pubs.acs.

org/JPCL Letter

Electrochemical Investigation of Porosity in Core−Shell

Magnetoplasmonic Nanoparticles
Lemma Teshome Tufa, Van Tan Tran, Ki-Jae Jeong, Birhanu Bayissa Gicha, Bedasa Abdisa Gonfa,
and Jaebeom Lee*
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ABSTRACT: Porous core−shell nanoparticles (NPs) have emerged as a promising material for
broad ranges of applications in catalysts, material chemistry, biology, and optical sensors. Using a
typical Ag core−Fe3O4 shell NP, a.k.a., magnetoplasmonic (MagPlas) NP, two porous shell models
were prepared: i.e., Ag@Fe3O4 NPs and its SiO2-covered NPs (Ag@Fe3O4@SiO2). We suggested
using cyclic voltammetry (CV) to provide unprecedented insight into the porosity of the core−
shell NPs caused by the applied potential, resulting in the selective redox activities of the core and
porous shell components of Ag@Fe3O4 NPs and Ag@Fe3O4@SiO2 NPs at different cycles of CV.
The porous and nonporous core−shell nanostructures were qualitatively and quantitatively
determined by the electrochemical method. The ratio of the oxidation current peak (μA) of Ag to
Ag+ in the porous shell to that in the SiO2 coated (nonporous) shell was 400:3.2. The suggested
approach and theoretical background could be extended to other types of multicomponent NP
complexes.

C ore−shell nanoparticles (NPs) are of great scientific

interest because of their unique features and broad
applications in energy, electromagnetic shielding, catalysis,
optoelectronics, sensors, drug delivery, and environmental
remediation.1 Recent studies using porous shells have shown
the advantages of large surface to volume ratios, permeability,
void spaces, confinement ability of pore channels and cavities,
and fast mass/charge transport.2 These properties usually offer
an abundant electroactive site for chemical reaction and have
potential applications in biomedicine and nanophotonics.3,4
Moreover, an in-depth understanding of the reaction between
the core surface and the surrounding environment helps a more
efficient nanostructure to be fabricated for the desired
application, where the surrounding environment may be a
designated shell or solvent if the shell is porous. The properties
and performance of nanomaterials rely mainly on their
composition, size, morphology, and structure. In the case of
the core−shell NPs, the combination of the inner core and the
outer shell is a crucial factor, along with composition, shape, and
structure, to determine their properties and intended
applications.5 The most common methods for characterizing
the core−shell nanostructures include electron microscopic,
spectroscopic, scattering, and thermal gravimetric analyses.6
Electrochemical analysis is also a conventional robust tool to
characterize NPs.7−9 The Bard group pioneered an electro-
chemical characterization method to monitor the formation of
Ag@Ag2O NPs by cyclic voltammetry (CV) analysis.10 The
evidence of the formation of a Ag2O shell on a Ag core by
thermal treatment of Ag NPs was characterized by CV using a
gold electrode in a cast Nafion film containing carbon as a
conductive matrix. The initial positive scan measured the free Ag
signal, whereas the initial negative scans measured the Ag2O
signal, providing information on trapped or core Ag. Compton
et al. also demonstrated electrochemical determination of the
sizes individual Au@Ag core−shell NPs based on their different
electrochemical activities.11 The electrochemically determined
core−shell sizes were in excellent agreement with transmission
electron microscopy (TEM) results. Furthermore, Tschulik et
al.12 demonstrated the combination of two independent
electrochemical methods, namely, cathodic and anodic particle
coulometry, to determine the sizes of magnetite (Fe3O4) NPs.
The technique allows the electrochemical measurement of a
single NP as well as the simultaneous verification of the results.
