Accepted Manuscript

Title: Continuous Synthesis of Silver Plates in a Continuous

Stirring Tank Reactor (CSTR)

Authors: Zengmin Tang, Woo-Sik Kim, Taekyung Yu

PII: S1226-086X(18)30298-3
DOI: https://doi.org/10.1016/j.jiec.2018.06.008
Reference: JIEC 4041

To appear in:

Received date: 23-3-2018

Revised date: 6-6-2018
Accepted date: 10-6-2018

Please cite this article as: Zengmin Tang, Woo-Sik Kim, Taekyung Yu, Continuous
Synthesis of Silver Plates in a Continuous Stirring Tank Reactor (CSTR), Journal of
Industrial and Engineering Chemistry https://doi.org/10.1016/j.jiec.2018.06.008

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 Continuous Synthesis of Silver Plates in a Continuous Stirring Tank Reactor
(CSTR)

Zengmin Tang,a Woo-Sik Kim,* a and Taekyung Yu,*a

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Department of Chemical Engineering, College of Engineering, Kyung Hee University, Yongin,
17104, Republic of Korea
*

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To whom correspondence should be addressed
Email: wskim@khu.ac.kr (W.-S. Kim), and tkyu@khu.ac.kr (T. Yu)

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Graphical Abstracts
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Large Ag plates were synthesized by using continuous stirring tank reactor (CSTR) in the ambient
temperature with a short mean residence time of 5 min, has a great improve surface enhanced
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Raman signal of methylene blue.

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Abstract: In this report, a continuous stirring tank reactor (CSTR) and batch reactor were used for
synthesis of silver (Ag) plates. The influences of agitation speed, molar ratio of AgNO3 to NaCl,
and concentration of reagent were investigated. Size analysis demonstrated that the size of Ag
plates synthesized by the CSTR was larger than the size of plates synthesized by the batch reactor.
The reason might be that low concentration of reagent and continuous supply of monomer in CSTR
are more favorable for growth of anisotropic structures. CSTR demonstrates good advantages for

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mass synthesis of Ag plates of large size.

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Keywords: Ag plates, continuous flow synthesis, CSTR, batch reactor

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1. Introduction
Due to their unique physical and chemical properties compared with bulk materials,
nanoparticles have great potential for innovative applications as catalysts, fuel cells, magnetic data
storage, solar cells, displays, and biomedicine [1-4]. Given the demand in industrial applications,
scaled-up production of nanomaterials has been an important research subject in recent years [5,
6]. Recently, most reported synthetic methods have used the batch reactor to prepare nanoparticles

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[7-11]. However, the traditional batch process has been limited to small-scale synthesis due to low
production yield and time-consuming steps [12, 13]. To obtain good control over the growth of

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nanocrystals, additional steps are needed in the synthetic procedure. In many syntheses of metal
nanocrystals, including silver (Ag) and gold (Au) nanoparticles, a complicated washing treatment

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is essential for good quality product [13, 14]. Therefore, due to growing demand in nanotechnology
industries, it is important to explore approaches achieving scaled-up and economically sustainable

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production of nanomaterials. Compared with batch synthesis, continuous synthesis can be

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considered more sustainable because continuous throughput can overcome limitations of
equilibrium and product inhibition. Monomers, considered building blocks for the growth of
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nanocrystals, can be supplied steadily by continuous operation, so that nanocrystals can be
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expected to grow without reagent limitation [15]. Therefore, continuous processes may achieve
mass production of nanomaterials on a scale to satisfy the increasing demands of industry [13-16].
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Over the last two decades, various continuous flow reactors based on a continuous tubular
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reactor have been used for the synthesis of nanomaterials, including tubular micro-reactor,
microfluidic chips, and continuous droplet reactor [17-19]. The continuous flow tubular micro-
reactor, which uses polyteterafluoroethylene (PTFE) tubes for a reacting system, has been used for
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the synthesis of various inorganic nanomaterials including copper (Cu), Au, and titanium dioxide
(TiO2) [20-23]. A silicon microchip system fabricated by lithography could typically be used for
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the synthesis of cadmium selenide (CdSe), which needs high reaction temperature and/or pressure
[24, 25]. A continuous droplet reactor using micro-emulsion flow has been used for the synthesis
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of metal nanoparticles dispersed in organic solvent [26, 27]. One of the most characteristic features
of tubular micro-reactors is effective separation of nucleation and growth by adjusting the parallel
micro-reactor [28-30], accurately controlling the size and morphology of the nanocrystal [31-33].
Recently, a spinning disk reactor has been used as a continuous reactor to synthesize inorganic
nanomaterials. Spinning disk reactors, which can accelerate the reaction rate by generating a highly

