See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/234025888

Effect of amine groups in the synthesis of Ag nanoparticles using

aminosilanes

Article in Materials Chemistry and Physics · November 2005

DOI: 10.1016/j.matchemphys.2005.04.023

CITATIONS READS

361 2,105

4 authors, including:

Agustin Frattini Nora Susana Pellegri

Instituto de Física Rosario Rosario National University
29 PUBLICATIONS 683 CITATIONS 57 PUBLICATIONS 1,377 CITATIONS

SEE PROFILE SEE PROFILE

Oscar de Sanctis
Instituto de Física Rosario
55 PUBLICATIONS 1,419 CITATIONS

SEE PROFILE

All content following this page was uploaded by Nora Susana Pellegri on 21 September 2018.

The user has requested enhancement of the downloaded file.

 Materials Chemistry and Physics 94 (2005) 148–152

Effect of amine groups in the synthesis of Ag nanoparticles

using aminosilanes
A. Frattini a,∗ , N. Pellegri b , D. Nicastro b , O. de Sanctis b
a Área Fı́sica, FCByF-UNR, Suipacha 531, 2000 Rosario, Argentina
b Lab. de Materiales Cerámicos, FCEIA-IFIR-UNR, Av. Pellegrini 250, 2000 Rosario, Argentina

Received 15 November 2004; received in revised form 23 March 2005; accepted 19 April 2005

Abstract

This work presents a simple method to produce silver nanoparticles through AgNO3 chemical reduction in a continuous media. Aminosilanes
act as catalytic reactors and superficial modifiers of Ag nanoparticles, inhibiting their growth and avoiding aggregation. Nanoparticles formation
is studied by UV–vis spectroscopy, atomic force microscopy (AFM) and dynamic light scattering (DLS) techniques. The extent of the reduction
reaction increases with either a higher aminosilane concentration or with aminosilanes with a higher number of amine groups. The number
of amine groups in the aminosilane has also a strong effect on the size of the resulting Ag particles. The morphology of the Ag nanoparticles
obtained is spherical and the mean size is of approximately 5 nm.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Chemical reduction; Atomic force microscopy (AFM); Optical properties

1. Introduction aqueous solutions with or without stabilizing agents [2–5],

thermal decomposition in organic solvents [6], chemi-
Noble metal nanoparticles have been intensely investi- cal and photo reduction in reverse micelles [7,8], ra-
gated due to their optical, catalytic and electric properties. diation chemical reduction [9] and microwave assisted
These characteristics make them suitable for a variety of po- [10], with typical advantages and disadvantages in each
tential applications on microelectronics. Metallic silver, in case.
particular, either in bulk or in nanoparticles, is a technologi- However, most of the procedures previously described,
cally important material. It shows unique properties normally yield stable silver dispersions only at relatively low concen-
related to noble metals (excellent conductivity, chemical sta- trations of metal; hence, they are not suitable for large-scale
bility, catalytic activity) besides other specific ones that can manufacturing.
be controlled depending on the particles size, the size dis- This work describes a simple method to produce Ag
tribution and shape (antibacteriostatic effects, non-linear op- nanoparticles in a continuous media. The silver nanoparticles
tical behavior, etc.) with an acceptable production cost [1]. are obtained from AgNO3 chemical reduction in ethanol, us-
Consequently, there is a remarkable interest in developing ing aminosilanes as catalysts and colloidal suspension sta-
procedures to produce silver nanoparticles dispersions on a bilizers. This reaction is attained employing aminosilanes
large scale. with different amine groups in alcoholic solution in order to
Several methods have been reported for metallic nanopar- achieve nanoparticles isolation and stable colloidal suspen-
ticles synthesis, including Ag ions chemical reduction in sion to control size. These compounds were used in differ-
ent AgNO3 :aminosilane ratio (w/w). Besides, aminosilanes
work as surface modifiers that avoid particles agglomera-
∗ Corresponding author. Tel.: +54 3414495467; fax: +54 3414802654. tion, and their action allows future manipulation of nanopar-
E-mail address: [email protected] (A. Frattini). ticles.

