Materials Chemistry and Physics 94 (2005) 429433

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 mechanismand kinetics of chemical reduction of silver were studied in this work by measuring the pHand 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 rst stage) with silver ion to form Ag
2
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
Due to its excellent electrical, thermal, optical and/or
catalytic properties, nanosized silver colloids have received
much attention in recent years [15] for various potential
applications as conductor, catalyst, and chemical sensor, etc.
Although there are many different techniques to synthesize
these nanosized silver particles, yet based on the literature
information, wet chemical method was probably the most
popular one for its simplicity, lowcost and easiness of manip-
ulation of the process.
Among the various chemical methods reported, many
reducingagents hadbeenattempted, includingformaldehyde,
hydrazine, glucose, ascorbic acid, ferric ion, ethylene glycol
[612], etc. Depending upon the reducing power of these
reagents, the synthesis reactions were then carried at various
temperatures to achieve reasonable rates. However, -ray or
UVirradiation [13,14] had also been utilized as an alternative
source to activate the reduction reaction. Yet in nearly all of
these works, only effects of processing variables on particle

Corresponding author. Tel.: +886 35 713691; fax: +886 35 715408.

E-mail address: kschou@che.nthu.edu.tw (K.-S. Chou).
characteristics were reported with little information or dis-
cussion on the reaction mechanism and kinetics leading to
the formation of silver colloids. Also, few reports on silver
conversion could be found in these literatures.
In general, the reduction reaction of metallic ions is sen-
sitive to the solutions pH. Moreover, it may also affect the
products morphology via the formation of certain species.
Lee et al. [15] reported that increase of pH led to a decrease
of aspect ratio of silver nanorods and an increase of monodis-
persity. The change in reduction rate of silver with pH was
explained as the possible reason. Fukuyo and Imai [16] var-
ied the morphology of silver by changing pH while using
ascorbic acid as the reducing agent. They proposed that the
degree of dissociation of ascorbic acid as the major reason
for the various morphologies observed in their work.
Huang et al. [17] studied the formation mechanism of
silver in a basic 2-propanol system. In their system, they
detected the existence of Ag
2
O via weak signals from elec-
tron diffraction. Also, two reaction steps were detected during
the formation of colloids. The initial process was autocat-
alytic and became predominant in increasing AgNO
3
or
NaOH, while the second reaction step was shown to yield
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) 429433
the kinetics of this stepmight be verycomplexinsome 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 nal
size and distribution of these silver colloids. In this paper,
well 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 AgNO
3
(Kojima,
Japan), dextrose (Tedia, USA), formaldehyde (Tedia, USA)
and NaOH (Union Chemical, Taiwan) were used for
this study. Polyvinylpyrrolidone (molecular weight 55,000;
Aldrich, Germany) was chosen as the stabilizer for synthe-
sized nanosized silver colloids. The reagents were mixed
thoroughly together with the addition of silver nitrate as the
last step to initiate the reduction reaction. The reaction tem-
perature was maintained by a water bath. Since the focus of
this workis onthe effect of alkaline ions, most of other param-
eters were therefore kept constant throughout this work, i.e.
the concentration of AgNO
3
was xed at 0.167 M, that of
reducing agent (either formaldehyde or dextrose) was kept at
two times of AgNO
3
concentration and the PVP quantity at
8 g PVPg
1
AgNO
3
. As to NaOH, its quantity was varied at
two levels, 0.2 and 0.6 (molar basis) of AgNO
3
and reaction
temperature between 45 and 75

C. To follow the reaction

kinetics, a pH electrode (Mettler Toledo Le 409, USA) and
silver electrode (Cole-Parmer, USA) were adopted.
3. Results and discussion
3.1. Reaction driving force
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
written as follows for either dextrose or formaldehyde as the
Fig. 1. Comparison of the standard chemical potentials for some reducing
agents in the presence or absence of alkaline ion (ref).
reducing agent:
Ag
+
+
1
2
C
6
H
12
O
6
+
1
2
H
2
O Ag +
1
2
C
6
H
11
O

7
+
3
2
H
+
(1)
Ag
+
+
1
2
CH
2
O +
1
2
H
2
O Ag +
1
2
HCOO

+
3
2
H
+
(2)
In Fig. 2, it shows that when no hydroxide ion was added
to the system, the Ag
+
would not be reduced by dextrose at
all, and hence indicating the necessity of OH

to this reduc-
tion reaction. It also implies that there is an energy barrier to
this reduction reaction. Yet, when hydroxide ion was added,
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
with time. A similar phenomenon was also observed when
formaldehyde was used as the reducing agent (not reported
here).
Fig. 2. Conversion of silver ion by dextrose after adding various quantity of
alkaline ion (reaction temperature =room temperature).
K.-S. Chou et al. / Materials Chemistry and Physics 94 (2005) 429433 431
Fig. 3. Kinetic data of (a) [Ag
+
] and (b) pH for conditions of
NaOH/AgNO
3
=0.2, and formaldehyde as the reducing agent.
3.2. Reaction mechanism
In Figs. 3 and 4, it showed representative kinetic results of
[Ag
+
] and [OH

