Vol. 46 No.

3 SCIENCE IN CHINA (Series B) June 2003

Mechanism and kinetics of 2-chlorophenol degradation in

drinking water by photo-electrochemical synergic effect
SONG Qiang ( ) & QU Jiuhui ()
State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Science, Chinese
Academy of Sciences, Beijing 100085, China
Correspondence should be addressed to Qu Jiuhui (email: jhqu@mail.rcees.ac.cn)

Received January 13, 2003

Abstract The synergic effect mechanism of photo-electrochemical oxidation is investigated in

detail through reaction products and kinetics analysis in a photo-electric integral reactor with
2-chlorophenol (2-CP) as the model pollutant. A kinetics model is constructed for the combinatorial
photo-electrochemical (CPE) degradation. A remarkable synergetic effect, which can significantly
enhance the mineralization rate of the CPE process, is verified by the comparison of apparent ki-
netic constants. In the CPE process, complemental effects with multi-level and multi-pathway for
pollutants degradation under our experimental conditions are speculated. It is proved that the deg-
radation pathways are not only the simple summation of that of photolysis and electrolysis, but the
formation of synergic effect through combination of several new acting approaches. The deg-
radation efficiency is enhanced considerably by three factors, control of electrode poisoning by the
UV irradiation, control of excitation and reaction trend of pollutants molecules by the UV irradiation,
and control of activation effect and transfer trend by the oriented direct current (DC) electric field.
An advanced oxidation system is set up through manifold of free radicals chain reactions in the
CPE reactions, so that the aqueous organics can be mineralized fast and completely. It is proven
by the kinetics analysis that the mineralization of organic pollutants is mainly attributed to the gen-

eration of very active hydroxyl radicals (OH ) in bulk solution from the CPE synergetic effect.
Keywords: 2-chlorophenol, photo-electrochemical synergic effect, kinetics model, drinking water, microelectrolysis, UV.

DOI: 10.1360/02yb0171

As the important parts of advanced oxidation processes (AOPs), photocatalysis and

electrocatalysis technologies have a good applicative promising in the removal of micropollutants
from water. But it is unpractical for photocatalysis with the catalytic reaction rate, the
3]
immobilization of catalyst, and the stability aspects, etc.[1 . One of the vital faults for the
application of electrocatalysis for removal organics is electrode fouling [4]. The anodic direct
electrons transfer reactions produce intermediates, i.e. phenoxy radicals, which are liable to couple
or react reversibly, forming a non-soluble passivating film on the electrode and resulting in the
deactivation of electrode. How to inhibit the electrode deactivation from the electrode fouling is
one of the problems in organic electrolysis industry[4]. The common approach to electrode
anti-fouling is using specific complicated electrode materials. Electrode fouling and the resulted
deactivation could be minimized by keeping the anode potential at a low positive value[5]. Current
research shows that, electric field-enhanced photocatalysis can improve the efficiency, but it is
 260 SCIENCE IN CHINA (Series B) Vol. 46

tric field-enhanced photocatalysis can improve the efficiency, but it is limited by catalytic materi-
als, cost-efficiency and applicability etc.[6,7]. Combinatorial methods with photo-enhanced elec-
trolysis or coalition of photolysis and electrolysis are few in literatures. Although a great deal of
mechanisms and kinetics researches have been found about the singular photochemical and elec-
trochemical process, there are few studies on the combinatorial photo-electrochemical (CPE)
process. In this paper, the coalition of low voltage, direct current (DC) electrolysis with mi-
cro-current and short wavelength ultraviolet (UV) photolysis are used for the treatment of drinking
water with micropollutants. A novel approach to control of electrode poisoning by applying of
short wavelength UV irradiation is studied. The mechanism and kinetics relations of synergic ef-
fect of CPE oxidation of 2-CP in dilute aqueous solution are also investigated, which afford the
fundamental basis of the improvement of electrode materials and reactor designation in order to
increase the degradation rates.

