Chemie

Ingenieur Combinatorial synthesis screening 467

Technik

Research Article

Screening of Multiparameter Spaces for

Silver Nanoprism Synthesis by Microsegmented
Flow Technique
Andrea Knauer*, and J. Michael Köhler
DOI: 10.1002/cite.201200206

In this work, a method of combinatorial variation of reactant solutions combined with an in situ UV-Vis readout of the
plasmonic properties during the wet-chemical synthesis of Ag nanoprisms in micro fluid segments is presented. Segment
sequences of clearly distinguishable compositions are generated by an automated flow rate program. By the help of two
combined slowly shifting and two contrariwise rapidly changing reactant flow rates, a two dimensional parameter space is
covered completely in steps of 20 %. Due to the sensitive main dipole mode of Ag nanoprisms, a combinatorial concentra-
tion variation during the growth step of the synthesis opens new possibilities regarding tuning of particle size and optical
properties. Here, within one combinatorial synthesis run, silver nanoprisms with edge length between 35 and 200 nm and
main plasmon resonances between 550 and 900 nm were obtained.
Keywords: Combinatorial synthesis screening, Droplet based microfluidics, Microcontinuous synthesis, Shape anisotropic
nanoparticles, Silver nanoprisms
Received: November 15, 2012; revised: February 03, 2013; accepted: February 11, 2013

1 Introduction
For many centuries, mankind has used noble metal nano-
particles. Gold and silver nanoparticles have been generated
in classical and medieval glasses for giving them an inten-
sive red or green color. The colloidal nature of these materi-
als was explained by Michael Faraday in the 19th century. It
was detected that these particles could not only be stabilized
in glasses but also in solutions. Nowadays, the beautiful col-
or of gold nanoparticles is not only of interest for decoration
but is also of interest for bio labeling, e.g. in molecular bio-
technology [1]. Beside gold, also other noble metals, silver in
particular, can form deeply colored colloidal solutions of
nanoparticles. The color of the solutions is dependent on
the electronic properties of the single particles which are de-
termined by their composition, size, and shape as well as by
the electrical and chemical conditions at their surfaces [2, 3].
These special properties of nanoparticles are of great impor-
tance for current and future applications as for example
their use in heterogeneous catalysis. Whereas the catalytic
activity of metallic silver is known and used for long a time,
– bandwidth. In fields of microfluidic nanoparticle synthesis,
Andrea Knauer (Andrea.Knauer@TU-Ilmenau.de), Prof. J. Michael
Köhler, Ilmenau University of Technology, Department of Physi-
cal Chemistry and Micro Reaction Technology, Gustav-Kirchhoff-
Straße 1, 98693 Ilmenau, Germany.
there are meanwhile also very interesting reactions that are
catalyzed by gold nanoparticles [4, 5]. The efficiency of such
heterogeneous reactions in liquid phase can be considerably
improved if the immobilized catalyst nanoparticles are
applied in a microcontinuous flow process or in continuous
flow two-step processes.
The addressing of well-defined optical and electronic
properties of metal nanoparticles demands for an accurate
control of the particle formation process. Reaction condi-
tions as temperature and pH have to be well controllable as
well as the mixing of reactants and the composition of the
reaction solution. Therefore, fast mass and heat transfer
steps are required, which are typical for microreaction tech-
nology. It was shown earlier that the synthesis of metal
nanoparticles can easily be realized in a microcontinuous
flow process [6, 7]. The mean size of particles can be shifted
within a certain range by tuning of the flow rate. This effect
indicates the dependence of reactant mixing on the particle
quality. Higher total flow rates cause a faster mixing, a high-
er homogeneity of nucleation, and result in a higher num-
ber of smaller particles. Lower mixing rates at lower total
flow rates lead to larger particles and larger size distribution
the required fast mixing demanded for the use of microfab-
ricated static micromixers. The emerging problem of reactor
fouling was met by a chemical modification of the hydrophi-
lic glass and silicon surfaces inside the reactor [7].