However, the quantitative and dynamic electrochemical
characterization of NPs is still limited to metal NPs throughout
their current (I)−potential (V) of oxidation/reduction. Addi-
tionally, Brunauer−Emmett−Teller (BET) analysis is the only
standard method for determining surface area and the porosity
of the nanomaterials. Nevertheless, in BET analysis, large
quantities of materials and clean and dry samples are needed.13
The lack of an accurate, inexpensive, and easy porosity
determination technique for nanomaterials with a small sample
size remains challenging. Therefore, it is important to develop a
Received: April 22, 2022
Accepted: June 23, 2022

© XXXX American Chemical Society https://doi.org/10.1021/acs.jpclett.2c01201

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Figure 1. Schematic diagram and electron microscopic characterization of Ag@Fe3O4 and Ag@Fe3O4@SiO2 NPs. (A) Schematic illustration of the
synthesis processes. (B) TEM image of Ag@Fe3O4. (C, D) HRTEM images of Ag@Fe3O4@SiO2. and (E) EDS elemental mapping of Ag@Fe3O4@
SiO2 NPs.

Figure 2. Electron microscopic, optical, and electrochemical characterization of Ag@Fe3O4 NPs. TEM images of Ag@Fe3O4 NPs after (A) 5 cycles,
(B) 10 cycles, (C) 15 cycles, and (D) 20 cycles of CV. (E) UV−visible spectra of Ag@Fe3O4 NP s before and after 5, 10, and 15 cycles of CV. (F) Cyclic
voltammogram of dissolution of Ag@Fe3O4 for 10 cycles in the potential range from −0.5 to 0.7 (G) HRTEM images of Ag@Fe3O4 after 5 cycles of
CV and the corresponding (H) EDS elemental mapping of Ag@Fe3O4 NPs.

reliable and robust electrochemical method with high accuracy Herein, we introduced the CV analysis method through
for porous core−shell structure determination. preferential removal from the core−shell nanocomposite to
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characterize the porosity of NPs through selective redox
activities of the core and porous shell components (Ag@
Fe3O4 and Ag@Fe3O4@SiO2) in dilute HCl. A conventional
method to investigate the electrochemical properties of NPs
involves their immobilization on the surface of electrode
materials.14,15 This film preparation technique was usually
used to probe the core and shell oxidation and reduction under
different experimental conditions. However, the preparation of
the film and sample attachment become crucial hurdling points
to reproduce reliable and robust analysis data. Meanwhile, in the
as-suggested analysis method, the electrochemical behavior of
Ag@Fe3O4 NPs was examined in a solution state (0.1 M HCl)
and with high surface energy NPs film in the potential range of
−0.5 and 0.7 V versus a Ag/AgCl reference electrode. The
electrochemical activities are obtained by CV using glassy
carbon (GC) and fluorine-doped tin oxide (FTO)-coated glass
electrodes. Our electrochemically characterized qualitative and
quantitative data are in good agreement with TEM measure-
ments of the surface morphology change of the NPs, indicating
that the electrochemical characterization of the porous core−
shell magnetoplasmonic (MagPlas) nanostructures is an
effective and alternative technique.
The Ag@Fe3O4 and double-shelled Ag@Fe3O4@SiO2 NPs
were fabricated; the experimental procedures are described in
detail elsewhere.16−18 Figure 1A shows the outline of the specific
synthesis procedure of Ag@Fe3O4 and Ag@Fe3O4@SiO2 NPs.
In the first step, the superparamagnetic Ag@Fe3O4 nanospheres
with a plasmonic Ag core and a magnetic Fe3O4 shell were
prepared in a closed system by reduction reactions of silver
nitrate, iron(III) nitrate, and sodium citrate. In the second step,
Ag@Fe3O4@SiO2 NPs were prepared by the Stöber method.
