72 Ind. Eng. Chem. Res.

2003, 42, 72-79

Adsorption of Silver onto Activated Carbon from Acidic Media:

Nitrate and Sulfate Media
Yongfeng Jia and George P. Demopoulos*
Department of Metals and Materials Engineering, McGill University, Montreal, QC, H3A 2B2 Canada

Adsorption of silver from acidic silver nitrate and sulfate media onto a peat-based activated
carbon was studied. The effects of pH, temperature, and zinc nitrate and zinc sulfate addition
on the adsorption kinetics and capacities were investigated. An XRD study showed that Ag(I)
was reduced to Ag(0) on the carbon surface during the adsorption process. Low pH, high zinc
salt concentration, and temperature are detrimental to the adsorption of silver. Second-order
reactions were involved in the process of silver adsorption with respect to Ag(I). Hydroquinone-
like surface oxygen functional groups were probably involved in the reduction reaction of Ag(I)
f Ag(0). The addition of butanol to the solution appreciably reduced the adsorption rate and
capacity of silver on the activated carbon. This indicates that graphene layer surfaces might
also be involved in the Ag(I) f Ag(0) reaction because of the enrichment of π-electrons on the
basal planes.

Introduction Therefore, it is of great importance to carry out

Activated carbons are carbonaceous materials with
well-developed porous structures consisting of hydro-
phobic graphene layer surface and hydrophilic surface
functional groups. These characteristics make them
useful as adsorbents, catalysts, and catalyst supports.
The adsorption of organic compounds is mainly con-
trolled by the porous characteristics, whereas, in many
cases, the adsorption of ionic species is determined by
the surface functional groups. The application of acti-
vated carbons to the adsorption of metals from aqueous
solutions falls into three categories: (1) recovery of
precious metals in hydrometallurgical processes;1-3 (2)
removal of toxic heavy metal ions from water;4-6 and
(3) preparation of carbon-supported catalysts.7-9 Most
applications of activated carbon to the recovery of
precious metals involve the adsorption of gold and silver
from cyanide media in a so-called carbon-in-pulp (CIP)
process in the gold industry. Extensive research has
been conducted in this area.1,2,10-16 Although no con-
sensus has yet been reached on the mechanism of the
adsorption of gold and silver cyanide ions, currently, it
is widely believed that gold and silver adsorption from
cyanide media can be characterized as occurring (i)
without chemical changes, i.e., as Au(CN)2- and Ag-
(CN)2-; (ii) predominantly on the hydrophobic graphene
layer surfaces in activated carbon;13-15 and (iii) mainly
as ion pairs, i.e., Au(CN)2-‚M+.1,16 In comparison, the
investigation of the adsorption of silver from acidic,
nitrate, sulfate, or chloride media is rather limited.17-19
Silver is present in a variety of industrial processes
involving noncyanide media; hence, it is of significance
to study the adsorption of silver from such media. On
the other hand, silver-impregnated activated carbon can
also be used as a catalyst either for the removal of toxic
substances from air20,21 or for the electrochemical
process in fuel cells,22-24 as an antibacterial material,25
and as an adsorbent for the treatment of wastewater
to remove cyanide.26,27
* To whom correspondence should be addressed. E-mail:
george.demopoulos@mcgill.ca. Fax: (514) 398-4492.
10.1021/ie020335k CCC: $25.00 © 2003 American Chemical Society
Published on Web 12/04/2002
investigations into the mechanisms and kinetics of the
adsorption of silver onto activated carbon from noncya-
nide media. Although there have been reports17,18 that
silver cation Ag(I) (in nitrate media) is reduced to
metallic silver Ag(0) when put into contact with carbon,
a detailed study on this subject is lacking.
The objectives of this work were to investigate some
mechanistic aspects of silver adsorption on activated
carbon from aqueous nitrate and sulfate media, includ-
ing the effects of pH and temperature, etc., on the
adsorption characteristics. High-concentration zinc sul-
fate and zinc nitrate background media were used
because of their existence in various hydrometallurgical
processes where silver needs to be recovered. Organic
species are widely present in the extractive metallurgy
industry. In most cases, they are preferentially adsorbed
by activated carbon compared to inorganic species.
Additionally, organic solvents are of interest in the
selection/design of an elution process. Therefore, the
effect of the addition of butanol on the adsorption of
silver is also addressed in this paper.
Experimental Section
Carbon Used. The activated carbon used in this
study was a peat-based carbon P supplied by Aldrich
with following characteristics: ultimate analysis [wt %
daf (dry-ash-free)] C 97.0, H 0.2, N 0.3, O 2.5 (by
difference); BET surface area (m2 g-1, from N2 adsorp-
tion at 77 K) 850; CO2 surface area (m2 g-1, 273 K, D-R
equation) 340; micropore volume (cm3 g-1, from extrapo-
lation of the Dubinin-Radushkevich (D-R) equation for
CO2 adsorption at 273 K) 0.14; total pore volume (cm3
g-1, from N2 adsorption at 77 K at p/p0 ) 1) 0.25.
The carbon was washed with water using a Soxhlet
extractor prior to the adsorption studies.
Titration Studies. The selective neutralization
method used to evaluate the amphoteric character of
the carbon surface was the scheme suggested by Boe-
hm.28 The amounts of various acidic functional groups
were measured by selective neutralization using NaH-
CO3, Na2CO3, and NaOH solutions. The basicity was

