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Catalysis Today 230 (2014) 205213

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Catalysis Today
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Dual functionality of TiO2 -yash nanocomposites: Water vapor


adsorption and photocatalysis
A.N. kte a, , D. Karamanis b , D. Tuncel a
a
Department of Chemistry, Bogazici University, Bebek 34342, Istanbul, Turkey
b
Department of Environmental & Natural Resources Management, University of Ioannina, 30100 Agrinio, Greece

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

Article history: TiO2 nanoparticles were in situ supported on lignite y ash (TiO2 -FA) and investigated by several tech-
Received 21 June 2013 niques. X-ray diffraction (XRD) analysis supplied information about the generation of anatase phase.
Received in revised form 7 January 2014 Scanning electron microscopy (SEM) images with energy dispersive X-ray analysis (EDX) revealed varia-
Accepted 26 January 2014
tions in the surface morphology of raw FA after TiO2 loading. Nitrogen adsorptiondesorption isotherms
Available online 20 February 2014
(BET) isotherms indicated the formation of a mesoporous structure. X-ray photoelectron spectroscopy
(XPS) conrmed the buildup of TiO2 nanoparticles on the FA matrix with the form of Ti4+ oxidation state.
Keywords:
The optimum FA content of the composite was found as 88%. The supported nanocatalysts were tested
Supported catalysts
Photocatalysis
for water vapor adsorption towards evaporative cooling of hydrophilic surfaces and for decolorization
Methyl orange and degradation of methyl orange (MO) under UV irradiation. The mesoporous TiO2 -FA was found to be
Water vapor adsorption hydrophilic with capillary condensation in the water vapor adsorption isotherm. Dark adsorption exper-
iments followed pseudo-second order kinetics and Langmuir type of isotherms. Kinetics was discussed
in terms of LangmuirHinshelwood model. The repeatability of photocatalytic activity was also tested.
H2 O2 used as an electron scavenger accelerated decolorization and degradation of MO.
2014 Elsevier B.V. All rights reserved.

1. Introduction There are growing concerns about FA disposal problems. There-


fore, research is needed to develop new alternative environmental
Environmental pollution is an increasing problem of recent friendly applications. Immobilizing TiO2 on the surface of FA, and
decades due to rapid industrialization and population growth then using this supported catalyst system for the treatment pro-
throughout the world [1]. Among many technologies to deal cesses, may be a good attempt to solve the problems described
with this problem, heterogeneous photocatalysis is regarded as a above.
promising technology to degrade harmful pollutants to nal non- Furthermore, chemical pollution in the urban environment is
toxic products [2]. TiO2 is the most investigated catalyst for the strongly connected with thermal pollution or the so called heat
treatment of contaminated aqueous and gaseous streams because island effect (temperature increase within cities) [9]. This results in
of its high stability, non-toxicity and inexpensiveness [3]. However, detrimental conditions to human health and increased energy con-
poor adsorption capacity, formation of rapid aggregates in a sus- sumption due to higher demand for cooling. Among the effective
pension and also recycling difculties restricted the utilization of measures are the increase of the area of green tract land (rooftop
bare TiO2 . Therefore, in practical applications, attempts have been plants) or the surface area of water (articial lakes) [10]. However,
made to immobilize TiO2 on some adsorbent materials without loss the high real estate value of urban space limits the wide applica-
of activity. Among these materials, silica, alumina, activated carbon, bility of these methods. The application of the composite is not
zeolites, clays, MCM, layered hydroxides and glass are commonly restricted in buildings. In fact, the composite can be easily applied
used ones [46 and references therein]. Obviously, cost reduction in pavements as well in order to ght the thermal and chemical
with the selection of an abundant and inexpensive matrix with pollution. In this case, a storm event will produce dilute solutions
complementary adsorption properties is of primary importance. containing an array of dissolved organics deposited on concrete sur-
Fly ash (FA) is one of the solid wastes largely produced from faces [11]. Therefore, the medium for the photocatalytic processes
power generation. Currently, its applications are only limited to can be aqueous.
civil engineering including cement and brick production [7,8]. Recently, there has been a renewal interest in the application of
the passive and building integrated evaporative cooling (BIEC) as
an alternative and sustainable way to cool the surfaces of a build-
Corresponding author. Tel.: +90 212 359 7390; fax: +90 212 287 2467. ing or the pavement of outdoor areas. In the BIEC application of
E-mail address: okteayse@boun.edu.tr (A.N. kte). porous materials, stored water or night sorbed moisture inside the

