Physica Status Solidi b - 2021 - Arcos-Pareja - Revealing the Synthesis of Triangular Silver Nanoplates A Study of the

RESEARCH ARTICLE
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Revealing the Synthesis of Triangular Silver Nanoplates: A

Study of the Photochemical Growth Mechanism around
the pH and Trisodium Citrate Variations
José Arcos-Pareja, Esteban D. Lasso, Carolina M. Ibarra-Barreno, Joselyn Benalcázar,
Kevin Robalino, Alexis Debut, Sarah Briceño, and Julio C. Chacón-Torres*
oscillation of conduction electrons within

Triangular silver nanoplates (T-SNPs) are synthesized via a facile, low-cost the nanoparticle as they interact with
photochemical process. It is proved that both the pH and the concentration of light.[3,4] The LSPR in T-SNPs can be tuned
trisodium citrate (TSC) are the key factors to describe the mechanism for the from the visible to the near IR spectrum
depending on the initial synthesis parame-
photochemical growth and modulation of the extinction band along the for-
ters,[5] and the final T-SNPs’ morphology
mation of T-SNPs. A precise photoreduction growth mechanism of T-SNPs is including their edges length, thickness,
proposed and confirmed by X-ray photoelectron spectroscopy (XPS) considering tip shape, and equilateral triangle aspect
the face block theory and the localized surface plasmon resonance (LSPR) in ratio.[5–12] It has been reported[6,7] that
T-SNPs revealing the optimal conditions for their growth to be at a neutral pH of the optical properties shown by T-SNPs
7, a concentration between 1.0 and 2.0 mM of TSC preferentially monodentate, open the possibility to use this nanostruc-
tured material in several fields. For
and using a 520 nm excitation energy. These results exhibit important impli-
instance, understanding the parameters
cations for the behavior of T-SNPs in a wide variety of plasmonic applications that for the correct formation of T-SNPs will
can be further moved to controlled surface-enhanced biomedical applications. open a novel branch of study in the field
of surface-enhanced Raman spectroscopy
(SERS) and plasmonic antennas due to
their unique chemical and physical proper-
1. Introduction ties when combined with advanced nanostructures like gra-
phene.[2,5,8,9,13–15] However, the desired application of T-SNPs
In the past decade, anisotropic metallic nanoparticles became a strongly depends on the region where their LSPR is located.
subject of interest since the first bulk-controlled synthesis of Ag To gain a fine control of this plasmon resonance, one has to pre-
nanoprisms (known as triangular silver nanoplates [T-SNPs]) was cisely understand the photoreduction growth mechanism of
reported via a photoinduced method.[1,2] T-SNPs show localized T-SNPs. In addition, this technique is strongly influenced by
surface plasmon resonances (LSPR) derived from the coherent the TSC and pH changes within the control of the growing pro-
cess of the T-SNPs. Thus, a clear description of the influence of
TSC in the growth mechanism process to turn spherical Ag
J. Arcos-Pareja nanoparticles (SNPs) into triangular nanoplates is necessary
Department of Physics and remains still a challenge until now for the precise synthesis
Freie Universität Berlin
Berlin 14195, Germany
of T-SNPs and their applications.[2,3,16,17]
In this work, we focused on studying the photochemical reduc-
E. D. Lasso, C. M. Ibarra-Barreno, K. Robalino, S. Briceño,
J. C. Chacón-Torres tion method as one of the most effective ones for a high-yield pro-
School of Physical Sciences and Nanotechnology duction of T-SNPs via a facile synthesis route involving the use of
Yachay Tech University just three chemical reagents: TSC, silver nitrate─AgNO3─and
Urcuquí 100119, Ecuador sodium borohydride─NaBH4─plus standard light-emitting diodes
E-mail: jchacon@yachaytech.edu.ec
(LEDs).[2,3,17–22] As it will be shown in the following, we developed
J. Benalcázar
Department of Physics
a mechanism to explain this photochemical growth of T-SNPs as a
University of Vienna function of the pH of the solution and the TSC concentration act-
Strudlhofgasse 4, Wien 1090, Austria ing as a capping agent when these anisotropic SNPs are exposed to
A. Debut different radiation wavelengths from 440 nm (blue), 520 nm
Centro de Nanociencia y Nanotecnología (green), 650 nm (red), and 300–700 nm (warm white). We have
Universidad de las Fuerzas Armadas ESPE used the face block theory and LSPR to explain the growth mech-
Sangolquí 171103, Ecuador
anism in T-SNPs revealing the optimal conditions for a homoge-
The ORCID identification number(s) for the author(s) of this article nous 100 nm T-SNPs growth using a pH of 7.0 and 1.0 mM of
can be found under https://doi.org/10.1002/pssb.202100189. TSC when exposed to green light. By means of X-ray photoelectron
