540–7546 | 7543
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7544 | J. Mater. Chem. C, 2013, 1, 7540–7546 This journal is ª The Royal Society of Chemistry 2013
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This journal is ª The Royal Society of Chemistry 2013 J. Mater. Chem. C, 2013, 1, 7540–7546 | 7545
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7546 | J. Mater. Chem. C, 2013, 1, 7540–7546 This journal is ª The Royal Society of Chemistry 2013