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sheared liquid film at the disk/liquid interface, have been used for the synthesis of Ag, zinc oxide
(ZnO), iron oxide (Fe3O4), and magnesium hydroxide (Mg(OH)2) nanoparticles [34-37]. In this
study, we used another type of continuous reactor, the continuous stirring tank reactor (CSTR), to
investigate CSTR’s effect on the mass production of nanoparticles.
Different from tubular micro-reactors, CSTR is the most basic continuous reactor in chemical
processes. The mixing process can be accomplished by mechanical agitation or magnetic stirring,

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which can achieve complete uniformity of concentration and temperature. Interestingly, the
concentration profile of reagent in CSTR is different from that of the flow tubular reactor or the

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batch reactor. Normally, a batch reactor has a temporal concentration gradient, and a tubular
reactor provides a spatial concentration gradient over time, whereas the concentration of reactant

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in the CSTR quickly decreases due to dilution and can be maintained at low concentration by
continuous injection [38-41]. Concentration of reagent in the synthesis process has been

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considered a critical factor affecting the morphology of nanocrystals.

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Typically, in the synthesis of anisotropic nanomaterials including 1D nanowires and 2D
nanoplates or nanosheets, the reaction rate is an important factor for nanomaterials with a high
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aspect ratio [1, 40-42]. The reaction rate can be controlled by varying several reaction conditions
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including reagent concentration, reaction temperature, addition of an additive reagent, and amount
of reactive reagent [43, 44]. For example, in the synthesis of Ag nanowires, addition of chloride
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ion (Cl−) can be used to decrease the reaction rate, thus leading to the formation of long Ag
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nanowires with a high aspect ratio [45-47]. However, these methods can sometimes be detrimental
to the large-scale synthesis and application of nanomaterials. The low concentration of reagent
requires a large volume of solvent, a low reaction temperature leads to long reaction times, and an
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additive reagent on the surface of nanomatetrials also could reduce the catalytic activity [48-50].
Using this concentration profile in CSTR, we thought that it would be possible to obtain positive
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results in the synthesis of anisotropic nanomaterials by simply adjusting the type of reactor without
changing other reaction conditions.
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In this report, we investigated the effects of two types of reactors, the batch reactor and CSTR,
on the fabrication of 2D nanostructures. Even though the same reaction conditions were used, the
size and thickness of Ag plates synthesized using the batch reactor and the CSTR were different
due to the different concentration profiles of reagent in these two types of reactor. The Ag plates
synthesized by using the CSTR were larger than plates synthesized by using the batch reactor

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under the same experimental conditions. We also studied the change in size and thickness of the
Ag plates by varying the reaction conditions of agitation speed and molar ratio of reagents.

2. Experimental section
2.1 Materials.
Silver nitrate (AgNO3, purity ≥ 99%), sodium chloride (NaCl), polyvinylpyrrolidone (PVP, MW

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= 55,000), and methylene blue (certified by the BSC, MW = 319.85) were purchased from Aldrich.
An ammonium hydroxide solution (NH4OH, 30% in aqueous solution) and hydrogen peroxide

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(H2O2, 30-33% in aqueous solution) were purchased from SAMCHUN Chemicals.

