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Chemical Engineering and Processing 102 (2016) 186–193

Contents lists available at ScienceDirect

Chemical Engineering and Processing:


Process Intensification
journal homepage: www.elsevier.com/locate/cep

Droplet synthesis of silver nanoparticles by a microfluidic device


Lei Xua,b,* , Jinhui Penga , Mi Yanc , Di Zhangb , Amy Q. Shenb,d,**
a
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Faculty of Metallurgical and Energy Engineering, Kunming University of
Science and Technology, Kunming 650093, PR China
b
Mechanical Engineering, University of Washington, Seattle, WA 98195, USA
c
Faculty of Mathematical and Physical Sciences, University College London, London WC1E 6BT, UK
d
Micro/Bio/Nanofluidics Unit, Okinawa Institute of Science and Technology Graduate University, Okinawa 904-0495, Japan

A R T I C L E I N F O A B S T R A C T

Article history: Silver nanoparticles are synthesized by the reduction of metal salt solutions from sodium borohydride in
Received 16 May 2015 a microfluidic chip. The influence of different operating conditions on silver particle diameter,
Received in revised form 21 January 2016 morphology, size distribution, and elemental compositions has been investigated. The results
Accepted 24 January 2016
demonstrated that ethylenediaminetetraacetic acid (EDTA) serving as a complexant significantly
Available online 27 January 2016
affected the particle size of synthesized silver nanoparticles. An increase in the silver nanoparticle mean
diameter was observed with decreasing NaBH4/AgNO3 molar concentration ratios, and increasing fluid
Keywords:
flow rates.
Silver nanoparticles
Microfluidics
ã 2016 Elsevier B.V. All rights reserved.
Droplet synthesis
Reduction method

1. Introduction [18]. The lack of precise control of batch synthesis gives rise to a
larger variation in the final crystal structure, size distribution, and
The synthesis of noble-metal nanoparticles has been an active particle size polydispersity [19,20].
research area because noble-metal nanoparticles exhibit intrigu- These performance parameters can be significantly improved
ing physical and chemical properties, which have found applica- by introducing sufficient mixing and rapid mass transfer during
tions in photovoltaic technology, catalysis, information storage, aqueous reduction process, which in turn can control both the
optoelectronics, biomedicine, and environmental technology physical and chemical properties of Ag nanoparticles.
[1–5]. In particular, silver (Ag) nanocrystals have been extensively Microreactors have recently attracted much attention due to
studied due to their excellent performance in a broad range of their high heat and mass transfer rates over batch reactors, as well
applications including metal-enhanced fluorescence, localized as easier control of experimental conditions such as residence
surface-enhanced Raman scattering (SERS), surface plasmon time, temperature, pressure, and flow rates [16]. Precise manipu-
resonance (LSPR), imaging, sensing, catalysis, and antimicrobial lation of experimental conditions to synthesize Ag nanoparticles
technology [6–11]. There are many established chemical processes can be achieved by rapid mixing of reactants and precise control of
for synthesizing Ag nanoparticles with different shapes, such as reagent concentrations inside a microreactor [20,21]. For example,
rod/wire, sphere, bipyramid, bar, decahedron, and cube with a Zhao et al. [21] reported that microfluidic reactors could control
pentagonal cross section [1,2,12–15]. Several research groups the reaction more precisely than bulk batch reactors with
demonstrated that the aqueous chemical reduction method was improved mixing and mass transfer performance. Compared to
efficient and has been widely used in the synthesis of nano- bulk batch reactors, continuous flow microreactors can generate
materials owing to its low cost, limited equipment requirements, nanoparticles with smaller mean particle sizes and narrower
high yield, simple operation, and ease of control [16,17]. However, particle size distributions. Ju et al. [22] reported continuous
conventional reduction method for batch synthesis involves the synthesis of zeolite NaA in a microchannel reactor. It took 1/10 of
atom-by-atom particle growth by using the precipitation process the crystallization time needed in the batch system to synthesize
zeolite NaA in the microchannel reactor. In particular, zeolite NaA
synthesized in the microchannel reactor also had smaller mean
particle sizes with narrower particle size distributions than those
* Corresponding author. Fax: +86 871 65138997.
** Corresponding author.
produced in the batch synthesis. Moreover, Xu et al. [23] enhanced
E-mail addresses: xulei_kmust@aliyun.com (L. Xu), amy.shen@oist.jp mass transfer performance of liquid–liquid system by microfluidic
(A.Q. Shen). droplet flows, reducing the mass transfer time from 4.0 s to 0.4 s

