Abstract
The reaction mechanism and kinetics of chemical reduction of silver were studied in this work by measuring the pH and silver concentration
as functions of reaction time. The main objective here is to elucidate the role of alkaline ion in the synthesis of nanosized silver colloids
using either formaldehyde or dextrose as the reducing agent. On the reaction mechanism, it was proposed that alkaline ion reacted initially
(the first stage) with silver ion to form Ag2 O, which was instantly converted to silver and the solution became acidic as a result. During the
second stage, silver ion decreased gradually and continuously. Its rate of decrease was shown to follow the [Ag+ ]2/3 kinetics with an apparent
activation energy of about 15.0 kcal mol−1 for both dextrose and formaldehyde systems. Moreover, it was also found that the values of rate
constant from silver kinetics were proportional to the quantity of NaOH added at the beginning of these reactions.
© 2005 Elsevier B.V. All rights reserved.
0254-0584/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2005.05.029
430 K.-S. Chou et al. / Materials Chemistry and Physics 94 (2005) 429–433
2. Experimental
Fig. 3. Kinetic data of (a) [Ag+ ] and (b) pH for conditions of Fig. 4. Kinetic data of (a) [Ag+ ] and (b) pH for conditions of
NaOH/AgNO3 = 0.2, and formaldehyde as the reducing agent. NaOH/AgNO3 = 0.6, and dextrose as the reducing agent.
3.2. Reaction mechanism it might be possible to capture some Ag2 O if the reaction
was performed at very low temperature, e.g. −45 ◦ C. By all
In Figs. 3 and 4, it showed representative kinetic results of means, this fact implied that the transformation from Ag2 O
[Ag+ ] and [OH− ] with time for formaldehyde and dextrose to Ag was very fast within these reaction systems. Huang et
system at three different reaction temperatures. Both species al. [17] used the term “autocatalytic” reaction to describe the
exhibited abrupt changes initially and followed by gradual reduction of silver in the presence of colloids. It was possible
and continuous changes, suggesting a very fast reaction at that the reduction of Ag+ to Ag occurred on the surface of
the beginning and then a slower reaction at the later stage existing colloids in the system.
for this process. When AgNO3 was mixed with NaOH only, For this reaction system, the reduction of silver ion into
one obtained pure Ag2 O precipitate. However, if a reducing silver might be divided into two stages, with one involving
reagent was also added, the product became pure Ag. It is Ag2 O at the beginning of this process and the other one being
possible that at the very beginning of this synthesis process ordinary reduction reaction shown by Eq. (1) or (2) for later
some Ag2 O was formed by the following reaction: periods. From Eq. (1) (or (2)), one can also notice that the sto-
2Ag+ + 2OH− ↔ Ag2 O + H2 O (3) ichiometric ratio between silver ion and hydrogen ion is 2:3,
i.e. for each mole of silver consumed; there is a correspond-
This Ag2 O precipitate might serve as nuclei for subse- ing generation of hydrogen ion (or equivalent consumption
quently formed Ag colloids to lower the energy barrier of of alkaline ion). However, if one looked at the kinetic data
formation. Due to the very low pH value of the solution, exhibited in Figs. 3 and 4, it is easy to realize that the order
Ag2 O would quickly dissolve back to release Ag ion for con- of magnitude for [Ag+ ] is about 1.0 × 10−1 M while that for
version to Ag colloids. However, in reality, it was extremely [H+ ] is 10−3 (pH value ∼3). The difference is quite signif-
difficult to detect any Ag2 O (as evidenced by XRD) in these icant. It hence implied here that after the initial period, the
samples, no matter how soon we tried to separate the pre- hydrolysis of water should be included for consideration for
cipitate from the solution. Huang et al. [17] mentioned that the reactions. Another pH related reaction, the dissociation of
432 K.-S. Chou et al. / Materials Chemistry and Physics 94 (2005) 429–433
−rAg+ ∼
= k1 [Ag+ ]
3/2
(5)
After integration, one then obtains the working equation
as:
1
= k1 t + a (6)
[Ag+ ]0.5 Fig. 5. Kinetic fitting for silver ion concentrations: (a) formaldehyde system,
NaOH/AgNO3 = 0.2 case; and (b) dextrose system NaOH/AgNO3 = 0.6 case.
If one plots 1/[Ag+ ]0.5 versus time, the rate constant k
1 can
then be obtained from the slope. The fitting is now exhibited
in Fig. 5a and b for the two reducing agents used in this work.
Quite reasonable linear fitting is observed, suggesting the cor-
rectness of this proposed kinetic model. Furthermore, one can
plot these rate constants from different temperatures accord-
ing to the Arrhenius equation as exhibited in Fig. 6. All four
sets of results showed the similar activation energies of about
15.0 kcal mol−1 . This finding strongly indicates that the reac-
tion mechanism of silver conversion during the second stage
is the same regardless of reducing agent or quantity of NaOH
added. This finding is consistent with the notion that during
the second stage of this reaction system, reduction of silver
might occur on the surface of existing colloids. More investi-
gation is however required to further elucidate this aspect of
reaction mechanism.
Also one can notice from Fig. 6 that the rate constant
is higher when more NaOH is added to the system for either
dextrose or formaldehyde cases. A comparison between these
rate constants for different NaOH addition is then made and
the results are exhibited in Table 1. It is very interesting to
note that the ratios of k for two different NaOH additions are
about the same and in the range from 3.1 to 5.8, with an aver- Fig. 6. Arrhenius plot of rate constants for silver conversion under various
age of about 4.3. According to previous discussions, addition conditions.
K.-S. Chou et al. / Materials Chemistry and Physics 94 (2005) 429–433 433