0920-5861/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2014.01.031
206 A.N. kte et al. / Catalysis Today 230 (2014) 205213

pores are evaporated during the hot day and the porous surface ( = 1.54 A) operating at 40 kV and 40 mA and scanning rate
temperature is reduced due to the release of the latent heat [12]. of 2 min1 . The nitrogen adsorption/desorption isotherms were
Accordingly, TiO2 supported catalysts could produce a multifunc- obtained at 77 K by using Quantachrome Nova 2200e automated
tional composite with building application prospects of enhanced gas adsorption system. The specic surface areas were deter-
water vapor adsorption and surface solar evaporative cooling in mined by using multi-point BET analysis and the pores sizes were
addition to the degradation of pollutants. measured by the BJH method of adsorption. The surface mor-
Several researchers have investigated the degradation ability of phologies were determined by using scanning electron microscopy
the TiO2 loaded FA catalysts under certain preparation and reac- (SEM) in combination with energy dispersive X-ray analysis on
tion conditions [13,14]. Very recently, Visa et al. showed that the an ESEM-FEG/EDAX Philips XL-30 instrument operating at 20 kV
TiO2 /y ash composite can be used for the combined methyl- using catalyst powders supported on carbon tape. Si and Ti concen-
orange and cadmium simultaneous removal and also removal of trations in the composites were measured by the proton induced
heavy metals and surfactants [15,16]. However and to the best gamma ray emission (PIGE) technique at the Tandem accelerator of
of our knowledge, there are no articles in the scientic litera- the NCSR Demokritos. In X-ray photoelectron spectroscopy (XPS)
ture that present combined processes under sun irradiation with tests, Thermo Scientic K-Alpha X-ray Photoelectron Spectrom-
different and simultaneous utilization of the solar spectrum. In eter equipped with a hemispherical electron analyzer and Al K
the line of these studies, we have also examined ZnO loaded FA micro-focused monochromator was used. The areas of peaks were
systems [17]. The objective of this work is to extend the usage estimated by calculating the integral of each peak after subtracting
of TiO2 supported FA catalysts in bifunctional applications for a Shirley background and tting the experimental curve to a combi-
environmental and energy prospects, which to the best of our nation of Lorentzian/Gaussian lines. The UVvis diffuse reectance
knowledge has not been reported before. In this context, TiO2 spectra (UVvis DRS) of the FA, 0.25 M ZnO and all supported
nanoparticles were in situ synthesized on the FA matrix and char- catalysts obtained by using UVvis spectrophotometer (UV-2450,
acterized by several techniques. The materials were evaluated for Shimadzu) equipped with an integrating sphere reectance acces-
the moisture sorption on FA with or without TiO2 buildup. The sory. The baseline correction was done by BaSO4 . The spectra were
sorption isothermic process and kinetics were phenomenologically recorded in the range 200600 nm for the catalysts and the FA
described. Decolorization and degradation of methyl orange (MO) using BaSO4 as reference. Moisture sorption isotherms were deter-
was followed under UV illumination in the absence and presence mined by applying a modied version of the discontinuous method
of H2 O2 . ASTM E96-80. According to the method, samples were placed in
sealed desiccators with saturated salt solutions for controlling rel-
2. Experimental ative humidity while temperature was air-conditionally controlled
at 25 C and were periodically weighed. The moisture content was
2.1. Materials calculated as the difference of mass measurements in different time
periods and the initial dry state.
Fresh lignite by-product of y ash, coded FA, was obtained
from the major lignite power plant of Agios Dimitrios, Greece
2.4. Photocatalytic experiments
(1595 MW). It was collected in a dry state from the electrostatic
precipitators of the power station, ground by hand, sieved to a frag-
MO, selected as the probe molecule, is produced as a carcino-
ment size less than 200 m and used without any pretreatment
genic compound in the concentration range of 32.70.327 mg L1
in the experiments. The major constituents were SiO2 (42.82%),
[19,20]. Thus, the 3.27 mg L1 was used in our experiments unless
Al2 O3 (20.82%), Fe2 O3 (4.57%), CaO (23.45%), MgO (1.74%), K2 O
concentration effect of MO was tested. Reaction systems were set-
(1.31%), TiO2 (1.47%), Na2 O (0.32%), ZnO (0.01%). According to ASTM
up by adding 0.2 g of catalysts into 200 mL of MO in a pyrex ask,
C 618 standard, this FA was C type due to the quantity of CaO
with an inlet for the air circulation and an outlet for the collection
(more than 10% with 23.45%) and the sum of SiO2 , Al2 O3 , Fe2 O3
of aliquots, was used for all experiments. The ask was located in
(more than 50% with a total of 70.48%). Degussa P-25 (TiO2 ) was a
an irradiation box, equipped with eight black light lamps (Philips
generous gift from Degussa Ltd. Titanium tetraisopropoxide (98%,
TL 15 W/5BLB) of 320440 nm and cooled by a fan. The lamps were
Aldrich), acetic acid (96%, Merck), methyl orange (Merck), H2 O2
positioned to surround the ask with an incident photon ux of
(30%, Merck), were used as provided by the suppliers without fur-
4.7 1015 photons/s. Prior to illumination, to ensure the equilib-
ther purication.
rium of adsorption process, suspensions were magnetically stirred
in the dark for 30 min. UVvis spectrophotometer (UV-2450, Shi-
2.2. Preparation of the photocatalysts
madzu) was used to monitor the absorbance spectra of MO as a
function of illumination time. The decrease of the band at 274 nm
TiO2 was prepared using a solgel method [18]. Briey, 20 mL of
indicated degradation of MOs aromatic moiety while the one at
titanium tetraisopropoxide was added gradually to 80 wt% acetic
464 nm was followed for the decolorization of MO solution. The
acid solution under continuous stirring for 2 h at 50 C to pro-
natural pH of FA in water was 11 due to its alkaline nature. All
duce a transparent sol. Depending on the loading of TiO2 on
experiments were performed at room temperature and at pH 8.5
the support, requisite amount of titania-sol was added to the
(3.27 mg L1 MO in the presence of 25% TiO2 -FA) without con-
aqueous suspension of the FA (initially 2 g in water for 2 h).
cerning the degradation intermediates. Also, measurements were
After agitation and extensive washings, the catalysts were dried,
conducted at least twice and the average value was recorded. The
calcinated at 500 C and ground into ne powder with 10% TiO2 -
degradation and decolorization rate percentages of MO were cal-
FA, 25% TiO2 -FA and 40% TiO2 -FA labels. 25% TiO2 was also
culated by the following equation:
prepared by using the above procedure in the absence of the sup-
port. C0 C
Degradation (or decolorization)% = 100 (1)
C0
2.3. Characterization techniques
where C0 is the initial concentration of MO and C is the concentra-
The X-ray powder diffraction (XRD) analysis were recorded tion of MO after t minutes UV irradiation. For the experiments
on a Rigaku-D/MAX-Ultima diffractometer using Cu K radiation conducted in the presence of H2 O2 (used as an electron scavenger),
A.N. kte et al. / Catalysis Today 230 (2014) 205213 207