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2.2 Synthesis of Ag plates in the batch reactor.
The synthesis of Ag plates in the batch reactor was conducted in an 80-mL glass bottle (Fig. S1)

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with mechanical agitation by slightly modifying a previously reported method [51]. First, 36 mL

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of aqueous solution consisting of 0.4 mmol AgNO3 and 0.2 g PVP was prepared. The pH of the
solution was adjusted to 10.6 by using NH4OH solution. Then, 0.2 mmol NaCl was added to the
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above solution to prepare AgCl nanoparticles. After the solution became turbid, 4 mL of H2O2 (9%
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aqueous solution diluted from original H2O2 solution) was injected into the reacting solution. At
standard conditions, the molar ratio between AgNO3 and NaCl was 2. The reaction solution was
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agitated with different stirring speeds at room temperature for 20 min, and the product was
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collected by centrifugation and washed with deionized (DI) water several times.

2.3 Synthesis of Ag plates in a CSTR.

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To synthesize Ag plates in a CSTR (Fig. S2), two feed solutions were prepared. Feed solution
1 was AgCl nanoparticle suspension prepared by mixing 4 mmol of AgNO3 with 2 mmol of NaCl
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in 400 mL of water in the presence of 2 g PVP and 0.6 mL NH4OH. At standard conditions, the
molar ratio between AgNO3 and NaCl was 2. Feed solution 2 was 50 mL of the 9% H2O2 aqueous
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solution. These two feed solutions were simultaneously injected into the reactor using two pumps.
To maintain a volume equivalent to the batch operation, the reactor was first filled with 40 mL
water, and the ratio of flow rate of feed solution 1 (7.2 mL/min) and feed solution 2 (0.8 mL/min)
was 9:1. The products were collected by pumping out the reactor at a flow rate of 8 mL/min. The

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mean residence time (τ) was 5 min, and the size and thickness of the Ag plates were controlled by
varying the agitation speed and molar ratio between AgNO3 and NaCl.

2.4 SERS measurement preparations.

Methylene blue (MB) was chosen as a probe molecule, and 4 mL of Ag plates with the same
concentration but different aspect ratios R (L/T) were prepared. The plate concentration was

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investigated by ICP and was around 0.8 mg/mL. Then, 2 mL of 0.1 mol/L MB solution was added
to the Ag plates and nanoparticles to obtain a suspension. The suspension was stirred for 24 h at

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room temperature by magnetic stirrer. Then, 100 uL of suspension was dropped onto a glass slide
and dried in an oven to prepare for SERS spectrum measurement.

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2.5 Characterization.

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The size and thickness of the Ag plates were observed by scanning electron microscopy (SEM,

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LEO SUPRA 55 Microscope). The crystal structure of the products was detected by X-ray
diffraction (XRD, Rigaku D-MAX/A diffractometer at 35 kV and 35 mA). The SERS spectra were
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measured by inVia Raman microscope (Renishaw, RENISHAW plc, U.K.). Inductively coupled
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plasma spectrometer (ICP) analyses were measured by Direct Reading Echelle ICP (LEEMAN).
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3. Results and discussion

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To investigate the effects of different types of reactors on the fabrication of 2D nanostructures,

we apply the same synthetic route for Ag plates in two reactors, the batch reactor and CSTR, and
use a slightly modified synthetic method based on a previous method [51]. In the batch reactor,
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quasi-cubic AgCl with an average dimension of 333.56 ± 52.3 nm is first synthesized by

precipitation of a portion of AgNO3 with NaCl, as shown in Fig. S3. The Ag(I) in the solution of
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quasi-cubic AgCl and AgNO3 can be then reduced by H2O2, forming Ag plates in the presence of
PVP as a capping agent.
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For the CSTR (Fig. 1), two feed solutions are prepared. Feed solution 1 contains AgCl
nanoparticles, and feed solution 2 contains H2O2 as a reducing agent. These two feed solutions are
then pumped into the reactor, and the products are collected by pumping out the reactor. The mean
residence time (τ) is set at 5 min. The effect of mean residence time on the composition of final
products is studied. When the synthesis of Ag plates in CSTR is conducted with mean residence

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times of 1 min and 12 min, both products are a mixture of Ag and AgCl as shown in Fig S4. A
short mean residence time is not enough to complete the reaction between Ag(I) and H2O2, and an
excessively long mean residence time can decrease the H2O2 concentration in the reactor, leading
to incomplete reduction of AgCl. One sample from the batch reactor at a reaction time of 5 min
exhibits small Ag nanoplates of size less than 5 μm and AgCl particles (JCPDS file no. 04-0783)
(Fig. S5), which demonstrates that a relatively long reaction time (around 20 min) is needed.