] with time for formaldehyde and dextrose

system at three different reaction temperatures. Both species
exhibited abrupt changes initially and followed by gradual
and continuous changes, suggesting a very fast reaction at
the beginning and then a slower reaction at the later stage
for this process. When AgNO
3
was mixed with NaOH only,
one obtained pure Ag
2
O precipitate. However, if a reducing
reagent was also added, the product became pure Ag. It is
possible that at the very beginning of this synthesis process
some Ag
2
O was formed by the following reaction:
2Ag
+
+2OH

Ag
2
O +H
2
O (3)
This Ag
2
O precipitate might serve as nuclei for subse-
quently formed Ag colloids to lower the energy barrier of
formation. Due to the very low pH value of the solution,
Ag
2
Owould quickly dissolve back to release Ag ion for con-
version to Ag colloids. However, in reality, it was extremely
difcult to detect any Ag
2
O (as evidenced by XRD) in these
samples, no matter how soon we tried to separate the pre-
cipitate from the solution. Huang et al. [17] mentioned that
Fig. 4. Kinetic data of (a) [Ag
+
] and (b) pH for conditions of
NaOH/AgNO
3
=0.6, and dextrose as the reducing agent.
it might be possible to capture some Ag
2
O if the reaction
was performed at very low temperature, e.g. 45

C. By all
means, this fact implied that the transformation from Ag
2
O
to Ag was very fast within these reaction systems. Huang et
al. [17] used the term autocatalytic reaction to describe the
reduction of silver in the presence of colloids. It was possible
that the reduction of Ag
+
to Ag occurred on the surface of
existing colloids in the system.
For this reaction system, the reduction of silver ion into
silver might be divided into two stages, with one involving
Ag
2
Oat the beginning of this process and the other one being
ordinary reduction reaction shown by Eq. (1) or (2) for later
periods. FromEq. (1) (or (2)), one can also notice that the sto-
ichiometric ratio between silver ion and hydrogen ion is 2:3,
i.e. for each mole of silver consumed; there is a correspond-
ing generation of hydrogen ion (or equivalent consumption
of alkaline ion). However, if one looked at the kinetic data
exhibited in Figs. 3 and 4, it is easy to realize that the order
of magnitude for [Ag
+
] is about 1.0 10
1
M while that for
[H
+
] is 10
3
(pH value 3). The difference is quite signif-
icant. It hence implied here that after the initial period, the
hydrolysis of water should be included for consideration for
the reactions. Another pHrelated reaction, the dissociation of
432 K.-S. Chou et al. / Materials Chemistry and Physics 94 (2005) 429433
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,
well treat only the kinetic data of silver ion in this work.
3.3. Kinetic analysis
In the following, well 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:
r
Ag
+ =
d[Ag
+
]
dt
= k

1
[Ag
+
][C
6
H
12
O
6
]
1/2
(4)
Since the concentration of reducing agent varies propor-
tionally with silver ion, the above equation can then be sim-
plied to:
r
Ag
+

= k
1
[Ag
+
]
3/2
(5)
After integration, one then obtains the working equation
as:
1
[Ag
+
]
0.5
= k
1
t +a (6)
If one plots 1/[Ag
+
]
0.5
versus time, the rate constant k
1
can
then be obtained from the slope. The tting is now exhibited
in Fig. 5a and b for the two reducing agents used in this work.
Quite reasonable linear tting 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 nding 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 nding 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. Acomparison 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-
age of about 4.3. According to previous discussions, addition
Fig. 5. Kinetic tting for silver ion concentrations: (a) formaldehyde system,
NaOH/AgNO
3
=0.2case; and(b) dextrose systemNaOH/AgNO
3
=0.6case.
Fig. 6. Arrhenius plot of rate constants for silver conversion under various
conditions.
K.-S. Chou et al. / Materials Chemistry and Physics 94 (2005) 429433 433
Table 1
Comparison of rate constants between different reaction conditions for both
dextrose and formaldehyde systems
Reducing agent Formaldehyde
T (

C) 45 55 65
Rate constants k NaOH/AgNO
3
=0.6 0.0193 0.047 0.122
NaOH/AgNO
3
=0.2 0.0063 0.0097 0.021
k(0.6)/k(0.2) ratio 3.1 4.8 5.8
Average 4.6
Reducing agent Dextrose
T (

