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Materials Chemistry and Physics 94 (2005) 429–433

Effect of alkaline ion on the mechanism and kinetics of chemical


reduction of silver
Kan-Sen Chou ∗ , Yu-Chieh Lu, Hsien-Hsuen Lee
Department of Chemical Engineering, National Tsing Hua University, 101, Sec 2, Kuang-Fu Road, Hsinchu 30013, Taiwan

Received 4 February 2005; accepted 16 May 2005

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.

Keywords: Silver reduction; Alkaline ion; Mechanism; Kinetics

1. Introduction characteristics were reported with little information or dis-


cussion on the reaction mechanism and kinetics leading to
Due to its excellent electrical, thermal, optical and/or the formation of silver colloids. Also, few reports on silver
catalytic properties, nanosized silver colloids have received conversion could be found in these literatures.
much attention in recent years [1–5] for various potential In general, the reduction reaction of metallic ions is sen-
applications as conductor, catalyst, and chemical sensor, etc. sitive to the solution’s pH. Moreover, it may also affect the
Although there are many different techniques to synthesize product’s morphology via the formation of certain species.
these nanosized silver particles, yet based on the literature Lee et al. [15] reported that increase of pH led to a decrease
information, wet chemical method was probably the most of aspect ratio of silver nanorods and an increase of monodis-
popular one for its simplicity, low cost and easiness of manip- persity. The change in reduction rate of silver with pH was
ulation of the process. explained as the possible reason. Fukuyo and Imai [16] var-
Among the various chemical methods reported, many ied the morphology of silver by changing pH while using
reducing agents had been attempted, including formaldehyde, ascorbic acid as the reducing agent. They proposed that the
hydrazine, glucose, ascorbic acid, ferric ion, ethylene glycol degree of dissociation of ascorbic acid as the major reason
[6–12], etc. Depending upon the reducing power of these for the various morphologies observed in their work.
reagents, the synthesis reactions were then carried at various Huang et al. [17] studied the formation mechanism of
temperatures to achieve reasonable rates. However, ␥-ray or silver in a basic 2-propanol system. In their system, they
UV irradiation [13,14] had also been utilized as an alternative detected the existence of Ag2 O via weak signals from elec-
source to activate the reduction reaction. Yet in nearly all of tron diffraction. Also, two reaction steps were detected during
these works, only effects of processing variables on particle the formation of colloids. The initial process was autocat-
alytic and became predominant in increasing AgNO3 or
∗ Corresponding author. Tel.: +886 35 713691; fax: +886 35 715408. NaOH, while the second reaction step was shown to yield
E-mail address: kschou@che.nthu.edu.tw (K.-S. Chou). a reaction order close to 1 [17]. They also acknowledged that

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

the kinetics of this step might be very complex in some experi-


ments. In view of this literature information, the information
regarding the formation reactions of silver is still not very
clear, though most researchers knew how to control the final
size and distribution of these silver colloids. In this paper,
we’ll report our efforts on studying the reaction kinetics of
the formation of nanosized silver colloids in an attempt to
gain more insight of its synthesis process.

2. Experimental

Reagent grade chemicals, including AgNO3 (Kojima,


Japan), dextrose (Tedia, USA), formaldehyde (Tedia, USA) Fig. 1. Comparison of the standard chemical potentials for some reducing
and NaOH (Union Chemical, Taiwan) were used for agents in the presence or absence of alkaline ion (ref).
this study. Polyvinylpyrrolidone (molecular weight 55,000;
Aldrich, Germany) was chosen as the stabilizer for synthe- reducing agent:
sized nanosized silver colloids. The reagents were mixed 1 1 1 3 +
thoroughly together with the addition of silver nitrate as the Ag+ + C6 H12 O6 + H2 O → Ag + C6 H11 O−
7 + H
2 2 2 2
last step to initiate the reduction reaction. The reaction tem- (1)
perature was maintained by a water bath. Since the focus of
this work is on the effect of alkaline ions, most of other param-
eters were therefore kept constant throughout this work, i.e. 1 1 1 3
the concentration of AgNO3 was fixed at 0.167 M, that of Ag+ + CH2 O + H2 O → Ag + HCOO− + H+ (2)
2 2 2 2
reducing agent (either formaldehyde or dextrose) was kept at
two times of AgNO3 concentration and the PVP quantity at In Fig. 2, it shows that when no hydroxide ion was added
8 g PVP g−1 AgNO3 . As to NaOH, its quantity was varied at to the system, the Ag+ would not be reduced by dextrose at
two levels, 0.2 and 0.6 (molar basis) of AgNO3 and reaction all, and hence indicating the necessity of OH− to this reduc-
temperature between 45 and 75 ◦ C. To follow the reaction tion reaction. It also implies that there is an energy barrier to
kinetics, a pH electrode (Mettler Toledo Le 409, USA) and this reduction reaction. Yet, when hydroxide ion was added,
silver electrode (Cole-Parmer, USA) were adopted. there was a spontaneous increase of silver conversion (or loss
of silver ions as detected by silver electrode) and this increase
was proportional to the quantity of NaOH added to the sys-
tem. After this, the conversion continued to increase mildly
3. Results and discussion with time. A similar phenomenon was also observed when
formaldehyde was used as the reducing agent (not reported
3.1. Reaction driving force here).