determined by the reaction of carbon with HCl. About
0.5 g of carbon was placed in 25 cm3 of each solution
(0.1 N), and the mixtures were allowed to stand for 72
h at room temperature. The mixtures were separated
by filtering. The amount of each base neutralized by the
carbon was determined by back-titration using 0.1 N
HCl solution, whereas the amount of HCl consumed by
the basic groups in carbon was determined by back-
titration using 0.1 N NaOH.
Silver Adsorption Studies. The silver compound
used was AgNO3, which was added to distilled water, 2
M Zn(NO3)2, 2 M ZnSO4 matrix solution at natural pH,
or 2 M ZnSO4 matrix solution with pH adjusted using
HNO3 and H2SO4. The kinetics studies were carried out
by contacting 1.5 g of activated carbon with 500 mL of
120 ppm Ag(I) solution under constant agitation. A
2-cm3 aliquot of solution was taken at various time
intervals using a syringe and a 0.02-µm filter to monitor
the change of Ag(I) concentration, which was deter-
mined by ICP-AES analysis. The amounts of silver
adsorbed onto the carbon were determined by difference.
The adsorption isotherms were determined by adding
various amounts of activated carbon (0.1, 0.3, 0.5, 0.7,
0.9, 1.5, 3, and 5 g) to a series of beakers containing
200 mL of solutions with 120 ppm Ag(I) and with the
pH adjusted to the desired levels. Because, in some
cases, desorption occurred after adsorption for some
time, the retention times used to determine the adsorp-
tion capacities under different conditions were deter-
mined by the maximum adsorption in the kinetics
studies.
X-ray Diffraction (XRD) Studies. Powder XRD
patterns were obtained on a Philips PW1710 diffracto-
meter equipped with a copper target (Cu KR1 radiation,
λ ) 1.540 60 Å), a crystal graphite monochromator, and
a scintillation detector. The divergence slit was auto-
matic, and the receiving slit was 0.2°. The instrument
was run at 40 kV and 20 mA by step-scanning from 10°
to 100° 2θ in increments of 0.02° 2θ with a counting
time of 0.5 s for each step. Activated carbon samples
were prepared by contacting 0.5 g of carbon with 100
mL of AgNO3 solution (120 ppm silver, pH 1.5 and 4.5)
and 2 M ZnSO4 solution (120 ppm silver, pH 4.5) for
periods corresponding to the maximum adsorption times
in the kinetics studies. The samples were washed with
distilled water, air-dried at room temperature, and
ground to a fine powder. The powder sample was placed
in a sample holder with a 15 × 20 × 2 mm cavity and
mounted in the sample chamber. The operation was
carried out at room temperature and atmospheric
pressure.
Results
Titration Studies. The acidic surface groups present
in activated carbon include (1) carboxylic acid groups;
(2) derivatives of carboxylic acid groups such as car-
boxylic anhydride, lactone, and lactol groups; and (3)
phenolic groups. These groups are weakly acidic and the
acidity constants differ by several orders of magnitude.
According to Boehm,28 only the strongly acidic carboxylic
groups are neutralized by NaHCO3, whereas those
neutralized by Na2CO3 are thought to be the lactone,
lactol, and carboxyl groups. The weakly acidic phenolic
groups react only with strong alkali NaOH. Therefore,
by selective neutralization using bases of different
strengths, the surface acidic functional groups in car-
bons can be characterized both quantitatively and
Ind. Eng. Chem. Res., Vol. 42, No. 1, 2003 73
Table 1. Selective Neutralization Results for the Carbon
before and after Adsorption of Silver (0.2 mmol g-1) at
pH 4.5 from AgNO3 Solution
HCl NaHCO3 Na2CO3 NaOH
sample (mequiv g-1) (mequiv g-1) (mequiv g-1) (mequiv g-1)
blank carbon 0.79 0.02 0.05 0.34
carbon + Ag 0.63 0.14 0.16 0.52
qualitatively. Neutralization with HCl characterizes the
amounts of surface basic groups, such as pyrones and
chromenes. The basic properties are ascribed to surface
basic groups and the π-electron system of the carbon
basal planes. The selective neutralization results for the
activated carbon before and after adsorption of silver
are shown in Table 1. The titration results indicate that
the activated carbon used in this study is a basic H-type
carbon that contains about 0.3 mequiv g-1 of phenolic
groups but negligible amounts of carboxylic and lactone
groups. The carboxylic-like acidic oxygen functional
groups are usually involved in ion-exchange reactions,
thereby significantly enhancing the adsorption of metal
cations.6,29 These effects can be minimized as a result
of the negligible amounts of stronger acidic oxygen
functional groups. Part of the phenolic groups constitute
the hydroquinone-like groups, which were postulated to
be involved in the redox reaction occurring during silver
adsorption. The titration results for the carbon after the
adsorption of silver reflect the overall acid/base proper-
ties of the surface of the carbon and metallic silver.
Therefore, the variation of the acidic oxygen functional
groups in the activated carbon as a result of reaction
with silver cannot be assessed by comparison of the
titration results before and after the adsorption of silver.
Measurement of ζ-potential of the activated carbon
shows that the isoelectric point (pHpzc) is around 4.
XRD Studies. The XRD patterns of the activated
carbon powder after the adsorption of silver from (1)
AgNO3 solution at pH 4.5 (designated as C-Ag-4.5), (2)
AgNO3 solution at pH 1.5 (designated as C-Ag-1.5), and
(3) AgNO3 in 2 M ZnSO4 solution at pH 4.5 (designated
as C-Ag-Zn-4.5) are shown in Figure 1. It is apparent
that Ag(I) was reduced to metallic silver during adsorp-
tion under all conditions used in this study. The wet
samples were also examined by XRD, and the resultant
patterns showed no significant difference from those of
the corresponding dry samples; hence, the reduction of
silver did not occur during drying. Four strong sharp