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468
High mixing rates and low risks for reactor fouling can be
achieved if a microsegmented flow is applied instead of
static micromixers [8]. In this case, the aqueous solutions of
reactants are forming droplets which have nearly the inner
diameter of the capillary and are embedded in an immisci-
ble and inert carrier liquid. This liquid wets the wall and
reduces the contact between the wall and the reaction com-
ponents. The formation of micro fluid segments is also re-
sponsible for the appearance of an ideal plug-like transport
and is related to a very narrow residence time distribution.
The segment transport is accompanied by the induction of a
stable flow field inside the aqueous segments, which sup-
ports a very fast mixing of the reactant solutions [9 – 11].
This technique was used for both, formation of salt-like
micro and nanomaterials [12] and the synthesis of quantum
dots [13, 14]. It could be shown that this method can also be
advantageously applied for the synthesis of metal nanoparti-
cles and it was found that in particular Au/Ag core/shell
particles can be generated with high homogeneity [15]. A
high homogeneity of primary formed particles is not only
important for the synthesis of core shell particles but is also
essential for the growth of non-spherical nanoparticles. A
narrow size distribution and very high yield of triangular sil-
ver prisms were achieved in a segmented flow-based synth-
esis procedure [16].
The high homogeneity of products obtained from the seg-
mented flow process is due to constant sizes, distances and
motions of the single fluid segments. The segmented flow
ensures constant flow behavior and constant conditions for
transport of mass and energy if the fed reactant streams are
kept constant. On the other hand, it is possible to shift the
flow rates in order to realize a variation of reactant composi-
tions. Such a flow rate shift can be easily performed by com-
putational control of the applied syringe pump system. Up
to several thousand different start concentrations can be im-
plemented inside individual fluid compartments in a typical
microfluidic experiment [17, 18]. This allows to screen che-
mical reactions in two or even higher dimensional concen-
tration spaces. The novel method for parameter screening
during the synthesis of shape-anisotropic silver nanoparti-
cles, which is introduced in this work for the first time, is in
general very promising for the evaluation of the effect of
concentration variations on nucleation, aggregation, growth
and shell formation of nanoparticles. In this work the com-
binatorial synthesis screening was applied to the system of
triangular silver nanoparticles by utilizing the major advan-
tage of this method, the possibility to alter the concentration
ratios of the educts during the synthesis combined with an
optical in situ readout of the product particles plasmonic
properties. This enables both, a fine tuning of the lateral
extension of the nanoprisms as well as a fine tuning of the
spectral position of the main plasmonic resonance wave-
length.
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A. Knauer, M. Köhler
2 Strategy of Screening of Metal
Nanoparticle Formation by Micro Fluid
Segment Technique
2.1 Mechanisms of Particle Formation in Micro
Fluid Segment Sequences and Process Steps
To generate a segmented flow, a continuous carrier stream of
an immiscible organic liquid was firstly dosed into the reactor
channel. Then, the generation of segments takes place at the
first injection unit, which comprises two oppositely posi-
tioned injectors from which the first two reactant solutions
are continuously dosed into the presented carrier stream. At a
second injection unit, further educts can be dosed into the
preformed segments. The synthesis of silver nanoprisms fol-
lows a seed-induced strategy, which was published first by
Aherne and coworkers [19]. It is noticeable that within the
batch protocols for both the synthesis of the seed nanoparti-
cles as well as for the nanoprism growth a slow dosing of silver
nitrate to the presented reactant mixture is required. A fast
addition of silver nitrate would increase the surface potential
of the already present nanoparticles due to the sudden excess
of Ag+. This could lead to a zero-crossing of the surface poten-
tial, which will directly cause an uncontrolled particle aggre-
gation. With the nanoparticle synthesis in micro fluid seg-
ments, no time-dependent addition of AgNO3 is required [16].
Due to the high segment internal mixing rates and homoge-
neous mixing conditions, which particularly support fast
redox reactions, no special conditions have to be considered
with the addition of silver nitrate during the micro-flow-
through synthesis. It is already known that the segment inter-
nal convection is accelerated with increasing flow rates [11].
To obtain homogeneous, high quality seed particles with a
narrow size distribution, a high volume flow rate has to be
applied. Since the reduction of silver ions by sodium borohy-
dride is a rapidly proceeding reaction combined with a fast in-
itial nucleation, optimum mixing conditions are required to
keep the time interval of seed crystal nucleation low and, thus,
to promote the formation of a high amount of nanoparticles
with a comparatively smaller average diameter. The growth
of Ag nanoprisms takes place in a second process step. It
could already be shown that the synthesis of triangular sil-
ver nanoprisms in micro fluid segments is advantageous
according size distribution and yield of the desired shape
[16]. Since the nanoprism growth process is determined by
a slow deposition of Ag0 moderate flow rates can be applied.
Medium flow rates also facilitate a thorough spectral analy-
sis of the colloidal solution in each micro fluid segment.
2.2 Micro-Flow-Through Setup and Reactor
Assembly
Both the initial generation of the silver seed particles as
well as the subsequent nanoprism growth step demand a
reactor setup and fluidic conditions, which are specially
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Ingenieur Combinatorial synthesis screening 469
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adapted to the requirements of the individual