0254-0584/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2005.04.023
 A. Frattini et al. / Materials Chemistry and Physics 94 (2005) 148–152 149

2. Experimental steps ment used was a JASCO Model V-530 UV–vis spectropho-
tometer.
In a dark container to prevent early photoreduction, Dynamic light scattering (DLS), Nicomp particle size
300 mg of AgNO3 (Fluka, 99.95%) are added to 180 cm3 (Model 380 PSS, Santa Barbara, USA), was used to mea-
of ethanol (Merck, 99.8%) at a temperature of 60 ◦ C, sure the diameter distribution function of nanoparticles at a
stirring constantly. Different aminosilanes are dissolved fixed scattering angle of 90◦ .
in ethanol and then dispersed in a solution of alcohol–
AgNO3 previously prepared under stirring to finally obtain
AgNO3 :aminosilane ratios of 1:5, 1:10 and 1:15. 3. Results and discussion
The aminosilanes used were:
The reduction of silver ions in different solutions gener-
• 3-aminopropyltrimethoxysilane (APS) (Aldrich, 97%);
ally yields colloidal silver with particle diameter of several
• 3-(2-aminoethylaminopropyl)trimethoxysilane (AES)
nanometers. These particles have specific optical properties
(Aldrich, 97%);
indicated by the presence of intense absorption band at
• N-[3-(trimethoxysilyl)propyl]diethylenetriamine (ATS)
400–415 nm caused by collective excitation of all the free
(Aldrich Tech.).
electrons in the particles [11]. It is known that the presence
The chemical structure of the three compounds is shown of catalysts during the formation of metal nanoparticles can
in Fig. 1. influence the resulting nanoparticles morphology and size
After the preparation of the solution, an air or nitrogen re- [12]. Ag nanoparticles formation can be identified by a color
flux process is carried out during 1 h. Then, the Ag nanopar- change in the solution without precipitation and by UV–vis
ticles covered with aminosilanes are stored in amber flasks. spectra of the prepared products.
For atomic force microscopy (AFM) images, a drop of Table 1 shows that Ag nanoparticles formation is favored
nanoparticles alcoholic solution is placed over a pristine mica when the aminosilane concentration increases as well as
substrate on air atmosphere, the solvent evaporates naturally when the number of amine groups is greater in the aminosi-
and then the AFM measurements are taken. lane.
The AFM images were obtained using NanoTec ELEC- The progress of reduction reaction and formation of sil-
TRONICA equipment with tapping mode configuration at ver nanoparticles was monitored by the appearance and in-
room air temperature. A SiN tip supported by a silicon can- crease of the characteristic plasmon absorption band centered
tilever (0.76 N m−1 spring constant and 71 kHz resonance around 410 nm and the vanishing of the peaks located around
frequency) was used. 280 nm that are attributed to the absorption by complexes of
UV–vis spectra were performed employing a diluted Ag Ag+ and the Ag4 2+ intermediate reduced species or by small
nanoparticles solution and ethanol as reference. The instru- clusters of Ag atoms.
For 1:10 AgNO3 :ATS ratio (Fig. 2), the reaction is al-
most completed after 1 h of refluxing treatment, only a very
weak absorption band is observed around 280 nm. A very
homogenous colloidal suspension (transparent and yellow-
ish brown color) of nanosized particles was obtained. The
following evolution of the absorption spectra shows that the
completion of the process occurs between 4 and 24 h, while
the plasmon absorption peak is blue-shifted [5,7].
In order to study long-term stability of the Ag nanoparti-
cles in colloidal solutions, normalized UV–vis spectra were
obtained for an ethanol solution containing ATS covered Ag
nanoparticles (1:5 AgNO3 :ATS ratio), at different periods of
storage (after refluxing process), as shown in Fig. 3. An ab-
sorption band around 400 nm is observed in all spectra due
to Ag nanoparticles surface plasmon resonance. A very weak
absorption at 280 nm is also observed, indicating an almost

Table 1
Ag nanoparticles formation for different AgNO3 :aminosilanes ratio
1:5 1:10 1:15
APS No No Yes
AES No Yes Not studied
Fig. 1. Chemical structure of aminosilanes used as superficial modifiers. ATS Yes Yes Not studied
150 A. Frattini et al. / Materials Chemistry and Physics 94 (2005) 148–152