Fig. 1. (A) XRD patterns of FA and supported catalysts (A: Anatase). (B) SEM and mapping images of FA and 40% TiO2 -FA. (C) Nitrogen adsorption/desorption isotherms and
(D) pores size distribution plots of FA, 10% TiO2 -FA, 25% TiO2 -FA and 40% TiO2 -FA.

10 mM H2 O2 concentration was added to the supported catalyst- 3.1.2. SEM (EDX-mapping) analysis
MO solution before UV irradiation. In SEM images, the FA shows spherical and non-shaped particles
(Fig. 1B). The EDX analysis demonstrates Si, Al and Ca as major, Mg,
K, Ti and Fe as the minor constituents of the support (not shown).
3. Results and discussion
The Ti percentages are found as 0.2% and 0.4% in the bulk and on
the sphere of the FA, respectively. For 40% TiO2 -FA, the appearance
3.1. Characterization of catalysts
differs with the formation of smooth layers on top of the aggre-
gates (40% TiO2 -FA-a and 40% TiO2 -FA-b). The EDX-spot analysis
3.1.1. XRD analysis
displays signicant increments in the Ti percentages; 21.3% on the
XRD patterns of raw FA and the supported catalysts are shown
sphere 1 and 53.3% on the aggregate 2 . This is also illustrated
at both low-angle (2 < 10 ) and high-angle (20 < 2 < 60 ) ranges
in Ti mappings where Ti signal dominated on top of the sphere
(Fig. 1A). The crystallinity of TiO2 nanoparticles is very low in the
and the bright-edged agglomerate. The optimum FA content of the
presence of 10% TiO2 -FA. However, anatase diffractions of d 101,
TiO2 -FA composite was evaluated as the average of EDX spot mea-
d 200, d 105 and d 211 at 25.4 , 48.2 , 54.2 and 55.3 (2) are
surements and proton induced gamma ray emission (PIGE) bulk
detected in the patterns of 25% TiO2 -FA and 40% TiO2 -FA with wider
measurements and was found 88%.
and lower intensities. The signals are not intensied for the 40%
TiO2 -FA, indicating the existence of a saturation effect at the 25%
TiO2 loading. Rutile phase does not form in the synthesis of the 3.1.3. Nitrogen adsorption isotherms
supported catalysts, as evidenced by the peak absence at 27.4 (2). Nitrogen adsorptiondesorption isotherms and pore size distri-
The crystalline sizes (DTiO2 ) calculated by using Scherrers equation butions are shown in Fig. 1C and D, respectively. The FA reveals
for the broadening of (1 0 1) anatase peak reection, was found as Type II isotherms, specic of non-porous materials. Isotherms
15.1 nm (for 25% TiO2 -FA) and 18.1 nm (40% TiO2 -FA) (Table 1). of the supported nanocatalysts follow Type IV sorption behavior
Although TiO2 nanoparticles do not show a signicant difference in [21]. It is associated with capillary condensation taking place in
dimensions, the decrements in the reections of the raw support the mesopores at P/P0 [22,23]. The pore size distribution curves
suggest their uniform distribution throughout the surface and bulk. display that the pores of the supported catalysts are in typical
208 A.N. kte et al. / Catalysis Today 230 (2014) 205213

Table 1
Binding energy (eV) values and atomic number ratios.

Catalysts Ti O 1s
Ti 2p3/2 Ti 2p1/2 Ti 2p1/22p3/2 splitting (eV) Bulk O2 OH SiOTi Ti 2p3/2 to 2p1/2 Ti/O

TiO2 (Degussa P25) 458.59 464.27 5.68 529.86 2 0.44


25% TiO2 458.59 464.21 5.62 529.80 2.1 0.43
25% TiO2 -FA 458.59 464.29 5.70 529.76 531.35 532.94 2.1 0.15
FA 529.11 531.34 532.78