peaks at 38.12°, 44.26°, 64.36°, and 77.25° 2θ were
observed for the three samples, which are the charac-
teristic diffraction lines of Ag(111), Ag(200), Ag(220),
and Ag(311) of the FCC (face-centered cubic) silver
crystal phase. This indicates that measurably large
silver crystallites were formed in the activated carbon
after it came into contact with Ag+ ions in aqueous
solutions. The broad peaks at around 26.60° and 44.64°
2θ are the amorphous features of activated carbon
consisting of graphite-like microcrystallites arranged in
a random manner, corresponding to the graphite(002)
and graphite(100) lines. The second broad peaks at
44.64° 2θ overlap with Ag(200) diffraction lines. For the
samples prepared by adsorption from AgNO3 solution
at pH 4.5 (C-Ag-4.5) and AgNO3 in 2 M ZnSO4 matrix
at pH 4.5 (C-Ag-Zn-4.5), a weak diffraction peak was
observed at 81.51° 2θ on each of the XRD patterns,
which is the Ag(222) characteristic diffraction line. It
is not visible in the XRD pattern of the sample prepared
at pH 1.5 (C-Ag-1.5). The Ag(400) diffraction line at
97.89° 2θ is barely visible in all three XRD patterns.
74 Ind. Eng. Chem. Res., Vol. 42, No. 1, 2003
Figure 1. XRD patterns of carbon P after adsorption of silver
from various media.
The above results are further confirmed by examining
the d values of the diffraction lines at 38.12°, 44.26°,
64.36°, and 77.25° in 2θ, which are 2.36, 2.05, 1.45, and
1.24 Å, respectively, matching very well with the d
values of Ag(111), Ag(200), Ag(220), and Ag(311) of the
reference. It was observed in the laboratory tests that
the color of the activated carbons changed to light gray
after they came into contact with the above solutions,
indicating that Ag(I) was reduced to metallic silver Ag-
(0) on the surface of the activated carbon.
Significant differences were observed in the intensi-
ties of the peaks in the XRD patterns of the three
samples prepared under various conditions. C-Ag-4.5
had the strongest diffraction lines at Ag(111), Ag(200),
Ag(220), and Ag(311), followed by C-Ag-Zn-4.5, whereas
C-Ag-1.5 shows the weakest corresponding peaks. This
indicates that the reduction reaction of silver on the
surface of activated carbon is not favored by high acidity
and high concentration of zinc sulfate in the solution.
The 2 M ZnSO4, either dissociated (40% mol at 25 °C,
pH 0.5-4.5) or as neutral molecules,30 probably prevents
Ag+ ions from effectively accessing the carbon surface.
The AgSO4- complex ion also forms in sulfate media,31
which reduces the activity of Ag+ (aq). As a result, the
loading capacity is decreased. The protons are probably
involved in the redox reactions of the carbon surface
with silver cations. The variations of pH probably alter
the redox potential of the activated carbon, thereby
changing the process of the Ag(I) redox reaction with
carbon.
Adsorption Kinetics. The term “adsorption” is used
here to describe the process during which the silver
species are loaded onto the surface of the activated
carbon either with or without chemical changes, al-
though it is more precise to call this process “deposition”
in some cases when the silver ions are reduced to
metallic silver, as shown by the XRD studies.
Figure 2. Kinetics of adsorption of silver onto carbon P from
AgNO3 aqueous solution at pH 1.5 and 4.5, 25 °C.
The adsorption kinetics were studied to assess the
time required for the systems to reach equilibrium. The
results of adsorption from AgNO3 aqueous solutions (pH
1.5 and 4.5) at 25 °C are shown in Figure 2. It is
apparent that equilibrium was almost achieved within
5 h for the adsorption carried out at pH 4.5. Prolonged
standing resulted in little change in the amount of silver
adsorbed. It is also obvious from Figure 2 that lower
pH is detrimental to the adsorption of silver from AgNO3
solution. The maximum amount of silver adsorbed on
the activated carbon at pH 1.5 was dramatically reduced
to about 0.25 mmol g-1, i.e., two-thirds of the equilib-
rium amount at pH 4.5. It was observed from the XRD
study that, at pH 1.5, silver was initially reduced to
metallic silver at the maximum adsorption point; hence,
it is very likely that silver reduction on the surface of
activated carbon was not favored at low pH. Another
mechanism is that the carbon surface shows less affinity
for silver cations at low pH (<pHPZC) because excess
positive charges are generated when the pH is lowered.
This is applicable to most physisorption systems largely
governed by electrostatic interactions. A striking phe-
nomenon was observed for the adsorption at pH 1.5 after
around 20 min (maximum adsorption) in that the
adsorption process reversed and desorption occurred.
The desorption was quite rapid in the first few hours
and then gradually slowed. Only 10% of the adsorbed
silver was retained on the activated carbon after 52 h.
The XRD study of the activated carbon put into contact
with Ag(I) solution at pH 1.5 for 20 min showed that
Ag(I) was reduced to Ag(0) as can been seen in Figure
1. It is obvious that Ag(0) on the carbon surface was
reoxidized in acidic solution, which reversed the adsorp-
tion process.
Figure 3 shows the effect of the addition of 1% v/v
butanol on the adsorption of silver onto activated
carbon. Apparently, the adsorption of silver was sup-
pressed by the organic solvent, indicating that the two
species are competing for the same sites on the surface
of the activated carbon. A mass-transfer barrier effect
by the butanol adsorbed along the transport channels
cannot be ruled out; however, the adsorption of silver
was fast in the beginning, with more than 0.19 mmol
g-1 adsorbed in 5 h, after which the adsorption slowly
reached a plateau. The overall adsorption capacity of
silver was significantly reduced by the addition of
butanol.

