Separation and Purication Technology 47 (2005) 7379

Adsorption and electrocatalytic dechlorination of pentachlorophenol

on palladium-loaded activated carbon bers
Chunyue Cui, Xie Quan

, Shuo Chen, Huimin Zhao

School of Environmental and Biological Science & Technology, Linggong Road, Dalian University of Technology, Dalian 116024, China
Received 22 November 2004; received in revised form 26 May 2005; accepted 2 June 2005
Abstract
The palladium-loaded activated carbon ber (Pd/ACF) adsorption/electroreduction process was employed for electrocatalytic dechlorination
of pentachlorophenol (PCP) solution. PCP in water was adsorbed onto Pd (4.2 wt.%)/ACF rst and then the PCP was degraded at a constant
current. At 25 mA/cm
2
, the degradation of PCP was 94.8% after electrolysis of 200 min and phenol was the main product with a yield of
86.1% and a current efciency of 17.4%. After being reused three times, the Pd (4.2 wt.%)/ACF cathode still had acceptable electrocatalytic
activity.
2005 Published by Elsevier B.V.
Keywords: Electrocatalytic dechlorination; Activated carbon ber; Palladium; Pentachlorophenol
1. Introduction
Contamination of water and soil by chlorophenolic com-
pounds now represents a signicant environmental burden
due to their widespread industrial use, inherent toxicity and
persistence in the environment [1]. Chlorophenols are usually
used as the intermediates for organic synthesis, wood preser-
vatives and pesticides. The toxicity of these compounds is
connected with the chlorine content, and their biodegrad-
ability is strongly affected by chlorine substitution in the
molecules. Most chlorophenols are listed as priority pollu-
tants by the US EPA [2].
Highly chlorinated aromatic compounds are recalcitrant
towards disposal. Biological treatment of low concentration
of such materials in aqueous waste streams often leaves the
chlorinated compounds untreated or required a long time, e.g.
several days [3,4]. The chemical hydrodehalogenation meth-
ods have been developed based on zero-valent metals, such
as iron, known as dissolving metal reductions [58]. Iron has
been used to dechlorinate compound containing one or two
carbon atoms [5,6]. Treatment of halogenated aromatic com-
pounds has been suffered slow reaction rate [7,8]. Therefore,

Corresponding author. Tel.: +86 411 84706140; fax: +86 411 84708084.
E-mail address: quanxie@dlut.edu.cn (X. Quan).
it is desirable to develop efcient and safe alternative tech-
nology for the dechlorination of chloroaromatic compounds.
Recently, the electrochemical reductive approach has
been suggested as a promising method for detoxication
of chlorine-containing aromatic hydrocarbons [914]. This
methodensuredthe selective removal of chlorine atoms under
mild experimental conditions without using the highly reac-
tive reducing agents. As a result, the much less toxic dechlo-
rinated products could be treated further by more convenient
and economic means, for example, biodegradation. In par-
ticular, electrochemical processes have been developed for
the destruction of carbonhalogen bonds. However, in many
eases, the effective performance required the use of non-
aqueous reaction media mainly aprotic solvents [1519] or
environmentally unpleasant cathode materials, such as mer-
cury or lead [9,10,15], which made such methods unattrac-
tive. Recently, the dehalogenation of aromatic compounds
in aqueous medium by electrochemical hydrodehalogena-
tion using Pd as catalyst has been reported [1114]. Dabo et
al. reported 99% conversion of pentachlorophenol to phenol
over Pd (5 wt.%)/Al
2
O
3
entrapped in a reticulated vitreous
carbon electrode at 75

C [12]. In general, electrochemi-

cal hydrodehalogenation of low concentration compounds in
aqueous solution observed low current efciency and high
energy consumption. These features render the approach
1383-5866/$ see front matter 2005 Published by Elsevier B.V.
doi:10.1016/j.seppur.2005.06.005
74 C. Cui et al. / Separation and Purication Technology 47 (2005) 7379
unattractive with respect to the treatment of large volumes
of organic wastewater with low concentrations.
Activated carbon ber (ACF) is widely used for water
purication due to its high adsorption capacity and fast
adsorption rates for organics [20]. And Pd is usually
employed as catalyst loaded on inert supports like carbon
for the electrochemical reactions [21]. In present work, we
reported an adsorption/electroreduction process using Pd
loaded ACF for the treatment of pentachlorophenol (PCP).
Special attentions were paid to the adsorption capacity of
Pd/ACF, the catalytic activity and the inuence of current
density on the efciency of PCP dechlorination.
2. Experimental
2.1. Chemicals and materials
The following chemicals were used as received: pen-
tachlorophenol (PCP, >99%, Fanghua Agent Company,
China); tetramethyl-ammonium chloride (TMAC1, >99%,
Kemiou Agent Company, China); methanol, acetone,
dichloromethane and acetonitrile (HPLC-grade, Tedia Agent
Company, USA); PdCl
2
(>99%, Tianjin Chemical Reagent
Company, China).
ACF made from polyacrylonitrile resin was supplied by
Anshan Activated Carbon Fiber Company, China.
2.2. Apparatus and procedures
2.2.1. Preparation of Pd/ACF electrode
After cleaned with deionized water, the ACF was boiled
in 1 M HNO
3
for 3 h, then rinsed with deionized water and
dried for 24 h at 100

