Electrochemical synthesis of silver nanoparticles in solutions of rhamnolipid

Orest Kuntyi1, Artur Mazur1, Andriy Kytsya2 ✉, Olena Karpenko2, Liliya Bazylyak2, Ivanna Mertsalo1,
Tetiana Pokynbroda2, Alla Prokopalo2
1
Department of Chemistry and Technology of Inorganic Substances, Lviv Polytechnic National University, Lviv, 79013,
Ukraine
2
Department of Physical Chemistry of Fossil Fuels of the Institute of Physical-Organic Chemistry and Coal Chemistry named
after L.M., Lytvynenko of the National Academy of Sciences of Ukraine, Lviv 79060, Ukraine
✉ E-mail: kytsya@nas.gov.ua

Published in Micro & Nano Letters; Received on 26th March 2020; Revised on 14th May 2020; Accepted on 31st May 2020

The electrochemical method of synthesis of silver nanoparticles (AgNPs) using ‘sacrificial’ silver anode as a source of Ag+, microbial origin
surfactant (rhamnolipid, RL) as a stabiliser of AgNPs and electric current as a reducer is presented. Using of cyclic voltammetry it was
determined that RL concentration and temperature are the main factors influencing the rate of anodic dissolution of silver and cathodic
reduction of the formed complex [AgRL]+. Increasing of RL concentration leads to increasing of the cathodic currents that indicate the
increase of the rate of AgNPs formation. With increasing the temperature from 40 to 60°C the values of the anode and cathodic currents
increase to 1.5 times, this indicates the predominant diffusion nature of the influence of the temperature on the synthesis of AgNPs.
Obtained AgNPs were investigated using transmission electron microscopy and it was found that increasing of concentration of surfactant
leads to decreasing of the size of AgNPs, whereas increasing of temperature, on the contrary, leads to increasing of mean size of AgNPs.
Synthesised AgNPs showed significant antimicrobial activity against the bacterial phytopathogens Xanthomonas campestris and
Agrobacterium tumefaciens. It has been shown that AgNPs stabilised by RL are characterised by low phytotoxicity.

1. Introduction: Among colloidal solutions of the different metal
nanoparticles (MNPs) the solutions of silver nanoparticles
(AgNPs) have the widest application in different branches of the
industry in particular in medicine [1–4], catalysis [1, 5, 6], the
sensor systems [7–9] etc. It is well known that the functional
properties of MNPs including AgNPs depend on their shape and
size [10–13]. Therefore, the development of methods for controlled
synthesis of MNPs in general and AgNPs, in particular, is one of the
priorities in the modern chemistry of nanomaterials [14–18].
The formation of stabilised MNPs using the surfactants (Surf) in
solutions is a multi-stage and multifactor process and generally can
be described as follows: (i) reduction of metal ions to atoms (1);
(іi) nucleation (2), i.e. the association of M 0 atoms into nanoclusters
(MNCs); and (iii) the growth of MNCs in MNPs (3)
M z+ + ze  M 0 (1)
mM 0 + xSurf  Mm · Surf x


(MNCs) (2)
 