The thickness of an amorphous SiO2 shell was controlled by
different reaction times. The TEM image in Figure 1B reveals
Ag@Fe3O4 NPs are composed of two different components, a
dark Ag single crystal core and a gray nanosized Fe3O4 with
different porosities, where the porosity was characterized by
TEM. The average diameter of the MagPlas NPs is about 110
nm, in which the Ag core is ∼50 nm and the Fe3O4 shell is ∼30
nm. Figure 1C,D shows high resolution transmission micros-
copy (HRTEM) images of Ag@Fe3O4@SiO2 NPs with a silica
layer thickness of ∼15 nm. The silica shell thickness was
regulated by changing the concentration of tetraethyl
orthosilicate (TEOS) and the reaction time.17 The HRTEM
image shows that the Ag@Fe3O4@SiO2 NPs are spherical with
uniform size and shape as illustrated in the Supporting
Information (Figure S1A,B). Elemental analysis of the particles
using energy dispersive X-ray spectroscopy (EDS) is shown in
Figure 1E, revealing the presence of silver, iron, silicon, and
oxygen in a composite material. These results proved that the
orderly arranged Ag@Fe3O4 and double-shelled Ag@Fe3O4@
SiO2 hierarchical structures have been successfully synthesized.
The nitrogen adsorption−desorption isotherms confirmed the
presence of uniform mesopores with a BJH (Barrett−Joyner−
Halenda) pore diameter of 20.23 nm for Ag@Fe3O4 NPs. The
BET (Brunauer−Emmett−Teller) surface area and mesopore
volume were measured as 27.96 m2 g−1 and 0.14 cm3 g−1,
respectively (Figure S2).
The electrochemical analysis has been conducted to
characterize the porosity of the synthesized NPs. Figure 2
shows the outline of the electrochemical analysis and
mechanism. The electrochemical behavior of Ag@Fe3O4 NPs
was examined in a solution state (0.1 M HCl) in the potential
range of −0.5 and 0.7 V versus a Ag/AgCl reference electrode.
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To ensure the source of reduction/oxidation peaks of core−shell
Ag@Fe3O4 NPs, each cyclic voltammogram of the Fe3O4 and Ag
NPs in 0.1 M HCl solution was measured for three and ten
cycles, respectively. Figure S3A,B shows the cyclic voltammo-
grams of the Fe3O4 NPs. The broad peak observed at about −1.0
V corresponds to the reduction of an electroactive Fe3O4 shell
(Fe3+ → Fe2+), and there was no additional broad reduction
peak observed for successive cycles, indicating complete
electrochemical reduction of the process involving the surface
removal of the Fe3O4 NP.19 Figure S3C,D shows the cyclic
voltammograms of the Ag NPs with corresponding reduction
peak potential (Ered) values of −0.21 V and −0.28 V for the first
and successive cycles, respectively. This is due to the strong
dependence of the peak potential on the metal coverage of the
surface of the electrode in an electrochemical reverse system.20
The cathodic current corresponds to the reduction of Ag+ →
Ag0, and Ered shifts to the negative potential region with
increasing number of cycles. The reverse oxidation peak
potential (Eox) was observed at 0.05 V. For Ag@Fe3O4 NPs
(Figure S3E,F), in the cathodic (reduction) potential sweep, the
broad peak was observed at −0.15 V, which is most likely related
to the reduction of the electroactive Fe3O4 shell (Fe3+ →
Fe2+),21 and for successive cycles, there was no appearance of
additional broad reduction peaks of Fe3O4 except the oxidation
peak of Ag at 0.055 V. In the second cycle, the maximum peak of
the core Ag was observed at the same potential of the first cycle,
indicating the dissolution of the core and shell. Upon increasing
the number of cycles, the oxidation peaks of the core were
increased due to the uncompleted oxidation of Ag ions on the
film surface. When comparing the core−shell structures to the
pure metal particles, it is notable that the oxidation and
reduction peaks are shifted toward more negative potentials,
indicating a composite character of the NPs.22
Note that the surface compositions of each core−shell NP
made up of identical atoms are not equal. They have significant
differences in free energy and reactivity depending on the facets
and morphologies of the topmost layer, which govern the
electrochemical tendency of an element to dissolution.23
Therefore, the electrochemical signals from many homogeneous
core−shell NPs on the electrode in the solution state represent
the colligative property of the NPs. Furthermore, in a
nanocomposite made up of two different metals, the metal
with the lower reduction potential is more readily dissolved and
exposed to an etchant. The characterization of a core−shell
particle is of eminent importance not only in identifying the core
and shell structure but also in understanding the mechanism
underlying the reaction process. Figure 2A−D shows TEM
images of Ag@Fe3O4 NPs at different numbers of CV cycles in
0.1 M HCl solution. The formation of the hole-like structure was
formed due to the dissolution of the core by the applied
potential in 0.1 M HCl solution. With the successive scans, there
were increases in the oxidation peaks of Ag until all Ag cores
were totally dissolved. As expected, the cyclic voltammogram
curves show a reduction peak around −0.15 V that corresponds
to the reduction of the Fe3O4 shell (eq 1) and Ag+ → Ag0 (eq 2).
