Catalysis Communications 89 (2017) 81–85

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Catalysis Communications

journal homepage: www.elsevier.com/locate/catcom

Short communication

Heterogeneous catalytic ozonation of p-chloronitrobenzene (pCNB) in

water with iron silicate doped hydroxylation iron as catalyst
Yue Liu a,⁎, Shiyuan Wang a, Weijin Gong a, Zhonglin Chen b, Haifang Liu a, Yanping Bu a, Ying Zhang a
a
School of Energy & Environment Engineering, Zhongyuan University of Technology, Zhengzhou, zhongyuan Road 47, China
b
State Key Laboratory of Urban Water Resources and Environment, School of Municipal & Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China

a r t i c l e i n f o a b s t r a c t

Article history: In this communication, synthesis of iron silicate (IS) doped hydroxylation iron (IS-FeOOH) and its catalytic activ-
Received 19 July 2016 ity in ozonation of p-chloronitrobenzene (pCNB) was reported and the mechanisms of pCNB removal were de-
Received in revised form 22 September 2016 duced. The XRD and HR-TEM analyses indicated that the IS-FeOOH were mainly composed by amorphous IS
Accepted 23 October 2016
and FeOOH. IS-FeOOH exhibited significant catalytic activities. The EPR spectrum results showed that IS-
Available online 28 October 2016
FeOOH could promote ozone decomposition into hydroxyl radicals (·OH), resulting in the increased removal
Keywords:
of pCNB. The catalytic reusability studies demonstrated that IS-FeOOH kept its catalytic activity in five consecu-
Heterogeneous catalytic ozonation tive cycles.
FeOOH © 2016 Elsevier B.V. All rights reserved.
Hydroxyl radicals
Reusability

1. Introduction
Heterogeneous catalytic ozonation has gained increasing attention
in water and wastewater treatment field, owing to its higher oxidation,
lower negative influence on water quality, less cost and more feasible
for practical application [1]. To date, several researchers have been suc-
cessfully using various materials as heterogeneous catalyst in ozonation
process to degrade organic pollutants in aqueous solution, such as metal
oxides [2], supported metals [3], oxyhydroxide [4], and some porous
materials [5]. Compared with the ozonation alone, these catalysts can
significantly enhance the degradation efficiency of organic pollutants.
Different catalytic mechanisms for degradation different organic matter
were also proposed, including the promoted generation of hydroxyl
radicals (·OH), the promotion of the mass-transfer efficiency through
the surface of the catalyst adsorption on the ozone and pollutants in
aqueous solution [6,7]. Our previous work also indicates that heteroge-
neous catalytic ozonation using manganese silicate enhances the ozone
degradation [8]. In continuation of searching for new and efficient cata-
lysts for catalytic ozonation processes, herein we report iron silicate (IS)
doped hydroxylation iron (IS-FeOOH) as a catalytic material candidate
for the first time.
IS which is a common Fe-Si complex has been used as the catalyst for
ozonation, due to its high density of surface hydroxyl groups and stable
structure. Furthermore, the complexation of Fe and Si may increase the
physical strength of the IS [9]. FeOOH is a common catalyst in the het-
erogeneous catalytic ozonation system, which plays an important role
in catalysis through promotion of ozone decomposition into ·OH [10,
11]. In this study, IS doped FeOOH was prepared and used for catalytic
ozonation.
p-Chloronitrobenzene (pCNB) is a typical halogenated nitro aromat-
ic compound, and which is frequently used as an important intermedi-
ate in the fields of the production of dyes, pesticides, pharmaceuticals
and rubber chemicals. And large amount of it is detected in some
main drinking water sources after it usage [12]. Moreover, it possesses
a wide range of toxicities for humans and animals such as genotoxicity,
immunotoxicity and carcinogenis [13]. pCNB scarcely reacts with ozone
alone, because the reaction rate constant of pCNB with O3 is only 1.6
(M·s)− 1. However, with ·OH is 2.6 × 109 (M·s)−1. Therefore, pCNB
was selected as the model pollutant to test the catalytic activity of the
IS-FeOOH in this study.
In this communication, we have reported on the preparation of IS-
FeOOH and degradation of pCNB by using the synthesized IS-FeOOH.
The synthesized mechanism, catalytic activity and reusability of the IS-
FeOOH on the degradation of pCNB were investigated.
2. Experimental section
2.1. Materials and reagents