mesoporous region of 2040 A (Fig. 1D). The supported nanocata- (TiO2 -Degussa P25) corroborate the indication for the creation of
lysts indicate higher pore volumes (0.019 cm3 g1 for 10% TiO2 -FA, TiOSi bond.
0.048 cm3 g1 for 25% TiO2 -FA, 0.061 cm3 g1 for 40% TiO2 -FA) The atomic number ratio of Ti 2p3/2 to 2p1/2 is found to be 2 for
than that of the FA (0.009 cm3 g1 ). This results in bigger surface TiO2 (Degussa P25). The similar ratios obtained in the presence of
areas (15.97 m2 g1 for 10% TiO2 -FA, 29.64 m2 g1 for 25% TiO2 - 25% TiO2 (2.1) and 25% TiO2 -FA (2.1) demonstrate successful cre-
FA, 37.84 m2 g1 for 40% TiO2 -FA) in comparison to the area of ation of TiO2 nanoparticles in the synthesized materials. The ratios
the FA (5.61 m2 g1 ). The transformation of FA structure into a of Ti to O (based on Scoeld photoionization cross sections of the
mesoporous adsorber with in situ growth of TiO2 nanoparticles core level photoelectrons) are found as 0.44 (TiO2 (Degussa P25))
is expected to extend the energy and environmental application and 0.43 (25% TiO2) , which are close to that expected from the stoi-
prospects of the coal residues. The increased adsorbent surface area chiometry of TiO2 [36]. However, TiO2 loading on the surface of the
and thus, the availability of more adsorption sites are expected to FA decreases the ratio of Ti to O (0.15), due to the higher oxygen
induce an improved-and combined- moisture sorption character content of the whole matrix in the presence of FA.
and decomposition ability of the supported catalysts. These prop-
erties are discussed in the following sections thorough enhanced 3.1.5. UVvis DRS analysis
capillary condensation in the water vapor adsorption isotherms and UVvis absorption spectroscopies of the raw FA, 25% TiO2 and
decolorization-degradation of MO pollutant. the supported are presented in Fig. 3. The support shows an absorp-
tion tail in between 200 and 600 nm. The characteristic absorption
edge of the TiO2 is not observable in the supported catalysts
3.1.4. XPS analysis
even with 40% TiO2 loading. Instead, they resemble mostly to the
XPS analysis was performed on the raw FA, TiO2 (Degussa P-
absorption spectra of the FA and the proles extend to the longer
25), 25% TiO2 and 25% TiO2 -FA (Fig. 2). Binding energy shifts are
wavelength regions. The masking role of the support, however,
observed in all samples and hence, the instrument is calibrated
does not affect the performances of the supported catalysts under
using the carbon peak (C-1s) at 285 eV as in the other studies
UV irradiation, i.e., efcient decolorization and degradation rates
[24,25]. Survey spectrum of 25% TiO2 -FA contains Ti 2p and O 1s
are noticeable due the higher surface areas and larger pore vol-
peaks (Fig. 2a). TiO2 (Degussa P-25) was used as a reference for the
umes. Meanwhile, visible light activity is not expected to be high
25% TiO2 and 25% TiO2 -FA catalysts. Fig. 2b displays a doublet corre-
for the supported catalysts. Modications in the proles seem to
sponding to Ti 2p3/2 and 2p1/2 core levels for TiO2 (Degussa P-25),
be little higher than the sum of the absorbances of FA and TiO2 ,
25% TiO2 and 25% TiO2 -FA. The peak positions and also the peak
indicating minor alteration in the crystal structure of the photo-
separations of Ti 2p3/2 and 2p1/2 for 25% TiO2 and 25% TiO2 -FA
catalytically active TiO2 in order to justify a high absorbance in the