http://dx.doi.org/10.1016/j.cep.2016.01.017
0255-2701/ ã 2016 Elsevier B.V. All rights reserved.
L. Xu et al. / Chemical Engineering and Processing 102 (2016) 186–193 187

with the average droplet diameter ranging from 550 mm to polydimethylsiloxane (PDMS) and a curing agent were purchased
130 mm; and mass transfer rates were 10–1000 times higher from Dow Corning Co. (Midland, MI).
compared with that of the traditional liquid–liquid systems.
Similar microreactors have also been adopted to synthesize a 2.2. Fabrication of microfluidic devices
wide range of nanomaterials [24–27]. In addition, continuous
synthesis or droplet synthesis by utilizing microreactors provides Soft lithography techniques were employed to fabricate PDMS
improved homogeneity of reaction solutions and yields more microfluidic devices [32]. The PDMS prepolymer and the curing
uniform products [19,20,28–31]. agent were mixed in a 10:1 ratio (v/v), and poured onto a silicon
In this work, silver (Ag) nanoparticles were synthesized by the wafer patterned with SU-8 photoresist. The sample was then
reduction of aqueous metal salt solutions, with sodium borohy- degassed in a desiccator for an hour, and the PDMS mixture was
dride (NaBH4) serving as the reduction agent, in a microfluidic baked for 2 h at 65  C in an oven. The PDMS replica was bonded
device. The general chemical reaction to produce Ag nanoparticles with the glass slide with oxygen plasma treatment, and left in an
is based on reaction equation below [20]. oven at 65  C for 2 days prior to experiments.
1 1
AgNO3 þ NaBH4 ! Ag þ H2 þ B2 H6 þ NaNO3 ð1Þ 2.3. Synthesis of silver nanoparticles
2 2
We used water soluble polymer polyvinylpyrrolidone (PVP) to The flowchart of the experimental process is shown in Fig. 1.
stabilize Ag nanoparticles generated by the aqueous reduction Prior to carrying out the experiments different concentrations of
method [15,20]. We also systematically investigated the influence AgNO3 solution (see Table 1) and 0.01 M NaBH4 solution were
of different operation parameters on the size, shape, and mixed at room temperature, with argon gas being bubbled through
morphology of Ag nanoparticles. both solutions for 30 min. A small amount (2–3 ml) of complexant
(either ammonium hydroxide solution (NH4OH at 28.0–30.0 wt%)
2. Experimental method or EDTA) was added to the AgNO3 solution. The PVP at a
concentration of 3.0 g/l was added to the AgNO3 complex solution
2.1. Materials as a dispersant. The pH value of the AgNO3complex solution and
NaBH4 solution was adjusted to 10–12 by using NaOH solutions,
Silver nitrate (AgNO3, purity 99%), sodium borohydride (NaBH4, respectively.
purity 99%), polyvinylpyrrolidone (PVP, average Mw = 360,000), A microfluidic chip was used to produce Ag nanoparticles (see
ammonium hydroxide (NH4OH, 28.0–30.0%), ethylenediaminete- Fig. 2). The length, width, and height of the channel are 10 mm,
traacetic acid (EDTA, purity 99%), and sodium hydroxide (NaOH, 200 mm and 50 mm, respectively. Two aqueous solutions flew into
purity 99%) were purchased from Sigma–Aldrich (St. Louis, MO, a co-flowing oil stream, which formed segmented droplets with
USA). Sylgard 184 silicone elastomer kits including proper flow rates of the three streams. The oil stream consists of

Fig. 1. Flowchart of Ag nanoparticles synthesis and characterization processes.


188 L. Xu et al. / Chemical Engineering and Processing 102 (2016) 186–193

Table 1
Processing conditions of silver nanoparticles.