Mm · Surf x + nM 0  M(m+n) · Surf y


(MNPs) (3)
The limiting stage of the formation of MNPs is the reduction
reaction (1) which determines the nucleation rate [19–21].
Activation energy (Еа) of the reduction reaction (1) significantly
exceeds the values of Еа for the processes (2) and (3). For
example, Ea of nucleation of AuNPs is 92.7 kJ·mol–1 and Ea of
their growth is equal to 24.6 kJ·mol–1 [21]. The main factor affect-
ing the rate of MNCs formation as well as their growth and, accord-
ingly, geometry of formed MNPs, is the mass transfer. First of all,
this is the mass transfer of Mz+ ions and a reducing agent which
concentration often determines the shape and size of the synthesised
nanoparticles [22]. Therefore, ensuring of a given concentration of
these precursors in situ is one among the conditions for the con-
trolled formation of MNPs in aqueous solutions.
As it was shown on the example of the investigation of the
formation of AgNPs [21, 23–25], the nature of the reducing agent
and anions also has a significant role in nucleation which is based
on the reaction (1). However, the most famous methods of the
preparation of colloidal solutions of stabilised AgNPs which are
based on the use of precursors, namely soluble silver salts and
synthetic [26, 27] or natural origin [4, 8, 14, 25, 28–30] reductants,
do not always provide the possibility to synthesise the nanoparticles
of given size and shape. From this point of view, the electro-
chemical synthesis of AgNPs is promising and it is intensively
studied in the last decade [31–40]. The main significant
advantage of the electrochemical synthesis of AgNPs over chemical
synthesis is the minimisation of precursors in solution, and exclud-
ing of the reducing agent from the reaction mixture (see Table 1).
At the same time, the use of metallic precursors can be also
excluded from the procedure of synthesis applying soluble silver
anodes [32, 33, 35–40]. Thus, the electrochemical methods
of AgNPs synthesis may realise the controlled manufacturing
of nanoparticles with predicted size and meet the criteria of green
synthesis [28, 41] by analogy with the of laser ablation technique
[1, 26, 42–44].
The most of working solutions contain mainly only the
surfactants (as stabilisers of AgNPs) but there are known methods
for the synthesis of AgNPs in distilled water at high voltages
(20 V) in absence of surfactants [32]. For the electrochemical
synthesis of AgNPs different methods of the current supply are
used namely galvanostatic technique [31, 34], polarity changing
[32, 33, 38], current pulse [35]. Combined methods for the
synthesis of AgNPs in which the solutions of silvers complexes
are obtained by electrolysis using sacrificial silver anodes followed
by chemical reduction of organic matter [39, 40] are also known.
The Letter presents the results of the study of synthesis of
colloidal solutions of AgNPs stabilised with biosurfactant-
rhamnolipids (RLs) using the ‘sacrificial’ silver anodes in cyclic
voltammetry mode. RLs are surface-active products of microbial
synthesis of the strain Pseudomonas sp. PS-17 [45–47].
Compared to chemical surfactants biosurfactants have a number
of advantages such as the effectiveness at the extreme values
of temperature and pH, biodegradability and low toxicity,

802 Micro & Nano Letters, 2020, Vol. 15, Iss. 12, pp. 802–807
& The Institution of Engineering and Technology 2020 doi: 10.1049/mnl.2020.0195
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Table 1 Conditions of electrochemical synthesis of AgNPs

Precursors Cathode Anode Regimes of electrolyse λmax, nm AgNPs size, Ref.

nm
silver salt Stabiliser

AgNO3 PVPa rotating platinum galvanostatic manner at ∼22°C 420 5–15 [31]
platinum
— — silver silver U = 20 V, t = 20−95°C, polarity — 2–20 [32]
changing (30–300 s)
— Pluronic® f127 silver silver U = 20 V, polarity changing (4 min) 450 − 460, 540 − 560 <100 [33]
AgNO3 Na-alginate platinum platinum icathode = 5–50 mA cm−2, 0.5–10 min 405–440 10–30 [34]
— PVPa silver silver current pulse, 5–10 mA 420 10–55 [35]
— Bu4NPF6 in DMF platinum silver E = − 1.10 V 420 30 [36]
— Na3C6H5O7 silver silver U = 12 V, 2 h, ∼22°C 416 19.7 ± 4.3 [37]
— NaPAb silver silver revers. current (1 Hz), 6 V, 40–60°C 490–530 2–10 [38]
— chitosan platinum silver electrolyse (U = 2 V) followed by 420 2–16 [39]
UV irradiation (λmax = 254 nm)
— — silver silver 0.8–1.0 V followed by reduction — <20 [40]
by MeOH, EtOH or PrOH
a
PVP – polyvinyl pyrrolidone; bNaPA – sodium polyacrylate.

