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Ceramics International 40 (2014) 76937699
www.elsevier.com/locate/ceramint
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.
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
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
Table 2
Texture parameters of chitosan, ZrO2, chitosan/ZrO2, Pd/ZrO2 and Pd-chitosan/ZrO2 nanoparticles.
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
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
400
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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