Abbreviations: IS, iron silicate; FeOOH, hydroxylation iron; IS-FeOOH, iron silicate
doped hydroxylation iron; DMPO, 5, 5-dimethyl-1-pyrroline N-oxide.
⁎ Corresponding author.
E-mail address: yue5757@sina.com (Y. Liu).
The pCNB stock solution was prepared by dissolution 100 mg pCNB
(99.5% purity, Merck, Germany) into 1 L Milli-Q ultra-pure water
(18 MΩ cm, Millipore Q Biocel system), and stored in an amber flask.

http://dx.doi.org/10.1016/j.catcom.2016.10.022
1566-7367/© 2016 Elsevier B.V. All rights reserved.
82 Y. Liu et al. / Catalysis Communications 89 (2017) 81–85

Other chemicals used in this study were analytical grade, except as 3. Results and discussion
noted.
The volumetric flasks were washed by soaking them into chromic 3.1. The preparation mechanism and characterization of the IS-FeOOH
acid and rinsing with distilled water. The other glassware was muffled
overnight at 673 K. Sodium silicate is an ionic compound and a strong base-weak acid
salt. It can easily dissolve in water to form silicic acid. Under the weak
alkaline or neutral conditions, silicic acid exit in the form of H3SiO− 4
2.2. Catalyst preparation and H4SiO4. As shown in the Seq. 1, during the process of silicic acid po-
lymerization, it mainly occurs four coordinating combined reaction be-
The IS-FeOOH was prepared using Fe (NO3)3 and Na2SiO3 as pre- tween silicate molecule and anion of silicic acid. Under the acid
cursor. A 150 mL volume of 0.1 M Na 2 SiO 3 was slowly added to condition, silicic acid exits in the form of H5SiO−
4 and H4SiO4, and the po-
150 mL of 0.1 M Fe(NO3)3 solutions (pH b 2.0, adjusted by HNO3 so- lymerization occurs mainly in the following manner (Seq. 2) [17].
lution) at room temperature under magnetic stirring at the speed of
100 rpm. When the pH of the suspension was 7.0, the dropping of
Na2SiO3 solution was stopped. Then pH of the suspension was ad- ðSeq:1Þ
justed higher than 12 by NaOH solution, and it was incubated at
313 K for 24 h. The precipitate was then collected, washed and
dried according to our previous publication [14]. To further study
the catalyst IS-FeOOH, we also synthesized IS according to the liter-
ature [9].