Figure 3. Kinetics of adsorption of silver onto carbon P from
AgNO3 aqueous solution in the presence and absence of 1% v/v
butanol at 25 °C, pH 4.5.
Figure 4. Effect of background salts on the kinetics of adsorption
of silver onto carbon P at 25 °C, pH 4.5.
The adsorption kinetics of silver on activated carbon
from 2 M Zn(NO3)2 and ZnSO4 solutions are illustrated
in Figure 4. The results clearly show that the silver
adsorption capacity was markedly decreased by the
addition of 2 M Zn(NO3)2 and ZnSO4, with sulfate
having a more negative effect. After reaching the
maximum adsorption, desorption of silver occurred until
an equilibrium was achieved. Therefore, it is reasonable
to conclude that, in addition to adsorption in the reduced
form Ag(0), some silver was also adsorbed physically in
other ways, which was later desorbed probably as a
result of the competitive adsorption of zinc ions because
negative charges were generated at pH 4.5 (>pHpzc). The
decrease in the adsorption of silver from 2 M Zn(NO3)2
and ZnSO4 solutions is probably due to the partial
suppression of the Ag(I) f A(0) reduction reaction by
the high ionic strength of the background electrolytes
together with the competitive adsorption of zinc ions.
Additionally, in sulfate medium, the formation of AgSO4-
complex ions, which lowers the Ag+ activity, thus
contributing more to the reduced adsorption capacity.
Figure 5 shows the adsorption kinetics of silver from
2 M ZnSO4 solution as a function of pH and tempera-
ture. It can be seen that a large fraction of loaded silver
at 55 °C and pH 4.5 desorbed spontaneously, as in the
case at 25 °C, indicating that there was a competitive
adsorption between Ag(I) and other species, probably
Ind. Eng. Chem. Res., Vol. 42, No. 1, 2003 75
Figure 5. Kinetics of adsorption of silver onto carbon P from 2
M ZnSO4 solution as a function of pH and temperature.
zinc ions. Comparison with the corresponding adsorp-
tion profile at 25 °C clearly shows that both the
maximum and equilibrium adsorption capacities of
silver were lower at high temperature. The ratio (1/2)
and amount (0.12 mmol g-1) of silver due to reversible
adsorption at 55 °C are twice the corresponding values
at 25 °C (1/4 and 0.06 mmol g-1, respectively). It is
reasonable to attribute the temperature effect to the
exothermic nature of the physical adsorption that is
believed to be responsible for the reversible fraction of
silver adsorption.
It can also be seen from Figure 5 that low pH had a
notably negative effect on the adsorption of silver from
ZnSO4 solution. The maximum adsorption capacity at
pH 1.5 was much lower than that at pH 4.5. Moreover,
whereas about half of the loaded silver was reversibly
adsorbed at pH 4.5, all of the silver adsorbed at pH 1.5
within 1 h was completely desorbed after 24 h. This
implies that silver can be recovered from acidic media
only through control of the adsorption time. In addition
to the recovery of silver from acidic media, the observed
reversal of the adsorption process is also of relevance
to the preparation and application of carbon-supported
silver catalysts where caution should be taken in acidic
environments to avoid losing silver from the carbon and,
hence, losing the catalytic activity.
The reduction reaction of Ag(I) on the surface of
activated carbon can be expressed as
Ag+(aq) + Cred(s) f Ag0(s) + Cox(s) (R1)
where Cred and Cox represent reduction sites and cor-
responding oxidation sites in activated carbon, respec-
tively. The plots of 1/C against t, where C represents
the concentration of Ag+ and t represents the time, are
shown in Figures 6 and 7. Here, we focus only on the
period from the beginning to the point where the
maximum adsorption was reached, i.e., before desorp-
tion started. Thus, the time scales of the plots were set
to the time corresponding to the maximum adsorption.
It is apparent from Figures 6 and 7 that all of the
1/C vs t plots gave linear relationships, indicating that
second-order reactions were involved. Therefore, the
adsorption of silver from AgNO3, 2 M Zn(NO3)2, and 2
M ZnSO4 solutions is second-order with respect to Ag+-
(aq). The rate law expression of the reaction is rate )
kC2. The rate constants of the reactions were calculated
76 Ind. Eng. Chem. Res., Vol. 42, No. 1, 2003