C. The surface area of the ACF was

determined by the BET method.
PdCl
2
with various concentrations in 1 M HCl solutions
were deposited into the ACF by incipient-wetness method.
The Pd-impregnated ACF was then dried at 80

C for 4 h
and was electroreduced in 0.3 M H
2
SO
4
solution. Surface
characterization of the Pd/ACF was performed by Scanning
Electron Microscope (SEM, JSM-5600L, UK) and X-ray
Diffractometer (XRD, LabxXRD-6000, Shimadzu, Japan)
using Cu K as radiation. Contents of Pd were determined
by ICP-AES (Advantage, IRIS, USA.).
2.2.2. Electrocatalytic reactor
Electrocatalytic dechlorination of PCP was carried out
in a Teon-made H-cell divided into two compartments by
cation-exchange membrane (Naon N324, Dupont Com-
pany, USA), as shown schematically in Fig. 1. The volume
of each electrolyte compartment was 50 mL. The working
electrode was a piece of Pd/ACF (15 mm15 mm3mm
and 70 mg in weight), which was xed on tile titanium
mesh. The working electrode was placed in the cathodic
compartment. The catholyte was a 40% methanol aqueous
solution with 0.25 M TMAC1 supporting electrolyte. The
Fig. 1. Two-compartment cell used for the electrolyses. (A) Pt anode; (B)
cation exchange membrane; (C) Pd/ACF cathode; (D) magnetic bar; (E)
reference electrode; (F) potentiostat.
counter-electrode was a platinumplate with the dimension of
10 mm10 mm0.2 mm. Anodic compartment was lled
with 1 M NaOH supporting electrolyte. A saturated calomel
electrode (SCE) was used as the reference electrode. The
electrolysis was performed at a constant current and 40

C. A
potentiostat (DJS-292, Shanghai Rex Instrument Co., China)
was used as power source.
2.2.3. Analytical method
PCP concentrations in solution and on the Pd/ACF elec-
trode were measured at different intervals during electrolysis
separately. Pd/ACF electrode was extracted with 25 mL mix-
ture of acetone and dichloromethane (1:1, v/v) plus 0.2 mL
30% HC1 (shaking at 250 rpm for 4 h). The above proce-
dure was repeated six times. The solvent fractions were
combined and dried on a rotary evaporator (Shanghai Bio-
chemistry Instrument Co., China). The resulted sample was
dissolved in acetonitrile and analyzed by HPLC (PU-1580,
UV-1575, Jasco, Japan) at 220 nm with a Kromasil ODS
column (250 mm4.6 mm, 5 m). The mobile phase was
acetonitrile:water (0.1% acetic acid) =3:2 (v/v) at a ow rate
of 1 mL/min. The volume of the injected sample was 20 L.
Identication of intermediates was carried out with an HP
6890 gas chromatography (GC) coupled with 5973N mass
selective detector (MSD) with a capillary column (HP-5 MS,
30 m0.25 mm0.25 m, Agilent, USA). The ow rate of
carrier gas (He) was 1.0 mL/min. A solvent delay at 8 min,
and full scan mode was used. The oven temperature was
increased from 40 to 260

C (hold for 20 min) at a rate of

15

C/min. The injector temperature was 260

C, and the ion

source temperature was 230

C. The MSDwas operated with

the electron impact (El) mode with the electron energy being
70 eV.
3. Results and discussion
3.1. Characterization of ACF
The structural parameters of ACF were calculated from
the nitrogen isotherms. Surface area (S
BET
) was 1335.4 m
2
/g,
C. Cui et al. / Separation and Purication Technology 47 (2005) 7379 75
Fig. 2. SEM micrographs of (A) virgin ACF and (B) Pd (4.2 wt.%).
Fig. 3. XRD patterns of (A) virgin ACF and (B) Pd (4.2 wt.%)/ACF.
micropore volume was 0.5857 cm
3
/g and average pore diam-
eter was 2.13 nm.
3.2. Distribution of palladium on the ACF
The SEMmicrographs of the ACF and Pd (4.2 wt.%)/ACF
are shown in Fig. 2. The ACF (Fig. 2A) appeared as at
bers without any visible pores. The uniformly dispersed Pd
particles were seen on ACF (Fig. 2B).
Fig. 3 shows the XRD patterns of the Pd (4.2 wt.%)/ACF
where peaks for Pd particles were observed [22] while, as
expected, no Pd signal for the ACF.
3.3. Adsorption kinetics and isotherms of PCP on ACF
and Pd/ACF
The adsorption kinetics curves of PCP on ACF and Pd
(4.2 wt.%)/ACF are plotted using 100 mL of 200 mg/L PCP
solution in a series of 250 mL asks under the conditions
of 20

