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Ceramics International 40 (2014) 76937699
www.elsevier.com/locate/ceramint

Environmental remediation from thiophene solution by photocatalytic


oxidation using a Pd/ZrO2chitosan nanocomposite
M.Y. Abdelaala,b,n, R.M. Mohameda,c
a
Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia
b
Chemistry Department, Faculty of Science, Mansoura University, ET-35516 Mansoura, Egypt
c
Advanced Materials Department, Central Metallurgical R&D Institute, Helwan 11421, Egypt
Received 19 November 2013; received in revised form 23 December 2013; accepted 24 December 2013
Available online 2 January 2014

Abstract

A modied solgel technique was used to prepare ZrO2 nanoparticles through impregnation of ZrO2 with Pd and/or chitosan (CS).
The composite photocatalyst of Pd/ZrO2 was characterized by XRD, TEM, UVvis, Pl, and BET and the photocatalytic activity was investigated
under visible light irradiation by using a thiophene solution as a model pollutant. The results revealed the inuence of the type and amount of
the catalyst where CS can effectively prevent the agglomeration of ZrO2 nanoparticles. UVvis spectroscopic investigation indicated also that the
ability of the composite to absorb visible light is greatly improved. The catalyst was reproducible without signicant loss in its activity during the
rst ve cycles.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: B. Nanocomposites; Thiophene removal; Chitosan; Visible photocatalysis

1. Introduction removal of sulfur-containing compounds from gasoline


through the photocatalytic oxidation.
Degradation of the hazardous organic materials is of great The efciency of the material as photocatalyst can be
importance from an environmental point of view [15]. Many determined based on particle size, band gap, surface area,
organic pollutants in water or air streams can be removed by life-time of the electronhole pair, stability, and other physical
means of photocatalytic oxidation. Sulfur-containing organic and chemical properties [7]. Various pathways, such as
compounds are potential pollutants present mainly in fuel oils varying the preparation method, oxide mixing, and doping,
which are difcult to be removed [6]. Thiophene is one of the were explored to improve the properties of catalysts toward a
main compounds in this class present in gasoline and it is the desired function [812].
most difcult one to be oxidized using the conventional Band gap width of the photocatalyst is an important criterion
oxidative desulfurization processes. The inertness of thiophene in the choice of the photocatalyst. For instance, TiO2 photo-
in this process is mainly due to the aromatic nature and catalyst has a band gap of 3.03.2 eV and it has been subjected
low electron density on the sulfur atom which renders the to several treatments including mixing with semiconductors,
oxidation of thiophene molecules more difcult. Therefore, it doping with various metals, and various preparation methods
was crucial to develop an effective photocatalyst for the to enhance its catalytic activity and surface area, adjust its band
gap, and decrease the possibility of charge carriers recombina-
tion [1315].
n
Corresponding author at: Chemistry Department, Faculty of Science, King ZrO2 is an attractive photocatalyst due to its high specic
Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia.
Tel.: 966 500096707.
surface area and thermal stability in addition to other optical and
E-mail addresses: myabdelaal@gmail.com, electrical properties [16,17]. Hence, it is used in photocatalytic
magdyabdelaal@yahoo.com (M.Y. Abdelaal). gas-phase oxidation of methanol and hexane [18]. Pt/ZrO2

0272-8842/$ - see front matter & 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.12.110
7694 M.Y. Abdelaal, R.M. Mohamed / Ceramics International 40 (2014) 76937699