1 Materials and methods

1.1 Experimental set-up and chemicals

The CPE oxidation experiment was performed in a batch reactor system as shown in fig. 1,
including a cylindrical integral reactor, a 30
W UV lamp (P30T8, Atlantic Ultraviolet
Co., USA), a potentiostat (LPS302A, Beijing
Dahua Electronic Co.) and a peristaltic
pump. The barrel-shaped electrodes and UV
lamp were arranged coaxially with a quartz
glass tube surrounding the lamp. The cath-
ode is the external barrel made of stainless
steel of 0Cr18Ni9Ti, and the anode is the inner
barrel of RuO2/TiO2/Ti mesh. The effective
volume of CPE reactor is 6500 mL, and the
Fig. 1. Scheme of the reactor system. 1, Water outlet pipe; 2, distance between the electrodes is 30 mm.
ultraviolet luminous tube; 3, quartz tube; 4, anode; 5, stainless
steel cathode; 6, teflon insulative gasket; 7, water distribution
All the connecting hoses are made of sili-
device; 8, water inlet pipe; 9, metering pump; 10, aeration inlet cone. The raw solution was simulated using
pipe; 11, water solution tank; 12, sampling hatch; 13, porous plug; the distilled water and 2-CP with an accurate
14, DC power supply.
concentration. All the chemicals were used
with the grade of analytically pure above. The water used for standard solutions and instrumental
analysis was tri-distilled water.

1.2 Analysis methods

2-CP and its intermediates were identified by GC-MS (5890 Series II Gas Chromato-
graph-5971 Series Mass Selective Detector, Hewlett Packard Co., USA). Total organic carbon
(TOC) concentration was measured by a TOC analyzer (Phoenix 8000 TOC Analyzer, Tek-
 No. 3 PHOTO-ELECTROCHEMICAL SYNERGIC DEGRADATION OF 2-CP 261

man-Dohrmann Co., USA) and chloride ion was detected by an ion chromatography analyzer
(Dionx 4500i, Dionx Co., USA).

1.3 Experimental mode

The experiments were operated circularly and sampled at a fixed time at the outlet point of
the reactor. The removal rates of 2-CPs and TOCs were taken as the evaluation indexes.

2 Results and discussion

2.1 Apparent kinetic rate constants for the CPE oxidation and analysis of solution
The linear fitting of kinetics equations for 2-CP and TOC degradation by UV photolysis
alone, DC electrolysis alone, and CPE oxidation (UV + DC) are shown in table 1. Obviously, all
the reactions are followed pseudo-first order kinetics. For 2-CP degradation, the order of the k
(slope) values is as follows: 0.0226 min1(CPE) 0.0198 min1 (UV) 0.0021 min1 (DC).
The rate constant of CPE oxidation is larger than the sum of k value of the UVs and DCs alone.
A similar and more remarkable rule is also effective for the TOC degradation (0.014 min1
0.0072 min1 + 0.0023 min1 = 0.0095 min1). It is affirmed in kinetics that the synergic effect is
existed remarkably in CPE oxidation. It is proved that the UV photolysis is the main reason to
dechlorinate and remove the 2-CP but it cannot mineralize it effectively. The DC electrolysis is
more effective on the decomposition of TOC. It is found that the CPE process could sharply in-
crease the removal rate of TOC, so that it should be taken as the synergic effect. Comparison of
the apparent first-order kinetics rate constant of CPE oxidation to that of other AOPs, i.e. with
photo-, electro-, or sonic techniques for the removal of monochlorophenols from literatures is
shown in table 2. It is shown that the CPE oxidation is highly competitive and promising.
Table 1 Apparent kinetics formula of 2-CP and TOC for three treatment conditions
Treatment conditions 2-CP TOC
UV+DC y = 0.0226x 0.0171, R2 = 0.9914 y = 0.014 x + 0.1922, R2 = 0.9159
UV y = 0.0198x 0.1198, R2 = 0.9856 y = 0.0023 x + 0.0599, R2 = 0.8336
DC y = 0.0021x + 0.0518, R2 = 0.8434 y = 0.0072 x + 0.0949, R2 = 0.9524
1
Experimental conditions: pH = 8, aeration with O2 for 450 mLmin , DC voltage is 5 V, UV wavelength is 253.8 nm,
2-CP is 5 mgL1, circulation flux is 350 mLmin1, time unit is min.