Figure 8. Adsorption isotherms of silver onto carbon P from

AgNO3 and 2 M ZnSO4 solutions at 25 °C, pH 4.5.
Figure 6. Plots of 1/C versus time for the adsorption of silver
onto carbon P from AgNO3 solution at 25 °C.

Figure 9. Effect of pH on the adsorption capacities of silver on

carbon P from 2 M ZnSO4 at 55 °C.

lated half-lives of the reactions also match reasonably

well with the experimental values.
Figure 7. Plots of 1/C versus time for the adsorption of silver Adsorption Capacities. The adsorption capacities
onto carbon P from 2 M Zn(NO3)2 and 2 M ZnSO4 solutions. of silver on activated carbon were determined on the
basis of the maximum adsorption for the reversible
Table 2. Rate Constant and Half-Life of Silver adsorption processes. Figure 8 shows the effect of 2 M
Adsorption on Carbon P
ZnSO4 matrix on the adsorption capacity of silver on
rate constant half-life (min) activated carbon. It is apparent that the silver adsorp-
media and conditions (mol-1 dm3 min-1) 1/kC0 experimental tion capacity was dramatically reduced by ZnSO4. The
AgNO3, 25 °C, pH 4.5 144.4 6.30 10.2 adsorption capacity of Ag(I) is about one-half that from
AgNO3, 25 °C, pH 1.5 98.3 9.42 9.60 a solution of AgNO3 alone. This is in good agreement
AgNO3/2 M ZnSO4, 21.8 41.7 33.0 with the XRD results that sample prepared from 2 M
25 °C, pH 4.5 ZnSO4 had lower diffraction peak intensity. Silver ions
AgNO3/2 M ZnSO4, 25.7 36.0 30.0 are known to form AgSO4- complex ions31 in sulfate
55 °C, pH 4.5
AgNO3/2 M ZnSO4, 23.4 39.6 N/A
media; hence, the activity of Ag+(aq) is reduced, and as
55 °C, pH 1.5 a result, the reduction reaction of Ag(I) to Ag(0) is
AgNO3/2 M Zn(NO3)2 66.1 13.7 18.0 partially suppressed. Competitive adsorption of zinc ions
25 °C, pH 4.5 might also occur, which, in turn, would reduce the
adsorption of silver.
Figure 9 shows the effect of pH on the adsorption
according to the slopes of the 1/C vs t plots and listed capacity of Ag(I) on activated carbon. It can be seen that
in Table 2. The rate constant for the adsorption of silver low pH is detrimental to the adsorption of silver on
from AgNO3 solution is reduced by lower pH. It can also activated carbon. The adsorption capacity of silver was
be seen that the reaction rate constant is significantly significantly reduced by the high acidity at pH 1.5. The
decreased in the presence of 2 M Zn(NO3)2 or ZnSO4, adsorption capacity of Ag(I) on the activated carbon at
whereas the effects of pH and temperature are not pH 4.5 was twice that at pH 1.5. It can be inferred that
appreciable. The half-life for each reaction was calcu- hydrogen ions were involved in the redox reaction of
lated according to the relation t1/2 ) 1/kC0 and compared Ag(I) with the carbon surface, which was unfavorable
with the experimental half-life in Table 2. The calcu- for the reduction of Ag(I).