It had been mentioned by many researchers that the addi-


tion of alkaline ion is necessary to carry out the reduction
reaction of metallic ions. From the thermodynamic point of
view, the reducing power of a reagent can be compared on the
basis of its standard reducing potential [8]. In Fig. 1, the stan-
dard potentials (25 ◦ C, 1 M) of formaldehyde and hydrazine
[18] in the presence or absence of OH− ion were plotted.
As one can notice from the standard potentials, hydrazine
is a stronger reducing agent compared with formaldehyde
and the reducing powers of both reagents are increased under
alkaline condition.
However, there is also a kinetic consideration to these
reduction reactions. Shown in Fig. 2 are the conversion data
of silver by dextrose as functions of time and quantity of
added hydroxide ions. In general, the overall reaction can be Fig. 2. Conversion of silver ion by dextrose after adding various quantity of
written as follows for either dextrose or formaldehyde as the alkaline ion (reaction temperature = room temperature).
K.-S. Chou et al. / Materials Chemistry and Physics 94 (2005) 429–433 431

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

PVP molecule need also be considered. When PVP molecule


is dissolved in water, the solution becomes acidic. At the
same concentration as for this work, the solution pH is about
3.0. In other words, changes in pH value should be related
to three reactions: hydrolysis of water, chemical reduction of
silver ion and dissociation of PVP molecule. For simplicity,
we’ll treat only the kinetic data of silver ion in this work.

3.3. Kinetic analysis

In the following, we’ll analyze only the rate of changes


during this second section of reduction for [Ag+ ] concentra-
tions under various conditions. Exhibited in Figs. 3 and 4 are
kinetic results using either dextrose or formaldehyde as the
reducing agent. Both sets of data will be treated similarly as
follows.
According to Eq. (1), the rate of change of silver ion can
be expressed as follows:
d[Ag+ ]
−rAg+ = − = k1 [Ag+ ][C6 H12 O6 ]1/2 (4)
dt
Since the concentration of reducing agent varies propor-
tionally with silver ion, the above equation can then be sim-
plified to:

−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

Table 1 determined to be 15.0 kcal mol−1 , independent of reduc-


Comparison of rate constants between different reaction conditions for both
dextrose and formaldehyde systems
ing agent and quantity of alkaline ion in the beginning
of reactions. Moreover, these rate constants from differ-
Reducing agent Formaldehyde
ent conditions were also found to be proportional to the
T (◦ C) 45 55 65 quantity of NaOH added. This finding is consistent with
Rate constants k NaOH/AgNO3 = 0.6 0.0193 0.047 0.122 the proposal that during the second stage of reaction, silver
NaOH/AgNO3 = 0.2 0.0063 0.0097 0.021 reduction might occur on the surface of existing colloids.
k(0.6)/k(0.2) ratio 3.1 4.8 5.8 In other words, when one added more NaOH to the sys-
Average 4.6
tem, one would get more Ag nuclei surface area for the
Reducing agent Dextrose second stage reaction and hence a faster reaction rate.
T (◦ C) 45 60 75
Rate constants k NaOH/AgNO3 = 0.6 0.00674 0.019 0.0498 Acknowledgement
NaOH/AgNO3 = 0.2 0.00211 0.00463 0.011
k(0.6)/k(0.2) ratio 3.2 4.1 4.5
Average 3.9 The authors wish to thank National Science Council for
financial support of this work (Grant number NSC 90-2214-
E007-010).
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and its quantity was proportional to the quantity of NaOH. As
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