ðSeq:2Þ
2.3. Ozonation procedure
In the process of IS-FeOOH synthesis, when the Fe(NO3)3 solution as
The catalytic ozonation experiments were performed in batch mode strong acidic solution, is mixed with the solution of Na2SiO3, the above
at 293 ± 1 K in a 1.2 L glass flat-bottomed flask equipped with gas inlet reactions (Seq. 2) should occur simultaneously. Due to the instability
and outlet. Ozone was produced from pure oxygen using the CF-G-3- of OH2 bonds, Fe-Si complexes are most likely to form, and form IS.
010 g ozone generator (Qingdao guolin, China) and bubbled into the When the pH of the suspension was 7.0, the titration of sodium silicate
bottom of the reactor through a silica bubble diffuser for a desired peri- solution into Fe(NO3)3 solutions was stopped, which makes the poly-
od to reach the desired dissolved ozone concentration. The desired merization occur along the Seq. 2. Then the pH of the suspension was
amounts of catalysts and pCNB stock solution were then immediately adjusted to N12 by sodium hydroxide solution. The objective of
dosed into the reactor, and the reactor was instantly sealed by the cap. adjusting pH was (1) to generate FeOOH according to the following re-
Then, the magnetic stirrer was turned on to initiate the experiment. action (Seq. 3);
The samples were withdrawn at a predetermined time intervals (0, 1,
3, 5, 10, 15 min) and the reaction was quenched by Na2S2O3 solution Fe3þ þ OH– →FeOOH þ H2 O ðSeq: 3Þ
(0.1 mol/L). All the experiments were conducted three times and the
average date and error bars were shown in the figures. For comparative (2) to make the unsaturated surface of FeOOH and IS adsorb abundant
purposes, adsorption on IS-FeOOH, IS catalytic ozonation experiment, of hydroxyl ion, resulting in the formation of surface hydroxyl groups.
five reusability experiments and the ozonation alone experiments According to the saturated deprotonation results, the density of sur-
were performed with the same system under identical experiment face hydroxyl groups on IS is 2.573 × 10− 2 mol/g and IS-FeOOH is
conditions. 3.169 × 10−2 mol/g, respectively. In addition, the condensation reaction
may occur between the surface hydroxyl groups of the FeOOH and IS to
form IS-FeOOH. In other words, IS-FeOOH is not a simple physical mix-
2.4. Analytical method ture of FeOOH and IS. This viewpoint was confirmed by the results of
XRD.
The concentration of ozone in aqueous solution was measured using Fig. 1 showed the XRD pattern of the synthesized IS-FeOOH and IS.
the indigo method via spectrophotometry [15]. The concentration of The broad peak in the range of 2 θ from 20° to 30° was typical of amor-
pCNB was analyzed according to our previous publication using a liquid phous silica [14]. The weak peaks observed at 18.083°, 35.9°, 41.3° and
chromatograph (HPLC, LC-1200, Agilent, USA) with UV detection at
265 nm [14]. The structure and morphology of the prepared IS-FeOOH
catalyst was investigated by Transmission Electron Microscope (TEM)
(Japan, with a FEI Tecnai G2 F30) and powder X-ray diffraction (XRD)
patterns were on a BrukerD8 Advance Diffractometer with Cu Kα radi-
ation (λ = 1.5418 Å). The saturated deprotonation method was used to
measure the density of surface hydroxyl groups of the catalyst according
to the described by Laiti [16]. The electron paramagnetic resonance
(EPR) spin-trapping experiments were used to determine the ·OH gen-
erated in the ozonation processes and the EPR spectrum was measured
with an EPR spectrometer (Bruker EMX-8/2.7 ESR spectrometer with
ER4102ST cavity) under the following experimental conditions: X-
field sweep; sweep width 100.00 G; center field 3480.00 G; frequency
9.751 GHz; static field 3490.00 G; power 4.0 mW. The samples were
scanned and accumulated to 10 times for 20.972 × 10 s. The metals