Table 2 Comparison of apparent kinetic rate constants of several AOPs for degradation of monochlorophenols
Pollutants Initial concentration/mgL1 Treatment conditions Apparent rate constant/min1 Ref.
2-chlorophenol 11.06 sonolysis, pH5.7 0.0048 [8]
5 UV/TiO2 0.00003391 [9]a)
20 UV/TiO2 0.000448 [10]
400 electrolysis, Ti/PbO2 0.0075 [11]
600 electrolysis, Ti/SnO2 0.009 [11]
3-chlorophenol 10 sonolysis, pH5.4 0.0044 [8]
20 UV/TiO2 0.0004373 [10]
4-chlorophenol 10 sonolysis, pH5.1 0.0033 [8]
20 UV/TiO2 0.0004586 [10]
153 electrochemical dechlorination 0.0053 [12]
a) It was calculated from the empirical formula by Tseng et al. for rate constant of 2-CPs photocatalysis degradation: r =
3.98[C]1.15, in which C is the concentration of 2-CP (mmol/L).
 262 SCIENCE IN CHINA (Series B) Vol. 46

GC-MS chromatograms of 2-CP degradation with UV photolysis alone, DC electrolysis

alone, and CPE oxidation for 30 min are illustrated in fig. 2. It is shown in fig. 2 that in the case of
UV photolysis alone, the chemical bonds of the organic molecules are broken off so that many
intermediates are produced. It is revealed that, the UV degradation intermediates predominantly
are quinones or dechlorinated hydroxylated aromatics, i.e. benzoquinone, hydroquinone, and
catechol etc. The degradation rate of 2-CP (16.47 min) by UV photolysis alone is faster. The deg-
radation reaction by electrolysis alone may be through two pathways, direct electrons transfer on

anode or oxidation with the electro-generated adsorbed oxidative OH radicals[13]. The interme-
diates from the former pathway may polymerize on the electrode surface and result in the fouling
and deactivation of the anode, which ultimately restrain the rate of removal of 2-CP[4]. Owing to

the limitation of mass transfer, the range of action of the electro-generated OH radicals is very
restricted so that it can only oxidize the organics around the electrode surface. However, the de-

gree of oxidation reaction of OH radicals is deep to production of CO2 with a slow rate [11]. Be-
cause of the weak current of electrolysis, the rate of removal of 2-CP is slower, and the intermedi-
ates are fewer than that of the photolysis alone. The intermediates of electrolysis alone are mainly
aliphatics carboxylic acids, i.e. maleic, and oxalic acids etc. The intermediates produced by CPE

oxidation almost cannot be detected under our conditions, because the main oxidant is OH radi-
cals. Owing to the strong oxidative action of the synergic effect, the organic intermediates can be
mineralized directly. Thus the products of CPE oxidation are not like the cases of photolysis or
electrolysis in which aromatics or aliphatics are accumulated in the solution as intermediates. The
UV254 irradiation has strong excitation action to the organic molecules, which will accelerate the
breakage of organics[14]. It also may be the reason of losing in samples pretreatment procedure[4],
as for the products of CPE oxidation are mainly a slight of easily soluble small molecules.

Fig. 2. GC-MS chromatograms comparison of 2-CP degradation under different conditions for 30 min. 1, Pretreated sample; 2,
sample only treated by UV; 3, sample only treated by DC; 4, sample treated by CPE process.
 No. 3 PHOTO-ELECTROCHEMICAL SYNERGIC DEGRADATION OF 2-CP 263

2.2 Experiments with addition of bicarbonate ions

In order to validate the role of OH radicals
in the CPE oxidation, bicarbonate ion (3

mmol/L), a typical hydroxyl radicals (OH )
scavenger[15] and common component in the
natural water, is added into the raw solution. The
difference of degradation rates for 2-CP and
TOC with and without bicarbonate ions added is
illustrated in fig. 3. It is obvious that the rate of
2-CP disappearance only decreases a little, and
the evolution rate of chlorine is nearly un-
Fig. 3. Comparison of 2-CP, TOC and chlorine ions con-
changed, but the TOCs disappearance rate is
centrations versus time with and without the addition of bi-
declined sharply, indicating that the photolysis carbonate ions under CPE condition.
reaction of 2-CP is hardly influenced by the ad-

dition of bicarbonate ions, but the TOC is mainly removed by the pathway of OH reaction.