DOI: 10.1002/pssb.202100189 spectroscopy (XPS), we confirmed that the TSC in monodentate
Phys. Status Solidi B 2021, 258, 2100189 2100189 (1 of 8) © 2021 Wiley-VCH GmbH
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form binds preferentially to the {111} facet of Ag crystal allowing process finalizes when the Agþ ions are completely consumed.[25]
the preferential orientation growth of T-SNPs. These results excel This SPR growth mechanism in T-SNP strongly suggests that the
on the optimization of the parameters to synthesize T-SNPs as particle growth is based on the rate of the photon absorption and
potential antiviral agents, biomedical sensors, or as surface- near field intensity as proposed within the catalytic photo-oxidation
enhanced photonic nanostructures. mechanism reported by Maillard et al.[16] Thus, the larger the exci-
tation wavelength, the larger the anisotropic flat nanostructures
formation as it is confirmed by our broadest longitudinal SPR
2. Results and Discussion band when exposed to red light (see Figure 1a–red LED).
At this point, we can start making some initial statements: the
Despite the fact that absorption spectroscopy is the tool of choice
highest concentration of T-SNPs is observed during the exposure
to confirm the existence, and quality in the formation of T-SNPs
to blue and green wavelengths, and the higher the radiation
as conducted by Jin et al.[1] when identifying dipole and quadru-
energy, the stronger the T-SNPs fingerprint, but also the poly-
pole resonances; we instead have studied the extinction spectra
from our T-SNPs as obtained from our UV–vis spectrometer. morphic 400 nm component. Thus, we can initially state that
The latter has to do with the fact that absorption spectroscopy the ideal excitation energy for T-SNPs growth is found to be close
tends to: 1) constraint the precise shape analysis of metal nano- to 520 nm, as shown in Figure 1a.
particles[23] and 2) the quadrupolar and dipole resonances tend to Based on our first findings, we decided to further compare the
be less evident when just absorption spectrum is acquired.[23] two particular wavelengths that showed the highest growth of T-
Thus, the use of an extinction spectrum becomes more reliable SNPs (3 times higher) when compared with the other wave-
for this kind of analyses as done by different authors.[6,7] lengths used. For this purpose, we developed a systematic
As shown in Figure 1a), the extinction spectrum from the con- metrology method to describe the factors that may disrupt the
trol (pristine–black) SNPs sample is mainly composed by a single growth process of T-SNPs during the photoconversion procedure
peak at around 400 nm, that is regularly assigned to the presence to give a clear insight into the essential factors to modulate the
of spherical SNPs of around 5–10 nm as our starting control mate- photochemical growth mechanism and the optimal conditions
rial.[3,24] After 18 h of irradiation, the photochemical reaction took for T-SNPs formation.
place, and the SNP’s transformation was confirmed by the Our first parameter to be varied was time as an independent
changes in the wavelength- and time-dependent UV–vis spectra variable in our experiment. The control seed solution of SNPs
shown by Figure 1. The extinction spectrum was clearly changed (black circles) was compared with different irradiation condi-
from the pristine material and two new peaks raised: the first peak tions. In Figure 1b,c, we show the fingerprint in T-SNPs to evolve
at 330 nm corresponding to the quadrupolar transversal (out-of- and become more intense as a function of exposure time. In the
plane) mode, and a second band wavelength dependent between case of the blue radiation (440 nm) light, this component
500 and 800 nm assigned to the dipolar in-plane or longitudinal locates around 500 nm.[3] The evolution of this band depends
surface plasmon resonance (SPR) in anisotropic flat nanostruc- on time and it is not controllable–it does not have a continuous
tures.[10] This last peak is defined as the fingerprint of T-SNPs intensity increase–as shown in Figure 1b. In addition to this fact,
and its resonance frequency depends on the excitation energy used the polymorphic 400 nm peak also increases as a function of time
during the photoreduction process.[3] It is clear the influence of the as an indicator of a nonoptimal growth process of T-SNPs. When
excitation energy along the growth process of the T-SNP. For analyzing the exposure to green radiation (520 nm, Figure 1c),
instance, the photoexcitation of the longitudinal SPR in T-SNP we observed a continuous growth of the 580 nm mode character-