Fig. 2. UV–vis spectra of Ag nanoparticles covered with ATS and prepared

under nitrogen atmosphere, 1:10 ratio. Fig. 4. UV–vis spectra of Ag nanoparticles covered with ATS (1:10), AES
(1:10) and APS (1:15).
complete AgNO3 reduction. Besides, no remarkable differ-
ences were observed between nanoparticles solution spectra the APS covered particles show a plasmon absorption band
taken at 7 days, 15 days and 3 months from preparation, sug- centered at 422 nm and a narrower FWHM (0.42 eV). That
gesting system stability. great red-shift of the plasmon absorption as well as the nar-
In Fig. 4, a comparison between APS (1:15 AgNO3 :APS rower bandwidth, if the dipole approximation upholds valid
ratio), AES (1:10 AgNO3 :AES ratio) and ATS (1:10 for this size range, indicate that the APS covered particles
AgNO3 :ATS ratio) covered nanoparticles is shown. The are much bigger than the ones synthesized with AES and
UV–vis absorption spectra of the AES and ATS covered ATS.
nanoparticles exhibit similar features with peaks centered at Finally, to study Ag nanoparticles isolated from their dis-
403 and 407 nm and full wave of half maximum (FWHM) persing environment, a nanoparticles powder was prepared
of 0.53 and 0.48 eV, respectively. Taking into consideration evaporating ethanol, and then stored in a sealed flask under
the fact that the average size of the ATS covered particles is nitrogen atmosphere.
around 5 nm (shown below in Fig. 6). These results would A portion of this powder was redispersed in ethanol pro-
evidence that the size of particles synthesized with AES and ducing stable colloids with extinction spectra very similar
ATS are located on the intrinsic size region, where the dipole to the original ones (Fig. 5). This result is very important
approximation is valid and occurs in a 1/R dependence of the because it proves that there is no degradation of Ag nanopar-
plasmon bandwidth [13]. ticles when they are separated from their dispersing environ-
Consequently and considering that the bandwidth is not ment.
inhomogeneously broadened due to different particle size Typical AFM images of surface morphology (two-
distributions, it is possible to infer that AES covered par- dimensional (2D) view in Fig. 6) do not show nanoparticles
ticles are smaller than ATS covered ones. On the other hand, clustering due to the fact that aminosilanes act as superficial

Fig. 3. UV–vis spectra of Ag nanoparticles covered with ATS and prepared Fig. 5. UV–vis spectra of Ag nanoparticles in ethanol before and after re-
under nitrogen atmosphere, 1:5 ratio. dissolution.
 A. Frattini et al. / Materials Chemistry and Physics 94 (2005) 148–152 151

inferred from the AFM images (Fig. 7a) and this study gives
an average diameter of 5.14 nm with S.D. 1.02, showing a
good particle size distribution.
Furthermore, the average hydrodynamic radius of these
particles was measured by DLS showing an average size of
5.3 nm with S.D. 1.1 nm (20.2%) consistent with the results
described above. The distribution is shown in Fig. 7b.
The reduction of Ag+ to Ag requires a relatively high neg-
ative redox potential. The reduction of silver ion at 60 ◦ C
in a polar Lewis base solvent (ethanol) with aminosilanes,
resulted in spontaneous reduction of the silver salt and the
growth of silver nanoparticles depending on the number of
amino groups in aminosilanes used and on their concentra-
tion. For ATS, although the reaction takes more than 4 h to
be completed, the formation of nanosize Ag particles starts
almost immediately after the catalyst agent is added to the
AgNO3 /ethanol solution, irrespective of the AgNO3 :ATS ra-
tio used. In contrast, in the case of the AgNO3 solution in
Fig. 6. Two-dimensional (2D) AFM topographic image of Ag nanoparticles
ethanol with APS, precipitation over flask walls occurred af-
covered with ATS (1:5) placed over a mica substrate.
ter longer refluxing times and no absorption band character-
istic of surface plasmon resonance was observed in remnant
modifiers avoiding this harmful behavior. Although in AFM solutions for 1:5 and 1:10 AgNO3 :APS ratios. A stable Ag
images, particles seem to be very close to each other, they particles colloidal solution was only obtained using a higher
keep their morphology and individuality, and the geometry AgNO3 :APS ratio, which was equal to 1:15.
of the particles is spherical. This characteristic is repeated in Amine groups can be attributed a key role in the reduction
different areas of the sample, with higher or lower population of Ag+ . And this may be due to the coordination between
density of nanoparticles. The size of the nanoparticles can be N and Ag+ , which may decrease the potential of Ag+ /Ag