synthesis. The setup, which was used for the Ag
seed nanoparticle synthesis is explained in detail
in [16]. Five syringes were mounted on a multi-
axis computer-controlled syringe pump system
(Cetoni NeMESYS, Cetoni GmbH, Germany).
The syringes were connected by PTFE tubing
(inner diameter: 0.5 mm, Bohlender GmbH,
Germany) to standard fluid connectors, which
are commercially available as HPLC equipment
(IDEX Health & Science LCC, USA). For the pre-
paration of the silver seed nanoparticles an aqu-
eous solution of 2.5 mM sodium citrate is dosed
firstly into the presented carrier stream (per-
fluoro(methyldecalin)), whereby the segment
generation takes place. At two following oppos-
ing injectors, the surfactant PSSS (poly(sodium
styrenesulphonate), 70 000 Dalton; 0.5 g L–1) and
the reducing agent sodium borohydride are
added to the preformed segments. The particle
formation is initiated by addition of AgNO3 via
the fifth injection unit. A high total flow rate of
about 1600 lL min–1 forwards a fast segment in- Figure 1. Experimental microfluidic arrangement used for the Ag nanoprism
ternal mixing. Despite the high volume flow growth under conditions of combinatorial variation of the reactant concentra-
rates a stable segmentation with clearly sepa- tions.
rated equidistant, equal sized segments of a
length of approximately 1 mm were observed.
For the prism growth process in connection with the here 2.3 Concentration Spaces
presented combinatorial variation of reactant concentrations
a second reactor, which is schematically shown in Fig. 1, In Fig. 2, the automated flow rate run utilized for the
was constructed. It consists of two opposing double injec- combinatorial variation of the educts concentration is
tors and a front-side inlet for supplying the carrier stream. shown. During the automated combinatorial experiment,
Again, PTFE tubing with an inner diameter of 0.5 mm was a complete two dimensional parameter space is covered in
used to connect the syringes to the reactor components as steps of 20 % by a set of flow rate changes, which are con-
well as for the construction of the knot mixer with a total trolled by the data of the flow rate program. The principle
length of 100 cm, which follows directly the last pair of of this investigation is based on a stepwise alteration of
injectors. The system of two opposing injectors is necessary two slowly shifting flow rates, by keeping the sum of this
for the realization of the combinatorial variation of the reac- flow rates constant, which are in turn overlain by two fast
tant concentration. Via respectively one injector a reactant is changing flow rates, in sum again constant. Since it is
added, whose concentration can be adjusted by the opposite known, that the flow rate has a significant impact on the
injector by dilution. The dilution takes place by a simple physical properties of microfluidically synthesized nano-
adjustment of the individual flow rates. Thus, at injector 1 a particles, steady fluidic conditions are achieved due to an
mixture containing a high amount of Ag seed nanoparticles always constant volume flow, rate. The individual flow
is inserted, which is diluted to a desired degree by injector 2 rates of each reactant stream for each single combinatorial
through addition of the same but seed particle free reactant step can be directly taken from Fig. 2. For the presented
mixture as before. The same procedure is applied at injector experiments, a linear-linear variation of the reactant con-
3 and 4 for the dilution of the silver nitrate concentration. A centrations was chosen. The course of the programmed
flow rate of 200 lL min–1 is sufficient for the growth process flow rate runs can be significantly diverse. By this meth-
of the Ag nanoprisms. With this flow rate, a volume ele- od, also three and higher dimensional parameter spaces
ment of the stream will be transported with a velocity of can be covered and the concentration adjustment can also
17 mm s–1. The growth process of the Ag nanoprisms starts follow a non-linear course [18, 20].
with the addition of AgNO3 into the preformed segments.
Each segment will reach the flow-through cell for spectro-
photometric analysis, which is mounted to the reactor chan-
nel in a distance of 1270 mm downstream the last injection
units after a time interval of 75 s.