C and 250 rpm. Experimental data was applied to the

Lagergren rate equation [23]:
q
t
= q
e
(1 e
k
L
t
) (1)
where q
e
and q
t
(both in mg/g) are the amounts of PCP
adsorbed at equilibrium and at any given time t (h), respec-
tively, and k
L
(h
1
) is the Lagergren rate constant. Fig. 4
shows the adsorption kinetic curves of PCP on the ACF and
Pd (4.2 wt.%)/ACF. The parameters were calculated by non-
linear regression (Table 1). From Fig. 4 and Table 1, it could
Fig. 4. Adsorption kinetics of PCP on ACF and Pd (4.2 wt.%)/ACF at 20

C.
76 C. Cui et al. / Separation and Purication Technology 47 (2005) 7379
Table 1
The Lagergren parameters for PCP on ACF and Pd (4.2 wt.%)/ACF at 20

C
q
e
(mg/g) k
L
(h
1
) r
2
ACF 273.7 0.22 0.996
Pd (4.2 wt.%)/ACF 267.9 0.19 0.998
Fig. 5. Adsorptionisothermof PCPonACFandPd(4.2 wt.%)/ACFat 20

C.
be seen that the load of 4.2% of Pd did not lead to signicant
changes in the adsorption rate.
The adsorption isotherms of PCP on ACF and Pd
(4.2 wt.%)/ACFat the temperature of 20

Cand pH7.50 were

measured according to the Mollah method [24] (Fig. 5). The
adsorption isotherms can be correlated well by the Freundlich
model:
Q = k
F
C
1/n
(2)
where Qis adsorptioncapacity(mg/g), Cthe equilibriumcon-
centration in solution (mg/L), n (dimensionless) the empirical
parameter that represents the heterogeneity of the site ener-
gies and k
F
(mg/g) (L/mg)
1/n
the unit capacity factor. k
F
and
n are indicators of adsorption capacity and adsorption inten-
sity, respectively. Fig. 5 shows the adsorption capacity was
slightly affected by the impregnation with Pd (4.2 wt.%), and
Table 2 displays the corresponding parameters calculated for
the adsorption isotherms. The results implied that ACF has an
excellent adsorption capacity for PCP in solution; for exam-
ple, a 1 mg/L PCP solution produces an equilibrium loading
of about 174 mg PCP/g of Pd (4.2 wt.%)/ACF at 20

C. Such
high adsorption capacity is crucial considering the removal
of PCP from the aqueous solution.
Table 2
The Freundlich isothermparameters for PCPon ACFand Pd (4.2 wt.%)/ACF
at 20

C
k
F
(mg/g) (L/mg)
1/n
n r
2
ACF 191.7 6.36 0.998
Pd (4.2 wt.%)/ACF 170.1 6.00 0.996
3.4. Electrocatalytic dechlorination of PCP on Pd/ACF
at various current densities
PCP was adsorbed on the Pd (4.2 wt.%)/ACF before elec-
trolysis by mixing 100 mLPCP solution (200 mg/L, pH7.50)
in a 250 mL ask. The ask was sealed and placed in a ther-
mostatic shaker (250 rpm, 20

C) for 25 h.
The degradation of PCP and yield of phenol were calcu-
lated by the Eqs. (3) and (4):
degradation of PCP =
m
ads
(m
sol
+m
ACF
)
m
ads
100% (3)
where the m
ads
was the initial amount of PCP adsorbed on
the Pd (4.2 wt.%)/ACF before electrolysis; m
sol
and m
ACF
were the amounts of PCP residue in the catholyte and on the
Pd/ACF after electrolysis, respectively,
yield of phenol =
M
phenol
M
PCP
100% (4)
where the M
PCP
was the initial amount (in moles) of adsorbed
PCP and M
phenol
were the amount of phenol in the catholyte
and on the Pd/ACF after eletrolysis.
The degradation of PCP and the yield of phenol from
electrocatalytic dechlorination over the cathode of Pd
(4.2 wt.%)/ACF at different current densities are presented
in Fig. 6. As seen from Fig. 6, the higher current density,
Fig. 6. Dechlorination of PCP at Pd (4.2 wt.%)/ACF (PCP adsorption
240 mg/g) cathode at different current densities: catholyte volume 50 mL;
0.25 M TMACl; MeOH 40% (v/v); temperature 40