Sample Metal salt Reducing agent Surfactant Complexant Flow rate


1 0.001 M AgNO3 0.01 M NaBH4 3.0 g/l PVP – 10 ml/h
2 0.001 M AgNO3 0.01 M NaBH4 3.0 g/l PVP NH4OH 10 ml/h
3 0.001 M AgNO3 0.01 M NaBH4 3.0 g/l PVP EDTA 10 ml/h
4 0.0025 M AgNO3 0.01 M NaBH4 3.0 g/l PVP EDTA 10 ml/h
5 0.0025 M AgNO3 0.01 M NaBH4 3.0 g/l PVP EDTA 20 ml/h
6 0.0025 M AgNO3 0.01 M NaBH4 3.0 g/l PVP EDTA 30 ml/h

Fig. 2. Schematics of the synthesis process of silver nanoparticles by using a microfluidic chip at room temperature. The width and the height of the channel are 200 mm and
50 mm, respectively.

mineral oil with the surfactant Span 80 (3% w/v), which acts as a elemental compositions were analyzed with different operating
continuous phase. Surfactant Span 80 was used to reduce conditions. To assess the effect of complexant on the final
interfacial tension between the oil and aqueous phases to reduce characteristics of Ag in the process of aqueous reduction reaction,
coalescence of droplets in the microchannel. The microfluidic NH4OH and EDTA were used as a complexant in the experiment.
synthesis was performed at room temperature (25  2  C). The Fig. 3 shows the size and morphology of the silver nanoparticles
complex solution AgNO3, the aqueous mixture containing NaBH4, synthesized by a microfluidic chip by using samples 1, 2, and 3 (see
and the mineral oil were pumped into the microchannel using Table 1), respectively, exhibiting different morphologies and
digitally controlled syringe pumps (PHD 2000 Infusion, Harvard particle size distributions. When the complexing agent was
Apparatus, USA). The experiments were conducted at different absent, silver nanoparticles were irregular with larger particle
flow rates ranging from 10 ml/h to 30 ml/h. The experimental size, and wide particle size distribution. The non-uniformity in the
conditions are listed in Table 1. size is evident from the particle size distribution, with the
estimated mean particle diameter being 13.2 nm (Fig. 3A and A0 ).
2.4. Material characterizations Comparing with sample 1 when NH4OH was added as a
complexant, silver nanoparticles remained irregular shaped.
The Ag nanoparticles size and morphology are characterized by However, the particle size decreased significantly, with the
using transmission electron microscopy (TEM, JEM-2100F, 200 kV, estimated mean particle diameter being 9.1 nm (Fig. 3B and B0 ).
JEOL). For TEM imaging, we deposited a suspension of droplet When EDTA was added as a complexant, silver nanoparticles
containing Ag nanoparticles on a copper-grid-supported, perforat- became mostly spherical, uniform in particle size, with good
ed, transparent carbon foil. Sample analysis was further conducted dispersion. The particle size distribution showed the mean
by using a XRD-7000S diffractometer (Shimadzu, Ltd., Kyoto, diameter of 4.9 nm (Fig. 3C and C0 ). Therefore, Fig. 3C shows that
Japan) ranging from 2u = 10 to 90.0 with a step of 0.050 under Cu the particle size is very small under the same scale. In addition, the
Ka radiation (l = 1.54060 Å). The UV–vis spectrometry was used to calculate of standard deviation is based on Eq. (2).
identify the silver nanoparticles and the average size of nano- vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u N
particles was estimated by using a spectrometer (UV-2450, u1X
SN ¼ t ðx  xÞ2 ð2Þ
SHIMADZU) which operated in the range of 300–700 nm with a N i¼1 i
resolution of 1 nm/s.
where S is the standard deviation, xi andxis the particle diameter
3. Results and discussion and mean particle diameter, respectively. Thus, the mean particle
diameter from Fig. 3A–C were estimated to be 13.2  4.3 nm,
By using droplet microfluidics, silver nanoparticles were 9.1  2.7 nm and 4.9  1.2 nm, respectively. Hence EDTA demon-
synthesized, and their size, size distribution, morphology, and strated to have a significant effect on the particle size of spherical
L. Xu et al. / Chemical Engineering and Processing 102 (2016) 186–193 189

