This article was downloaded by: [Aston University]

On: 20 January 2014, At: 03:53

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Journal of Environmental Science and Health, Part

A: Toxic/Hazardous Substances and Environmental
Engineering
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lesa20

Oxidation products and degradation pathways of 4chlorophenol by catalytic ozonation with MnOx/Al2O3/TiO2 as catalyst in aqueous solution
a

Lili Qi , Jie Yao

a b

, Hong You , Ran Zhang , Chunhui Feng & Sjack Van Agtmaal

State Key Laboratory of Urban Water Resource and Environment , Harbin Institute of
Technology , Harbin , P. R. China
b

National Engineering Centre of Urban Water Resources , Harbin Institute of Technology ,

Harbin , P. R. China
c

Evides Industriewater , Rotterdam , Netherlands

Published online: 26 Nov 2013.

To cite this article: Lili Qi , Jie Yao , Hong You , Ran Zhang , Chunhui Feng & Sjack Van Agtmaal (2014) Oxidation products
and degradation pathways of 4-chlorophenol by catalytic ozonation with MnOx/-Al2O3/TiO2 as catalyst in aqueous solution,
Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances and Environmental Engineering, 49:3,
327-337, DOI: 10.1080/10934529.2014.846657
To link to this article: http://dx.doi.org/10.1080/10934529.2014.846657

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the Content) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Journal of Environmental Science and Health, Part A (2014) 49, 327337

C Taylor & Francis Group, LLC
Copyright 
ISSN: 1093-4529 (Print); 1532-4117 (Online)
DOI: 10.1080/10934529.2014.846657

Oxidation products and degradation pathways of

4-chlorophenol by catalytic ozonation with
MnOx/ -Al2O3/TiO2 as catalyst in aqueous solution
LILI QI1, JIE YAO1,2, HONG YOU1, RAN ZHANG1, CHUNHUI FENG3 and SJACK VAN AGTMAAL3
1

State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, P. R. China
National Engineering Centre of Urban Water Resources, Harbin Institute of Technology, Harbin, P. R. China
3
Evides Industriewater, Rotterdam, Netherlands

Downloaded by [Aston University] at 03:53 20 January 2014

To identify the intermediates of 4-chlorophenol (4-CP) and bring forward the degradation pathways in the process of catalytic
ozonation of 4-CP, 4-CP was ozonated with MnOx/ -Al2 O3 /TiO2 (MAT) catalyst, and 4-CP was almost decomposed within
30 min, the mineralization reaching above 94.1% at 100 min. The evident reduction of the degradation with the addition of the
radical scavenger tert-butanol (TBA) and the stronger spin-adduct signals of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) indicated
that 4-CP was oxidized primarily by hydroxyl radical (OH). Analysis of GC-MS, HPLC and IC confirmed that aromatic compounds
and carboxylic acids were predominant oxidative organic intermediates of 4-CP in catalytic ozonation.The main degradation steps
were hydroxylation of 4-CP and the formation of hydroquinone, 4-chlororesorcinol and 4-chlorocatechol. The low molecular weight
(LMW) acids, such as malic, malonic, oxalic, acetic, and formic acid, were formed from the further oxidation of the intermediates.
Keywords: 4-chlorophenol, catalytic ozonation, MAT catalyst, degradation pathways.

Introduction
As one type of Chlorophenols (CPs), 4-CP, widely exists
in industrial wastewater, a priority pollutant by the US
EPA and National Environmental Monitoring Centre of
China because of its high toxicity and difficulty to be biodegraded.[1] Heterogeneous catalytic ozonation, a promising
process of advanced oxidation processes (AOPs), has received much attention for the degradation of refractory
organic pollutants due to its high effectiveness.[2,3] The catalyst activity in ozonation mainly depends on its ability to
adsorb ozone on the surface leading to the ozone decomposition to hydroxyl radicals (OH).[4] With the mesoporous
structures and large surface areas, Al2 O3 /TiO2 , few reported in catalytic ozonation, may be more suitable as catalyst support for the uniform dispersion of active components and more active sites for catalytic reactions. Mn2 O3 ,
Mn3 O4 and MnO2 , because of their structural flexibility,
are mostly reported as active component reflected the most
efficient activity in ozone decomposition.[5,6]
Address correspondence to Hong You, State Key Laboratory
of Urban Water Resource and Environment, Harbin Institute
of Technology, Harbin 150090, P. R. China; E-mail: youhong@
hit.edu.cn
Received April 25, 2013.

As far as the pathways of 4-CP degradation by ozonation were concerned, few intermediates and degradation
steps have been reported. Andreozzi[7] proposed that two
main open-ring products were obtained and the attack of
O3 on the benzene ring was presumed to be the key step
of the degradation by ozonation alone. Brillas and Brillas and Sauleda [8] stated that the main intermediates of
4-CP degradation were 4-chloro-1, 3-dihydroxybenzene, 4chloro-1,2-dihydroxybenzene, and other open-ring products by catalytic ozonation.Beltran et al.[9] put forward
hydroquinone and few carboxylic acids as the main byproducts of 4-CP in the process of O3 /VUV/TiO2 . Poznyak
and Vivero[10] compared the decomposition products at
different pH values in the process of ozonation alone,
and obtained that hydroxylation and dechloration were
the possible mechanism path in the early stage of 4-CP
degradation.
The objective of this study was to identify the intermediates of 4-CP and bring forward the degradation pathways by catalytic ozonation with MAT as catalyst. GC-MS,
HPLC and IC analysis were used to determine the formation of the intermediates during 4-CP decomposition. The
processes at different pH values were compared to illustrate the pathways of 4-CP degradation by OH and O3 ,
and the feasible pathways were proposed for the catalytic
ozonation.