C.
C. Cui et al. / Separation and Purication Technology 47 (2005) 7379 77
Table 3
The electrochemical reduction of PCP at various current densities
Current density
(mA/cm
2
)
Cathode potential
(V)
pH Current efciency
of phenol
production (%)
10 0.90 to 1.06 7.507.88 22.1
15 1.13 to 1.28 7.508.91 21.0
20 1.32 to 1.44 7.509.25 19.8
25 1.47 to 1.59 7.509.87 17.4
the higher degradation efciency and yield of phenol. 94.8%
of degradation was obtained after 200 min of electrolysis at
25 mA/cm
2
, while the value was 63.8% at 10 mA/cm
2
. And
the yield of phenol was 86.1%at 25 mA/cm
2
being about two
times of that at 10 mA/cm
2
.
Table 3 shows that the current efciency of complete
dechlorination to phenol was signicantly affected by the
applied current density. The highest current density led to
the lowest current efciency. High current density need more
negative potential to be applied. This fact may be related to
the competition of side reactions, mainly hydrogen evolu-
tion, which was not favorable for the contact of PCP with
the electrode [13]. These kinds of side reactions will result in
lower efciencies at higher current density and more nega-
tive potential. In present experiment, the production of H
2
at
potential of 1.20 V was observed visually. The pH of solu-
tion increased gradually with the increase of current density,
suggesting that the rate of water electrolysis increase with the
current density.
3.5. Catalytic activity of the catalyst
The Pd (4.2 wt.%)/ACF working electrode was used three
times at the current density of 25 mA/cm
2
to test the cat-
alytic activity. After each run, the used Pd/ACF was shaken at
250 rpm for 4 h in a mixture of acetone and dichloromethane
(1:1, v/v) plus 0.2 mL 30% HCl. The above procedure was
repeated six times to remove the adsorbed organic com-
pounds. The analysis shows that no phenols were detected
in the sixth extract. Fig. 7A shows that the degradation ef-
ciency decreased from 94.8 to 65.1% when the electrode
was used three times. Fig. 7B shows that the yield of phe-
nol decreased from 86.1 to 37.3% after the electrode was
used three times. The three times used Pd/ACF still had a
much higher electrocatalytic activity than bare ACF consid-
ering that PCP degradation efciency was only 36.5% and
no phenol was detected with the bare ACF acting as work-
ing electrode. The results of this experiment indicate that
the Pd plays an important role in the dechlorination of PCP.
The SEM micrograph of used Pd/ACF is given in Fig. 8, and
there is no evident difference between the images of used
and fresh Pd/ACF (Figs. 8 and 2B). The results of ICP-AES
analysis show that 10.5% of the initial amount of Pd leached
from Pd/ACF after being used three times. The decrease of
catalytic activity may be attributed to the loss of Pd or the
inactivation of catalyst.
Fig. 7. Relation between degradation of PCP (adsorption 200 mg/g) and
catalyst reused times for (a) fresh catalyst; (b) once used catalyst; (c) two-
time used catalyst at Pd (4.2 wt.%)/ACF cathode at 25 mA/cm
2
; 0.25 M
TMACl; MeOH 40% (v/v); temperature 40

C.
3.6. Identication of intermediate products by GC/MS
The extracts from the Pd/ACF electrode and electrolyte
solution were analyzed by GC/MS and main results are
shown in Fig. 9. After 40 min of electrolysis, ve kinds
of main dechlorination products were detected includ-
ing tetrachlorophenols (TetraCP), trichlorophenols (TriCP),
Fig. 8. SEM micrograph of three times used Pd/ACF.
78 C. Cui et al. / Separation and Purication Technology 47 (2005) 7379
Fig. 9. GC/MS analysis of electrocatalytic dechlorination of PCP on Pd (4.2 wt.%)/ACF cathodes at 25 mA/cm
2
: (A) 0 min; (B) 40 min; (C) 100 min; (D)
200 min.
Fig. 10. Degradation pathways of PCP on Pd (4.2 wt.%)/ACF Electrode.
dichlorophenols (DiCP), chlorophenols (CPL) and phenol
(PNL). After 200 min, only phenol and small amount of
chlorophenols were detected. On the basis of the above
results, the dechlorination pathways of PCP in Pd/ACF cath-
ode are proposed as Fig. 10.
4. Conclusions
Pd/activated carbon ber showed high adsorption capac-
ity for PCP (k
F
=170.1 (mg/g) (L/mg)
1/6
, n =6.00) and high
dechlorination efciencies of up to 94.8% with phenol as the
C. Cui et al. / Separation and Purication Technology 47 (2005) 7379 79
main products (86.1% in yield). A further improvement in
stability of the Pd/ACF is required.
Acknowledgments
This work was nancially supported by Nature Sci-
ence Foundation of China (20337020) and National Basic
Research Program of China (2003CB415006).
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