catalyst led to H2-yields up to 29% in steam reforming of bio- A sample of 3 g from the obtained ZrO2 nanoparticles were
ethanol [19]. ZrO2SiO2 mixed oxide showed bitter stability and added to 0.2 g PdCl2 in 50 ml of distilled water to prepare Pd/
photocatalytic efciency [20,21] and reported as a temperature ZrO2 nanoparticles through impregnation. The resulting nano-
assisted catalyst [23,24]. Hence, visible range illumination of particles were collected after evaporation of water while
ZrO2SiO2 would increase the photocatalytic efciency of the stirring the suspension and calcined in air at 550 1C for 5 h.
catalyst under direct sunlight irradiation as visible light constitutes The obtained sample was assigned as Pd/ZrO2 of 0.03 M ratio
 40% of the total emitted solar energy [25]. Effect of zirconia to of Pd to ZrO2.
silica ratio on methane reforming with CO2 was reported also ZrO2CS nanoparticles were prepared by dissolving 10 g
with high efciency [22]. zirconium(IV) propoxide in 20 ml ethanol (95%), 10 ml HCl
Chitosan (CS) is known as the most abundant natural (5%), and 40 ml double-distilled water until a clear sol was
biopolymer after cellulose. It is a cationic polymer obtained formed. The obtained sol was added drop wise to 1 g of CS
by partial N-deacetylation of chitin. It has reactive hydroxyl dissolved in 100 ml of 5% aq. acetic acid solution while
(OH) and amino (NH2) groups and exhibits unique adsorption constant stirring and was stirred further for 1 h. The resulting
and chelating abilities for all heavy metal ions and for drug nanoparticles were separated after the pH being adjusted to 9
delivery systems [2629]. CS is an excellent bio-matrix for the with ammonia solution, washed, dried for 24 h at 100 1C, and
production of nanoparticles or quantum dots of different then calcined in air at 550 1C for 5 h. The obtained sample was
inorganic photocatalysts including, but not limited to, CdS assigned as ZrO2CS. ZrO2CS samples were impregnated
[30,31], ZnS [32], ZnO2 [33], and Cu2O [34]. It facilitates the with Pd using the same method described above for the pure
separation and recovery of nanosized materials as it prevents ZrO2 to prepare Pd/ZrO2CS nanoparticles of 0.03 M ratio of
successfully the agglomeration of nanosized photocatalysts Pd to ZrO2.
during the nanoparticles growth [35]. Hence, CS was used
during the preparation of ZrO2 to beat the agglomeration 2.2.2. Characterization of composite catalyst
problem. The specic surface area of the samples was determined
The band gap of a catalyst should be tuned down to from the adsorptiondesorption isotherms of N2 at  196 1C
wavelengths in the visible range to be able to excite on using Chromatech (a Nova 2000 series apparatus) and apply-
illumination with sunlight. Hence, the current work is aiming ing BET equation. All samples were degassed under vacuum at
to prepare and characterize Pd/ZrO2 photocatalyst via a 200 1C for 2 h prior to measurement. Particle size was
modied solgel method in the presence of CS to overcome determined by X-ray diffraction (XRD) analysis with a Bruker
the agglomeration of the ultrane powder and to transfer the axis D8 instrument using Cu K radiation ( 1.540 ) at
absorption of ZrO2 into the visible region by impregnation of room temperature. The crystallite size of composite catalysts
Pd. The photocatalytic performance of Pd/ZrO2 photocatalyst was calculated using the Scherrer Eq. (1).
was estimated through the degradation of thiophene under
d B=1=2 cos 1
visible light irradiation.
where d is the average particle size of the investigated material,
2. Experimental methods B is the Scherer constant (0.89), is the wavelength of the
X-ray beam, 12 is the full width at half maximum of the
2.1. Materials diffraction peak, and is the diffraction angle. The surface
morphology of catalysts was examined using a transmission
High molecular weight CS of high purity was supplied by electron microscope (TEM) (JEOL-JEM-1230). Samples were
Aldrich, Milwaukee, WI, USA and used as received. Thio- suspended in ethanol and ultra-sonicated for 30 min prior
phene ( Z 99%), zirconium(IV) propoxide 70 wt% solution in loading into TEM. Photoluminescence (Pl) emission spectra
1-propanol, ethanol, PdCl2 ( 499.9%), HCl, ammonia, and were recorded with a Shimadzu RF-5301 uorescence spectro-
acetic acid were purchased from Sigma-Aldrich and used photometer. Band-gap energies of the samples were deter-
without further purication. All solutions were prepared with mined by UVvisible diffuse reectance spectra (UVvis-
double-distilled water. DRS) in air at room temperature using a UV/vis/NIR spectro-
photometer (V-570, JASCO, Japan) in the wavelength range of
2.2. Methods 200800 nm. The band gap energies were calculated from the
following equation.
2.2.1. Preparation of composite catalyst Eg 1239:8= 2
ZrO2 nanoparticles were prepared modied solgel method.
A 10 g zirconium(IV) propoxide was dissolved 20 ml ethanol where Eg is the band gap (eV) and is the wavelength of the
(95%), 10 ml HCl (5%), and 40 ml double-distilled water to absorption edges (nm).
form a clear zirconium sol. Then, we add ammonia solution
(25%) to form zirconium hydroxide precipitated. After wash- 2.2.3. Photocatalysis experiment
ing, separation and drying of the precipitate overnight at A suitable amount of the photocatalyst was dispersed in a
100 1C, the sample was calcined at 550 1C for 5 h to produce solution of thiophene in acetonitrile where the initial sulfur
ZrO2 nanoparticles assigned as ZrO2. content was 600 ppm. The adsorption/desorption equilibrium
M.Y. Abdelaal, R.M. Mohamed / Ceramics International 40 (2014) 76937699 7695