328
Materials and methods

Qi et al.
get pollutants were circulated by the ozone gas from the
bottom of the reactor.

Chemicals
Analytical grade reagents 4-CP (Shanghai Wulian Chemical Factory, P. R. China), TBA (Tianjin Shuangchuan
Chemical Factory, P. R. China), DMPO (SigmaAldrich Co., LLC., USA), Manganese Nitrate (Tianjin Shuangchuan Chemical Factory), Aluminum chloride
(Chengdu Xiya Chemical Factory, P. R. China), Titanium tetrachloride (Chengdu Xiya Chemical Factory), and
sodium thiosulphate (Tianjin Shuangchuan Chemical Factory) were used in the experiments.

Downloaded by [Aston University] at 03:53 20 January 2014

Catalyst preparation
First, 4060 mesh -Al2 O3 /TiO2 (AT) prepared by coprecipitation method was used as the supports, and the
catalysts were synthesized by impregnation method with
Mn(NO3 )2 aqueous solution, and then dried at 100 C for
12 h after being washed several times with deionized water,
and then calcined at 500 C for 5 h.
Ozonation procedure
The experiments were carried out in a three-phase fluidized
bed reactor (with the inside diameter of 50 mm, 470 mm
height and 1 L volume) with 1 L model water containing
100 mg/L 4-CP (shown in Fig. 1). Ozone, produced from
DHX-SS-1G ozone generator (Harbin Jiujiu Electrochemical Engineering Technology Co., Ltd., China), was fed into
the ozonation reactor through a porous titanium plate at
the bottom of the reactor, and ozone, catalysts and the tar-

Analytical method
The compound 4-CP was determined by a Shimadzu
(Kyoto, Japan) LC-10AVP HPLC equipped with a COSMOSIL C-18-AR-II column (250, 4.6 mm i.d.) at 280 nm.
The mobile phase was an aqueous mixture (70% methanol
and 30% water) at a flow rate of 0.1 mL/min. The total organic carbon (TOC) was measured by TOC-VCPN
(Shimadzu). The concentration of residual ozone in aqueous solution was measured by spectrophotometer using
indigo method.[11] Specific surface area, total pore volume
and average pore size of the catalysts were measured by
the Brunauer-Emmett-Teller (BET) method. The crystal
phases of the catalysts were identified on an X-ray diffractometer (XRD, D/max-rB, Japan) with Cu K radiation
( = 0.15405 nm). X-ray photoelectron spectroscopy (XPS;
Electrophysics, Fairfield, CT, USA) was performed with a
PHI5700 system equipped with a Mg K radiation (300 W,
12.5 kV). The C1s peak from the adventitious carbon was
used as an internal reference with a binding energy of
284.62 eV. Hydroxyl radical (OH) was checked with EPR
(EMX-EPR, Bruker, Karlsruhe, Germany) under the following experimental conditions: X-field sweep; center field
3510.00 G; sweep width 100.00 G; static field 3410.00 G;
frequency 9.868303 GHz; power 2.25 mW.
The sample was scanned and accumulated 8 times for
20.48 s. A gas chromatograph-mass spectrometer (GC-MS,
6890GC/5973MS, Agilent, USA) was used for qualitative
analysis of intermediate products for the 4-CP degradation
by catalytic ozonation. The 6890 GC method: the initial
tempreture of oven 45 C, maximum tempreture of 325 C,
initial time 3.00 min and equilibration time 0.50 min.
Methyl tertiary butyl ether and methylene chloride were
used as the extracting agent, respectively.
The samples were concentrated to 1 mL and subjected to
GC-MS determination. The organic acids and free chloride
ions were determined by a Dionex (Sunnyvale, CA, USA)
IC-3000 ion chromatograph equipped with an IonPac
(Sunnyvale, CA, USA) AG11 guard column (4 50 mm
I.D.). The identification and concentration calculation were
similar to the method used in HPLC analysis. The eluent
was sodium hydroxide (45.0 mmol/L) at a flow rate of
1.0 mL/min. The column temperature was 30 C and the
curb was 110 mA.

Results and discussion

Catalyst characterization
Fig. 1. Schematic diagram of experimental apparatus for catalytic
ozonation.

The main characteristics of the catalysts were summarized

in Table 1, including metal content analysis, and pore size
distribution. The phase composition was investigated by

329

Degradation pathways of 4-chlorophenol by catalytic ozonation

Table 1. Characteristics of the AT and MAT catalysts.