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470 A. Knauer, M. Köhler

Figure 2. Automated flow rate

variation for the realization of
the coverage of a 2D parameter
space in steps of 20 % with line-
ar-linear flow rate courses.

3 Experimental within one combinatorial step but significantly in the com-

parison of two or more steps.
3.1 Nanoparticle Synthesis, Process Monitoring In Fig. 3a the optical spectra of the colloidal nanoprism
and Nanoparticle Characterization solution, which was synthesized under the conditions of
combinatorial step 13, are shown. Although the spectral
A detailed description of the synthesis of the silver seed position of the main dipole resonance mode of the flat, tri-
nanoparticles with regard to the chemical and fluidic condi- angular silver nanoprisms is very sensitive towards small
tions has already been published in a previous work and can changes in the environment, the spectra of the single seg-
be directly taken from [16]. For the combinatorial variation ments of step 13 are sufficiently congruent. In Fig. 3b the
of the concentration parameters within the prism growth same spectra are given with an arbitrary y-offset to indicate
solution, reactants were premixed and distributed to four the equality in shape. In this described manner, the extinc-
syringes as shown in Tab. 1. According to the flow rate tion spectrum of each generated segment from each combi-
ratios given in Fig. 2, in each individual combinatorial step natorial step was taken. An average spectrum from a se-
Ag nanoprisms with different physical properties will be quence of segments, which follow each other in one
generated. At a constant dosing of the reactants and a combinatorial step, was calculated and considered represen-
homogeneous generation of the micro fluid segments, the tative for the analyzed step. Thus, the method of the in situ
physical properties of the product particles will not differ spectrophotometry is highly statistically and reproducible.
In order to achieve highly resolved
Table 1. Overview of the used chemicals and their distribution among the syringes.
absorption spectra, an UV-VIS light
source (AvaLight-D(H)-S, Avantes
Syringe Substance Concentration [mmol L–1] Volume [mL] Inc., USA) and an optical spectro-
photometer (AvaSpec-1024, Avantes
syringe 1 carrier medium – 5
(inlet1) perfluoro(methyldecalin) Inc., USA) were connected by fiber-
optic cables to the reactor capillary.
syringe 2 H2O – 5
The duration of one combinatorial
(injector 1)
C6H8O6 50 0.1 step was set to 45 s. This gives a total
seed nanoparticle solution – 0.5
time of 28.5 min for the whole combi-
natorial run. In total, 7473 segments
syringe 3 H2O – 5.5 were generated, 206 per combinator-
(injector 2)
C6H8O6 50 0.1 ial step. The consumption of chemi-
cals is remarkably low. Thus, 554 lL
syringe 4 AgNO3 1 2.5
(injector 3) of AgNO3 and 831 lL of the seed
nanoparticles mixture were con-
syringe 5 H2O – 2.5 sumed in 36 experiments. In detail
(injector 4)
36 experiments with each 206 repeti-