Fig. 3. The TEM image (A–C) and the particle size distribution (A0 –C0 ) of the silver nanoparticles prepared by a microfluidic device by using samples 1, 2, and 3, respectively
(see Table 1).

silver nanoparticles synthesis. However, we are not able to 393 nm and 554 nm, while the LSPR band maximum in the UV–vis
elaborate on the particle morphology differences from Fig. 3. spectroscopy from samples 2 and 3 occurred at about 421 nm and
In batch processes, Kamat et al. obtained silver nanoparticles 407 nm, respectively. It was found that the surface plasmon
with particle size ranging between 35 nm and 50 nm [33]. Bright resonance absorption exhibited slight red-shift when NH4OH or
et al. claimed that all the Ag nanoparticles obtained by using EDTA EDTA was adopted as a complexant. In addition, compared with
had diameters less than 60 nm with the highest percentage less sample 3, the band of samples 1 and 2 is wider. The difference in
than 20 nm, and the mean major axis diameters was around 14 nm the shape of the plasma band suggested the change in particle size
[12]. While conducting experiments in batch reactor, particle size under different wavelengths [35,36]. These results implied that the
fell in the scale of 10–14 nm according to Mulfinger et al. [34]. In particle size distribution of samples 1 and 2 is broader, with
our work, the mean particle diameter as low as 5 nm could be different shaped Ag particles, evidenced by the TEM images and
achieved utilizing a microfluidic chip. the particle size distribution (Fig. 3). Patil et al. [20] reported that
Variations in size, shape, and elemental compositions of Ag higher the value of the peak width at half maximum, the more
nanoparticles prepared by microfluidics with different initial polydispersity in nanoparticles, which is in agreement with our
samples also affected their localized surface plasmon resonance present work.
(LSPR) absorption, which can be characterized by the UV–vis The crystal structure of silver nanoparticles was identified by
spectroscopy. The effect of complexant (NH4OH and EDTA) was XRD. Fig. 5 shows the XRD pattern of silver nanoparticles
depicted in Fig. 4. Sample 1 has two LSPR absorption peaks at synthesized by a microfluidic device of sample 1. Five characteristic
190 L. Xu et al. / Chemical Engineering and Processing 102 (2016) 186–193

peaks for silver corresponding to Miller indices (111), (2 0 0),


(2 2 0), (3 11) and (2 2 2) were observed. All diffraction peaks match
well with the reference silver (PDF: 87-0597). Moreover, Scherrer
equation (3) is used to calculate the size of silver crystalline
nanoparticles as follows:
Kl
D¼ ; ð3Þ
bcosu
where D,K, l, b, and u are the average diameters of the crystalline
domains, the shape factor, the X-ray wavelength, the width of the
peak (full width at half maximum), and the Bragg’s diffraction
angle, respectively. The line width of the (111) XRD peak was used
to calculate the Ag crystallite size [2u = 38.16 ]. The specific values
of K = 0.890, l = 0.154 nm (the wavelength of Cu Ka), and
b = 0.599 were used by using the instrument software JADE 5.0.
The calculations illustrated an average size of the Ag crystallites of
13.88 nm, in good agreement with the TEM observation of sample 1
(Fig. 3A and A0 ).
Fig. 4. UV–vis absorption spectrum of Ag nanoparticles prepared by a microfluidic Feng et al. reported that EDTA played a crucial role in the
chip at various complexants under room temperature. (For interpretation of the formation of Ag/Ag homojunction nanoparticles while the size of
references to color in the text, the reader is referred to the web version of this
Ag nanoparticles depended on the reductant concentrations [37].
article.)
In the present work, the molar concentration of AgNO3 solution at
0.001 M and 0.0025 M were utilized. The molar concentration of
NaBH4 solution was however fixed at 0.01 M for all two cases of
AgNO3 molar concentrations, which led to the NaBH4/AgNO3 molar
concentration ratio of 10:1 (sample 3) and 4:1 (sample 4),
respectively. The mixing flow rate was maintained at 10 ml/h.
Fig. 6 shows the size and morphology of silver nanoparticles
synthesized by a microfluidic device with sample 4. Comparing
Fig. 3C and Fig. 6, the effect of NaBH4/AgNO3 molar concentration
ratio on the appearance of silver nanoparticles can be demonstrat-
ed. The particle size distribution was more skewed to the right with
the mean particle diameter much higher at lower NaBH4/AgNO3
molar concentration ratio, and the particle size distribution
showed the mean diameter of 7.4  1.5 nm for sample 4 (Fig. 6A
and B).
Fig. 7 depicts the UV–vis absorption spectrum of silver
nanoparticles obtained at two NaBH4/AgNO3 molar concentration
ratios. It was found that the LSPR band maximum in the UV–Vis
spectroscopy of sample 4 occurred at about 399 nm, which
exhibited slight blue-shifting comparing to sample 3. Additionally,
with increase in the concentration of AgNO3 (i.e., at lower NaBH4/
AgNO3 molar concentration ratio), the absorbance peak intensity
Fig. 5. XRD patterns of silver nanoparticles prepared by a microfluidic device with increased. Patil et al. [20] reported that a decrease in the AgNO3
sample 1 (see Table 1).
molar concentration corresponded to a decrease in the absorbance