Downloaded by [Aston University] at 03:53 20 January 2014

AT
MAT

Mn (wt.%)

A/T mass ratio

Mn/AT mass ratio

SBET (m2/g)

Pore volume (cm3/g)

Average pore diameter (nm)

0
12.27

0.6865
0.6865

0
0.6641

138.1981
117.1784

0.389905
0.399897

11.2854
14.0775

XRD, as shown in Figure 2, in which weak diffraction

peaks were observed around 28.8 , 33.5 , 37.5 , 56 and
56.8 , which were related to the presence of small amounts
of MnOx. The peaks near 28.8 , 37.5 and 56.8 were verified for MnO2 crystal in the form of pyrolusite, and small
ones around 33.5 and 56 were attributed to Mn2 O3 [12, 13],
in agreement with the XPS results in Figure 3, where the
Mn2p3/2 of MAT was found to fit well by two peaks of
641.6 and 642.5 eV, indicating that the oxidation states of
manganese were Mn3+ and Mn4+.[14,15] The distribution of
Mn3+ and Mn4+ were 8.41 at% and 2.33 at%.
The O 1s spectra of MAT shown in Figure 3c can be
attributed into three peaks, 529.7 eV (57.79% of total area),
531.5 eV (38.05% of total area), and 533.5 eV (4.04% of
total area). The peaks were respectively assigned to lattice
oxygen (O2 or Mn-O-Mn), the oxygen defect states and
the surface-adsorbed molecules (OH, H2 O etc.), playing
a major role in the catalytic process.[1620]

dation of the compound. Oxidizable intermediates could be

removed during initial reaction, and the refractory products could be decomposed in the rest of the reaction. The
declination of pH from initial 6.6 0.1 in 4-CP solution
of 100 mg/L to pH 3.3 0.1 indicated the information of

Degradation efficiency of 4-CP under different condition

From Figure 4a, it could be found that adsorption of 4CP on MAT resulted in a slight removal of 4-CP compared
with the process of catalytic ozonation, fluctuating between
1.0 and 2.0%. Figure 4a and 4b showed the results of 4-CP
degradation and the removal of TOC under two different
conditions, ozonation alone and ozonation/MAT. It was
observed that the degradation of 4-CP was almost completed within 30 min in both cases, and the mineralization
reached above 94.1% at 100 min in the presence of MAT,
meaning that the degradation of 4-CP includes several steps
and some intermediates occurred during the initial degra-

Fig. 2. XRD patterns of MAT catalyst.

Fig. 3. XPS spectra analysis of the synthesized MAT catalyst. (a)

Wide-range scan, (b) Mn 2p, and (c) O 1s.

Downloaded by [Aston University] at 03:53 20 January 2014

330

Qi et al.

Fig. 5. Degradation efficiencies of 4-CP at different initial pH.

Experimental conditions: temperature 20 1 C; initial 4-CP concentration 100 mg/L; catalyst 2.0 g/L; ozone applied 2.0 mg/L.

Fig. 4. Degradation (a) and mineralization (b) of 4-CP by ozonation alone and catalytic ozonation. Experimental conditions: temperature 201 C; initial pH 6.6 0.1; initial 4-CP concentration
100 mg/L; catalyst 2.0 g/L; ozone applied 2.0 mg/L.

oxidizable acidic intermediates. The increase of pH from

3.3 0.1 to 6.0 suggested further catalytic decomposition
of oxidizable acidic intermediates.
The compound 4-CP has the electron-withdrawing properties of chlorine atom, which is hardly attacked by
ozone,[21] and removal mechanisms of ozonation for the
organic compounds in aqueous solution include direct reaction by selective molecular ozone and indirect reaction
by non-selective radicals, like OH. OH was induced from
ozone decomposition, possessing much higher oxidizing
potential and being more powerful oxidant than molecular
ozone.[22] The reaction rate constant of 4-CP with ozone
alone was only 3.4 106 L/(mols),[23] while the constant
with OH was 7.6 109 L/(mols).[24] Therefore, it could
preliminarily be concluded that the degradation of 4-CP
was mainly attributed to OH oxidation in the process of
ozonation alone and catalytic ozonation.

catalytic ozonation. The increase of pH value could lead

more OH from ozone decomposition, which could enhance the degradation of organic substance. Degradation
efficiencies of 4-CP under different initial pH (2.5711.13)
were shown in Figure 5.
Figure 5 indicated that at low pH, removal efficiency of
4-CP degradation was high due to the presence of catalyst MAT, and when the initial pH value of the solution
rose from 6.61 to 11.13, the removal efficiency of 4-CP increased significantly by catalytic ozonation, from 94.09%
to 97.82% within 20 min. The initial pH could change the
surface properties of the catalyst, and affect the existing
form of organic pollutants in solution which could cause
the changes the interaction between organic molecules and
the surface of the catalyst, further leading to the change of
4-CP degradation. In addition, CO2
3 was generated constantly in the process of the organic pollutant degradation,
which would lead to the inhibition of OH production from
ozone decomposition.
Ozonation includes direct manner by ozone and an indirect reaction via OH simultaneously,[25, 26] and the kinetics
of the two reactions was assumed to be second-order (firstorder in the concentrations of ozone, OH and the compounds that react with the former). The degradation rate
of 4-CP in the processes of ozonation alone and catalytic
ozonation could be expressed as follows:
d[4CP]/dt = kO3 [4CP][O3 ] + kOH [4CP][OH] (1)
where kO3 and kOH were the first-order degradation rate
constants for ozonation and OH reaction respectively. It
is reported by Elovitz and von Gunten[27] that the ratio
of [OH] over [O3 ] was constant in the process of ozone
decomposition:

Effect of initial pH value on 4-CP degradation

pH value may cause changes in the nature of the catalyst
surface, affecting the production of OH in the process of

RCT =

[OH]
[O3 ]

(2)

Downloaded by [Aston University] at 03:53 20 January 2014

Degradation pathways of 4-chlorophenol by catalytic ozonation

Fig. 6. Plots of ln([4-CP]t /[4-CP]0 )-t for 4-CP degradation at different pH.