Figure 10. Effect of temperature on the adsorption capacities of
silver on carbon P from 2 M ZnSO4 at pH 4.5.
The effect of temperature on the adsorption capacity
of silver from 2 M ZnSO4 is illustrated in Figure 10. It
is obvious that the adsorption capacity of Ag(I) on
activated carbon decreased with increasing tempera-
ture. It has long been believed that the capacity of
physical adsorption is favored by low temperature
because of the exothermic characteristics of adsorption.
The adsorption of silver involving the redox reaction of
Ag(I) with the surface of activated carbon is also favored
by low temperature under the conditions used in this
study.
Discussion
Activated carbons are well-known to catalyze many
oxidation reactions,32-34 which suggests that activated
carbons are able to accept electrons as a result of the
existence of unpaired electrons at the crystallite edges.34
In addition, activated carbons can also catalyze reduc-
tion reactions because of their amphoteric characteris-
tics, namely, separate acidic and basic sites on their
surfaces.35 The redox properties of activated carbons are
most likely related to the edge sites where oxygen
functional groups are located. It is well-established that
carbon surfaces are made up of at least two chemically
different sites, i.e., graphene layer surfaces and func-
tional groups on the edges. Oxygen functional groups
are the commonest functionality in activated carbons,
which consist at least five markedly different types of
surface groups: carboxylic, lactonic, phenolic, carbonyl,
and etheric. Quinone/hydroquinone-like groups34,35 are
proposed to be mainly responsible for the redox char-
acteristics of carbon, although other groups such as
lactones might be involved in redox reactions, whereas
the carboxylic-like groups are responsible for the ad-
sorption of metal ions through an ion-exchange mech-
anism.6 Hydroquinone-like groups are classified into
phenolic groups, which are determined using the selec-
tive neutralization method proposed by Boehm.28 There
are about 0.3 mequiv g-1 of phenolic groups in the
carbon, a fraction of which are probably involved in the
redox reaction. Two mechanisms might be involved in
the adsorption of silver under the conditions in this
study: reduction of Ag(I) to Ag(0) and adsorption of
silver ions and/or AgSO4- complex ions.
While silver ions were reduced to metallic silver as
shown in the results, the transfer of electrons would
result in simultaneous oxidation of hydroquinone-like
Ind. Eng. Chem. Res., Vol. 42, No. 1, 2003 77
groups to quinone-like groups in activated carbon as
suggested in the literature.35 The half-reaction of Ag(I)
reduction to Ag(0) is
Ag+(aq) + e- f Ag0(s) (R2)
(e0 ) 0.7996 V)
The simultaneous oxidation of the surface functional
groups in activated carbon is treated as an analogue to
simple hydroquinone/quinone conversion
(e0 ) 0.699 V)
The redox potential of eq R2 varies according to the
concentration of silver ions and is expressed by the
Nernst equation
e(1) ) e(1)0 -
RT
0.434F
log
1
( )
aAg+
(1)
where R is the gas constant, 8.314 Pa m3 K-1 mol-1; T
is the temperature, K; and F is the Faraday constant,
96 485.3 C mol-1
The maximum Ag+ concentration used in this study
was 120 ppm. The activities of Ag+ were calculated by
the activity coefficients and concentrations of Ag+ under
various conditions generated by an OLI Stream Ana-
lyzer,37 with which the redox potentials of the half-
reaction R2 were derived according to the Nernst
equation (see Table 3). Apparently, the redox potentials
of Ag+/Ag for the concentrations used were much lower
than the standard potential (0.7996 V) and decreased
appreciably with decreasing concentration of Ag+. The
addition of 2 M Zn(NO3)2 and ZnSO4 into the AgNO3
aqueous solution measurably reduced the Ag+/Ag po-
tential, thereby hindering the reductive adsorption of
Ag+ onto activated carbon. The redox potential also
decreased with increasing temperature.
The redox potential of quinone/hydroquinone in eq R3
is strongly dependent on the pH of the medium accord-
ing to the following relationship35
RT
e(2) ) e(2)0 - pH (2)
0.434F
The potentials at various pH’s were calculated and
are listed in Table 4. It is obvious that the quinone/
hydroquinone potential decreases markedly with in-
creasing pH. The overall redox reaction by combining
the two half-reactions R2 and R3 takes places only when
the reaction potential difference (i.e., electromotive
force) is positive, that is
RT
E ) e(1) - e(2) ) (e(1)0 - e(2)0) + (log aAg+ + pH) > 0
0.434F
(3)
The reaction is favored by higher Ag+(aq) activity and
lower acidity as a result of an increase in the reaction
78 Ind. Eng. Chem. Res., Vol. 42, No. 1, 2003
Table 3. Ag(I)/Ag Redox Potentials at pH 5
AgNO3
25 °C
total Ag(I) in
solution (ppm) 120 1 120
CAg+ (M) 1.1 × 10-3 9.3 × 10-6
γAg+ 0.97 1.0
aAg+ (M) 1.06 × 10-3 9.3 × 10-6
e (V) 0.623 0.502
Table 4. Quinone/Hydroquinone Potentals at Various
pH’s
e (V)
pH 25 °C 55 °C
1 0.640 0.634
2 0.581 0.568
3 0.521 0.503
4 0.462 0.438
5 0.403 0.373
6 0.344 0.307
potential difference. That is probably why Ag(I) adsorp-