promotes their growth along the longitudinal direction of the istic in the formation of T-SNPs at this green excitation wave-
nanoplates when longer wavelengths are used.[25] This enhanced length,[3] whereas the intensity of the polymorphic peak
process continues together with a faster consumption of large remained “steady” as compared with the control sample. The
amounts of Agþ ions until the longitudinal SPR is out of reso- later revealed that we do still have polymorphic SNPs dispersed
nance within the light excitation wavelength and the reaction in our solution and this transformation process started even
becomes less efficient at this point. The photochemical growth before the irradiation (black–control), but their ratio with respect
Figure 1. UV–vis extinction spectra of T-SNPs. a) Wavelength-dependent T-SNPs formation during 18 h of irradiation. b) Time-dependent analysis of a
seed solution irradiated just with a blue light. c) Time-dependent analysis of a seed solution irradiated just with a green light.
to the T-SNPs is much lower after 8 h of radiation time and the not get substantially affected by the TSC. The role of TSC gives
photochemical growth process did not finalize as the Agþ ions more stability to the solution but increasing its concentration also
are not totally consumed. slows down the reaction rate. In addition, we observed that values
To expand our understanding of the mechanism of the reaction of TSC of 2 mM create a broad distribution of SNPs sizes not opti-
process, we conducted a variation in the pH and the TSC concen- mal for T-SNP formation (Figure 2b–pink).
tration for the green- and blue-irradiated samples (Figure 2). We Our results for the blue irradiation revealed the optimal pH to
used sodium hydroxide and nitric acid to regulate the pH of the be also at neutral conditions (pH of 7.2–Figure 2c–red). We can
solution, which implies the addition of OH or Hþ ions accord- see as in the green irradiation that by increasing or lowering the
ingly to find the best conditions for growing T-SNP. Our results pH (12.5 < pH < 7.9 or 6.9 < pH < 6.5), the photoconversion for
for the green irradiation revealed the optimal pH to be around 7.2 the formation of T-SNP is also inhibited with just polymorphic
(Figure 2a–blue). We can see that by increasing the pH slightly SNPs (peak centered at 400 nm). We also noticed that when
(7.9), we immediately started tuning the nanoparticle shape using a pH of 12.5, this peak is enhanced (more than 2 times
making them larger, but not necessarily triangular as desired, the control sample) with a small size distribution. In general,
which means that they could agglomerate and form large clusters we confirmed also for the blue irradiation that varying the pH
as observed by the width distribution in Figure 2a–dark yellow. By did not improve the photochemical T-SNP formation process
increasing the pH (12.5 < pH < 7.9), the photoconversion for the being the optimal one at neutral conditions when blue or green
formation of T-SNP is absolutely inhibited (no peaks at 330 nor irradiation light sources are used.
580 nm) leaving just one peak centered at 400 nm indicating that Regarding the TSC concentration for the green irradiation, we
polymorphic nanoparticles of around 3–5 nm were formed. We found the optimal TSC value to be at 2 mM of TSC (Figure 2d–
also noticed that our 580 nm peak has a large width (broadening blue). We can observe that by increasing the TSC concentration
of 19%), indicating a different size distribution in addition to the the characteristic 580 nm mode gets also monotonically reduced
expected T-SNP. Thus, we can confirm that our final sample was while the intensity of the polymorphic peak at 400 nm is also
mainly conformed of T-SNP with additional shapes.[2,10,25] increased, being both components affected by the TSC concen-
Regarding the concentration of TSC for when green irradiation tration. In addition, we observed that values of TSC of 1 mM cre-
is used, we found the optimal TSC value to be at 1 mM of TSC ate a broad distribution of SNPs sizes not optimal for T-SNP
(Figure 2b–blue). We show that by increasing the TSC concentra- formation (Figure 2d–orange) and an extremely enlarged concen-
tion the characteristic 580 nm mode gets monotonically reduced, tration of polymorphic nanoparticles (more than 3 times the con-
whereas the intensity of the polymorphic peak at 400 nm does trol sample).
Figure 2. UV–vis extinction spectra of T-SNPs irradiated with blue or green sources. Seed solution exposed to green light as a function of a) changes in the
pH from 7.2to 12.5 during 6 h, and b) TSC concentration evolution from 1.0 to 3.63 mm during 8 h irradiation. Seed solution exposed to blue light as a