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To be consistent with the batch reactor synthesis, the CSTR is first filled with 40 ml of water. It
takes approximately 30 min to achieve steady state in size and thickness of Ag plates (Fig. S6). To

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standardize comparison, all CSTR analyses are performed by using samples obtained after 50 min.
XRD measurements confirm that the products synthesized by the batch reactor and CSTR are

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metallic Ag (Fig. S7a, Fm3m, a = 4.086Å, Joint Committee on Powder Diffraction Standards
(JCPDS) file no. 04-0783). The TEM image, SAED pattern, and HR-TEM image (Fig S7 b-d)

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show that the top and bottom planes of Ag plates are enclosed by facet (111). The changes in size

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and thickness of Ag plates synthesized by using these two reactors were investigated by changing
the agitation speed and molar ratio of AgNO3 and NaCl.
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Agitation speed. Figures 2a to 2e show SEM images of Ag plates synthesized by using the
CSTR at different agitation speeds of 100, 200, 500, 1000, and 1500 rpm, respectively. As shown
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in Fig. 2f, the size of all Ag plates is approximately 10 μm, indicating no significant change due
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to agitation speed. The thickness of the Ag plates decreases slightly from 260 ± 15.63 to 180 ± 9.3
nm by increasing the agitation speed from 100 to 1500 rpm. Compared with the CSTR products,
the variation in size and thickness of the Ag plates synthesized in the batch reactor is significant.
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When the agitation speed increases from 100 to 1500 rpm in the batch reactor (Fig. 3 a-e), the size
of the Ag plates decreases from 7.3 ± 2.3 to 4.6 ± 1.8 μm, and the thickness also decreases from
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326 ± 21.2 to 70 ± 11.6 nm with increasing agitation speed (Fig. 3f). It is well known that high
agitation speed in a batch reactor can accelerate the nucleation rate, leading to the formation of
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small nanoparticles [52, 53]. When we use the batch reactor, both size and thickness of the Ag
plates decreases with increasing agitation speed, which agrees well with previous reports. In the
CSTR, growth of the Ag plate can be protected from the effect of rotation speed, so the size and
thickness of Ag plates can be maintained or suffered only a slight reduction. Because the Ag
precursor in CSTR is continuously injected, there is no large change in concentration of monomer

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(Ag atom). Sufficient monomer can facilitate growth of Ag plates to relatively large dimension
even at high rotation speed.
Interestingly, the mean size of the Ag plates synthesized by the CSTR is larger than that of the
Ag plates synthesized by the batch reactor over the entire range of agitation speed. The reagent
concentration in the batch reactor and CSTR may be considered the key factor to significant
differences in the size of Ag plates [1, 40, 54]. According to previous reports, all reagents in the

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batch operation have a high concentration at the outset and then exponentially decrease during the
reaction. The concentration of reagents in the batch reactor can be described approximately as

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given in Fig. 4a [38]. In the CSTR, the concentration of all reagents starts from zero before the
feed solutions pump into the reactor. The concentrations increase with time and reach a steady

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state at a relatively low constant concentration. The concentration profile in CSTR can be
expressed approximately as given in Fig. 4b [39]. In order to confirm the effect of concentration

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of reagent in these two reactors, an experiment was performed at low reagent concentration in the