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 Chemie
Ingenieur Combinatorial synthesis screening 471
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amount of sample volume. The obtained product

a) particles were additionally characterized using
the SEM technique (Hitachi S-4800 FE-SEM,
Hitachi High Technologies America, Inc., USA).
The particle size distribution of the silver seed
nanoparticles and in the case of Ag nanoprisms
the Stokes equivalent sphere diameter were de-
termined by differential centrifugal sedimenta-
tion (DCS, DC 20000, CPS Instruments Inc.,
USA).

3.2 Chemicals and Materials

All of the following chemicals were used as re-

ceived from the supplier. Sodium citrate (Merck
KGaA, Germany, purity: 99 %), poly(sodium sty-
renesulphonate) (PSSS) (Acros Organics, USA,
70 000 Dalton), sodium borohydride (Merck
KGaA, Germany, purity: 99 %), and silver nitrate
(Merck KGaA, Germany, purity: 99 %) were used
b)
for the synthesis of the seed nanoparticles. For
the subsequent Ag nanoprism growth, ascorbic
acid (Merck KGaA, Germany, purity: 99.7 %) was
utilized as a softer reducing agent. Perfluoro-
methyldecalin (F2 Chemicals Ltd., UK) was used
as carrier liquid. All solutions were prepared
with ultrapure, particle-filtered water (water fil-
tration system: Aqua purification G 7795, Miele,
Germany) at a specific electric resistivity of
18.2 MX cm.

4 Experimental Results and

Discussions

The generation of silver seed nanoparticles was

realized using the experimental arrangement
given in [16] under the application of a high total
flow rate of 1606 mL min–1. In Fig. 4, the weight-
based DCS size distribution spectra of the flow-
Figure 3. In situ extinction spectra of single segments of one combinatorial step. through generated Ag seed nanoparticles as well
a) The superposition of all individual spectra represents the data recording of the
real-time analysis. b) Arbitrary splitting of the single spectra by a manually
as of the corresponding batch synthesized nano-
adjusted y-offset to demonstrate the high reproducibility by the equal shape particles are given. Obviously, the nucleation
of the spectra. occurs in case of the micro-flow-through syn-
thesis in a narrow time interval due to enhanced
tions were carried out in one single combinatorial run. The mixing conditions. This results in a narrow FWHM (full
high number of repetitions of each experiment demon- width at half maximum) of the particle size distribution and
strates the high statistical value of the introduced method. in a smaller average diameter of the obtained Ag seed parti-
From 25 of 36 experiments Ag nanoprisms with different cles. With batch synthesized nanoparticles, a second peak at
physical properties emerged. The remaining 11 experiments about 10 nm indicates the onset of aggregation. The weight-
can be considered as reference experiments in which at least based DCS data shows that a not negligible amount of materi-
one crucial reactant flow rate was set to zero. After the opti- al is lost this way in aggregates, which cannot grow to regular
cal spectra of each generated segment were taken, some nanoprisms by further deposition of silver. Furthermore, the
chosen fluidic conditions were later adjusted manually and FWHM of the batch generated seed particles is 5.2 nm larger
operated continuously to collect a comparatively higher than the corresponding flow-through obtained seed particles.