tion was detrimentally affected by low pH and the
addition of 2 M Zn(NO3)2 and ZnSO4, which increased
e(2) and decreased e(1), respectively. The effect of tem-
perature is dependent on the combination of silver ion
activity and pH, i.e., if (log aAg+ + pH) is positive, the
effect of temperature on the reaction potential difference
will be positive. Under the conditions used in this study,
the sign of (log aAg+ + pH) is negative; hence, increasing
temperature is detrimental to the adsorption of silver,
as observed in the results.
Phenolic groups with hydroquinone characteristics in
activated carbon are probably responsible for the reduc-
tion of Ag(I) to Ag(0). This means that only the phenolic
groups containing structures shown in eq R3 were
involved in the reaction. The e0 value of quinone/
hydroquinone varies according to the size of the sub-
strate to which the carbonyl/hydroxyl groups are at-
tached (e.g., e0 ) 0.699 V for one-ring and 0.468 V for
two-ring species).38 In activated carbon, hydroquinone-
like groups are located on various types of edges of
microcrystallites of various sizes. Therefore, the poten-
tials of these groups vary, and the potential of the
activated carbon is the overall reflection of the potentials
of all of the functional groups involved. The calculation
in this work is simplified to the quinone/hydroquinone
pair to elucidate the effects of pH and temperature. The
oxidation of hydroquinone groups to quinone groups
during the process of Ag(I) reduction should involve the
release of protons into the solution as shown by eq R3.
This was confirmed by the observation of decrease in
pH during reaction; however, no quantitative relation
has been established. This phenomenon might be due
to the amphoteric nature of the activated carbon, which
contains separate and noncoincident acidic and basic
sites. Some of the protons released during Ag(I) adsorp-
tion were probably adsorbed by the basic sites. In this
study, it was observed that Ag(I) reductive adsorption
was not favored by low pH because of the decreased
reaction potential difference. At pH 1.5, Ag(I) was
reduced to metallic silver in the first instance and then
almost completely desorbed. This behavior is largely
attributed to the competitive diffusion of Ag+ and H+
to the surface of activated carbon. Some of the silver
ions reaching the carbon surface were reduced to
metallic silver initially before the carbon was saturated
with protons (E > 0). After equilibration of the protons,
the reaction potential difference was reversed to nega-
AgNO3 + 2 M ZnSO4 AgNO3 + 2 M Zn(NO3)2
25 °C 55 °C 25 °C
120 120
4.34 × 10-4 3.24 × 10-4 6.63 × 10-4
0.41 0.41 0.74
1.78 × 10-4 1.33 × 10-4 4.66 × 10-4
0.578 0.570 0.602
tive (E < 0), thereby leading to the reoxidation of Ag(0)
to Ag(I), possibly accompanied by a reversible conversion
of quinone to hydroquinone.
The addition of butanol to AgNO3 solution markedly
reduced both the rate and the adsorption capacity of
silver, indicating that butanol and silver ion might
compete for similar surface sites in activated carbon.
Hence, it can be inferred that graphene layers were
possibly involved in the reduction reaction of Ag(I) f
Ag(0) in addition to the hydroquinone-like groups,
because butanol should be preferentially adsorbed on
the hydrophobic graphene layer surfaces. The oxygen
functional groups of hydroquinone-type sites directly
involved in the reduction reaction of Ag(I) f Ag(0) were
assumed to be the conjugated base of hydroquinone
groups. The conjugated acid/base pair maintains an
equilibrium in aqueous solution that is significantly
dependent on the pH of the medium
Solid carbon is regarded as a p-type semiconductor
in which holes are generated by the net migration of
electrons toward the surface.35 The basal plane surfaces
exposed are enriched in π-electrons with depletion in
the bulk. Thus, the graphene layers will show the
characteristics of Lewis bases and behave as electron
donors. This suggests that some of the reduction reac-
tion of Ag(I) f Ag(0) might have occurred on the
graphene layer surfaces.
In addition to reduction to metallic silver, the silver
ions might also be adsorbed on the insignificant amount
of carboxylic related groups (∼0.05 mequiv g-1) by an
ion-exchange mechanism.6 Physisorption of silver ions
and AgSO4- complex ions might take place at pH’s
above and below the PZC, respectively. In the case of
adsorption from Zn(NO3)2 and ZnSO4 media at pH above
PZC, zinc ions are possibly involved in competitive
adsorption with silver ions, which, as a result, decreases
the adsorption of silver.
Conclusions
Two mechanisms might be involved in the adsorption
of silver from acidic nitrate and sulfate media: chemi-
sorption and physisorption. Silver ions were reduced to
metallic silver on the surface of activated carbon P
during the adsorption of silver from AgNO3, 2 M Zn-
(NO3)2, and 2 M ZnSO4 solutions. The adsorption
kinetics are second-order with respect to Ag+(aq). Low
pH and the addition of 2 M Zn(NO3)2 and ZnSO4 were
detrimental to the adsorption of silver, with sulfate
having a more negative effect. At pH 1.5, silver was