Fig. 6. The TEM image (A) and the particle size distribution (B) of the silver nanoparticles prepared by a microfluidic chip with sample 4 (see Table 1).
L. Xu et al. / Chemical Engineering and Processing 102 (2016) 186–193 191

concentration of reactant was maintained at 0.025 M AgNO3 and


0.01 M NaBH4. EDTA was used as a complexant. Fig. 8 shows the
changes occurring in the microfluidic device when the flow rates
are changed.
In the present work, silver nanoparticles were synthesized by
the reduction of aqueous metal salt solutions, with sodium
borohydride serving as the reduction agent, in a microfluidic
device. The chemical reaction rate is very fast, and the nucleations
take place within a short time. The diffusion of ions to the
interphase is rather slow in laminar flow and hence at faster flow
rates the diffusion of ions to the interphase is limited, which results
in formation of fewer Ag nanoparticles nuclei. The nucleation stage
is followed by the growth of the particles [41,42]. The growth of
particles from the limited nuclei proceeds until all of the solute in
droplets has been consumed. Therefore, the droplet size has a
certain effect on the distribution of the particles. There are many
factors effect the size of the droplet. Such as flow rate of the
aqueous liquid, temperature, Weber number (We) and Ohnesorge
number (Oh), etc., Nguyen et al. [43] reported that the droplet size
Fig. 7. UV–vis absorption spectrum of Ag nanoparticles prepared at various NaBH4/
will decrease with increasing flow rate. Stan et al. [44] reported
AgNO3 molar concentration ratios. (For interpretation of the references to color in
the text, the reader is referred to the web version of this article.) that independent control of drop size and velocity in microfluidic
flow-focusing generators using variable temperature and flow rate.
value, resulting in reduction in the average particle size, which In addition, the Weber number (We) is a dimensionless value
agrees with our work, supported by the TEM images (Fig. 3C and useful for analyzing fluid flows where there is an interface between
Fig. 6). Many authors have associated the red-shift of the surface two different fluids:
plasmon resonance of the silver nanoparticles with their size
increase, which may not be the universal case [38–40]. Song et al. rv 2 L
We ¼ ð4Þ
argued that increased size and crystallinity, less surfactant coating, s
variations in shape and surface morphology of particles all And Ohnesorge number (Oh) is a dimensionless number that
contributed to the increased intensities of the LSPR absorption. relates the viscous forces to inertial and surface tension forces, and
With an increase in nanoparticle sizes, the LSPR peak would it is defined as:
exhibit slight blue-shift [41]. pffiffiffiffiffiffiffiffi
To study the effect of flow rates in the microfluidic chip on m We
Oh ¼ pffiffiffiffiffiffiffiffiffi ¼ ð5Þ
synthesis of silver nanoparticles, experiments were conducted at rs L Re
different flow rates ranging from 10 ml/h to 30 ml/h. The

Fig. 8. Image of silver nanoparticles formed in the PDMS microfluidic device at different flow rates of 10 ml/h (A and A0 ) and 30 ml/h (B and B0 ), respectively.
192 L. Xu et al. / Chemical Engineering and Processing 102 (2016) 186–193