are quite similar to that of TiO2 (Degussa P-25) (Table 1), indicat-
visible range.
ing the presence of a single oxidation state of Ti (Ti4+ ), typical of
Ti in the TiO2 lattice. The values are also in good agreement with
that of TiO2 (anatase) [2628]. The O 1s signal for TiO2 (Degussa 3.2. Adsorption and photocatalytic applications
P-25) and 25% TiO2 shows a well resolved bulk oxide (O2 ) peak at
529.86 and 529.80 eV, respectively (Fig. 2c). Similar binding energy 3.2.1. Kinetics and Isotherms of water vapor sorption
values of the bulk oxide were reported in the studies of Riakar et al. A typical water vapor sorption kinetics at 62% RH of the TiO2 -FA
[29] and Simmons et al. [30]. The O 1s spectra of the FA and 25% sample is shown in Fig. 4a. The pseudo-rst-order rate equation was
TiO2 -FA appear with wider and asymmetric peaks (Fig. 2c). For the used to describe the water vapor sorption kinetics on the prepared
raw FA, the O 1s signal is deconvoluted by three subspectral com- catalysts. The tting parameters of the rate constant k1 (min) and
ponents of MgO and TiO2 (529.11 eV, 17.8% spectral area), CaO and the equilibrium capacity wo (g/g) 25% TiO2 -FA for 62% RH were
Al2 O3 (531.34 eV, 46.1% spectral area) and SiO2 (532.78 eV, 36.1% determined as 7 h and 0.14 g g1 , respectively.
spectral area) components of the FA [31,32]. Although the O 1s sig- The hydrophilicity of the supported nanocatalysts was inves-
nal for 25% TiO2 -FA also posseses three components, they differ in tigated by the water vapor adsorption isotherms. From very low
their constituents in comparison to those noticed in the FA. The relative humidity, the water vapor adsorption of 25% TiO2 -FA is
peak at 529.76 eV with 33% of total oxygen is attributed to oxide higher than the raw FA and the differences increase with increas-
(O2 ) in the TiO2 lattice. The secondary peak at 531.35 eV with 40% ing relative humidity (Fig. 4b). The equilibrium adsorption of
of total oxygen is assigned to hydroxyl (OH) species on the sur- water vapor on the FA exhibits a Type III isotherm indicating the
face. The difference between the binding energies of the OH and hydrophobicity of the material with chemisorption rather than
O2 species is found as 1.59 eV, which is close to the reported dif- physisorption and monolayer sorption even at high relative pres-
ferences of 1.241.8 eV (Table 1) [33 and references therein]. The sure. In contrast, water vapor isotherms of the 25% TiO2 -FA show
third component at 532.94 eV with 27% of total oxygen is attributed a Type V behavior due to the transformation of the hydrophobic
to the formation of TiOSi bond. The electron density around the y ash to a hydrophilic mesoporous form with capillary con-
Ti atoms decreases due to the greater electronegativity of Si via O densation at high relative humidity. Similar to activated carbon,
bonded to Ti. Thus, an increase in the binding energy (about 0.5 eV) water vapor adsorption on TiO2 supported FA preferentially occurs
is expected in comparison to SiO2 (532.5 eV) [3335]. Moreover, the in low hydrophilic sites at low relative pressures. The mono-
shift in the Ti 2p1/2 signal to 464.29 eV in the presence of the sup- layer formation is followed by multilayer sorption (at relatively
ported nanocatalyst relative to 464.21 eV (25% TiO2 ) and 464.27 eV higher pressures) and nally by capillary condensation (at the more
A.N. kte et al. / Catalysis Today 230 (2014) 205213 209