On the reverse scan, the oxidation peaks at 0.05 V are related to
the oxidation of Ag → Ag+ (Figure 2F). However, the Fe anodic
peak was not observed in the given potential range. This was
confirmed by the UV−visible spectrum (Figure 2E). The
absence of the Ag peak after the electrochemical dissolution of
Ag NPs may be induced by the formation of AgCl(s). These
results indicate that etching becomes enormous at the higher
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Figure 3. Computational simulation and diffusion coefficients of the porous Ag@Fe3O4 core−shell NPs. (A, B) Computational simulation results on
the electrolyte concentration gradient in the shell at 100 ms as a function of the shell distance from a core surface (S1, S2, and S3 depict respective
core−shell Ag@Fe3O4 NPs with different shell porosities of 1 × 10−17 (S1), 1 × 10−15 (S2), and 1 × 10−13 (a.u.) (S3)). (C) Cyclic voltammograms of
[Fe(CN)6]3− at the porous Ag@Fe3O4 modified GCE and (D) anodic peak current versus potential of part (C).

number of CV cycles due to increased conversion of Ag NPs to
Ag ions.
Fe3O4 + 2e− + 8H+ F 3Fe2 + + 4H 2O
Ag + Cl− F AgCl + e−
Figure S4 shows optical images, surface plasmon scattering,
and electrochemical characterization of Ag@Fe3O4 NPs. The
optical images, surface plasmon scattering measurements, and
detailed description are shown in the Supporting Information.
Recording optical properties has become an important
alternative for bulk and single NP electrochemistry.24 Ag NPs
are typical highly scattering plasmonic materials at a designated
optical wavelength, and hence, the dark-field illumination
enables the NPs present on an electrode to be visualized as
diffraction-limited features in the optical field.
The proposed electrochemical reaction mechanism of the
porous Ag@Fe3O4 core−shell NPs is shown in Figure S5A. The
Ag core was oxidized or stripped at the potential EAg, and the
Fe3O4 shell was also oxidized at the potential EFe. The half
reduction reaction of Ag is Ag+ + e− → Ag, E0 = 0.800 V, and that
of Fe is Fe3+ + e− → Fe2+, E0 = 0.770 V vs standard hydrogen
electrode (SHE).25 That is, the reduction potential of the core is
more positive than the shell. As a result, the first oxidation scan
of the MagPlas core−shell exhibited a stripping peak for the
shell. Meanwhile, in the reverse scan, the reduction process was
shown for both the core and the shell. This dealloying process
increases the exposure of the Ag content in the core−shell,
resulting in a continuous increase of the oxidation current peaks
(Iox) of the remaining particle until the Ag oxidation potential is
reached and the particle is fully oxidized. Depending on the
(1) electrolytes and the scan rate, surface reorganization of the
remaining Ag might additionally occur on partially leached NPs,
(2) causing oxidation peaks. Additionally, the formation and
evolution of a cavity were derived by both the etching electrolyte
(HCl) and the electrochemical potential. However, the rate of
dissolution of the core−shell is low for chloride-containing
materials. The dissolution times of porous Ag@Fe3O4 NPs were
measured in H2O2 and NaCl. The dissolution time of the core
and shell was significantly lower in NaCl than in H2O2 solutions.