i.e. they are environmentally friendly. The unique properties of bio-
surfactants (emulsification of fats and carbohydrates, reduction of
the surface tension of solutions, regulation of wetting, the effect
on capillary processes, increase in the permeability of cell
membranes) determine the prospects for their use in agriculture,
medicine, environmental protection, enhanced oil recovery etc.
Biosurfactants can be used as stand-alone products, as well as for
the creation of complex agents [47]. At the same time, the colloidal
solutions of AgNPs stabilised by RL molecules exhibit high anti-
bacterial and chemotactic activities [47–49]. That is why herein
we present the electrochemical method of synthesis of colloidal
solutions of AgNPs using ‘sacrificial’ silver anodes. The novelty
of discussed technique is the joint using of ‘sacrificial’ silver
anodes as a source of Ag+, RL as a stabiliser of AgNPs and electric
current as a reducer. Such a method of synthesis is promising in the
technological aspect that is important for the manufacturing
of bactericides as well as corresponds to the criteria of ‘green’
synthesis of colloidal solutions of AgNPs.
2. Experimental
2.1. Еlectrochemical investigations and preparation of AgNPs:
Electrochemical studies were carried out by cyclic voltammetry
using a galvanostat/potentiostat. A silver plate (99.99% mas)
(21 mm × 35 mm) and platinum plate (25 mm × 28 mm) were used
as the working and auxiliary electrodes. Saturated silver chloride
electrode (Ag/AgCl) mounted with a Luggin capillary contained
1 mol l−1 KNO3 was used as the reference electrode.
RL which is the surface-active product of the microbial synthesis
of the strain Pseudomonas sp. PS-17 was obtained according to the
method described in [50].
The experiments were performed in aqueous solutions of mono-
rhamnolipid (RL) with a concentration of 0.5, 1 and 2 g l−1 at
temperature 40 – 60°C and pH = 8.5. pH value was provided by
the addition of 2 M sodium acetate solution. The silver electrode
was polarised within the potentials of + 1.0 to −1.5 V at potential
scan rate 20 mV s−1. Electrochemical studies and electrochemical
synthesis of AgNPs were performed in a thermostated
three-electrode cell.
2.2. Measurements: The UV–visible (UV–vis) spectra of colloidal
solutions were recorded using a UV-mini-1240 spectrophotometer
(Shimadzu, Japan).
Transmission electron microscopy (TEM) images of the samples
were recorded using a JEM-I230 (JEOL, Japan) with an
acceleration voltage of 80 kV. The samples for TEM investigations
were prepared by drying of 0.05 μl of silver sol on the carbon net
at room temperature. The diameters of obtained AgNPs were
determined using TEM images by comparison of the sizes of
individual particles with the scales presented on images.
2.3. Antimicrobial activity and phytotoxic effect: Antimicrobial
activity of nanoparticles was evaluated by the minimum inhibitory
concentration (MIC) – the lowest concentration of antimicrobial
agents that inhibits the growth (visible) of the microorganisms
Xanthomonas campestris (X. campestris) and Agrobacterium tume-
faciens (A. tumefaciens) after incubation in a 24-well round-bottom
microplate at 37°C for 20 h. To determine the minimum bactericidic
concentration (MBС) the subcultures from each transparent tubes
of MIC series were cultured on agar plates (on medium without
nanoparticles). MBС is the lowest AgNPs concentration which
did not show growth after incubation at 37°C for 20 h [51, 52].
Fungicidal activity was studied by the disk diffusion method
against fungi Alternaria alternata (A. alternata), Fusarium
oxysporum (F. oxysporum), Rhizoctonia cerealis (R. cerealis) in
accordance with the method.
The phytotoxicity of the nanoparticle solutions was studied on
the test plant garden cress (Lepidium sativum): seeds were soaked
for 3 h in the solutions with the studied concentrations, grown for
7 days, germination was tested on the third day and phytotoxic
effect – on seventh day. The phytotoxic effect (PE, %) was
determined as a ratio of shoot length of test plants to the shoot
length of control:
  
PE = L0 − Lx /L0 × 100%
where PЕ is phytotoxic effect, L0 is the shoot length of test plants;
Lx is the shoot length control plants.
Assessment of the toxicity of the solutions was carried out on a
five-point scale [53].
3. Results and discussion: RL are biosurfactants whose molecules
contains O-donor ligands as a part of сarbohydrate group [53]:
where R = CH((CH2)6CH3)–CH2–C(O)O–CH
((CH2)6CH3)–CH2–COOH.
Such a molecule may form complexes due to the formation of a
donor-acceptor bond between O atoms of сarbohydrate group and
metal ions [54–56]. During the electrochemical synthesis of
AgNPs in RL solutions using sacrificial anodes the following

Micro & Nano Letters, 2020, Vol. 15, Iss. 12, pp. 802–807 803
doi: 10.1049/mnl.2020.0195 & The Institution of Engineering and Technology 2020
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basic electrode reactions occur: density increases from 0.97 to 1.54 mA cm−2 (∼1.5 times) with
increasing temperature from 40 to 60°C (Fig. 2), i.e. it is similar
+
anode:Ag + RL  AgRL +e−


(4) to that observed with the anode currents. At E = 0.1 V the increase
of the reduction currents is slightly higher – from 0.73 to 1.54
+ 0 mA cm−2 (2.1 times higher) which indicates the mixed diffusion-
cathode: AgRL +e−  AgRL



(5) kinetic nature of the effect of temperature on the cathodic
reaction (5).
Obtained neutral complexes [AgRL] are unstable; therefore they Additionally, the stability of the process of dissolution of the
combine into nanoclusters (AgNCs) and nanoparticles stabilised silver anode has been investigated (Fig. 3). It was found that the
by RL molecules. To establish the influence of electrolysis
conditions on the implementation of these processes we studied
the electrochemical behaviour of silver depending on the concentra-
tion of RL and temperature and the influence of these factors on the
sizes of AgNPs.