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batch reactor. As shown in Fig. 4c and 4d, Ag plates with a large mean size of 16.62 ± 5.6 μm
were synthesized when all reagent concentrations (including AgNO3, NaCl, and H2O2) were
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diluted 10 times. Low initial concentration of all reagents would slow the reaction rate, which
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contributes to growth of Ag plates with large size. However, reducing the concentration of all
reagents to obtain large Ag plates is not ideal for mass production. In the CSTR, large Ag plates
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can be fabricated while maintaining an undiluted concentration of all reagents in feed solution. By
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comparing the batch reactor and the CSTR, the CSTR shows a great advantage in synthesis of
large Ag plates.
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AgNO3/NaCl molar ratio. In the present synthesis, the reaction between AgNO3 and NaCl can
be given as
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AgNO3 (aq) + NaCl (aq) →AgCl (s) + NaNO3 (aq)

The addition of Cl− ions into this solution would be expected to slow the reaction rate between
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Ag(I) and H2O2, because AgCl has a low standard reduction potential (𝐸𝐴𝑔𝐶𝑙∣𝐴𝑔 = 0.2333 V)
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compared with the Ag+ ion (𝐸𝐴𝑔 + ∣𝐴𝑔 = 0.7996 V). Here, the amount of NaCl is variable. When the

synthesis is conducted in the absence of NaCl, the reaction between AgNO3 and H2O2 is so fast
that only spherical Ag nanoparticles with diameters of approximately 400 nm are synthesized (Fig.
5 a and b). When the molar ratio of AgNO3/NaCl in the batch reactor is set at 1.25, and most

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AgNO3 translates into AgCl, the SEM image (Fig. 5c) of products shows Ag plates formed at about
8.24 μm, but also a small quantity of particles intermixed with the Ag plate products. The XRD
pattern (Fig. 5d) reveals that product as a mixture of metallic Ag (JCPDS file no. 31-1238) and
AgCl (JCPDS file no. 04-0783). This observation indicates that the amount of Cl− ions is an
important factor in controlling the shape and composition of products by controlling the reaction
rate in the batch operation.

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To further investigate the influence of Cl− ions, we varied the molar ratio between AgNO3 and
NaCl in both the batch reactor and the CSTR while keeping the rotation speed at 200 rpm and

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mean residence time at 5 min. As shown in Fig. 6, the size and thickness of the Ag plates in the
batch reactor decrease from 7.2±1.5 to 1.9±0.8 μm and from 315±22.6 to 85±12.3 nm,

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respectively, with increasing molar ratio of AgNO3/NaCl from 2 to 40. These results can be
explained by the different reaction rate between Ag(I) and H2O2. At high AgNO3/NaCl molar ratio

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(such as 40), a large quantity of Ag+ ions causes a fast reaction, resulting in homogeneous

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nucleation and formation of a large number of Ag nuclei; therefore, the quantity of monomers is
insufficient for the growth of large Ag plates from Ag nuclei. The quantity of Cl− ions in the batch
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operation is therefore very important for controlling the size of Ag plates. In the batch reactor, to
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increase the mean Ag plate size, the method of choice is to decrease the molar ratio of AgNO3/NaCl
within certain limits. Once the molar ratio of AgNO3/NaCl was reduced to 1.25, a high initial
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concentration of AgCl could not be reduced completely by H2O2. This indicates that there are few
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ways to increase the concentration of Cl− ions while maintaining pure Ag product in the batch
reactor.
However, when the above synthesis was conducted in the CSTR, the size of the Ag plates
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increased from 9.89±1.9 to 16.75±3.9 µm while maintaining their thickness of approximately 250
nm as the molar ratio of AgNO3/NaCl increased from 2 to 40 (Fig. 7). Compared with the batch
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operation, the monomers for growth of Ag plates in CSTR can be in steady supply because the Ag
precursor is continuously injected into the reactor [54]. This indicates that we can fabricate large
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Ag plates with minimal use of Cl− ions.