As shown in Figure S6, the TEM image of Ag@Fe3O4 NPs
treated in NaCl remained unchanged in 24 h for Fe3O4, whereas
those treated in H2O2 for 15 min showed a change in the
morphology and a UV−vis spectra peak shift. The resonance
wavelength is slightly blue-shifted due to a decrease in the Ag NP
size during etching. Ag@Fe3O4 NPs exhibit a shift in the spectra
indicative of the fact that their scattering effect dominates their
absorption due to the electronic interband transitions in
Fe3O4.26 Therefore, the dissolution of porous Ag@Fe3O4 NPs
is strongly affected by the applied potential.
The volume of the core being etched is calculated and
analyzed based on the data of the etched area (A). It is
challenging to estimate the etching volume based on the
observed TEM image because TEM images are the projection of
the 3D structure in 2D. It is a reasonable hypothesis that a
porous dealloyed composite particle has a mass activity near that
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Figure 4. Electron microscopic and electrochemical characterization of NPs: TEM images of (A) Ag@Fe3O4@SiO2 with SiO2 shell thicknesses of (A)
17 nm, (B) 20 nm, and (C) 25 nm. Cyclic voltammogram of (D) Ag@Fe3O4@SiO2 with a SiO2 shell thickness of 17, 20, and 25 nm in 0.1 M HCl at a
scan rate of 100 mV/s. Cyclic voltammograms of (E) Ag@Fe3O4 and (F) Ag@Fe3O4@SiO2 NPs with a SiO2 thickness of 25 nm after 1.2 V potential
applied for 10 s.
of the planar electrode with a dealloyed depth equal to the
diameter. By assuming a spherical shape for the etched space, the
etched volume is approximated as follows:
4 3
Vetched = πr
3 r2
because Aetched = πr2
4 ijj AAg + yzz
πj z
3 jk π z{
3/2
Vetched =
(3)
Curves of the entire etched volume as a function of cycle number
and electrochemical etching of the core−shell NPs are shown in
Figure S5B.
The diffusion of the electrolytes is a critical parameter to
analyze the relevance between electrochemical analysis (I or V)
and the porosity of the materials. The redox processes in the
bulk part of active electrode materials is generated by directed
diffusion of the charge carriers and is proportional to the square
of the scan rate (eq 4). In order to justify the relevance of the
diffusion of the electrolyte through porous NPs, three core−
shell Ag@Fe3O4 NPs with different shell porosities of 1 × 10−17
(S1), 1 × 10−15 (S2), and 1 × 10−13 (S3) were simulated at a
diffusion coefficient (1 × 10−6 m2s−1) of the solution for 100 ms
by COMSOL Multiphysics 5.2a software (COMSOL Inc.
Burlington, U.S.A.), where the porosities of S1−S3 are
arbitrarily selected to show a porosity dependence. Figure
3A,B shows the change in the concentration of electrolyte in the
shell at 100 ms as a function of shell distance (d) from the Ag
surface. These plots reveal that as the distance increases from the
core, the concentration of the electrolyte increases. Moreover,
the higher the porosity of a shell dramatically increases the
concentration of the electrolyte in the shell. This is attributed to
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the oxidation of the core. For instance, the core oxidation is
limited by the maximum concentration of Ag+(aq). The
maximum concentration (Cmax) of Ag+(aq) in the solution can
be determined by the following equation:27,28
Cmax = ρ
2 ln 2NADt
where ρ is the density of the NP, r is the radius of NP, NA is
Avogadro’s number, and t is the diffusion time. The diffusion
coefficient of [Fe(CN)6]3−(aq) was determined on a GCE
modified with porous Ag@Fe3O4 NPs. For a disc-shaped
working electrode, the diffusion coefficient (D) is determined by
the Randles−Sevick equation.29
0.447F 3/2An3/2D1/2Cv1/2
ip =
R1/2T1/2 (4)
where n is the number of electrons involved in the reduction, ip is
the peak current, D is the diffusion coefficient, v is the scan rate,
C is the concentration, A is the surface area of the electrode, F is
the Faraday constant, T is the absolute temperature, and R is the
ideal gas constant. By taking the diameter of the working
electrode as 3 mm, the diffusion coefficient calculated from the
line fitted to the anodic ip versus ν1/2 according to the above
equation was 1.29 × 10−6 cm2/s (Figure 3C,D). There is a
discrepancy between this value and the diffusion coefficient for
ferricyanide reported in the literature. This was due to the
electrochemical oxidization and reduction of Fe3O4 and
formation of Fe3+/2+.30 A buildup of oxide on an electrode’s
surface can lower its diffusion coefficient constant.31 The
oxidation and reduction peaks are separated due to the diffusion
of the reactants toward and from the surfaces of the electrode.