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Figure 4. The weight-based DCS size distribution spectra show a
comparison of batch and micro-flow-through generated silver
seed nanoparticles. The microfluidically prepared nanoparticles
have a significant smaller FWHM since the optimum mixing con-
ditions prevent particle aggregation and irregular growth.
On the basis of homogeneous seed nanoparticles, the
growth of Ag nanoprisms can be performed in a second
microfluidic process step. The investigations on the batch
synthesis of silver nanoprisms, which were published by
Aherne and colleagues [19], have clearly shown that the edge
length of the silver prisms can be adjusted by changing the
seed particle density in the growth solution. At a constant
presence of Ag+ a lower amount of seed particles will lead to
the formation of larger nanocrystals, a high amount of seed
particles will forward a higher number of respectively smal-
ler Ag nanoprisms. Based on this principle the experiments
for the combinatorial synthesis were conceived. During the
combinatorial experiment, the density of the seed nanoparti-
cles is adjusted by slowly shifting flow rates (see Fig. 2). The
first of the corresponding inlet streams contains a mixture
of ascorbic acid and seed particles, the second stream con-
tains ascorbic acid in the same concentration. The slow flow
rate change is overlain by two fast alternating flow rates,
through which the effective silver nitrate concentration is
varied. No nanoprisms growth occurs at those combinatorial
steps in which the flow rate of one essential reactant is set
to zero, which is the case in the steps 6, 7, 18, 19, and 30 – 36.
This results in totally 25 different synthesis experiments
from which clearly distinguishable Ag nanoprism popula-
tions emerge. A highly regular dependence of the silver
prisms size from the chemical conditions in the individual
combinatorial steps is reflected by the in situ UV-Vis spectra
in Figs. 5a – e and the size distribution spectra in Figs. 6a
and b, which display the Stokes equivalent sedimentation
diameter of the flat, triangular nanoplates.
It is well known that the spectral position of the plasmon
resonance wavelength depends on the particle size [21, 22].
With increasing particle size, the absorption peak is red-
shifted. For all preset AgNO3 concentrations a distinct red
shift of the main plasmon mode was observed at decreasing
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A. Knauer, M. Köhler
seed nanoparticle concentration. In case of a constant seed
particle density, a decrease of the silver nitrate concentration
leads to the formation of smaller silver nanoprisms and con-
nected thereto a shift of the main plasmon resonance wave-
length towards lower values. In Fig. 5f an overview of the
recorded optical information is given. From this diagram it
can be concluded that it is possible to fine-tune the spectral
position of the main dipole resonance mode of the micro-
fluidically synthesized silver nanoprisms by a simple varia-
tion of the flow rate ratios in a spectral range between 550
and 900 nm with high exactness. These findings are con-
firmed by the DCS analysis. In addition to the optical in situ
analyses, all variations of seed nanoparticle densities were
analyzed by differential centrifugal sedimentation for silver
nitrate concentrations ranging from 1 mM and 0.4 mM. It
can be seen that the Stokes equivalent sphere radius is
slightly smaller in case of 0.4 mM (21, 24, 27, 30, 39 nm)
compared to the conditions of particle formation in pre-
sence of 1 mM AgNO3 (24, 26, 29, 34, 45 nm). Since the par-
ticles sediment in the centrifugal force field in a sphere
equivalent behavior, the actual edge length can only be mea-
sured by SEM analysis. The corresponding edge lengths
were determined to be 35, 60, 80, 130, and 180 nm in case
of 0.4 mM AgNO3 and 40, 70, 90, 145, and 200 nm for the
conditions at 1 mM silver nitrate addition. A high yield of
the desired shape is confirmed by the characteristic shape of
the optical spectra and also by SEM analysis. Three exam-
ples of different sized silver prisms obtained from different
combinatorial steps are given in Fig. 7.
5 Outlook: Concepts of Microfluidic
Screenings in Multiparameter Spaces
for Realization of New Types of
Nanoparticle Architectures
Since the method of 2D combinatorial parameter screening
during the micro-flow-through synthesis of shape anisotro-
pic silver nanoparticles in micro fluid segment sequences
has proven to be successful, one can consider going a few
steps further. In three or higher dimensional parameter
spaces, more information on the investigated particle system
can be gathered at once. An additional screening of the depen-
dence of the investigated nanoparticles’ physical properties
on the reducing agent concentration, on the pH value, or on
the ion strength is possible. By screening of the influence of
different ligands or ligand systems it is possible to achieve
new insights in shape or aggregation control. From such
studies, new synthesis protocols or parameter optimizations
for novel nanoscale materials could emerge. It is also possi-
ble to combine the combinatorial parameter screening with
thermal activation or cooling. Thus, information on kinetic
effects during the nanoparticle formation could be obtained,
which is enormously important to understand the first
phase of the nucleation – a field of knowledge over which to
date only little or contrarian information is published.
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 Chemie
Ingenieur Combinatorial synthesis screening 473
Technik