Therefore, Eq. (2) could be rewritten as


d [4CP] dt = kobs [4 CP] ;

(3)

where kobs was the apparent degradation rate constant of

whole system.
kobs = kO3 [O3 ] + kOH RCT [O3 ]

(4)

The reaction rate equation of 4-CP degradation was deduced by the integration of Eq. (3):
ln ([4 CP]/[4 CP]0 ) = kobs t

(5)

The effect of ozone concentration was studied (pH =

2.5711.13) on pseudofirst-order plot for 4-CP degradation under different processes, as given in Figure 6, in which
all reactions followed pseudofirst-order kinetic model at
different initial pH value. The results demonstrated that
the enhancement of pH to the process of catalytic ozonation accelerated the degradation rate of 4-CP by a rate
constant of 0.07841 min1, 0.09507 min1, 0.13446 min1,
0.17769 min1 and 0.20623 min1, respectively.

331

Fig. 7. Effect of TBA on the degradation of 4-CP. Experimental

conditions: temperature 20 1 C; initial pH 6.6 0.1; initial
4-CP concentration 100 mg/L; catalyst 2.0 g/L; ozone applied
2.0 mg/L; TBA 100 mg/L.

the processes of ozonation alone and catalytic ozonation at

30 min.
According to the report, the rate constant of OH with
TBA was 10 times higher than that with 4-CP, which could
be considered as a relatively suitable indicator for radicaltype reaction of catalytic ozonation.[24] The results presented that the addition of TBA had a negative influence
on the degradation efficiency of 4-CP, indicating that TBA
captured OH competitively, which is consumed rapidly in
the processes, the main disadvantage of all oxidative degradation processes based on OH reactions.
Promotion of ozone decomposition by MAT
The formation of OH was determined by EPR and the
intensity of DMPO-OH adduct signals was compared in

Evidence of OH existence with TBA as radical scavenger

As a stronger radical scavenger, TBA, which could react
with OH and generate inert intermediates to terminate the
radical chain reactions, is commonly used as indicator of
hydroxyl radicals reaction.[28] TBA has a higher reaction
rate constant with OH (5 108 L/(mols)), compared
with ozone alone (3 103L/(mols)).[23, 28] The effect of
TBA on ozonation alone and catalytic ozonation of 4-CP
were illustrated in Figure 7, from which, it could be found
that the presence of TBA led to the significant influence
on the removal of 4-CP in the process of ozonation alone
and catalytic ozonation, suggesting that 4-CP degradation
followed the OH reaction mechanism. When 100 mg/L
of TBA was added into the aqueous solution, degradation
efficiency were respectively reduced to 36.4% and 39.1% in

Fig. 8. Comparison of the intensity of DMPO-OH adduct signal in the different processes. Experimental conditions: temperature 20 1 C; initial pH 6.6 0.1; initial 4-CP concentration
100 mg/L; catalyst 2 g/L; ozone applied 2.0 mg/L; initial DMPO
concentration 100 mmol/L.

332

Downloaded by [Aston University] at 03:53 20 January 2014

Qi et al.

Fig. 9. The GC-MS chromatogram of the main aromatic compounds by catalytic ozonation (color figure available online).

the processes of ozonation alone and ozonation/MAT, as

summarized in Figure 8. It was shown that the signal in
the process of ozonation/MAT was stronger than that of
ozonation alone, indicating that there are OH in both cases,
and ozonation/MAT could generate higher concentration
of OH under same experimental conditions compared to
ozonation alone due to the introduction of heterogeneous
surface, significantly for ozone decomposition process.

Figures 7 and 8 confirmed that 4-CP degradation may

be mainly attributed to OH oxidation. In fact, OH was
formed by a series complex matrix reactions including
the initiation, the propagation, and the termination steps
in aqueous solution containing molecular ozone, produc

ing the intermediates HO

2 , HO2 , O3 , HO3 , O , O2 ,
[2931]
and HO4 .
These species could react with ozone or
each other, or decompose to form OH, according to the

Downloaded by [Aston University] at 03:53 20 January 2014

Degradation pathways of 4-chlorophenol by catalytic ozonation

Fig. 10. The HPLC spectra of the standard and degraded samples
at 280 nm.

reactions listed as follows:[3034]

O3 + HO2 OH + 2O2 k1 = 1.6 109 M1 s1 (6)

6
1 1
O3 + HO
2 OH + O2 +O2 k2 = 2.8 10 M S
(7)

HO2 + HO2 OH + OH + O2
k3 = 3.5 109 M1 s1 (8)
10
+
1 1
s
(9)
O
3 + H OH + O2 k4 = 5.2 10 M
HO3 OH + O2 k5 = 1.4 105 s1
O + H2 O OH + OH k6 = 108 s1

(10)
(11)

Degradation intermediates and the pathways of 4-CP in the

catalytic ozonation
The aromatic products of 4-CP degradation. GC-MS was
used to identify unknown intermediates of 4-CP degradation in catalytic ozonation and Figure 9 showed the detection and identification of GC-MS chromatograms for main
aromatic products. In addition to the target pollutant 4-CP
(product 1, Fig. 9a), there were four aromatic intermedi-