Fig. 9. The TEM image (A) and the particle size distribution (B) of the silver nanoparticles prepared by a microfluidic device with sample 6 (see Table 1).

where m is the liquid viscosity, r is the liquid density, v is the results, and the droplet size is relatively large. In the present study,
velocity of fluid, s is the interfacial tension between the two fluids, however we used mineral oil to formed segmented droplets as the
L is the characteristic length scale (typically drop diameter), Re is carrier fluid of the silver nanocolloids aqueous (Fig. 8A0 and B0 ),
the Reynolds number, We is the Weber number. In the present mainly hope avoid the blockage of the microchannel. Therefore, we
work, the density of oil is 914 kg/m3; the interfacial tension is only study the effect of flow rate on the final particle size of
around 0.0026 N/m; the diameter of droplet is around 3e–4 m; the nanoparticles, and more research will be carried out to reveal the
viscosity of oil m is 0.08 Pa s; and the average velocity is around effect of flow velocity on the droplet size and the distribution of
0.27 m/s corresponding to 10 ml/h, and 0.83 m/s corresponding to nanoparticles in the future work.
30 ml/h since the cross sectionarea of the channel is 1e–8 m2. Fig. 9 shows the size and morphology of the silver nanoparticles
Therefore, the We number (rv2 D/s ) is 75.7 and 715.5, respectively. synthesized by a microfluidic chip with sample 6 at the flow rate of
pffiffiffiffiffiffiffiffiffi 30 ml/h. Synthesized silver nanoparticles are spherical and
And the Oh number ðm= rs LÞ is around 0.94.
Chan et al. [45] reported that the Ohnesorge number (Oh) uniform in size, with the mean diameter estimated to be
represents the importance of the viscous force relative to 7.6  1.8 nm. Comparing Fig. 6 and Fig. 8, an increase in the mean
interfacial tension and inertial forces. There had been examine particle diameter is correlated with an increase in the flow rate.
the relationship between the processing variables and the shape However, this correlation is not obvious with the flow rates ranging
and size of alginate microbeads when alginate microbeads were from 10 ml/h to 30 ml/h. In addition, some silver nanoparticles
cross linked through an extrusion-dripping method, showing the aggregated into clusters at the flow rate of 30 ml/h. Feng et al.
morphological transition at a critical Ohnesorge number (Oh > reported that the morphologies of Ag nanoparticles were sensitive
0.24). In our study, the Weber number (We) and Ohnesorge to the solution pH values. When the solution pH values are less or
number (Oh) are relatively large. This shown that the effect of more than 11, Ag-EDTA chelate compounds become unstable,
surface tension is limited and the stability of the droplets is weak at yielding aggregated Ag homojunction nanoparticles [37]. In the T-
higher flow velocity. This is in agreement with the experimental shaped microfluidic chip, the diffusion of ions to the liquid
interface is diffusion limited; hence the solution pH values of liquid
interface is less than 11. Therefore, some silver nanoparticles
aggregated into groups.
Fig. 10 shows the UV–vis absorption spectrum of silver
nanoparticles obtained at different flow rates. With increasing
flow rates, the absorbance peak intensity increased, with UV–vis
absorption spectrum showing broadened peak, indicating an
increase in the average particle size. Patil [20] and Kumar et al. [46]
found that the higher the flow rate, the larger the particle size.
With faster flows of reaction mixtures in a microreactor, the
residence time for nucleation is too short to complete the reaction,
but adequate to induce coalescence of newly produced nano-
particles, thereby yielding higher average particle size, evidenced
by TEM images. Our previous study also showed that in order to
obtain a narrow particle size distribution, the flow rate should be
minimized [42].

4. Conclusions

Silver nanoparticles with diameters as low as 5 nm were


synthesized by reduction of metal salt solutions with sodium
borohydride in a microfluidic device were investigated. EDTA was
adopted as a complexant and presented significant effect on the
Fig. 10. UV–vis absorption spectrum of Ag nanoparticles prepared at flow rates of
10 ml/h, 20 ml/h and 30 ml/h.
morphology and particle size control of spherical silver
L. Xu et al. / Chemical Engineering and Processing 102 (2016) 186–193 193

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