Fig. 3. UVvis DRS spectra of FA, 25% TiO2 , 10% TiO2 -FA, 25% TiO2 -FA and 40% TiO2 -
FA.

porous active sites that are created upon TiO2 build up on the FA
cenospheres).
Furthermore, a logistic function of the form
wo
w= (2)
1 + exp[k(b (p/po ))]
was tted to the experimental results. Eq. (2) exhibits a S-shape
behavior with an inection point b around 0.6, 0.22 g g1 for wo
and k equals to 8.85.
Therefore, 25% TiO2 -FA catalyst exhibits high water vapor
adsorption at RH higher than 50% and can be also used as a thermo-
responsive and solar cooling material for the utilization of the
water vapor absorption resonances and continuum in the visible
and infrared part of the solar radiation spectrum in addition to the
photodegradation applications.

3.2.2. Dark adsorption experiments


Results of experiments performed in the dark are shown in Fig.
S1a. MO percentages remaining in the solution are found as 85.5%
at 464 nm and 91.2% at 274 nm in the presence of only FA. However,
25% TiO2 -FA exhibits lower percentages (77% at 464 nm and 80% at
274 nm), demonstrating a better adsorption capacity in compari-
son to the support. After 30 min mixing in the dark, no signicant
change in the MO percentages is noticed.
The color of MO is yellow and its natural pH in water is 5.85.
Accordingly, MO is negatively charged in water solution due to
its pKa value of 3.4 [37]. The alkaline character of FA neutralizes
the acidic pH of the MO (pHFA+MO solution 11). Thus, repulsive forces
seem to be dominant among the FA surface and MO molecules (in
the anionic form). However, heterogeneity on the surface of the
FA, the existence of minor amounts of Fe2 O3 , TiO2 , ZnO within
the structure and also the pores (though they have very restricted
volumes) may create a kind of weak interaction with the MO
molecules. This results in decolorization, however, due to the dom-
inant grayish color of the FA cannot be visualized, instead can
be followed by the decrease in the absorption band at 464 nm.
Fig. 2. (a) XPS survey analysis of 25% TiO2 -FA, (b) Ti 2p XPS spectra of TiO2 (Degussa Moreover, the interaction may also vary the conjugation in the ben-
P25), 25% TiO2 and 25% TiO2 -FA, (c) O 1s XPS spectra of FA, 25% TiO2 -FA, 25% TiO2 zenic rings through the chromophore ( N N ) and resulting in
TiO2 (Degussa P25).
the limited decrement of the 274 nm band. For 25% TiO2 -FA, the
pH of solution with 3.27 mg L1 MO is 8.5, indicating a reduction
in the alkalinity of the FA solution. As a consequence, alteration
in the charge nature of the supported catalyst is expected with a
stronger adsorption effect of TiO2 nanoparticles. This may again
induces damage within the localized conjugation of the MO skele-
ton being responsible from the decrease in the 274 nm peak during
210 A.N. kte et al. / Catalysis Today 230 (2014) 205213

Fig. 4. Water vapor adsorption (a) kinetics of 25% TiO2 -FA and (b) isotherms of FA and 25% TiO2 -FA at 25 C.