Surface-enhanced Raman scattering (SERS) analysis. SERS is a technique that enhances the
Raman scattering cross-section of molecules in an environment of metal nanostructures [11, 55,
56]. To examine the dependence of SERS activity on the morphology, a comparison was

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performed by using Ag plates with the same particle concentration but different aspect ratio R
(L/T), 56.8 (plates in Fig. 1e) and 22.7 (plates in Fig. 5c). Fig. 8 shows SERS spectra of methylene
blue (MB) adsorbed on the surface of these two Ag plates. The peaks at 1624 cm-1, 1501 cm-1,
1392 cm-1, 1358 cm-1, and 446 cm-1 are assigned to MB [57]. To eliminate the signal variation
with surface placement, each sample was measured at three different points (In Fig. S8). Both
peaks at 1624 cm-1 for large Ag plates (R=56.8) are stronger than those of the small plates (R=22.7),

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showing that intensity of the Raman signal can be enhanced by increasing the R value of the Ag
plates.

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4. Conclusion

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We investigated the effects of two types of reactor, the batch reactor and CSTR, on the synthesis
of Ag plates. The use of the CSTR for the synthesis of large Ag plates has three advantages over

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the batch reactor. First, since it is a continuous reaction, the introduction of the reactant and the

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recovery of the product are simple, which is suitable for mass production. Second, it is easy to
produce anisotropic nanostructures because of the low reagent concentration without changing the
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overall reaction environment. Finally, due to continuous injection, another factor in controlling the
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reaction rate, it is possible to minimize the use of Cl− ions that can interfere with subsequent
applications of the Ag plates. In addition, Ag plates with large aspect ratio have a relatively strong
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SERS signal. We expect that the production of nanoparticles using the CSTR will be of great help
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in the mass production of other anisotropic nanostructures. We also think that this study can help
optimize the process for mass production of nanoparticles.
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Acknowledgements
This research was supported by the Basic Science Research Program through the National
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Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT, & Future Planning
(2014R1A5A1009799) and by a National Research Foundation of Korea (NRF) grant funded by
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the Korean government (MSIP) (NRF-2015R1C1A1A01054109 and NRF-

2016M3D1A1021140).

Appendices A. Supplementary data

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 Electronic Supplementary Material: Supplementary material (SEM images and XRD patterns of
Ag plate, Ag nanoparticle, and AgCl nanoparticle and size distribution of AgCl nanoparticles) is
available in the online version of this article.

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Appl. Surf. Sci. 1 (2015) 66.

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Fig. 1. Photograph of the continuously operating system for the synthesis of Ag plates using the
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CSTR.
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Fig. 2. SEM images of the Ag plates synthesized using the CSTR at different agitation speeds (a)
100, (b) 200, (c) 500, (d) 1000, and (e) 1500 rpm. (f) Size and thickness distribution of the plates.
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Fig. 3. SEM images of the Ag plates synthesized using the batch reactor at different agitation
speeds (a) 100, (b) 200, (c) 500, (d) 1000, and (e) 1500 rpm. (f) Size and thickness distribution of
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Fig. 4. Concentration profile of reagent in the (a) batch reactor and (b) CSTR during the reactions.
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(c) SEM image and (d) size distribution of the Ag plates prepared under the same conditions as in
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Fig. 3b, except that the synthesis was conducted with 10 times diluted reagent concentration.
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Fig. 5 (a) SEM image and (b) XRD pattern of Ag particles synthesized by batch reactor when no
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NaCl was supplied; (c) SEM image and (d) XRD pattern of products synthesized by batch reactor
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when the molar ratio of AgNO3 to NaCl was 1.25.

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Fig. 6. SEM images of the Ag plates synthesized by batch reactor at different molar ratios of
AgNO3/NaCl (a) 10, (b) 20, and (c) 40 while under conditions otherwise the same as those in Fig.
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3b in the batch reactor. (d) Size distribution of the Ag plates.

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Fig. 7. SEM images of the Ag plates synthesized at different molar ratios of AgNO3/NaCl (a) 10,
(b) 20, and (c) 40 while under conditions otherwise the same as those in Fig. 2b in CSTR. (d) Size
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distribution of the plates.

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Fig. 8 SERS spectra of MB-Ag plates (R=56.8) (red line a), MB-Ag plates (R=22.7) (blue line b),
and methylene blue (MB) (black line c).
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