a) d)

b) e)

c) f)

Figure 5. a – e) The average spectra of all combinatorial steps from which Ag nanoprisms emerged. The main dipole mode clearly shifts
with decreasing seed nanoparticle density towards higher wavelength. f) Conclusion of the optical data obtained in one combinatorial
run. The diagram shows that the spectral position of the main plasmonic resonance wavelength can be precisely tuned in the spectral range
between 550 and 900 nm under the chosen conditions.

6 Conclusions meter screening was used to investigate the response of the

optical absorption behavior during the growth of triangular
A two dimensional automated combinatorial variation of silver nanoprisms. The gradually changing physical proper-
the reactant concentrations was successfully implemented ties of the silver nanoprisms due to controlled dilution of
into a micro-flow-through system. This combinatorial para- the seed particle density as well as the metal salt concentra-

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474 A. Knauer, M. Köhler

a)
a)

b)
b)

c)

Figure 6. Weight-based DCS spectra of Ag nanoprisms from the

combinatorial steps 1, 12, 13, 24, 25 (a), which reflect the condi-
tions at constant high addition of AgNO3 (100 %) but stepwise
decreasing seed nanoparticle density. b) Results of medium
AgNO3 addition (40 %) but decreasing seed particle density.
The respective combinatorial steps are 4, 9, 16, 21, 28.

tion could be monitored online with high precision by in

situ UV-Vis spectrophotometry. With a programmed linear-
linear flow rate run, the main plasmonic resonance wave-
length of the investigated particle system could be shifted
under the given chemical conditions in a spectral range be-
Figure 7. SEM data of Ag nanoprisms from three different combi-
tween 550 and 900 nm. The narrow UV-Vis absorption natorial steps. An addition scale bar was embedded to mark a dis-
bandwidths indicated homogeneous product particles, tance of 100 nm. a) Ag nanoprisms derived from the conditions
which could be confirmed by additional DCS analysis. The of combinatorial step 4; b) Ag nanoprisms obtained from combi-
natorial step 16; c) product particles from combinatorial step 28.
SEM data demonstrated that nanoprisms with edge lengths
between 25 and 180 nm emerged from different individual
combinatorial steps. Thus, it could be demonstrated that the
The authors gratefully acknowledge the funding from
method of nanoparticle synthesis in micro fluid segment se-
the DFG (KO 1403/22-1). Furthermore, the authors
quences is well suited for a parameter screening and an ex-
would like to thank Andrea Csáki, Wolfgang Fritzsche
act tuning of the plasmonic properties and opens up new
and Matthias Thiele from IPHT Jena as well as Alexan-
possibilities for the investigation of new particle systems
der Groß and Mike Günther for the useful discussions.
with complex compositions or advanced structural architec-
Many thanks are also directed to Steffen Schneider and
tures.
Frances Möller for their technical support.