adsorbed chemically by reduction to metallic silver,
which was followed by virtually complete desorption
upon prolonged retention resulting from the reoxidation
of Ag(0) to Ag(I). Hydroquinone-like groups, which are
determined by Boehm’s titration in the activated carbon,
were probably involved in the Ag(I) f Ag(0) reaction.
The hydroquinone/quinone potential increased mark-
edly with decreasing pH, thereby decreasing the com-
bined reaction potential difference; as a result, the Ag(I)
f Ag(0) reaction is not favored by low pH. When the
pH was low enough to reverse the reaction potential
difference to negative, the initially reduced silver was
reoxidized. At pH 4.5, the adsorption of silver from
AgNO3 solution was irreversible, whereas silver was
partially desorbed after reaching the maximum adsorp-
tion from 2 M Zn(NO3)2 and ZnSO4 solutions. The
reversible adsorption possibly involved the competitive
adsorption of zinc ions with silver ions, whereas the
irreversible adsorption in both cases resulted from the
reduction of silver ions to metallic silver. The addition
of butanol to the system significantly reduced the silver
adsorption, which indicates that, in addition to hydro-
quinone groups on the edges, graphene layer surfaces
might also be involved in the silver reduction reaction,
as well as enriched π-electrons on the basal planes.
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Received for review May 6, 2002
Revised manuscript received October 11, 2002
Accepted October 20, 2002
IE020335K