the dark period. Additionally, the higher surface area and the larger where qmax (mmol g1 ) is the maximum capacity of the adsorbent
pore volume of the supported catalyst increase adsorption of MO and KL (L mmol1 ) is the Langmuir adsorption constant. The lin-
and results in lower decolorization percentages in comparison to earity obtained in the plots of Ce /qe versus Ce for both degradation
that of FA alone. and decolorization processes results in 0.9653 and 0.9981 correla-
For the adsorption details, the pseudo-second order equation in tion coefcients, respectively (Fig. S1e and f). From the slope of the
the integrated form is applied for 3.27 mg L1 (0.01 mmol L1 ) MO lines, Langmuir adsorption capacities are calculated as 0.015 and
on the 25% TiO2 -FA (Eq. (3)) 1.24 mg g1 for degradation and decolorization processes, respec-
  tively. 25% TiO2 -FA catalyst.
t 1 t Since higher coefcients are obtained with the Langmuir model,
= + (3)
qt k2 q2e qe it can be suggested that the adsorption sites are identical, energet-
ically equivalent and the adsorption process occurs through the
where qt (mmol g1 ) is the amount of adsorbed MO per gram of same mechanism for a monolayer adsorption at the maximum
adsorbent at time t (min), qe (mmol g1 ) the amount of adsorbed amount of adsorption. The adsorption of several dye molecules
MO per gram of adsorbent at equilibrium and k2 is the pseudo- reported in literature previously obey the Langmuir sorption
second order rate constant (min) [38,39]. The linearity obtained isotherm model [40] and our results also seem to be in agreement
in the plot of t/qt versus t results in 0.9674 (for degradation) and with this trend. The Langmuir model suggests that dye molecules
0.9763 (for decolorization) correlation coefcients (Fig. S1b). Thus, are adsorbed uniformly and that the TiO2 -FA materials are fairly
it is suggested that the adsorption is well consistent with the homogenous with the titania phase well dispersed in the FA matrix
applied kinetics. [40].
Adsorption isotherms are analysed in order to investigate the
interactions of adsorbate molecules with the adsorbent surface.
Due to their simplicity and their validity in a wide range of concen- 3.2.3. Photocatalytic activity under UV irradiation, kinetics and
tration, the Langmuir and Freundlich models are correlated to our reuse properties
experimental results to investigate the effect of surface heterogene- Photodegradation experiments were performed with the cat-
ity and sites of different afnity for MO adsorption on the supported alysts of different TiO2 contents (Fig. 5a). The percentages of MO
catalyst. The isotherm models are employed at ve different initial remaining in solution following the decolorization processes are
concentrations of MO (16.3, 8.17, 4.91, 3.27 and 1.62 mg L1 ). The found to be much lower than that of the degradation processes since
linearized form of the Freundlich isotherm is given by Eq. (4). it is more difcult to destroy the aromatic moiety of the substrate.
The best activity is noticed in the presence of 40% TiO2 -FA cata-
ln qe = ln KF + bF ln Ce (4)
lyst with the lowest MO remaining percentages (30.5% at 464 nm
where KF is the Freundlich constant, bF the adsorption intensity and 63.3% at 274 nm) in solution. Decrements in the TiO2 contents
constant and Ce is the concentration of MO at equilibrium. The line lower the performances of the catalysts.
ttings of ln qe versus ln Ce plot give 0.9395 (for degradation) and The 25% TiO2 -FA catalyst was further used to analyze the rate
0.8149 (for decolorization) correlation coefcients (Fig S1c and d). of reactions in the initial concentration range of MO from 16.3 to
The form of Langmuir isotherm is as follows 3.27 mg L1 . Pseudo-rst-order kinetics is conrmed by the lin-
earity in the plot of ln(C0 /C) versus t, where C0 is taken as the
Ce Ce 1 equilibrium concentration of MO (mg L1 ) after dark adsorption
= + (5)
qe qmax qmax KL and C is the concentration of MO at time t. The rate-constants
A.N. kte et al. / Catalysis Today 230 (2014) 205213 211

Fig. 5. (a) Photocatalytic activity of the supported catalysts under UV irradiation, (b) kinetic analysis and (c) reuse properties of 25% TiO2 -FA.