333

ates, including 4-benzoquinone (product 2, Fig. 9b), hydroquinone (product 3, Fig. 9c)), 4-chlorocatechol (product 4,
Fig. 9d), and 4-chlororesorcinol (product 5, Fig. 9e), consistent with HPLC detection (shown in Fig. 10). Previously
it had been confirmed that the active species OH could be
generated in the catalytic ozonation system,[35] the most reactive one, which could attack the para- or ortho-position of
the OH group or substitute the -Cl group of 4-chlorophenol
to form degradation products.[30] The detection of product
3, product 4 and product 5 could confirm these reactions.
Generally, the decomposition of ozone was suppressed
in the condition of low pH value (pH 2), in which
the direct reaction between ozone molecule and organic
pollutant was considered as the dominating reaction, on
the other hand, the decomposition of ozone was promoted
and proved as the only way under high pH value (pH 12),
i.e., OH as the main active one was used for the degradation.[36] To identify logical pathways for 4-CP degradation,
the intermediate products were measured under different
pH value conditions, and the quantitative analysis was
conducted correspondingly, shown in Figure 11.
The results of DMPO-OH adduct signals illustrate that
OH strength ratio of 1:2:3 were belonged to the different
pH value process (pH = 2.0 0.1, 6.6 0.1, and 13.0
0.1), as shown in Figure 11a, the degradation speed of
4-CP being slower under pH = 2.0 0.1 than that under
other two pH value conditions. As two main intermediate
products, hydroquinone and 4-chlorocatechol increased in
the first 20 min, the concentration reaching 0.051 mmol/L
and 0.038 mmol/L, and then decreased. A small number
of 4-chlororesorcinol was detected in 60 min, no more
than 0.002 mmol/L, preliminarily suggesting that ozone
molecule mainly attacked -Cl group and the ortho-position
of OH on 4-CP in the catalytic ozonation system.
Under normal condition (pH = 6.6 0.1, Fig. 11b),
the production and degradation of intermediate products
were similar with the results under high pH value condition
(pH = 13.0 0.1). Hydroquinone, 4-chlororesorcinol and
4-chlorocatechol were derived from the hydroxylation reactions from first degradation step. Therefore, it was deduced

Table 2. The detection of ring-opened products by GC-MS and IC.

Experimental conditions: temperature 20 1 C; initial pH 6.6 0.1; initial 4-CP concentration 100 mg/L; catalyst: 2.0 g/L; total ozone applied
1.0 mg/L.

334

Qi et al.

Downloaded by [Aston University] at 03:53 20 January 2014

Fig. 12. The concentrations of ring-opened intermediate from

4-chlorophenol by catalytic ozonation. Experimental conditions:
temperature 20 1 C; initial pH 6.6 0.1; initial 4-CP concentration 100 mg/L; catalyst: 2.0 g/L; total ozone applied 2.0 mg/L.

ozonation. 4-CP was degraded completely within 10 min

under pH = 13.0 0.1 (Fig. 11c).
The existence of a large number of OH could promote
rapidly the degradation of 4-CP in the catalytic ozonation, and result in low concentration of four main aromatic intermediates. Benzoquinone was detected in this
system, which were produced by losing two H from hydroquinone under the action of OH. The ortho-position
of the OH group on 4-CP was easier to be attacked, and
the yield of 4-chlorocatechol was much higher than that of
4-chlororesorcinol.[37]

Fig. 11. The reaction process and the yield of aromatic products
under (a) pH = 2.0 0.1, (b) pH = 6.6 0.1, and (c) pH = 13.0
0.1. Experimental conditions: temperature 20 1 C; initial 4-CP
concentration 100 mg/L; catalyst: 2.0 g/L; total ozone applied
2.0 mg/L.

that OH could determine the reaction speed and reaction

process in a great extent, implying that the addition reaction of hydroxyl group on the aromatic ring was the decisive
procedure in the first step of 4-CP degradation by catalytic

The ring-opened products of 4-CP degradation. In addition

to the formation of aromatic intermediate, seven kinds of
ring-opened products were also detected by GC-MS combining with IC, as given in Table 2. (E,E)2,4-hexadienal
(product 6) was identified with the time from 4 to 30 min in
the process of catalytic ozonation, and five LMW organic
acids were detected by IC as in Figure 12, such as malic
(product 7), malonic (product 8), oxalic (product 9), acetic
(product 10), and formic acid (product 11).
The concentration of chlorine ion remained
0.78 mmol/L after 30 min, which illustrates that
most of chlorine were dissociated from 4-CP, identical
with the fact that most of 4-CP was removed around
30 min (Fig. 11b). All organic acids were detected from the
beginning of the reaction, and most of them were degraded
within 60 min, agreed with the change of pH value in the
process of 4-CP degradation, from the initial 6.6 0.1
down to 2.5 0.1 after 30 min, and the low pH maintained
a short time. With the continuation of reaction, pH value
began to rise and lasted until the end of reaction, 6.0 0.1
at 60 min.
Its worth noting that benzoquinone was confirmed to
be formed during the 4-CP degradation by the catalytic