2.3 Apparent current efficiency (ACE)

According to the ideal total degradation reaction:
6CO2 + 16H2O + Cl + 26e

ClC6H4OH + 27OH (1)
Assume that the electric charge quantity equals the current multiplied by time, then in a given time
period the ACE can be written as follows[13]:
(TOC)experimental
ACE = 100, (2)
(TOC) theoretical
where (TOC)experimental is the experimental reduction value of TOC within the given time;
(TOC)theoretical is the theoretical value when all electric quantity passed system has been used to
remove TOC according to eq. (1). The following equation shows that, the ACE of CPE oxidation
is much higher than that of DC electrolysis alone:
ACE(ACE) = 72.21% ACE(DC) = 49.6%. (3)

2.4 Mechanism of synergic effect in the CPE process

In the above, it is found that the removal of TOC is mainly attributed to the radicals reaction

pathway in CPE oxidation. OH in the bulk solution is more effective than anodic oxidation[13].
From comparison of the data in literature[1], it indicates that the 2-CP degradation rate in our re-
search is slower than that of Fentons Reagents but faster than that of UV/TiO2s. The degradation
curve and the identification of some intermediates of CPE oxidation are similar to that of
UV/H2O2. The anode is not made of photocatalytical material, so the explanation with electric
field-enhanced photocatalysis cannot be simply applied here. Even while the anode contains TiO2,
there are not evidences to correlate the anodic oxidation and photocatalysis[16]. As for the reduc-
 264 SCIENCE IN CHINA (Series B) Vol. 46

tive potential of oxygen molecule is higher than that of hydrogen ion, the adsorbed dioxygen will
be reduced into H2O2 preferably on the cathode, which is proved by 18O isotope marker experi-
ments[17,18]. Therefore, a low voltage with micro-current and pure oxygen saturation are adopted in
our experimental runs to produce H2O2 on the cathode. In order to inhibit the hydrogen ions
competitively parasite reaction, we keep the lower voltage (5 V) and near basic of pH surrounding
which are favourable to producing H2O2[18].
Owing to the unique actions of CPE oxidation,

several pathways for OH radicals production
are coexisted in the system, including the elec-
[4,11,13]
tro-generated surface OH , radicals pro-
duced in the bulk solution by the UV excitation
and so on. The degradation routines under CPE
conditions are not mechanically the addition of
photolysis and electrolysis, but formation of
synergic effect of CPE process through a series
of novel combinatorial approaches as shown in
Fig. 4. Mechanism scheme of the synergic effect of CPE
fig. 4.
process.
Anodic reactions: OH generated from the
oxidation of OH and H2O molecules[11,13,19]:
H2O OH iads + H+ + e E0 = 2.33 V (4a)

OH OH iads + e (4b)

H2O2 HOi2 + H+ + e (4c)

Cathodic reactions: H2O2 generated from reduction of dissolved oxygen (DO) molecules[17,18]:
in acidic medium: O2 + 2H+ + 2e H2O2 (5a)
in alkaline medium: O2 + H2O +2e OH+ HO 2 (5b)

HO 2 + H2OH2O2+ OH (5c)
then H2O2 is diffused away from the cathodic area to the bulk solution and excited by the UV254
[1,13]
radiation to produce a lot of free OH :
H2O2 + h 2OH

(6)
The key reactions involved in the CPE oxidation are listed as follows:

2-CP
kUV
intermediate 1 + CO2 + H2O (in bulk solution, electric field enhanced) (7)

2-CP
kDC
intermediate 2 (on anode surface through electron transfer, UV-radiation enhanced)
(8)
 No. 3 PHOTO-ELECTROCHEMICAL SYNERGIC DEGRADATION OF 2-CP 265

k i
2-CP CO2 + H2O (around anode through electro-generated OH , UV-radiation enhanced)
anode,OH