function of c) changes in the pH from 7.2 to 12.5 during 6 h, and b) TSC concentration evolution from 1.0 to 3.63 mm during 8 h irradiation.
Table 1. Optimal parameters for T-SNPs formation. basis in solution. Whereas the transverse mode tends to shift
to a shorter wavelength. If we assume that the reduced Ag
Irradiation TSC concentration pH Optimal growth atoms are deposited proportionally to the near field intensity
wavelength [nm] [mm] time [h] enhancement at the surface position making this longer axis
440 2.0 7.2 More than 8 the preferential one for growing, this process is accelerated
520 1.0 7.2 More than 8 until the longitudinal plasmon wavelength shifts beyond the
irradiation wavelength. However, here we will provide a
detailed description of this mechanism under the effect of
Although effects of pH and TSC need to be further studied to pH and TSC variations and propose a complete picture on
establish the precise relation between growth and the photocon- the growth mechanism of T-SNP based on a silver seed solution
version process, we now disclosed the optimal parameters to (Figure 4).
grow T-SNPs using green and blue light sources, as shown in The seed synthesis method has been designed to induce a pho-
Table 1. Those findings are also confirmed by our high resolution tochemical reaction based on the initial shape of the “seed mate-
transmission electron microscopy (HRTEM) images where the rial,” in this case, spherical SNPs with excess of Agþ ions in
pristine material (Figure 3a) revealed consistent polymorphic solution, that will be further reduced by the TSC along the irra-
Ag nanostructures of around 5–10 nm average, and our final diation process.[17] Figure 4a shows the reduction process. For
T-SNPs (Figure 3b) being of around 100 nm with an equilateral our proposed mechanism, we consider the face-block theory
flat triangular shape with fine round vertices. In Figure 3a, we where the TSC binds preferentially to the {111} facet blocking
can see the formation of prisms in the seed solution as this the growth of this facet with respect to other preferential growing
micrograph was taken after 4 months of aging in the dark. It orientations for Ag crystals.[23] At this point, two of the three car-
is important to state that the conversion of silver could occur even boxylic groups from TSC bind to the surface of the silver nano-
in the dark (without induced photochemical radiation). This seed leaving the third one normal to the surface, making it
effect is well known as TSC could act not just as a capping agent responsible for the colloidal stabilization via electrostatic interac-
but also as a reducing agent.[21] Thus, aged seed SNPs exposed to tions.[26] Agþ ions are not reduced on the {111} facet but on the
TSC may get partially reduced Agþ resulting in several morphol- unoccupied facets inducing the nanoparticle growth to be flat-
ogies, which highlights the importance of TSC along the under- tened ending up with a large {111} surface. Thus, there exists
standing of the T-SNP formation. a preferential binding from the TSC molecule to the {111} Ag
facet as proposed by different groups.[24,27] The photochemical
2.1. Proposed Growth Mechanism in T-SNP process is then now driven by silver reduction–oxidation (redox)
cycles involving the reduction of silver cations by TSC on the
Maillard et al. reported that at the beginning of the reaction, the SNP surface and the oxidation of the smaller dissolved SNPs
seed SNPs absorb light isotropically due to their spherical by O2.[8] However, some studies suggest that TSC molecules
shape.[20] As some inhomogeneity occurs in the deposited sil- act as a defect promoter in the seed formation creating
ver layer, the particle starts to become ellipsoid-like, and the defects, vacancies or stacking faults along the crystalline
degenerate plasmon resonance splits into transverse and lon- formation.[25–28] However, the role of the TSC as a defect pro-
gitudinal modes. The longitudinal plasmon (along the longer moter is still unclear. The mechanism that we show in
dimension) shifts to longer wavelengths (toward 475 nm) Figure 4a combines both theories around the specific role that
absorbing this wavelength strongly on a rotationally averaged TSC has in the growth of T-SNP.
Figure 3. Transmission electron microscopy analysis of T-SNPs. a) Transmission electron microscopy (TEM) micrograph from our seed pristine sample
of SNPs. The inset shows a closeup of a mixture of SNPs with diverse shapes that indicate a transformation induced by TSC interactions with the
nanoparticles. The scale bar of the inset is 20 nm. b) TEM micrograph of a single S-TNP after 8 h of irradiation with a green light (520 nm).
electronegative seeds acting then as a nucleus in the crystal for-