Fig. 7. (a) Ag nanoparticles size distribution from AFM images and (b) obtained by DLS.
 152 A. Frattini et al. / Materials Chemistry and Physics 94 (2005) 148–152

4. Conclusions

Ag nanoparticles dispersions, 5 nm average size, were ob-

tained by chemical reduction of AgNO3 in aminosilanes al-
coholic solution.
Formation of Ag nanoparticles is favored with aminosi-
lanes concentration increase and with the number of amine
groups in the aminosilanes. The number of amine groups in
the aminosilane has also a strong effect on the size of the
resulting Ag particles.
Colloidal solutions are stable for long periods and parti-
cles can be redispersed after the separation of their alcoholic
environment without modification of their properties.
Aminosilanes act as superficial modifiers and catalytic re-
actors of Ag nanoparticles, inhibiting their growth and avoid-
ing aggregation.
Fig. 8. Coordination of amine groups for (a) APS and (b) AES and ATS.

(EAg+/Ag ) and promote the reduction of Ag+ . The extent of Acknowledgements

the reduction reaction increases with either a higher aminosi-
lane concentration or with aminosilanes with a higher number Authors want to thank the UNR, the CONICET and the
of amine groups. The number of amine groups in the aminosi- ANPCyT for their financial support.
lane has also a strong effect on the size of the resulting Ag
particles. However, the size differences are mainly between
the Ag particles synthesized with APS (one amine group) and References
the ones prepared with AES (two amine groups) or ATS (three
amine groups). This behavior would be attributed to the dif- [1] I. Capek, Adv. Colloid Interface Sci. 110 (2004) 49–74.
ferent manners of coordination of the Ag+ ions by the APS [2] L.M. Liz Marzan, I. Lado-Tourino, Langmuir 12 (1996) 3585.
[3] D.G. Duff, G. Baiker, Langmuir 9 (1993) 2301.
and the AES or the ATS. The APS with one amine group
[4] D.N. Glavee, K.J. Klabunde, C.M. Sorensen, G.C. Hadjipanayis,
behaves as a monodentate ligand (Fig. 8a). Contrarily, the Langmuir 9 (1993) 162.
AES and ATS with two and three amine groups, respectively, [5] I. Sondi, D.V. Goia, E. Matijevi, J. Colloid Interface Sci. 260 (2003)
could behave as bidentate ligand, chelating and/or bridging. 75–81.
Although, the formation of chelates with a central Ag+ ion [6] K. Esumi, T. Tano, K. Torigoe, K. Meguro, Chem. Mater. 2 (1990)
564.
would be restricted by steric effects, the bridging of two or
[7] H.W. Lu, S.H. Liu, X.L. Wang, X.F. Qian, J. Yin, Z.K. Zhu, Mater.
three Ag+ ions is feasible, each amine group of same molecule Chem. Phys 81 (2003) 104–107.
of AES or ATS ligands to one Ag+ ions (Fig. 8b). The manner [8] R. Trbojevich, N. Pellegri, A. Frattini, O. de Sanctis, P.J. Morais,
of coordination would be strongly affecting the formation of R.M. Almeida, J. Mater. Res. 17 (8) (2002) 973–980.
the intermediate reduced species, such as Ag4 2+ , as well as its [9] A. Henglein, Langmuir 17 (2001) 2329.
[10] H. Katsuki, S. Komarneni, J. Mater. Res. 18 (4) (2003) 747–750.
subsequent evolution for forming particles. Consequently, the
[11] U. Kreibig, M. Vollmer, Optical Properties of Metal Clusters,
AES and ATS attached molecules to the intermediate species Springer, Berlin, 1995.
would restrict more the growing of the particles than the APS [12] Y. Tan, Y. Li, D. Zhu, J. Colloid Interface Sci. 258 (2003) 244–251.
molecules. [13] S. Link, M.A. El-Sharef, J. Phys. Chem. B 103 (1999) 4212.

View publication stats