3.1. Electrochemical behaviour of silver in RL solutions: The

nature of the CVA curves points on significant dependence of
the anodic dissolution of silver on the surfactant concentration
(Fig. 1). In the concentration range of RL 0.5–2.0 g·l−1, for
E = 1 V an increase of the value of the anode current density was
observed within 1.03–3.31 mA cm−2 which is points on increasing
of the silver dissolution rate. This is caused by increasing of the
filling of the anode surface with adsorbed RL molecules which con-
tributes to the acceleration of reaction (4). The cathodic reduction
rate (5) increases proportionally to the silver anodic dissolution Fig. 3 Cyclic voltammograms of silver in 1.0 g l−1 RL solution
rate (4). The current maxima with E = 0.1 V increase from 0.31 to
1.35 mA cm−2 and at E = −1.5 V from 0.52 to 1.12 mA cm−2 at
the increase of RL concentration from 0.5 to 2.0 g l−1.
At the increase of temperature in the range of 40–60°С the
current density at E = 1 V, i.e. the anodic dissolution rate of
silver, increases from 2.12 to 3.28 mA cm−2 (increasing ca
1.5 times) (Fig. 2). This indicates on predominant diffuse nature
of the influence of the temperature factor on reaction (4).
The effect of temperature on the value of cathode currents
depends on the electrode potential. So, at E = −1.5 V, the current

Fig. 4 UV–vis spectra of AgNPs solution at the increasing number of CVA

cycles and the dependency of wavelength and OD of the solution on number
of CVA cycles. C (RL) = 1.0 g l−1, t = 50°С

Fig. 1 Cyclic voltammograms of silver at different RL concentrations (0.5,

1.0, 2.0 g l−1). t = 50 °С

Fig. 5 ТЕМ images of AgNPs obtained in RL solution

a С = 0.5 g l−1
b С = 1.0 g l−1
c С = 2.0 g l−1
Fig. 2 Cyclic voltammograms of silver at different temperatures (40, 50 і 60 d Histograms of the normal distribution of AgNPs at appropriate
о
С) in RL solution (1.0 g l−1) concentrations

804 Micro & Nano Letters, 2020, Vol. 15, Iss. 12, pp. 802–807
& The Institution of Engineering and Technology 2020 doi: 10.1049/mnl.2020.0195

character of CVA-curves did not change during 10 cycles. This fact
indicates an absence of passivation of the silver anode due to com-
plexation of Ag+ with сarbohydrate group of RL that it was
assumed above (4).
3.2. UV–vis spectra of AgNPs–RL solutions: Using of UV–vis
spectroscopy it was found that the optical density (OD) of AgNPs
solutions linearly increases with increasing of cycles number
(Fig. 4). At the same time, it must be noted some ‘induction
period’ which goes on during the starting 6 cycles of CVA and
may be corresponded to the nucleation stage. Linear increasing of
OD is accompanied by a blue shift of the position of the AgNPs
solution absorbance maxima that may be caused by the strong
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interaction of small silver particles and/or nuclei of the AgNPs
with the acidic groups of RL [57, 58]; such interaction is decreased
with the growth of particles due to decreasing of the ratio of ionised
surface silver atoms.
It must be noted that the similar changes of UV–vis spectra were
observed for all conditions of experiments carrying out. At the same
time obtained AgNPs solutions were stored at ambient conditions
for 2 months and any changes of UV–vis spectra were not observed
that indicates the stability of AgNPs in time.
3.3. TEM investigations of AgNPs: TEM investigations showed
that at RL concentration within 0.5–2.0 g l−1 and in the temperature
range 40–60°С solutions of AgNPs with a size range of 2–20 nm
are formed (Figs. 5 and 6). Moreover, with an increase of the RL
concentration in solution, a tendency toward a decrease of the
sizes of AgNPs is observed (Fig. 5) which is caused by complica-
tions of the growth of NCs and NPs due to the high concentration of
surfactant molecules and their micelles. A decrease in the range of
particle size dispersion is also observed (Fig. 5d). Such effect is
typical and decreasing of size of MNPs with increasing of ratio
[Surf]/[Mz+] is commonly observed both for chemical synthesis
of MNPs (AgNPs [14] and PdNPs [15]) and electrochemical
synthesis of AgNPs [38].
With increasing temperature the opposite tendency is observed:
an increase of the size of AgNPs (Fig. 6) and their size distribution
(Fig. 6d) and this effect is similar to that observed previously [38] at
the synthesis of AgNPs in solutions of sodium polyacrylate. This
is explained by the intensification of desorption processes and
correspondingly the weakening of the donor–acceptor interaction
in the surface complexes of RL→AgNPs between electron-donor
surfactant molecules and metal atoms of the nanoparticle.