mation starting the growth process for T-SNPs. Figure 3a shows
that this shape conversion does not necessarily require light to
proceed but the presence of TSC. Nevertheless, the use of light
will significantly reduce the reaction time from months to hours
and it will increase the efficiency of the process. Finally, based on
the face-block theory, the TSC will bind preferentially to the
{111} facet blocking the growth of this facet with respect to other
preferential growing orientations leading to the formation of Ag
polygons. The thickness of these polygonal nanoparticle struc-
tures will then strongly depend on the borohydride ions enhanc-
ing the preferential binding of citrate to the (111) facet, leading to
the formation of thinner nanoplates. The dipole plasmon of the
T-SNPs is localized at the tips of triangles and will further stop
providing energy for the photoreaction to occur, stopping the
growth kinetics in this particular direction[10] joined to a deple-
tion of Agþ ions in the TSC in solution that will hinder the polyg-
onal growth forming tips that will eventually end in T-SNPs.
2.2. The Effect of the pH in the Growth Mechanism of T-SNP
In Figure 4b, we show that OH and Hþ ions had a direct impact
in the preferential binding of TSC to {111} facet forming a nega-
tive shell barrier within the seed. The latter directly affects the
face-block process previously discussed and thus the final shape
of the nanostructure. For pH variations, our proposed mecha-
nism is based on the electrostatic repulsion interactions between
seeds contributed by the free ions OH and Hþ. The addition of
those ions drives the reaction in two distinct ways. In Figure 4b,
the two outcomes of the reaction are shown as a function of the
pH 7. When the seed solution has a pH lower than 7, the Hþ gets
attracted by the negative barrier of TSC that stabilizes the silver
seeds. Those positive charges act as a barrier for the silver ions.
Thus, silver ions cannot reach the surface of the seeds avoiding
the nucleation of the crystal and the T-SNPs growth gets inter-
rupted. On the contrary, for a pH higher than 7, the OH ions get
in the middle of seeds enlarging the negative barrier within
seeds. Thus, the OH ion acts as a passivator for the reaction
and again the T-SNPs growth gets interrupted. It is important
to notice that each case works differently and distinctive products
should be expected at the end of the reaction. That is, in
Figure 2a,c, it can be observed that for pH values higher than
10 the resonance at 400 nm increases in intensity promoting
the formation of undesired polymorphic seeds that will require
further study.
2.3. The Effect of the TSC in the Growth Mechanism of T-SNP
As shown in Figure 2b,d, the concentration of TSC is inversely