(9)
k
2-CP
cathode,H O
2 2

intermediate 3 (homogeneous reaction in bulk solution,
electric field enhanced) (10)
k i
2-CP
UV/H 2O2 ,OH
CO2 + H2O (radicals reaction in bulk solution, CPE composite enhancement)
(11)
Eq. (7) is the photolysis reaction enhanced by the electric field. The specific bonds of organic
molecules are broken off with the absorbance of UV irradiation higher than their bond cleavage
energy. UV254 luminous tube will emit small amount of shorter wavelength UV radiation which

can break a little of water molecule into OH radicals[20]. Therefore, a trace of organic could be
mineralized in photolysis reaction. Eq.(10) is the direct oxidation by H2O2 produced from the ca-
thodic area under the low potential. Because of the action of oriented electric field on the electri-
fied particles of organics and its intermediates, the recombination and reverse reactions of dissoci-
ated groups are restrained by the electric field force. It is helpful and could be concluded as one
face of CPE synergic effect.
Eq. (8) is the direct electron transfer reaction occupied on the anode surface. Eq.(9) is the

oxidation of organics by electro-generated OH radicals. The polymerization trend of the organic
macromolecule can be broken by the UV irradiation on the electrode surface[21], which prevents
the anode from fouling and deactivation, so as to accelerate the oxidation of OH, H2O, and or-
ganics. The organic solutes are excited to higher energy states by the UV irradiation, so that they
are easier to be degraded. The electric current efficiency could be improved effectively by the UV

enhancement. Eq. (11) is typical OH radicals reaction by the UV/H2O2 process consisting of
H2O2 produced from the cathodic area and the UV irradiation. A series of chain reactions are trig-
gered thereafter and all of these compose of the most important pathway for the CPE oxidation,

OH radicals reaction. The OH in the bulk solution also includes a little from adsorbed OH
radicals diffusion and minute of that produced by shorter UV cleavage of water[22]. Activation

energy between the active OH radicals and organic compounds is near to zero, so that the oxida-
tion is very fast, and the organochlorine groups of the haloaromatics can be destroyed effective-
ly[1].

2.5 Kinetics model of CPE synergic effect

It is shown in the above analysis that the elimination pathways of 2-CP are various as shown
by eqs.(7)(11). Among them, eq.(9) is so weak that it can be neglected in most cases[23]. Eqs. (8)
and (9) are surface reactions occurring around the anode surface, which are followed the kinetics
relation of surface reactions. As homogeneous reactions in the bulk solution, eqs. (7) and (11) can
 266 SCIENCE IN CHINA (Series B) Vol. 46

be described with the kinetic relation of homogeneous reactions. Therefore, the total rate expres-
sion for the CPE oxidation can be expressed by the summation of all heterogeneous and homoge-
neous reactions as follows (assume that the steady-state of the irradiation flux, absorbance of
compounds and hydraulics conditions etc. in the system):
d[2-CP]
= kDC i 2-CP + kanode,OHi i 2 CP i OHi + kUV i [2-CP]a
dt ads

+(k UV/H O i + kanodic,transter,OHi + k UV,OHi ) i [2-CP]b i [OH i ]cbulk , (12)

2 2 ,OH

where the first part represents the oxidation of direct electron transfer on the anode surface, kDC is
this pathways rate constant implying the impact of electrode material and voltage etc., and 2-CP
is the coverage percent fraction of 2-CP molecules adsorption on the electrode surface. The second

item is the oxidation through OH adsorbed on the anode surface, kanode,OHi is this pathways rate

constant, and 2-CP and OHi are the coverage percent fractions of the species adsorbed on the
ads

electrode surface, respectively. The third part is the UVs photolysis reaction, kUV is this pathways
rate constant implying the impact of photon flux, and the absorbance of species in the system, etc.