C) 45 60 75
Rate constants k NaOH/AgNO
3
=0.6 0.00674 0.019 0.0498
NaOH/AgNO
3
=0.2 0.00211 0.00463 0.011
k(0.6)/k(0.2) ratio 3.2 4.1 4.5
Average 3.9
of NaOHwould quickly convert Ag
+
into Ag nuclei via Ag
2
O
and its quantity was proportional to the quantity of NaOH. As
a result, the surface area available for subsequent reduction
reaction would also be in proportion and hence the reaction
rates. As to the slight increase of k values with reaction tem-
perature, it might be due to some new nuclei formation at the
high temperatures. Nevertheless, the proportional increase
of rate constants with increasing addition of NaOH is very
obvious and consistent with proposed mechanism.
4. Conclusions
Based on the results presented in this work, one can obtain
the following conclusions:
1. Most of the initially added alkaline ion reacted with Ag
+
to form an intermediate Ag
2
O, which was instantly con-
verted into silver by the reducing agent. The quantity of
added alkaline ion would decide howmuch silver could be
produced initially. After this initial period, silver ion was
reduced probably via existing silver colloids in the sys-
tem. Both silver ion and alkaline ion concentrations varied
gradually during this period. At this stage, the alkaline ion
may be involved in three reactions: reduction of silver ion,
water hydrolysis and dissociation of PVP molecule, while
silver ion only in the reduction reaction.
2. Kinetics for the silver conversionfollowedthe equationof:

d[Ag
+
]
dt
= k
1
[Ag
+
]
3/2
. The activation energy for k
1
was
determined to be 15.0 kcal mol
1
, independent of reduc-
ing agent and quantity of alkaline ion in the beginning
of reactions. Moreover, these rate constants from differ-
ent conditions were also found to be proportional to the
quantity of NaOH added. This nding is consistent with
the proposal that during the second stage of reaction, silver
reduction might occur on the surface of existing colloids.
In other words, when one added more NaOH to the sys-
tem, one would get more Ag nuclei surface area for the
second stage reaction and hence a faster reaction rate.
Acknowledgement
The authors wish to thank National Science Council for
nancial support of this work (Grant number NSC 90-2214-
E007-010).
References
[1] S. Magdassi, A. Bassa, Y. Vinetsky, A. Kamyshny, Chem. Mater. 15
(2003) 22082217.
[2] N. Pradhan, A. Pal, T. Pal, Colloids Surf., A 196 (2002) 247257.
[3] S. Nie, S.R. Emory, Science 275 (1997) 11021106.
[4] A.J. Haes, R.P. Van Duyne, Laser Focus World 39 (2003) 153156.
[5] L. Ye, Z. Lai, J. Liu, A. Tholen, IEEE Trans. Electron. Packaging
Manuf. 22 (1999) 299302.
[6] K.S. Chou, Y.S. Lai, Mater. Chem. Phys. 83 (2004) 8288.
[7] H.H. Nersisyan, J.H. Lee, H.T. Son, C.W. Won, D.Y. Maeng, Mater.
Res. Bull. 38 (2003) 949956.
[8] S.P. Wu, S.Y. Meng, Mater. Chem. Phys. 89 (2005) 423427.
[9] I. Sondi, D.V. Goia, E. Matijevic, J. Colloid Interface Sci. 260 (2003)
7581.
[10] K.Y. Kim, Y.T. Choi, D.J. Seo, S.B. Park, Mater. Chem. Phys. 88
(2004) 382388.
[11] G.D. Wei, Y. Deng, C.W. Nan, Chem. Phys. Lett. 367 (2003)
512515.
[12] P.V. Silvert, R. Herrera-Urbina, N. Duvauchelle, V. Vijayakrishnan,
K.T. Elhsissen, J. Phys. Chem. 6 (1996) 573577.
[13] H.S. Shin, H.J. Yang, S.B. Kim, M.S. Lee, J. Colloid Interface Sci.
274 (2004) 8994.
[14] H.X. Li, M.Z. Lin, J.G. Hou, J. Cryst. Growth 212 (2000) 222226.
[15] G.J. Lee, S.I. Shin, Y.C. Kim, S.G. Oh, Mater. Chem. Phys. 84
(2004) 197204.
[16] T. Fukuyo, H. Imai, J. Cryst. Growth 241 (2002) 193199.
[17] Z.Y. Huang, G. Mills, B. Hajek, J. Phys. Chem. 97 (1993)
1154211550.
[18] D.A. Skoog, D.M. West, F.J. Holler, Fundamentals of Analytical
Chemistry, 7th ed., Sauders College Publishing, Orlando, Florida,
USA, 1996 (Appendix 5).