leached from the catalyst into solution were determined using an induc-
tively coupled plasma atomic emission spectrometer (ICP-AES, Optima
5300DV, Perkin Elmer, USA). Fig. 1. The XRD pattern of IS-FeOOH and IS.
 Y. Liu et al. / Catalysis Communications 89 (2017) 81–85
62.681° were assigned to the (020), (211), (031), (002) reflections of
FeOOH (JCPDS Card No. 18-0639). Fig. 1 (b) shows that the IS was
amorphous. Some diffraction peaks of FeOOH didn't display in
Fig. 1(a) because the mass proportion of FeOOH particles in IS-FeOOH
catalyst was minimal and their spectrum signals were therefore weak
and apt to be covered by that from amorphous IS.
Fig. 2 (a)-(d) shows the HR-TEM images of IS-FeOOH catalyst. Fig. 2
(a) showed that there were abundant of crystallites embedded in the
amorphous matrix. Fig. 2 (b) showed that the crystallites were spinel
structure. According to the IS-FeOOH synthetic mechanism and XRD re-
sults, the crystallites are believed to be FeOOH crystallites. Fig. 2
(c) showed high resolution TEM images of the framed parts and the
Fig. 2 (d) showed its corresponding fast Fourier transform (FFT) pattern.
The FFT pattern revealed the FeOOH to be polycrystalline in nature. The
interlayer distances of oval area A and B in Fig. 2 (c) were measured, and
the distances were 0.5 nm and 0.44 nm, respectively, which
corresponded to the (211) and (031) planes (JCPDS Card No. 18-
0639), agreeing with the XRD patterns shown in Fig. 1.
3.2. Degradation efficiency of pCNB in the different processes and the detec-
tion of ·OH formation by EPR spectra
In order to study the catalytic activity of the as-synthesized IS-
FeOOH, different check experimental processes were performed. Fig. 3
(a) shows the degradation curves of pCNB as a function time in air/IS-
FeOOH, air/IS, ozone alone, ozone/IS-FeOOH and ozone/IS. The air/IS-
FeOOH process and air/IS leads to only 3.3% and 4.0% pCNB degradation
Fig. 2. HR-TEM images of IS-FeOOH catalyst.
83
after the reaction time of 15 min, respectively, indicating that the ad-
sorption of pCNB on the IS-FeOOH and IS are too low to contribute sig-
nificantly to its degradation efficiency. Moreover, it also proves that
the bubbling of gas into the reacting mixture does not produce extra de-
crease of pCNB. With ozone adding into the reaction, better pCNB degra-
dation rate was observed in the process of ozone/IS-FeOOH. The
removal rates of pCNB by ozone alone and ozone/IS-FeOOH processes
were 56.7% and 99.8% after 15 min of reaction, respectively. As shown
in Fig. 3 (b), the TOC removal rate after reaction time of 15 min by
ozone/IS-FeOOH process was 61.3%, which is 33.2% higher than that of
ozone alone. Compared with the cumulative effect of ozone alone and
adsorption of IS-FeOOH, an increment of approximately 39.8% of pCNB
degradation was observed with the IS-FeOOH catalytic ozonation pro-
cess. The experimental results suggest that the presence of the IS-
FeOOH catalyst has a synergistic effect with ozone for the degradation
of pCNB. When we compared the degradation rates of ozone/IS-
FeOOH with ozone/IS, it can be found that the presence of FeOOH in
the IS-FeOOH accelerated the degradation rate and removal of TOC re-
markably. For example, after ozone/IS-FeOOH for 1 min, the degraded
pCNB concentration was 72 μg/L, while that in ozone/IS was 59 μg/L.
For the removal of TOC, the value was increased from 52.1% in ozone/
IS to 61.3% in ozone/IS-FeOOH.
Most of researchers have suggested that in the processes of hetero-
geneous catalytic ozonation of organic pollutant, the great enhance-
ment in mineralization rate of organic pollutant is due to the ·OH
which is generated by the decomposition of ozone [18,19]. In order to
testify the ·OH between ozone/IS-FeOOH process and ozone alone, the
84 Y. Liu et al. / Catalysis Communications 89 (2017) 81–85