The fourth part is the oxidation of the OH radicals in bulk solution under the CPE condition,
k UV/H O i is the rate constant of UV/H2O2 pathway, kUV,OHi is the rate constant of reaction of
2 2 ,OH

OH radicals produced from the water cleavage by the super-short wavelength UV irradiation,

and kanodic,transfer,OHi is the rate constant of the reaction of free OH aroused from the adsorbed

OH radicals. There are evidences that diffusion of surface-bound OH radicals from the anode

into the bulk solution is minimal[4]. [2-CP] and [OH ] are the degree of activity in aqueous solu-
tion. Due to that the solution is very thin, the degree of activity can be taken as the concentration
values. Here a, b and c are all constants.
Averagely, the AOPs reactions are followed pseudo-first-order kinetics, it is shown that CPE
oxidation also follows pseudo-first-order experimentally, so let a = b = 1. Under steady-state con-

ditions, the OH production and elimination rate are also steady, and then a constant number of M
can be obtained as follows:
M = (kUV/H O i + kanodic,transfer,OHi + kUV,OHi ) i [OH i ]cbulk . (13)
2 2 ,OH

The OH evolution rate from the electrode process and the oxidation rate from direct electron
transfer are steady while the electrode conditions, the voltage and the solution constituents are
constant. On the surface of the electrode, 2-CP concentration is extremely low so that it can be

treated as a constant value. The coverage percentage of OH on the surface depending on the
evolution rate is also steady[4,11,19]. Therefore, the first and second parts in eq.(12) can be substi-
tuted with a constant of N as follows:
 No. 3 PHOTO-ELECTROCHEMICAL SYNERGIC DEGRADATION OF 2-CP 267

N = kDC 2-CP + kanode,OHi 2-CP OHi . (14)

ads

Let kUV equal a constant K, then eq .(12) can be rewritten as

d[2-CP]
= K [2-CP] + M [2-CP] + N. (15)
dt
Integration of eq.(15) versus time gives an implicit solution for [2-CP]:
N t N
[2-CP] = C0 + ie . (16)
K +M K+M
For the photolysis reaction alone we have N = 0, therefore, eq. (16) can be transformed into
[2-CP]= C 0 i et , (17)
which is a typical first-order kinetic equation and consistent to homogeneous reactions kinetic
relations.
For the sole electrolysis reaction we have K = 0, M = kanodic,transfer,OHi [OH ]cbulk , taking M

as M
, then
N t N
[2-CP] = C0 + ie . (18)
M M

As for the mineralization of 2-CP occurs mainly through the OH radicals reactions, effective

oxidants can be normalized to the OH , and the reductants are the organics. Based on the various

pathways of OH radicals production and different reaction sites for organics degradation, the
following deduction can be carried out. Similar results are obtained for TOC removal, so we have
d[TOC]
= kanode,OHi TOC OHi + (kUV/H O ,OHi + kanodic,transfer,OHi + k UV,OHi ) [TOC]b [OH i ]cbulk .
dt ads 2 2

(19)
The parameters in eq. (19) have the same meaning as that in eq. (12). Just like the treatment above,
we have Q = kanode,OHi TOC OHi , b = 1, then we obtain
ads

d[TOC]
= M [TOC] + Q. (20)
dt
Integration of eq. (20),
Q Q
[TOC] = C0 + et . (21)
M M
For the photolysis reaction alone, Q = 0, in this case, we have
[TOC] = C0et, (22)
which is a typical first-order kinetic equation and consistent to homogeneous reactions kinetic
relations.
For the electrolysis reaction alone we have M = kanodic,transfer,OHi i [OH i ]cbulk , taking M as M
,
 268 SCIENCE IN CHINA (Series B) Vol. 46

then
Q t Q
[TOC]= C0 + e

. (23)
M M
Justification of the kinetic model is provided subsequently based on experimental observa-
tions. Under CPE conditions (2-CP concentration is 5 mg L1, TOC is 2.70 mg L1, the time
unit is h), the experimental data obtained from our system are fitted into two linear equations
(concentration versus exp (t)) as follows:
[2-CP] = 5.4165 exp(t ) 0.5334, R2 = 0.9933, (24)
[TOC] = 2.7312 exp(t) 0.1164, R = 0.9828.
2
(25)
Obviously, eq. (24) and eqs. (16), (25) and (21) are consistent with each other, indicating that the
above kinetics mode is applicable to description of CPE process. From eqs. (24) and (16), it is
N
obtained that = 0.5334, which indicates that in the removal of 2-CP by CPE process, the
K +M
quota of electrode processs (N) is increased so much that it reaches half of the sum of photolysis