Figure 4. Proposed photoreduction growth mechanism in T-SNP divided
proportional to the intensity of the T-SNP peak 500 nm. When
into three sections: a) general growth conditions and chemical disclosure
of the TSC redox reaction within the silver atoms, b) sketch description on there exists an excess of TSC present in the solution, it will not
the effect of the pH in the growth of T-SNP, and c) sketch description on just bind to the {111} facet of the seed nanoparticle but to other
the effect of the TSC concentration in the growth of T-SNP. facets as well, slowing down the reduction rate of Agþ ions due to
a TSC agglomeration (Figure 4c). In addition, if the seed solution
First, TSC acts as an electron donor along a photo-oxidation is increased in size, then less TSC will bind to other facets rather
process of the seed leading out Agþ ions. In a second step, than {111}, and the photoreduction process will continue nor-
the silver ions will be reduced (attracted) by the highly mally under optimal conditions.
2.4. Disclosing the Growth Mechanism of T-SNP by X-Ray amount of oxygen (61–62%). This behavior is a clear indica-
Photoelectron Analyses tive for the presence of a larger Ag surface area derived from a
(111) Ag nanoprism formation, as shown in Figure 4, where
To verify the evolution in the formation of the final nanoparti- the optimal parameters for pH and TSC coexist as it will be
cle structure, XPS serves to unveil the molecular interactions described in the following.
and binding conditions along this experiment, as shown in In Figure 5b,e, the Ag3d regions are shown. The deconvolution
Figure 5, where the XPS spectra for seed SNPs and the trans- analysis allowed us to precisely determine the oxidation states of Ag
formed T-SNPs are compared. Among both samples, we can before and after the growth process to reveal the intrinsic chemical
cross check the growth mechanism for T-SNP and trace the composition for the formation of T-SNPs and their corresponding
initial and final state of this particular chemical reaction in bonding states, as shown here, and in Table 3 and 4. The charac-
the following way. 1) The elemental composition of both sam- teristic Ag0 3d5/2 and 3d3/2 splitted 6 eV correspond to the pres-
ple SNPs and T-SNPs are analyzed (Figure 5a,d) and shown in ence of metallic uncharged silver as expected in the literature.[29] for
Table 2, revealing the presence of carbon and oxygen function- both SNPs and T-SNPs. In addition, silver ions in Ag2O (Agþ) are
alities directly related to the presence of TSC, silicon from the present around 368 eV for both SNPs and T-SNPs samples in good
substrate, and silver from the SNPs. In addition, a slight agreement with the literature.[29,30] It is evident that the contribution
amount of Na from the sodium borohydride synthesis process. from this Agþ peak is higher for the T-SNPs than for the SNPs,
2) Two main elemental regions are studied in high resolution which implies a higher aggregation of Ag ions on the T-SNPs sur-
(Ag3d and O1s─Figure 5b,c,e,f, respectively) to disclose the face after the growth mechanism. In addition, there appear two
functional groups formed along the creation of T-SNPs. The more silver related peaks: silver monodentate and silver bidentate
elemental analysis in Table 2 shows the presence of SNPs 369 eV. The presence of these two peaks confirms the interaction
as the concentration of silver (Ag3d) is the same before and of the SNPs with the TSC solution along the chemical process by
after the photo-reduction process for SNPs and T-SNPs, the formation of COO─Ag functionalities. In this way, the carbox-
respectively (0.1%). In contrast, the concentration of carbon ylic acids were absorbed by the SNPs in the solvent solution. Then,
content is lowered after the photoreduction process for the this adsorption resulted in a net negative charged SNPs’ surface
T-SNPs (15.4–10.7%), keeping approximately the same attracting the Agþ causing different dentations between the
Figure 5. X-ray photoelectron spectroscopy analysis. a) Survey spectrum for seed SNPs, b) Ag3d region for seed SNPs, c) O1s region for seed SNPs,
d) survey spectrum for T-SNPs, e) Ag3d region for T-SNPs, and f ) O1s region for T-SNPs.
Table 2. Atomic percentages of the elements found at SNP and T-SNPs Table 4. Oxygen fitting parameters and peak assignment for the high-
samples. resolution section O1s.
Atomic [%] SNPs T-SNPs Sample Peak assignment Binding FWHM Reference
energy [eV] [eV] binding
O1s 61.2 62.2
energy [eV]
C1s 15.4 10.7
Seed SNPs AgO 528.27 1.08 528.4[33]
Ag3d 0.1 0.1 Silver (II) oxide (Voigt)
Na1s <0.1 – Ag2O 529.46 1.25 529.5[33]
Silver (I) oxide (Voigt)
COO─Ag monodentate (Voigt) 530.24 1.14 530.4[31,34]
carboxylic acids and the Ag ions. The negative surface charge effect
associated with the face-block theory where the TSC binds prefer- COO─Ag bidentate (Voigt) 531.29 1.53 531.2[31,34]
entially to the {111} facet[24] facilitates the growth of the Ag crystal in T-SNPs Ag2O 529.37 1.02 529.5[33]
preferential orientations confirming our mechanism as presented Silver (I) oxide (Voigt)
in Figure 4a. In the following, two of the three carboxylic groups COO─Ag monodentate (Voigt) 530.06 1.24 530.4[31,34]
from TSC bind to the surface of the silver nano-seed leaving the COO─Ag bidentate (Voigt) 531.28 1.07 531.2[31,34]
third carboxylic group normal to the surface making it responsible
for the colloidal stabilization of the nanoparticles via an electrostatic
interaction.[26] As we proposed in our mechanism, there exists a
the cost of the synthesis. Here, we have found that both the pH
preferential binding from the TSC molecule to the {111} Ag facet.
and the concentration of TSC are the key factors to describe the
The photochemical process is followed by silver reduction–oxida-
mechanism for the photochemical growth and modulation of the
tion (redox) cycles involving the reduction of silver cations by
extinction band in T-SNPs. We found the optimal conditions to
TSC on the SNP surface and the oxidation of the smaller dissolved
grow T-SNPs to be at a pH of 7 and between 1.0 and 2.0 mM of
SNPs by O2.[6] The later effect is shown in Figure 5c,f, where the
TSC concentration. We presented a detailed mechanism in the
O1s region is analyzed (see Table 4 for details). Here, we show the
formation of T-SNPs considering the face block theory and the
presence of silver oxides coexisting at the surface of the nanoparti-
LSPR in T-SNPs adding the effects of varying the TSC and pH
cle: AgO, Ag2O, and COO–Ag in mono- and bidentate forms. These
values of the seed solution. Finally, our photochemical method
oxygen functionalities are the result of the interaction between the
revealed that using a 520 nm excitation energy or a 440 nm light
SNPs or T-SNPs with the oxygen from the TSC. Finally, an impor-
source, we promote a higher yield of T-SNPs formation without
tant novel fact revealed after analyzing the O1s region before and
increasing the creation of polymorphic SNPs. Studying the role
after the transformation to T-SNPs is the confirmation that T-SNPs
of pH and TSC in the photochemical reduction is a step forward
grow preferentially in the presence of TSC in its monodentate form,
in understanding the T-SNPs formation as the reaction is very
as shown in Figure 4.
sensitive to any variation of those parameters. Further studies
of the reactivity of TSC in an acid and basic media are needed
3. Conclusions for a complete understanding on the preferential binding process
of the TSC. Our results exhibit important implications for the
T-SNPs have been synthesized toward a photochemical forma- behavior of T-SNPs in a wide variety of plasmonic
tion process that is facile and speeds the reaction time lowering applications that can be further moved to a controlled surface-
Table 3. Silver fitting parameters and peak assignment for the high-resolution section Ag3d.
Sample Peak assignment Binding energy [eV] Full width at half maximum Reference binding energy [eV]
(FWHM) [eV]
Seed SNPs Ag0 ! Ag 3d5/2 (Donaich S.) 367.66 0.5 367.7[27]