between the solution and photocatalyst suspension was estab- reaction system by centrifugation. The products and by-
lished by stirring in the dark for 30 min before being irradiated products were then analyzed by GC-FPD (Agilent 7890, FFAP
by a 500 W Xenon lamp as visible light source with a column) and GCMS.
maximum emission at about 470 nm. The wavelength is
controlled with a cut off lter (4 420 nm). Temperature
of the reaction solution was maintained at 12 1C by a stream of 3. Results and discussion
cooling water. The catalyst particles were separated from the
3.1. Characterization of composites

The XRD patterns of CS, ZrO2, Pd/ZrO2, ZrO2CS, and Pd/


Chitosan ZrO2CS in Fig. 1 showed that all composite samples contain
a zirconia phase with no obvious effect on the crystallization
process of ZrO2 upon addition of CS which played a
Pd/ ZrO2- Chitosan
promoting role in it where the phase characteristic diffraction
Intensity, a.u.

peaks of ZrO2 broadened and the diffraction peak intensity


ZrO2- Chitosan decreased. The average crystallite size of the composites was
calculated with Scherrer0 s equation using the full width at half
maximum of the X-ray diffraction peaks at 2 30.231
Pd/ ZrO2
corresponding to the most intense zirconia peak and it was
12.9, 12.4, 10.8 and 9.3 nm for ZrO2, Pd/ZrO2, ZrO2CS and
ZrO2 Pd/ZrO2CS composites, respectively.
TEM photographs of ZrO2, Pd/ZrO2, ZrO2CS, and Pd/
ZrO2CS in Fig. 2 showed a very serious agglomeration of
4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72 76 80
ZrO2 nanoparticles while ZrO2CS primary particles were
2-Theta
relatively uniform. It holds also true for Pd/ZrO2 and Pd/ZrO2
Fig. 1. XRD patterns of CS, ZrO2, Pd/ZrO2, ZrO2CS and Pd/ZrO2CS. CS nanoparticles where Pd was dispersed over uniform ZrO2

Fig. 2. TEM images of ZrO2 (A), Pd/ZrO2 (B), ZrO2CS (C) and Pd/ZrO2CS (D).
7696 M.Y. Abdelaal, R.M. Mohamed / Ceramics International 40 (2014) 76937699

Table 1
ZrO2
The band gap energy of chitosan, ZrO2, chitosan/ZrO2, Pd/ZrO2, and Pd/ZrO2
Pd-chitosan/ZrO2, nanoparticles. ZrO2-Chitosan
Pd/ZrO2-Chitosan
Sample Baud gap energy (eV)