3.4. Antimicrobial activity and phytotoxicity: It is well known that

antimicrobial activity of AgNPs increase with the decreasing of the
size of particles [59]. That is why we tested the antimicrobial
activity of AgNPs obtained at 50°C in 2 g l−1 solution of RL.
Fig. 6 ТЕМ images of AgNPs obtained in RL solution С = 2.0 g l−1
a t = 40°C Such a sample is characterised by small size (∼5 nm) and narrowest
b t = 50°C size distribution of AgNPs (see Fig. 6d).
c t = 60°C For modern plant growing the urgent problem is the development
d Histograms of the normal distribution of AgNPs at appropriate of new active and environmentally friendly antimicrobials that
temperatures inhibit pathogens of plant diseases – phytopathogenic bacteria
and fungi. That is why the plant pathogens X. campestris and
A. tumefaciens as well as fungi A. alternata, F. oxysporum and
Table 2 Antimicrobial activity of solutions of RL stabilised AgNPs R. cerealis were used for the testing of antimicrobial activity of
obtained AgNPs.
Microorganisms Dilutions (concentrations, g l−1) of solutions It was observed that the Аg–RL solutions had significant anti-
microbial activity in relation to the tested bacteria (see Table 2),
Аg–RL RL
but did not inhibit fungi F. oxysporum, R. cerealis, A. alternata
MІC МBC MІC МBC in the studied concentrations range.
Phytotoxicity (ecototoxicity) is an important indicator of the
X. campestris 1:128 (0.016) 1:64 (0.031) 1:16 (0.15) 1:8 (0.25) practical use of new preparations. The main criteria for phyto-
A. tumefaciens 1:64 (0.031) 1:32 (0.062) 1:8 (0.25) 1:4 (0.5) toxicity of Ag–RL were the germination of test plant and the phyto-
toxic effect, which were investigated at various concentrations

Table 3 Phytotoxicity of solutions of Ag–RL nanoparticles (2 g l−1)

Dilutions Seeds germination, % Shoot length, cm Phytotoxic effect, % Toxicity level

Control (H2O) 86 1.70 ± 0.03 — —

Ag–RL 1:0 88 1.41 ± 0.02 17 weak
1:2 90 1.45 ± 0.03 15 weak
1:4 98 1.46 ± 0.03 14 weak
1:8 92 1.45 ± 0.03 15 weak
1:16 92 1.62 ± 0.03 5 weak
1:32 84 1.71 ± 0.03 — —
1:64 86 1.80 ± 0.04 — —
1:100 90 1.76 ± 0.03 — —

Micro & Nano Letters, 2020, Vol. 15, Iss. 12, pp. 802–807 805
doi: 10.1049/mnl.2020.0195 & The Institution of Engineering and Technology 2020

(Table 3). It was shown that the studied solutions of Ag–RL nano-
particles did not inhibit the germination of watercress seeds.
It was established the weak phytotoxic effect of colloid solutions
of Ag–RL. It was observed at high concentrations (from 1.30 g l−1),
which means that the Ag–RL showed a low level of toxicity
(Table 3).
4. Conclusions: The formation of colloidal solutions of AgNPs
in solutions of RLs under conditions of cyclic voltammetry is
investigated. The main factors influencing the rate of anodic
dissolution of silver and the cathodic reduction of complex ions
[AgRL]+ are the RL concentration and temperature – increasing
of temperature and the RL concentration accelerate the formation
of AgNPs. It was found that with increasing of temperature from
40 to 60°C the values of the anode and cathodic currents increase
approximately in 1.5 times which indicates on predominant
diffusion nature of the influence of the temperature factor on the
formation of AgNPs. It was shown that increasing the RL concen-
tration leads to decreasing of the size of AgNPs, whereas with
increasing of the temperature the opposite effect takes place: the
sizes of nanoparticles were increased. Dependence of the OD
of working solutions on the number of cycles is almost linear
indicating the stability of the process of synthesis of AgNPs in time.
Electrochemically synthesised AgNPs stabilised with RL showed
significant antibacterial activity against the phytopathogens
X. campestris and A. tumefaciens as well as low level of toxicity.
So, electrochemically synthesised Аg–RL solutions can be
considered environmentally friendly.
5. Acknowledgments: This work was supported by the Ukrainian
Government (Project No 0118U000268)
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