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Piñero 2017 J. Phys. Conf. Ser. 786 012020
Piñero 2017 J. Phys. Conf. Ser. 786 012020
E-mail: siblanco@uis.edu.co
Abstract. Silver nanoparticles have a wide range of applications in the medical field, textile
and food industries. These and other applications can be found due to the relation between its
size and morphology. In this study the influence of bath temperature on the morphology and
size of silver nanoparticles are evaluated, which are obtained by chemical reduction of AgNO3
using three reducing agents: sodium borohydride, ascorbic acid and sodium citrate. The
evaluation carried out by the traditional UV-vis Spectrophotometric analysis and with High
Resolution Transmission Electron Microscopy. The UV-vis spectrum of the silver colloids
obtained by chemical reduction using three different reducing agents shows the effect of the
temperature change on the growing and aggregative process. The final effect on the
morphology, size and aggregation of the particles was confirmed by TEM. The result suggests
a change in the growing mechanism, conducted by aggregation of atoms at 5 and 20°C degrees
and aggregation of clusters at higher temperatures. Moreover in this work the main synthesis
methods of nanomaterials are described.
1. Introduction
Due to the silver nanoparticles properties, there are technological advances in order to bring the
development of a wide range of applications. Silver nanoparticles can be used in the medical field,
specifically in coated surgical instrument, textile and food industry; and as sensors because of its
electrochemical properties. On the other hand, it can be mentioned photoelectrochemical applications
as biological markers and actually forming nanocomposites for pipelines coatings [1-3]. These and
other applications of silver nanoparticles can be found due to the relation between its size and
morphology. According with several studies size and morphology are also related with the reducing
agent used in the chemical synthesis [4-6]. Characteristics and considerations can attribute a specific
application to the obtained nanoparticle [7]. This study evaluates the influence of bath temperature on
the morphology and size of silver nanoparticles obtained by chemical reduction of AgNO3 using three
reducing agents: sodium borohydride, ascorbic acid and sodium citrate. The evaluation carried out by
the traditional UV-vis Spectrophotometric analysis and with High Resolution Transmission Electron
Microscopy (HRTEM).
2. Experimental
Silver nanoparticles have been synthesized with chemical reduction of silver nitrate and three reducing
agents: sodium borohydride (NaBH4), ascorbic acid (C6H8O6) and sodium citrate (Na3C6H5O7). For the
study of the temperature effect a sequential analysis took place, where each temperature condition was
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Published under licence by IOP Publishing Ltd 1
CCEQ IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 786 (2017) 012020 doi:10.1088/1742-6596/786/1/012020
selected individually, increasing it on each synthesis and keeping constant the rest of the experimental
parameters as shown in Table 1.
In each case, the synthesis of the nanoparticles occurs by reaction with the reductive agents,
according to the following chemical reactions: [4-6].
2Ag++C6H8O6→2Ag°+C6H6O6+2H + (2)
4Ag++Na3C6H5O7→4Ag°+C6H5O7H3+3Na++H++O2 (3)
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CCEQ IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 786 (2017) 012020 doi:10.1088/1742-6596/786/1/012020
The evaluation was made changing the bath temperature between 5 and 40°C. The results from the
three mentioned temperatures show a similar response, with a small variation in the maximum; the
increment of the bath temperature between 30 and 40°C, produce a more relevant change in the
response. The shift to higher wavelength values and the reduction of the peak intensity are possible
related to a reduction on the number of particles or an increment on size. The increment on the
temperature could change the reaction kinetic, the movement of atoms on the solution (Brownian
movement) and the aggregative mechanisms of the nanoparticles. In this specific case, where the
spectrum shows one maximum with a small shift on the wavelength (less than 8 nm between 5 and
40°C degrees), the effect of the temperature could be related to an increment in the reduction kinetic
and the aggregation of atoms to the particle according to the classical LaMer mechanism [9].
Additionally, with the increment of the temperature to 40°C, the sodium borohydride could react to
produce hydrogen and boranes and decrease the reduction of silver ions [10]. Figure 1(b) shows the
spectrums obtained using ascorbic acid as reducing agent, in this case the responses are different, the
spectrums shows two secondary maximums and this characteristic behaviour can be related to the
production of non-spherical particles and the possible aggregation of the particles induced by a “glue”
effect of the stabilizer [11]. The particles could be produced by the aggregation of clusters, each ones
with a specific structure and growing modes. The temperature variation could affect the kinetic of the
reaction and the aggregation mechanism (oriented attachment, intraparticle ripening or overgrowth).
Figure 1c shows the spectrum of the colloids obtained using sodium citrate as reducing agent at 85°C,
the existence of various peaks and the bandwidth are related to a high dispersion of size and shape.
This dispersion could be related to a progressive nucleation mechanism, and an aggregative formation
of colloids, facilitated by the temperature increase. The UV-vis spectrums of the colloids obtained
using sodium borohydride as reducing agent are shown in Figure 1(a). The intensity of the peaks is
inversely proportional with the reaction temperature.
Figure 2 shows the images obtained by HRTEM of the nanoparticles synthesized at characteristic
temperatures. This result confirms what was suggested from UV-vis analysis. The particles obtained
using sodium borohydride at 5 and 20°C, shows and quasi-spherical shape that could be explained by
the growing model of LaMer with an atomic aggregation. Instead, the particles obtained at 30 and
85°C degrees show an irregular shape and aggregation of the particles.
Figure 2. HRTEM images of silver nanoparticles, obtained using sodium borohydride at 5ºC (a)
150000X and (b) 500000X; sodium borohidride at 20ºC (c) 150000X and (d) 500000X; ascorbic acid
at 30ºC (e) 100000X and (f) 500000X; and sodium citrate at 85ºC (g) 20000X and (h) 400000X.
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CCEQ IOP Publishing
IOP Conf. Series: Journal of Physics: Conf. Series 786 (2017) 012020 doi:10.1088/1742-6596/786/1/012020
4. Conclusions
The UV-vis spectra of the silver colloids obtained by chemical reduction using three different reducing
agents show the effect of the temperature change on the growing and aggregative process. The final
effect on the morphology, size and aggregation of the particles was confirmed by HRTEM. The result
suggests a change in the growing mechanism, conducted by aggregation of atoms at 5 and 20°C
degrees and aggregation of clusters at higher temperatures. To confirm this proposal an in-situ
evaluation of the growing mechanism is needed.
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