Chitosan

Intensity, a.u.
Pd/ZrO2chitosan 2.80
ZrO2chitosan 2.88
Pd/ZrO2 2.99
ZrO2 3.12

Pd/chitosan- ZrO2 350 400 450 500 550


0.8 Wavelength, nm
Chitosan- ZrO2
Pd/ZrO2 Fig. 4. Pl spectra of ZrO2, Pd/ZrO2, ZrO2CS and Pd/ZrO2CS.
ZrO2
0.6
spectra to understand the separation and recombination of the
photogenerated charges. Fig. 4 shows Pl spectra recorded for
F(R)

0.4 the excited samples at 265 nm at room temperature. The


emission wavelength of ZrO2 is different from those of Pd/
ZrO2, ZrO2CS, and Pd/ZrO2CS samples and Pl intensity
0.2 greatly increased in the following order: Pd/ZrO2 o ZrO2
CS o Pd/ZrO2CS. Pd plays as a trapping site to capture
photogenerated electrons from the conduction band and
0 separate the photogenerated electronhole pairs. It is generally
300 400 500 600 700 800 accepted that the inclusion of noble metal nanoparticles into
Wavelength (nm) semiconductor-based catalyst could enhance its light absorp-
Fig. 3. UVvis diffuse absorption spectra of ZrO2, Pd/ZrO2, ZrO2CS and Pd/
tion in the visible region leading to a red shift of the absorption
ZrO2CS. edge toward longer wavelengths. This indicates a decrease in
the band gap energy and that more photogenerated electrons
and holes could participate in the photocatalytic reactions. The
recombination mechanism or surface reactions of the photo-
nanoparticles. It reects the role of CS in the distribution generated charge carriers may be altered due to the modifying
uniformly of ZrO2 and Pd/ZrO2 nanoparticles. role of Pd as a noble metal on ZrO2 interface. This alteration
The optical absorption of a semiconductor is known as the would support activation of ZrO2 in the visible region. The
key factor in its photocatalytic activity which is related to its shift of the emission position could be attributed to the charge
electronic structure. The direct band gap energy for ZrO2, Pd/ transfer between Pd generated band and the conduction band
ZrO2, ZrO2CS, and Pd/ZrO2CS samples was calculated of ZrO2 as a semiconductor.
from the following Eq. (20 ) and shown in Table 1. The specic surface area (SBET) was 64, 45, 59, 40, and
E g 1239:8= 55 m2/g for CS, ZrO2, ZrO2CS, Pd/ZrO2, and Pd/ZrO2CS
nanoparticles, respectively. Besides, the total pore volume of
where Eg is the band gap (eV) and is the wavelength of the ZrO2 is higher than that of Pd/ZrO2 sample due to the partial
absorption edges (nm). blocking of pores by Pd metal deposition. SBET and St values
The band gap of pure ZrO2 sample was determined to be are mostly close to each other indicating the mesoporous
3.12 eV whose absorption edge suffered a red shift to a band nature of the photocatalyst. Table 2 presents the parameters of
gap of 2.99 eV after impregnation with Pd metal. However, the surface area and the data calculated from the t-plot.
absorption edge of ZrO2CS and Pd/ZrO2CS samples suf-
fered a great red shift to band gaps of Eg 2.88 and 2.80 eV, 3.2. Factors affecting the photocatalytic activity of thiophene
respectively. These results indicate a signicant improvement degradation
of the visible light absorption of ZrO2 samples by introduction
of Pd and CS species. Therefore, the modied impregnated 3.2.1. Effect of type of the photocatalyst
samples can be investigated for the visible light photocatalysis ZrO2, ZrO2CS, Pd/ZrO2, and Pd/ZrO2CS were used as
(Fig. 3). photocatalysts in the degradation of thiophene under visible
The transfer of the photogenerated electrons and holes in the light irradiation. The amount of the photocatalyst was 0.3 g
samples was studied with photoluminescence (Pl) emission used for 500 ml of 600 ppm of thiophene solution. The results
M.Y. Abdelaal, R.M. Mohamed / Ceramics International 40 (2014) 76937699 7697

Table 2
Texture parameters of chitosan, ZrO2, chitosan/ZrO2, Pd/ZrO2 and Pd-chitosan/ZrO2 nanoparticles.