Downloaded by [Aston University] at 03:53 20 January 2014

Degradation pathways of 4-chlorophenol by catalytic ozonation

335

Fig. 13. The deductive pathways of 4-CP degradation by catalytic ozonation. Experimental conditions: temperature 20 1 C; initial
pH 6.6 0.1; initial 4-CP concentration 100 mg/L; catalyst: 2.0 g/L; total ozone applied 2.0 mg/L.

ozonation, since benzoquinone and the derivatives were

very readily oxidized for the further reaction and were no
longer identified during the prolonged stages of ozonation, responsible for the colour changes during the reaction. According to the results obtained, the main aromatic
intermediates detected in this work were similar to those
observed in other AOPs experiments, confirming that OH
oxidation was the major reaction pathway in this catalytic
ozonation.[38]
Proposed pathways of 4-CP degradation. Based on the
products and the relevant analysis from GC/MS, HPLC
and IC, possible oxidation pathways for the 4-CP degradation were proposed and given in Figure 13. The catalytic
ozonation of 4-CP with MAT as catalyst includes the hydroxylation of aromatic ring, the transformation of aro-

matics to aliphatics by ring structures destruction and the

oxidation of aliphatic chains.
OH, generated from the surface of the heterogeneous
catalyst, with predominant high redox potential (E0 =
2.8 V), played crucial role in 4-CP degradation, leading to
the hydroxylation of the aromatic ring, the most important
in the process of catalytic ozonation.[39] It was well known
that an electrophilic addition reaction was considered as the
main factor for the reaction mechanism of OH with the
aromatic compounds.[40] Therefore, OH could attack the
4-CP molecule at the beginning of the reaction, resulting in
the occurrence of electron transfer and different reactions
according to the position of impact.[37]
4-Chlorocatechol (pathway1) and 4-chlororesorcinol
(pathway 2) would be formed while the substitution occurs after the electrophilic attack of OH at ortho-position

Downloaded by [Aston University] at 03:53 20 January 2014

336
of -OH and ortho-position of -Cl on 4-CP.[41] Simultaneously, if the substitution occurs at the position of -Cl, the
formation of hydroquinone would be generated (pathway
3) and the chlorine ion released by the radical additionelimination.[24]
Accordingly, the addition of OH to 4-chlorocatechol
and 4-chlororesorcinol both resulted in the formation of
1,2,4-trihydroxybenzene.[37] Hydroquinone could be further degraded to either benzoquinone through abstraction
of two hydrogens or 1,2,4-trihydroxybenzene by the reactions of hydrogen abstraction and addition of OH.[42]
In fact, 1,2,4-trihydroxybenzene could not be detected
under common oxidizing conditions, resulting from the
swing of the adjacent hydroxyl groups between the C C
bonds based on the strong electrophilic effect of hydroxyl
groups.[40] These bonds were easily oxidized and led to ring
opening reactions and the generation of aliphatic compounds, and the ring cleavage was so rapid that there
is no detectable amount of 1,2,4-trihydroxybenzene.[43]
1,2,4-trihydroxybenzene would be further oxidized to form
aliphatic acids by the damage of aromatic ring, and finally
be converted into carbon dioxide and water.
In addition, OH could attack selectively on the C-C
bonds between adjacent hydroxyl groups, and react directly
with 4-CP (pathway 4) and 4-chlorocatechol, producing
4-chloro-2,4-hexadien-1-ol and 4-chloro-2,4-hexadien-1,6glycol, and further degraded to (E,E)2,4-hexadienal and
adipic acid.[37] Thus, the degradations could produce muconic acid as OH reacts with benzoquinone, which were
followed by successive oxidations of hydroquinone.[44]
Moreover, OH reacting with the primary intermediates
mentioned above led to the cleavage of benzene ring and the
formation of oxygenated aliphatic compounds, which could
be degraded to carboxylic acids, such as malic acid, malonic
acid, oxalic acid, acetic acid, and formic acid identified by
the analysis of IC in this study.
Ozone molecule mainly attacked -Cl group and the orthoposition of OH on 4-CP, and produced 4-chlorocatechol
(pathway 1) and hydroquinone (pathway 3). The two
products could be further oxidized and generated 1,2,4trihydroxybenzene by oxidative addition reaction.[37] This
product was easily oxidized to cause the ring-opening reaction by ozone molecule, and could be transformed into
carbon dioxide and water in the end.

Conclusion
The experiments demonstrate that the performance of
4-chlorophenol degradation and mineralization were enhanced by heterogeneous catalytic ozonation with MAT as
catalyst, and OH oxidation displayed primarily in the removal of 4-CP in both the systems of ozonation alone and
ozonation/MAT. It could also be generated that the high
TOC removal of the ozonation/MAT was accelerated by
the formation of OH in aqueous solution.

Qi et al.
4-CP degradation was chiefly induced by OH attack
in catalytic ozonation, mainly producing hydroquinone, 4chlorocatechol, and 4-chlororesorcinol in the first step. Because of the ortho-position of -OH group is more active
than that of the -Cl group, less 4-chlororesorcinol was produced. The ring-opened reaction could be caused by the
direct break-age of the C C bond of 4-CP, producing 4chloro-2,4-hexadien-1-ol. The ring-opened products were
LMW organic acids, such as malic, malonic, oxalic, acetic
and formic acid, finally oxidized into carbon dioxide and
water. The possible six reaction pathways for 4-CP degradation by catalytic ozonation were proposed according to
the mechanisms of indirect reaction by non-selective hydroxyl radicals and direct reaction by selective molecular
ozone in aqueous solution.