þ
Ag (Voigt) 368.34 0.86 368.4[27]
COO─Ag bidentate (Voigt) 369.12 0.74 369.3[31]
COO─Ag monodentate (Voigt) 369.85 1.4 370.1[31]
þ [32]
Ag ion with COO from AgOH 371.14 1.11 370.5–371.6 ions combined with negative carboxylates
Ag0 ! Ag 3d3/2 (Donaich) 373.76 0.73 373.8[27]
T-SNPs Ag ! Ag 3d5/2 (Donaich)
0
367.64 0.47 367.7[27]
Agþ (Voigt) 368.30 0.94 368.4[27]
COO─Ag bidentate (Voigt) 369.46 1.13 369.3[31]
COO─Ag monodentate (Voigt) 370.71 1.17 370.1[31]
Ag ! Ag 3d3/2 (Donaich)
0
373.78 0.84 373.8[27]
enhanced antiviral therapy, virus diagnosis, and viral inhibition Received: April 30, 2021
applications. Revised: August 24, 2021
Published online: October 1, 2021
4. Experimental Section
[1] R. Jin, Y. Cao, C. A. Mirkin, K. L. Kelly, G. C. Schatz, J. G. Zheng,
Chemical Synthesis of SNPs: A conventional chemical reduction method Science 2001, 30, 1901.
was used.[3] Twenty-nine milliliters of silver nitrate AgNO3 (0.25 mM) was [2] J. Zhang, M. R. Langille, C. A. Mirkin, J. Am. Chem. Soc. 2010, 132,
mixed with 1 mL of TSC (30 mM) at constant stirring and room tempera- 12502.
ture (20–25 C), after 2 min of 10 μL of sodium borohydride NaBH4 [3] J. Saade, C. B. de Araújo, Mater. Chem. Phys. 2014, 148, 1184.
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RESEARCH ARTICLE

60 years of pss www.pss-b.com

Revealing the Synthesis of Triangular Silver Nanoplates: A

oscillation of conduction electrons within

electronegative seeds acting then as a nucleus in the crystal for-

2.2. The Effect of the pH in the Growth Mechanism of T-SNP

2.3. The Effect of the TSC in the Growth Mechanism of T-SNP

As shown in Figure 2b,d, the concentration of TSC is inversely

Seed SNPs Ag0 ! Ag 3d5/2 (Donaich S.) 367.66 0.5 367.7[27]

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