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The reaction kinetics correspond to the controlled diffusion
process of [Fe(CN)6]3− in the solution.32
The electrochemical approach to characterize and quantify
the porous and the nonporous core−shell NPs is proven for
Ag@Fe3O4 NPs and Ag@Fe3O4@SiO2 NPs (with different SiO2
shell thicknesses). TEM images of Ag@Fe3O4@SiO2 NPs
coated with different shell thicknesses (17, 20, and 25 nm) of
SiO2 are shown in Figure 4A−C. To identify the parameters
suitable for the CV characterization of the porous and the
nonporous samples, CVs of Ag@Fe3O4 NPs and Ag@Fe3O4@
SiO2 NPs were run by drop casting the NPs on GCE. Figure 4D
shows CV curves of different thickness SiO2 coated Ag@Fe3O4
NPs. The Ag oxidation signal decreases with increasing SiO2
shell thickness. Encapsulating NPs by chemical means has been
proposed for protection, but in solution-based processes, the
core material often oxidizes and corrodes during the coating
process itself.1 Thus, the small oxidation peak currents of silver
ion observed for coated SiO2 were produced during the
synthesis of NPs.
To quantify the ratio of the porous to the nonporous core−
shell NPs, CV curves of Ag@Fe3O4@SiO2 NPs with a SiO2 shell
thickness were analyzed (Figure S7A−C). The oxidation peaks
decreased with increased numbers of CV cycles and the
thickness of the SiO2 shell. Almost after the first cycle, no
sufficient access was shown for electroactive species, i.e., neither
Ag nor Fe3O4 reduced in the solution. The SiO2 layer isolates the
Ag core as well as an Fe3O4 shell from oxidation or reduction,
probably by preventing electron transfer from both Ag and
Fe3O4. In contrast to the Ag@Fe3O4 peaks, with successive
scans, there is a decrease in the oxidation and reduction peaks
because of the diffusion of exposed Ag+, formed in the oxidation
process, into the solution.
The same experiment was carried after the applied potential of
1.2 V for 10 s that showed that, by increasing the number of
cycles, both reduction and oxidation peaks of the core were
increased. The maximum peak current for dissolution of the core
was observed at the 60th cycle number, but upon increasing the
number of cycles above 60, the peak current decreased due to
the dissolution of NPs from the surface of an electrode or
chemical reaction between the HCl supporting electrolyte and
the Ag+ ion, resulting in the formation of the insoluble product
AgCl (Figure 4E). However, for 15 and 25 nm SiO2 coated
Fe3O4@Ag NPs (Figure S7D), the Ag core reduction showed a
low signal with increasing CV cycle numbers. The shell prevents
the electrochemical reaction of the core by blocking the
transport of ion or solvent.10 The ratio of the oxidation current
peak (μA) of Ag to Ag+ in the porous shell to that in the SiO2
coated shell was 400:3.2 (Figure 4E,F). Cyclic voltammograms
can distinguish between the shell and the core based on the
reduction peak position, and peak charge ratios give the shell/
core composition of the quantum dot.33 To confirm the reaction
of the core and shell NPs, TEM images and UV spectra of Ag@
Fe3O4@SiO2 NPs before and after electrochemic reaction for 20
cycles of the CV were recorded, and as shown in Figure S8, the
configuration of the core−shell was unchanged. Thus, electro-
chemical results and TEM analysis showed excellent agreement.