Acknowledgments
Research supported via funding coming from the SinoDutch Research Program for industrial waste water treatment, water reuse and Zero Liquid Discharge. A program
established in November 2011 in XiAn via cooperation between Evides (Rotterdam, the Netherlands), University of
Delft (Delft, the Netherlands), PEAS (XiAn, China) and
HIT (Harbin, China).

References
[1] Kang, S.W.; Shim, S.B.; Park, Y.K.; Jung, J. Chemical degradation
and toxicity reduction of 4-chlorophenol in different matrices by
-ray treatment. Radiat. Phys. Chem. 2011, 80, 487490.
[2] He, Z.; Zhang, A.; Song, S.; Liu, Z.; Chen, J.; Xu, X.; Liu, W.
-Al2 O3 Modified with praseodymium: an application in the heterogeneous catalytic ozonation of succinic acid in aqueous solution.
Ind. Eng. Chem. Res. 2010, 49, 1234512351.
[3] Fajardo, A.S.; Martins, R.C.; Quinta-Ferreira, R.M. Treatment of
a simulated phenolic effluent by heterogeneous catalytic ozonation
using Pt/Al2 O3 . Environ. Technol. 2012, 111.
[4] Nawrocki, J.; Kasprzyk-Hordern, B. The efficiency and mechanisms
of catalytic ozonation. Appl. Catal. B 2010, 99, 2742.
[5] Oyama, S.T. Chemical and catalytic properties of ozone. Cat. Rev.Sci. Eng. 2000, 42, 279322.
[6] Wang, X.Y.; Kang, Q.; Li, D. Catalytic combustion of chlorobenzene over MnOx -CeO2 mixed oxide catalysts. Appl. Catal. B 2009,
86, 166175.
[7] Roberto Andreozzi, R.M. Ozonation of p-chlorophenol in aqueous
solution. J. Hazard. Mater. 1999, 69, 303317.
[8] Brillas, E.; Sauleda, R. Mineralization of aniline and 4chlorophenol in acidic solution by ozonation catalyzed with Fe2+
and UVA light. Appl. Catal. B 2001, 29, 135145.
[9] Beltran, F.J.; Rivas, F.J.; Gimeno, O. Comparison between photocatalytic ozonation and other oxidation processes for the removal
of phenols from water. J. Chem. Technol. Biotechnol. 2005, 80,
973984.
[10] Poznyak, T.; Vivero, J. Degradation of aqueous phenol and chlorinated phenols by ozone. Ozone Sci. Eng. 2005, 27, 447458.
[11] Bader, H.; Hoigne, J. Determination of ozone in water by the indigo
method. Water Res. 1981, 15, 449456.
[12] Arena, F.; Trunfio, G.; Negro, J.; Fazio, B.; Spadaro, L. Basic evidence of the molecular dispersion of MnCeOx catalysts synthesized

Degradation pathways of 4-chlorophenol by catalytic ozonation

[13]
[14]

[15]

[16]

[17]

Downloaded by [Aston University] at 03:53 20 January 2014

[18]

[19]

[20]

[21]

[22]

[23]

[24]

[25]

[26]

[27]

[28]

[29]

via a novel Redox-Precipitation route. Chem. Mater. 2007, 19,

22692276.
Kim, S.C.; Shim, W.G. Catalytic combustion of VOCs over a series
of manganese oxide catalysts. Appl. Catal. B 2010, 98, 180185.
Masaya Chigane, M.I. Manganese oxide thin film preparation by
potentiostatic electrolyses and electrochromism. J. Electrochem.
Soc. 2000, 147, 22462251.
Liu, M.; Zhang, G.J.; Shen, Z.R.; Sun, P.C.; Ding, D.T.; Chen, T.H.
Synthesis and characterization of hierarchically structured mesoporous MnO2 and Mn2 O3 . Solid State Sci. 2009, 11, 118128.
Han, N.; Wu, X.; Chai, L.; Liu, H.; Chen, Y. Counterintuitive sensing mechanism of ZnO nanoparticle based gas sensors. Sens. Actuators, B 2010, 150, 230238.
Cao, X.; Wang, N.; Wang, L.; Mo, C.P.; Xu, Y.J.; Cai, X.L.; Guo,
L. A novel non-enzymatic hydrogen peroxide biosensor based on
ultralong manganite MnOOH nanowires. Sens. Actuators, B 2010,
147, 730734.
Ramstedt, M.; Shchukarev, A.; Sjoberg, S. Characterization of hydrous manganite (r-MnOOH) surfaces-an XPS study. Surf. Interface. Anal. 2002, 34, 632636.
Nesbitt, H.W.; Banerjee, D. Interpretation of XPS Mn(2p) spectra
of Mn oxyhydroxides and constraints on the mechanism of MnO2
precipitation. Am. Mineral. 1998, 83, 305315.
Ardizzone, S.; Bianchi, C.L.; Tirelli, D. Mn3 O4 and -MnOOH
powders, preparation, phase composition and XPS characterisation. Colloids Surf., A 1998, 134, 305312.
Brillas, E.; Calpe, J.C.; Cabot, P.L. Degradation of the herbicide
2,4-dichlorophenoxyacetic acid by ozonation catalyzed with Fe2+
and UVA light. Appl. Catal. B 2003, 46, 381391.
Kasprzyk-Hordern, B. Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment. Appl. Catal. B
2003, 46, 639669.
Potapenko, E.V.; Andreev, P.Y. Catalytic oxidation of alkylbenzenes
with ozone in acetic acid in the presence of strong acids. Petrol.
Chem. 2012, 52, 113118.
Pi, Y.Z.; Zhang, L.S.; Wang, J.L. The formation and influence of hydrogen peroxide during ozonation of para-chlorophenol. J. Hazard.
Mater. 2007, 141, 707712.
Hoigne, J.; Bader, H. Rate constants of reactions of ozone with
organic and inorganic compounds in water-I: non-dissociating organic compounds. Water Res. 1983, 17, 173183.
Hoigne, J.; Bader, H. Rate constants of reactions of ozone with
organic and inorganic compounds in water-II: dissociating organic
compounds. Water Res. 1983, 17, 185194.
Elovitz, M.S.; von Gunten, U. Hydroxyl radical ozone ratios during
ozonation processes. I.The Rct concept. Ozone Sci. Eng. 1999, 21,
239260.
Langlais, B.; Reckhow, D.A.; Brank, D.R. Ozone in Water Treatment: Application and Engineering, Lewis Publishers: Chelsea, MI,
1991.