(K) and OH radicals (M) reactions. It is because that the UV irradiation on the electrode surface
inhibits the electrode fouling firstly, and secondly excites the organics molecule to be degraded
more easily simultaneously. This is one of the representatives of synergic effect of CPE oxidation.
Q
From eqs. (25) and (21), = 0.1164 can be obtained, indicating that the OH radicals reaction
M
from the anode surface (Q) only owns 11.64% contributing share for the removal of TOC. The

main effort on the removal of TOC is afforded by the OH radicals reaction occurring in the bulk

solution (M) derived from the synergic effect of CPE process. The effect of electro-generated OH

is very limited relative to bulk OH reaction. The above shows that it is necessary to search for
more efficient electrocatalysis material as electrode and electrolysis parameters in order to in-
crease the oxidation efficiency of electrode process. Furthermore, it is important to increase the
yield of H2O2 in the cathodic area, and to improve the efficiency of synergic effect and the desig-
nation for reactor.

3 Conclusions

Depending on the kinetics model and reaction products analysis, a series of conclusions can
be reached as follows:
(i) Remarkable synergic effect is proved to be existed under the CPE conditions and espe-
cially dominative for the removal of TOC. The decomposition rate of TOC by CPE oxidation is
much higher than the sum of that of the sole UV photolysis or DC electrolysis treatment.
(ii) The main components of the synergic effect of the CPE oxidation include: (1) effective
control of the electrodes fouling and deactivation through the short wavelength UV irradiation; (2)
UV irradiation excitation of organic molecules to higher energy states which is much helpful to all
 No. 3 PHOTO-ELECTROCHEMICAL SYNERGIC DEGRADATION OF 2-CP 269

of the cleavage reactions and advanced oxidation reactions with hydroxyl radicals, OH ; (3) under
the action of DC electric field, the pollutants groups with different electric charges will be driven
to move to the opposite directions, so that the reverse reaction of photolysis and the polymeriza-
tion of intermediates can be restrained; (4) in the cathodic part dissolved oxygen is reduced into
H2O2, which diffuses to the bulk solution. Thereafter, the H2O2 and UV irradiation are consisted of

the typical AOPs combination of UV/H2O2, and the produced OH is the main oxidants responsi-
ble for the fast decomposition of TOC.
(iii) It is shown by the kinetics analysis that, more efficient electrocatalytic materials should
be discovered so as to increase the degradation efficiency and the removal share of TOC on the
electrode interface; at the same time, the reactor designation and operating conditions optimization
should be given further attention.
Acknowledgements This work was supported by the Preeminence Youth Science Fund of the National Natural Science
Foundation of China (Grant No. 50225824), the Knowledge Creation Engineering as one of the important directional projects
from the Foundation of the Chinese Academy of Sciences (Grant No. KZCX2-409), and the Tenth Five-Year Key Tackle Plan
from the Ministry of Science and Technology of China (Grant No. 2001BA904B11).