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 Chemie
Ingenieur
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References
[1] J. Reichert, A. Csaki, J. M. Köhler, W. Fritzsche, Anal. Chem.
2000, 72, 6025. DOI: 10.1021/Ac000567y
[2] A. K. Singh, D. Senapati, A. Neely, G. Kolawole, C. J. Hawker,
P. C. Ray, Chem Phys. Lett. 2009, 481, 94. DOI: 10.1016/
j.cplett.2009.09.045
[3] A. Pinchuk, U. Kreibig, A. Hilger, Surf, Sci. 2004, 557, 269.
DOI: 10.1016/j.susc.2004.03.056
[4] L. Abahmane, A. Knauer, J. M. Köhler, G. A. Groß, Chem. Eng.
J. 2011, 167, 519. DOI: 10.1016/j.cej.2010.08.078
[5] L. Abahmane, J. M. Köhler, G. A. Groß, Chem.-Eur. J. 2011, 17,
3005. DOI: 10.1002/chem.201002043
[6] J. M. Köhler, L. Abahmane, J. Wagner, J. Albert, G. Mayer,
Chem. Eng. Sci. 2008, 63, 5048. DOI: 10.1016/j.ces.2007.11.038
[7] J. Wagner, J. M. Köhler, Nano Lett. 2005, 5, 685. DOI: 10.1021/
Nl050097t
[8] S. L. Poe, M. A. Cummings, M. R. Haaf, D. T. McQuade,
Angew. Chem., Int. Ed. 2006, 45 (10), 1544. DOI: 10.1002/
anie.200503925
[9] I. Shestopalov, J. D. Tice, R. F. Ismagilov, Lab Chip 2004, 4,
316. DOI: 10.1039/B403378G
[10] H. Song, D. L. Chen, R. F. Ismagilov, Angew. Chem., Int. Ed.
2006, 45, 7336. DOI: 10.1002/anie.200601554
[11] D. Malsch, M. Kielpinski, R. Merthan, J. Albert, G. Mayer, J. M.
Köhler, H. Süße, M. Stahl, T. Henkel, Chem. Eng. J. 2008, 135
(S1), S166. DOI: 10.1016/j.cej.2007.07.065
Chemie Ingenieur Technik 2013, 85, No. 4, 467–475 © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Combinatorial synthesis screening 475
[12] A. Aimable, N. Jongen, A. Testino, M. Donnet, J. Lemaitre,
H. Hofmann, P. Bowen, Chem. Eng. Technol. 2011, 34, 344.
DOI: 10.1002/ceat.201000324
[13] Y. J. Song, J. Hormes, C. S. S. R. Kumar, Small 2008, 4, 698.
DOI: 10.1002/smll.200701029
[14] S. Duraiswamy, S. A. Khan, Small 2009, 5, 2828. DOI:
10.1002/smll.200901453
[15] A. Knauer, A. Thete, S. Li, H. Romanus, A. Csaki, W. Fritzsche,
J. M. Köhler, Chem. Eng. J. 2011, 166, 1164. DOI: 10.1016/
j.cej.2010.12.028
[16] A. Knauer, A. Csaki, F. Moller, C. Huhn, W. Fritzsche, J. M.
Köhler, J. Phys. Chem. C 2012, 116, 9251. DOI: 10.1021/
jp210842g
[17] J. L. Cao, D. Kursten, S. Schneider, A. Knauer, P. M. Gunther,
J. M. Köhler, Lab Chip 2012, 12, 474. DOI: 10.1039/c1lc20584f
[18] A. Funfak, J. Cao, A. Knauer, K. Martin, J. M. Köhler, J. Environ.
Monit. 2011, 13, 410. DOI: 10.1039/C0EM00162G
[19] D. Aherne, D. M. Ledwith, M. Gara, J. M. Kelly, Adv. Funct.
Mater. 2008, 18, 2005. DOI: 10.1002/adfm.200800233
[20] A. Knauer, J. M. Köhler, Chem. Eng. J. 2013, in press. DOI:
10.1016/j.cej.2012.10.008
[21] U. Kreibig, L. Genzel, Surf. Sci. 1985, 156, 678. DOI: 10.1016/
0039-6028(85)90239-0
[22] U. Kreibig, Z. Phys. D: At., Mol. Clusters 1986, 3 (2 – 3), 239.
DOI: 10.1007/BF01384813
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