Beltran, F.J.; Rivas, J.; Alvarez,

P.M.; Alonso, M.A.; Acedo, B. A
kinetic model for advanced oxidation processes of aromatic hydro-

[30]
[31]

[32]

[33]
[34]
[35]

[36]
[37]

[38]

[39]

[40]

[41]

[42]

[43]

[44]

337

carbons in water: application to phenanthrene and nitrobenzene.

Ind. Eng. Chem. Res. 1999, 38, 41894199.
von Gunten, U. Ozonation of drinking water: Part I. Oxidation
kinetics and product formation. Water Res. 2003, 37, 14431467.
Ernst, M.; Lurot, F.; Schrotter, J.C. Catalytic ozonation of refractory organic model compounds in aqueous solution by aluminum
oxide. Appl. Catal. B 2004, 47, 1525.

Pera-Titus, M.; Garca-Molina, V.; Banos,

M.A.; Gimenez, J.; Esplugas, S. Degradation of chlorophenols by means of advanced
oxidation processes: A general review. Appl. Catal. B 2004, 47,
219256.
Bailey, P.S. The reactions of ozone with organic compounds. Chem.
Rev. 1958, 58, 9251010.
Masschelein, W.J. Unit Processes in Drinking Water Treatment; Marcel Dekker: New York, 1992.
Sotelo, J.L.; Beltran, F.J.; Benitez, F.J.; Beltran-Heredia, J. Ozone
decomposition in water: kinetic study. Ind. Eng. Chem. Res. 1987,
26, 3943.
Beltran, F.J. Ozone Reaction Kinetics for Water and Wastewater
Systems; CRC Press: Boca Raton, FL, 2004.
Bian, W.J.; Song, X.H.; Liu, D.Q.; Zhang, J.; Chen, X.H. The
intermediate products in the degradation of 4-chlorophenol by
pulsed high voltage discharge in water. J. Hazard. Mater. 2011, 192,
13301339.
Oros-Ruiz, S.; Pedraza-Avella, J.A.; Guzman, C.; Quintana, M.;
Moctezuma, E.; delAngel, G.; Gomez, R.; Perez, E. Effect of gold
particle size and deposition method on the photodegradation of
4-chlorophenol by Au/TiO2 . Top. Catal. 2011, 54, 519526.
Zhao, L.; Sun, Z.Z.; Ma, J.; Liu, H.L. Enhancement mechanism of
heterogeneous catalytic ozonation by cordierite-supported copper
for the degradation of nitrobenzene in aqueous solution. Environ.
Sci. Technol. 2009, 43, 20472053.
Oturan, M.A.; Peiroten, J.; Chartrin, P.; Acher, A.J. Complete destruction of p-nitrophenol in aqueous medium by electro-Fenton
method. Environ. Sci. Technol. 2000, 34, 34743479.
Brillas, E.; Skoumal, M.; Cabot, P.L.; Centellas, F.; Arias, C.; Rodriguez, R.M.; Garrido, J.A. Mineralization of paracetamol by
ozonation catalyzed with Fe2+, Cu2+ and UVA light. Appl. Catal.
B 2006, 66, 228240.
Sui, M.; Xing, S.; Sheng, L.; Huang, S.; Guo, H. Heterogeneous
catalytic ozonation of ciprofloxacin in water with carbon nanotube
supported manganese oxides as catalyst. J. Hazard. Mater. 2012,
227228, 227236.
Gomez, M.; Matafonova, G.; Gomez, J.L.; Batoev, V.; Christofi,
N. Comparison of alternative treatments for 4-chlorophenol removal from aqueous solutions: Use of free and immobilized soybean peroxidase and KrCl excilamp. J. Hazard. Mater. 2009, 169,
4651.

Bodalo,
A.; Gomez,
J.L.; Gomez,
E.; Hidalgo, A.M.; Gomez,
M.;
Yelo, A.M. Elimination of 4-chlorophenol by soybean peroxidase
and hydrogen peroxide: Kinetic model and intrinsic parameters.
Biochem. Eng. J. 2007, 34, 242247.