The nonporous and porous core−shell nanostructures can be
qualitatively and quantitatively determined by the electro-
chemical method.
We characterized solution-phase core−shell MagPlas nano-
structures (Ag@Fe3O4, Fe3O4@Ag@SiO2) using CV, with
selective redox activities of core and shell components. The
electrochemical activities were obtained by CV using Ag@Fe3O4
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and Fe3O4@Ag@SiO2 coated GC and FTO electrodes. The
porous and nonporous core−shell nanostructures were
qualitatively and quantitatively determined by a facile electro-
chemical method. The ratio of the oxidation current peak (μA)
of Ag to Ag+ in the porous shell to that in the SiO2 coated
(nonporous) shell was 400:3.2. The electrochemically charac-
terized core−shell qualitative and quantitative information were
in excellent agreement with TEM based measurements,
successfully demonstrating the CV characterization of core−
shell MagPlas nanostructures. This approach provides a fast
analysis method, which has a simple sample preparation and uses
cost-effective instruments.
■ EXPERIMENTAL SECTION
Materials. Silver nitrate (AgNO3), iron(III) nitrate nonahydrate
(Fe(NO3)3·9H2O), ethylene glycol ((CH2OH)2), sodium
acetate trihydrate (C2H3NaO2·3H2O), poly(ethylenimine)
(PEI, MW 25 000), hydrochloric acid (HCl), tetraethyl
orthosilicate (TEOS, SiC8H20O4), and ammonia (NH3) were
all purchased from Sigma-Aldrich Chemicals (Seoul, Korea) and
used without further purification. Ultrapure water for all solution
preparations was prepared at Milli-Q grade (>18.2 mΩ cm−1).
Synthesis of Ag@Fe3O4. Ag@Fe3O4 core−shell NPs were
synthesized according to the previously reported one-step
solvothermal method.16,18,34 Detailed information is available in
the Supporting Information.
Synthesis of Ag@Fe3O4@SiO2. Three samples of Ag@
Fe3O4@SiO2 with the different SiO2 shell thicknesses were
prepared by varying the concentration of tetraethyl orthosilicate
(TEOS) and the reaction time. Typically, 0.6 mL of Ag@Fe3O4
(25 mg/mL) was mixed with 4 mL of ethanol and followed by
the addition of 0.2 mL of ammonia (28%). The resulting mixture
was sonicated for 10 min. Then, 15 μL of TEOS was slowly
injected into the mixture under sonication with constant shaking
and vortexing. After 30 min (15−17 nm), 1 h (20 nm), and 2 h
(25 nm), the Ag@Fe3O4@SiO2 core−shell NPs were collected
by a magnet, washed with ethanol 5 times, and finally dried in a
vacuum oven at 60 °C for 6 h.
Electrode Fabrication and Electrochemical Measurement.
A glassy carbon electrode (GCE) was polished to a mirror finish
with 0.3 and 0.05 μm aqueous alumina slurries (Al2O3),
respectively. To remove residual alumina slurries, the electrode
was sonicated successively in ethanol and deionized water.
Then, the electrode was dried under nitrogen purging. Ag@
Fe3O4/GCE and Ag@Fe3O4@SiO2/GCE were prepared by
drop casting 8 μL of Ag@Fe3O4 (0.5 mg/mL) and Ag@Fe3O4@
SiO2 (0.5 mg/mL) onto the surface of GCE and dried in air.
Electrochemical measurements were performed with a conven-
tional three-electrode system, which employed a Ag@Fe3O4 or
Ag@Fe3O4@SiO2 modified GCE as a working electrode, a Ag/
AgCl as a reference electrode, and a platinum wire as an auxiliary
electrode. CV studies were performed in deoxygenated 0.1 M
HCl.