Fig. 3. pCNB degradation experiments. (a) Promotion of the pCNB degradation in different processes; (b) TOC removal efficiency. Experiment conditions were: [pCNB]0 = 100 μg/L,
[O3]0 = 0.6 mg/L, [catalysts]0 = 500 mg/L, pH = 7.0 ± 0.5.

EPR spectra of DMPO-·OH were tested in aqueous solution using EPR
spin trapping technique with DMPO spin trap. As shown in Fig. 4(a), a
typical four-line EPR spectrum is monitored, and the intensity of
DMPO-·OH in the ozone/IS-FeOOH process is higher than the ozone
alone, which also implies that IS-FeOOH could accelerate the ozone de-
composition to generate highly oxidative ·OH. To verify the role of ·OH
in the process of ozone/IS-FeOOH, tert-butanol—a well-known ·OH
scavenger was used [20]. In Fig. 4(b), the presence of tert-butanol
even at a very low concentration (1.0 mg/L) shows a very strong influ-
ence on the degradation of ozone alone and IS-FeOOH catalyzed ozona-
tion processes. Moreover, when the tert-butanol concentration
increased to 20 mg/L, the pCNB degradation efficiency during ozonation
alone decreased from 56.7% to 12%, and the degradation rate of the IS-
FeOOH catalyzed ozonation dropped from 99.8% to 12.6%. The experi-
ment results indicated that the addition of tert-butanol at different con-
centrations negatively influences the pCNB degradation efficiency both
in the ozone alone and IS-FeOOH catalyzed ozonation process. The re-
sults suggested that·OH played an important role in the IS-FeOOH cat-
alyzed ozonation process.
3.3. Catalysis stability and ions release of the ozone/IS-FeOOH process
IS-FeOOH was mainly composed by the elements of irons, which was
restricted in the national water standard. Furthermore, with the release of
ions from the catalyst, the catalysis activity and stability can be affected.
Therefore it is necessary to study the stability of the repeatedly used IS-
FeOOH. So in this experiment, IS-FeOOH was further used repeatedly in
the catalyzed ozonation to determine whether the catalyst activity
would become depleted. At the same time, the concentration of the resid-
ual iron ions after catalyzed ozonation was analyzed to evaluate perfor-
mance stability of the catalyst. Catalyst powers used in the batch
experiment were reclaimed by filtration through a 0.45 μm cellulose ace-
tate filter, washed by large amount of ultra-pure water and dried at 80 °C,
and then stored in a dry vacuum oven for use in the next ozonation exper-
iment. The performance by IS-FeOOH catalytic ozonation in removing
pCNB is shown in Fig. 5 (a). When IS-FeOOH were reused five times, its
removal effectiveness was not affected significantly and the dissolution
of iron ions were 0.026 mg/L, 0.021 mg/L, 0.017 mg/L, 0.013 mg/L, 0.013
mg/L, respectively, which was much lower than the limit allowed in
drinking water in the United States (0.05 mg/L).
In order to further study the stability of used IS-FeOOH, the XPS re-
sults of unused and used catalyst (after five consecutive cycles) were
compared. The used IS-FeOOH XPS results are shown in Fig. 5 (b),
which are quite consistent with unused XPS pattern presented. These
results confirmed good stability of IS-FeOOH in ozonation process.
In conclusion, the synthesized IS-FeOOH is an efficient catalyst and
the use of the catalyzed ozonation by IS-FeOOH in drinking water treat-
ment is feasible.
4. Conclusions
Based on experimental data the following conclusions can be drawn:
(1) IS-FeOOH was successfully synthesized using Fe(NO3)3 and
Na2SiO3 as precursors. XRD, TEM analyses confirmed that IS-
FeOOH was mainly composed of IS and FeOOH.

Fig. 4. (a) The EPR spectra of DMPO-·OH from the different processes. Experimental conditions: [IS-FeOOH]0 = 500 mg/L, pH = 7.0 ± 0.5, [DMPO]0 = 100 mmol/L, [O3]0 = 2.0 mg/L.
(b) Effect of tert-butanol on the degradation of pCNB. Experimental conditions: [pCNB]0 = 100 mg/L, [O3]0 = 0.6 mg/L, [IS-FeOOH]0 = 300 mg/L, pH = 7.0 ± 0.1.
 Y. Liu et al. / Catalysis Communications 89 (2017) 81–85
Fig. 5. (a) Effect of catalyst recycles on the ozonation of pCNB. Experiment conditions were: [pCNB] 0 = 100 μg/L, [O3] 0 = 0.6 mg/L, [IS-FeOOH] = 500 mg/L, pH = 7.0 ± 0.5, reaction
time = 15 min; (b) The XPS pattern of IS-FeOOH used and unused.
(2) The use of IS-FeOOH in ozonation of pCNB significantly improves
the removal efficiency comparison with non-catalytic process.
(3) Catalyst activity can be explained by ·OH formation after interac-
tion of ozone with the catalyst surface.
(4) It was stressed out that catalytic activity of IS-FeOOH remains al-
most the same after five consecutive cycles and the leaching of
active component is insignificant regardless.
Acknowledgments
This work was financially supported by the National Natural Science
Foundation of China (51308561 & U1404523) and Key Scientific Pro-
gram of Higher Education Institutions (15A560002).
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