Catalyst Systems SBET (m2/g) St (m2/g) Total VP (ml/g) r ()

Chitosan 64 66 0.810 34
ZrO2 45 47 0.680 39
Pd/ZrO2 40 43 0.640 42
Chitosan/ZrO2 59 60 0.750 35
Pd-Chitosan/ZrO2 55 57 0.710 38

(SBET) BET-Surface area.


(St) surface area derived from Vl  t plots.
(Vp) total pore volume.
(r  ) mean pore radius.

100
ZrO2
90 Pd/ZrO2
80 CS-ZrO2
Conversion of thiophene, %

Pd/CS-ZrO2
70

Intensity, a.u.
60

50

40

30

20

10

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
0 10 20 30 40 50 60 70 80 90 100 110 120 130
2-Theta
Reaction time, min

Fig. 5. Effect of catalyst type on the photocatalytic degradation of thiophene. 500

400

shown in Fig. 5 indicate that ZrO2 has almost no photocatalytic


activity under visible light irradiation where there is no 300
Intensity, a.u.

absorption for ZrO2 in the visible region but only in the UV


region. Besides, the photocatalytic activity increased in the
order of Pd/ZrO2 o ZrO2CS o Pd/ZrO2CS which is in an 200

agreement with XRD, TEM and the band gap measurements.


Hence, Pd/ZrO2CS has the highest photocatalytic activity 100
among the investigated catalysts in the photodegradation of
thiophene. 0
To examine the photoproducts, the gas was introduced into 5 10 15 20 25 30 35 40 45 50 55 60 65 70
0.2 M aqueous NaOH solution for further analysis. After 2-Theta
addition of 0.2 M aqueous Ba(NO3)2 solution, a white Fig. 6. (a) Is the XRD pattern of the precipitate 1. (b) Is the XRD pattern of the
precipitate was obtained and denoted as precipitate 1. The precipitate 2.
XRD pattern of the white precipitate shown in Fig. 6a was
assigned to BaCO3 which is in a good agreement with the
photocatalytic oxidation reaction according to the conversion
standard card of ICDD-PDF No. 05-0378. This result indicates
Eq. (3).
that thiophene can be photocatalytically oxidized to CO2 and
trapped in an aqueous NaOH solution. When precipitate 1 Thiophene photocatalyst-CO2 SO3 H2O (3)
was tried to be dissolved in aqueous HNO3, some white
precipitate could not be dissolved and denoted as precipitate 2.
XRD pattern of precipitate 2 can be readily assigned to BaSO4 3.2.2. Effect of amount of the photocatalyst
as shown in Fig. 6b which is in a good agreement with The amount of the photocatalyst was an important factor in
the standard card of ICDD-PDF No. 24-1035. This indicates the photocatalytic efciency of thiophene degradation under
that thiophene can be oxidized to CO2 and SO3 in the visible light irradiation. The amount of Pd/ZrO2CS ranged
7698 M.Y. Abdelaal, R.M. Mohamed / Ceramics International 40 (2014) 76937699

100 revealed a promising recyclability of Pd/ZrO2CS


90
photocatalyst.
80
Conversion of thiophene, %

70 Acknowledgements
60
This paper was funded by the Deanship of Scientic
50
0.3g/l Research (DSR), King Abdulaziz University, Jeddah, under
40 0.6g/l grant number 130-106-D1434. The authors, therefore,
0.9 g/l
30
acknowledge with thanks DSR technical and nancial support.
1.2 g/l
20
1.6 g/l

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