References
1. Huang, C. P., Dong, C., Tang, Z., Advanced chemical oxidation: its present role and potential future in hazardous waste
treatment, Waste Management, 1993, 13: 361377.
2. Johnson, D. C., Feng, J., Houk, L. L., Direct electrochemical degradation of organic wastes in aqueous media, Electro-
chimica. Acta, 2000, 46: 323330.
3. Hoffmann, M. R., Martin, S. T., Choi, W. et al., Environmental applications of semiconductor photocatalysis, Chem. Rev.,
1995, 95: 6996.
4. Ezerskis, Z., Jusys, Z., Oxidation of chlorophenols on Pt electrode in alkaline solution studied by cyclic voltammetry, gal-
vanostatic electrolysis, and gas chromatography-mass spectrometry, Pure. Appl. Chem., 2001, 73: 19291940.
5. Rodgers, J. D., Bunce, N. J., Electrochemical treatment of 2,4,6-trinitrotoluene and related compounds, Environ. Sci.
Technol., 2001, 35: 406410.
6. Butterfield, I. M., Christensen, P. A., Curtis, T. P. et al., Water disinfection using an immobilised titanium dioxide film in a
photochemical reactor with electric film enhancement, Water Res., 1997, 31: 675680.
7. Hong, L., Cheng, S., Zhang, J. et al., Titanium dioxide as photocatalyst on porous nickel: adsorption and the photocatalytic
degradation of sulfosalicylic acid, Chemosphere, 1999, 38: 283287.
8. Serpone, N., Terzian, R., Hidaka, H. et al., Ultrasonic induced dehalogenation and oxidation of 2-, 3-, and 4-chlorophenol
in air-equilibrated aqueous media, Similarities with irradiated semiconductor particulates, J. Phys. Chem., 1994, 98:
26342640.
9. Tseng, J. M., Huang, C. P., Removal of chlorophenols from water by photocatalytic oxidation, Wat. Sci. Tech., 1991, 23:
377387.
10. DOliveira, J. C., Al-Sayyed, G., Pichat, P., Photodegradation of 2- and 3-chlorophenol in TiO2 aqueous suspensions, En-
viron. Sci. Technol., 1990, 24: 990996.
11. Polcaro, A. M., Palmas, S., Renoldi, F. et al., On the performance of Ti/SnO2 and Ti/PbO2 anodes on electrochemical deg-
radation of 2-chlorophenol for wastewater treatment, J. Appl. Electrochem., 1999, 29: 147151.
12. Cheng, I. F., Fernando, Q., Korte, N., Electrochemical dechlorination of 4-chlorophenol to phenol, Environ. Sci. Technol.,
1997, 31: 10741078.
13. Brillas, E., Sauleda, R., Casado, J., Degradation of 4-chlorophenol by anodic oxidation, electro-fenton, photoelec-
 270 SCIENCE IN CHINA (Series B) Vol. 46

tro-fenton, and peroxy-coagulation processes, J. Electrochem. Soc., 1998, 145: 759765.

14. Yatmaz, H. C., Wallis, C., Howarth, C. R., The spinning disc reactor-studies on a novel TiO2 photocatalytic reactor,
Chemosphere, 2001, 42: 397403.
15. Cossu, R., Polcaro, A. M., Lavagnolo, M. C. et al., Electrochemical treatment of landfill leachate: oxidation at Ti/PbO2 and
Ti/SnO2 anodes, Environ. Sci. Technol., 1998, 32: 35703573.
16. Lidia, S., Claudia, J., Santosh, N. K., A comparative study on oxidation of disperse dyes by electrochemical process, ozone,
hypochlorite and fenton regent, Wat. Res., 2001, 35: 21292136.
17. Brillas, E., Calpe, J. C., Casado, J., Mineralization of 2,4-D by advanced electrochemical oxidation processes, Wat. Res.,
2000, 34: 22532262.
18. Chen, J., Ollis, D. F., Rulkens, W. H. et al., Photocatalyzed oxidation of alcohols and organochlorides in the presence of
native TiO2 and metalized TiO2 suspensions, Part(II): Photocatalytic mechanisms, Wat. Res., 1998, 32: 669676.
19. Polcaro, A. M., Palmas, S., Renoldi, F. et al., Three-dimensional electrodes for the electrochemical combustion of organic
pollutants, Electrochimica. Acta, 2000, 46: 389394.
20. Shirayama, H., Tohezo, Y., Taguchi, S., Photodegradation of chlorinated hydrocarbons in the presence and absence of dis-
solved oxygen in water, Wat. Res., 2001, 35: 19411950.
21. Rodgers, J. D., Bunce, N. J., Electrochemical treatment of 2,4,6-trinitrotoluene and related compounds, Environ. Sci.
Technol., 2001, 35: 406410.
22. Panizza, M., Bocca, C., Cerisola, G., Electrochemical treatment of wastewater containing polyaromatic organic pollutants,
Wat. Res., 2000, 34: 26012605.
23. Shen, Y. S., Ku, Y., Lee, K. C., The effect of light absorbance of the decomposition of chlorophenols by ultraviolet radia-
tion and UV/H2O2 processes, Wat. Res., 1994, 28: 907914.