Characterization Techniques. Scanning electron micros-
copy (SEM) images were captured using a field emission
scanning electron microscope (FE-SEM S-4700; Hitachi,
Tokyo, Japan). Transmission electron microscopy (TEM) was
carried out with a JEM-2100F field emission electron micro-
scope (JEOL, Ltd., Tokyo, Japan). High resolution transmission
electron microscopy (HRTEM) images were captured using a
200 kV field emission transmission electron microscope
(TALOS F200X). Dark-field scattering measurements on SiO2
and FTO coated glasses were carried out using inverted dark-
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field microscopy (DFM) (Olympus GX51F5 microscope), and
surface plasmon resonance (SPR) was measured by a
spectrometer (IsoPlane Spectrograph of Princeton Instru-
ments). Brunauer−Emmett−Teller (BET) and Barrett−Joy-
ner−Halenda (BJH) (ASAP 2420 Accelerated Surface Area and
Porosimetry System, U.S.A.) were used to characterize the
specific surface area and pore sizes. UV−vis spectra were
measured by a UV−visible spectrometer (MRRAY, Scinco,
Seoul, South Korea), and linear sweep voltammetry, CV,
chronoamperometry, and electrochemical impedance spectros-
copy (EIS) were carried out by means of an Aviumstat
electrochemical interface (Eindhoven, Netherlands).
Computational Simulation. The shell porosity-dependent
diffusion dynamics of electrolytes were studied using a Chemical
Species Transport module (COMSOL Multiphysics 5.2a,
COMSOL Inc., Boston, MA, U.S.A.) (see SI for details). The
governing equation used in this module is
∂ ∂
(εc) + (ρc) + ∇·J + u·∇c = R + S
∂t ∂t (5)
where ε is the porosity, c is the concentration of chemical
species, ρ is the solid phase density of chemical species, J is the
flux, u is the velocity field, R is the reaction rate, and S is an
arbitrary term. On the left-hand side, the fourth term can be
assumed to be zero for an incompressible fluid. According to the
first term, the high porosity materials largely affect the reaction
rate in the variance of electrolyte concentrations.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpclett.2c01201.
Experimental section including synthesis of Ag@Fe3O4
NPs, optical images and surface plasmon scattering
measurements, and COMSOL simulation and additional
data and figures including TEM, HRTEM, HAADF, CV,
DF, SPS, plot of etched volume, schematic illustration
showing electrochemical oxidative etching, and UV−vis
spectra (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Jaebeom Lee − Department of Chemistry and Department of
Chemistry Engineering and Applied Chemistry, Chungnam
National University, Daejeon 34134, Republic of Korea;
orcid.org/0000-0002-4563-2883; Email: nanoleelab@
cnu.ac.kr
Authors
Lemma Teshome Tufa − Research Institute of Materials
Chemistry, Chungnam National University, Daejeon 34134,
Republic of Korea; Department of Applied Chemistry, Adama
Science and Technology University, 1888 Adama, Ethiopia;
orcid.org/0000-0001-6929-8464
Van Tan Tran − Faculty of Biotechnology, Chemistry, and
Environmental Engineering, Phenikaa University, Hanoi
10000, Vietnam; orcid.org/0000-0001-9566-2899
Ki-Jae Jeong − CAS Key Laboratory of Nanosystem and
Hierarchical Fabrication, CAS Center for Excellence in
Nanoscience, National Center for Nanoscience and
Technology, Beijing 100190, People’s Republic of China;
Department of Chemistry, Chungnam National University,
6091
pubs.acs.org/JPCL Letter
Daejeon 34134, Republic of Korea; orcid.org/0000-0002-
6526-3608
Birhanu Bayissa Gicha − Department of Chemistry, Chungnam
National University, Daejeon 34134, Republic of Korea;
Environmental Science Program, Haramaya University, 138
Dire Dawa, Ethiopia
Bedasa Abdisa Gonfa − Department of Applied Chemistry,
Adama Science and Technology University, 1888 Adama,
Ethiopia
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpclett.2c01201
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by National Research Foundation of
Korea (NRF-2021H1D3A2A01099457) and by Chungnam
National University (2021−2022).
■
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