of decolorization (or degradation) processes (k, min1 ) calculated underlying the photocatalytic reaction route, as a rst step, photo-
from the slopes of the lines in the same plot decrease with increas- lysis of MO is controlled and a negligible decolorization (about 4%)
ing concentration of MO (from 0.0026 (3.27 mg L1 ) to 0.0009 is found (Fig. 6a). This is consistent with the results of Yu et al. [47]
(16.3 mg L1 ) for decolorization and from 0.0016 (3.27 mg L1 ) to and Dvininov et al. [48]. Their comments for the stability of MO
0.0008 min1 (16.3 mg L1 ) for degradation). This can be a result toward light lies in the fact that in the absence of TiO2 catalyst, all
of blocking of the photocatalytically active sites on the supported the excited electrons return to the ground state in nanoseconds.
catalyst and reducing the interaction of photons with these sites. A series of comparative tests are then, conducted by employing
LangmuirHinshelwood model was also used to express the an electron scavenger, H2 O2 , under UV irradiation in the absence
kinetics by the following rearranged form [41]. and in the presence of the supported catalysts (Fig. 6a and b). The
concentration of H2 O2 in all experiments is kept constant as 10 mM
1 1 1
= + (6) since higher concentrations are known to consume photogenerated
R kKC k holes and hydroxyl radicals [49,50].
where R is the rate of decolorization (or degradation), K the adsorp- H2 O2 shows a stronger electron trapping property than O2 and it
tion coefcient of MO onto the 25% TiO2 -FA catalyst (L mg1 ) and improves the system efciency mainly by the formation of hydroxyl
k is the reaction rate constant (mg L1 min1 ). The linearity in the radicals (Eq. (7)) [4951].
plot of reciprocal of rate (1/R) against reciprocal of initial MO con-
H2 O2 + e OH + OH (7)
centration (1/C0 ) (Fig. 5b) proves the validity of the model for our
supported catalyst system. The values of K and k are found to The existence of H2 O2 in the solution decreases the remaining
be 0.788 L mg1 and 0.0237 mg L1 min1 (for decolorization) and MO percentage to 79% in 30 min irradiation time (Fig. 6a). Exten-
0.215 L mg1 and 0.0163 mg L1 min1 (for degradation). sion of the irradiation period does not induce further decrements,
For the each run of the recycling experiments the 25% TiO2 -FA is indicating that the excitation of MO is limited under the UV light.
ltrated, washed and calcined at 500 C for 2 h. After four cycles, the However, in the presence of the supported catalysts, MO percent-
percentage of MO remaining in solution is found to increase only ages decrease rapidly within one hour irradiation time (Fig. 6b).
approximately 2.5% (from 50.4% to 53% for decolorization process) Thus, the pronounced activity in the TiO2 -FA and H2 O2 systems
and 4.68% (from 72.3% to 77% for degradation process) (Fig. 5c). mostly depends on the activation of TiO2 nanoparticles under UV
These results indicate that the photocatalytic activity of 25% TiO2 - irradiation (Eq. (8)).
FA has repeatability. The insignicant loss of photoactivity can be
+
explained either by the presence of reaction by-products adsorbed TiO2 + h(UV) eCB + hVB (8)
on the photocatalyst after the rst run or by the loss of the photo-
catalysts during each collection and rinsing steps. For the efciency of the process, inhibition of electronhole pair
recombination is required. At this stage, H2 O2 traps the electrons
mostly from the conduction band of the TiO2 , increasing the num-
3.2.4. Effect of H2 O2 addition under UV irradiation
ber of hydroxyl radicals in the reaction media (Eq. (7)where e
Dye pollutants were also referred as antenna molecules [4245].
should be changed to eCB ). In the meantime, the limited number
After adsorption on the surface of semiconductors (like TiO2 ), they
of electrons produced with the direct excitation of MO molecules
are able to absorb visible light and inject electrons into the con-
can also be inactivated by H2 O2 molecules. This enhances the direct
duction band of TiO2 . Thus, the oxidized antenna molecules induce
(Eq. (9)) and/or indirect (Eqs. (10) and (11)) oxidation of MO with
charge separation, widen the photoresponse of TiO2 from UV to the
the valence band holes (hVB + ) via hydroxyl radicals (Eq. (12)).
visible region and create a unique route to use visible light from
+
the sun [46]. Since MO shows absorption in the emission spectrum h+ + MO MO MO (decolorization and degradation) (9)
of the lamps, a question arises; whether it behaves as an antenna
molecule or not? In order to provide more insight to the mechanism h+ + H2 O OH + H+ (10)
212 A.N. kte et al. / Catalysis Today 230 (2014) 205213

The efciency of H2 O2 can also be ascribed for the formation


of hydroxyl radicals by homolytic cleavage of the bonds into two
hydroxyl groups (Eq. (13)) [49,50].

H2 O2 + h OH + OH (13)

However, since MO decolorization is not accelerated only in the


presence of H2 O2 after 30 min irradiation (Fig. 6a), this route of
hydroxyl radical generation and their subsequent attack cannot be
considered for the destruction of the MO moiety.

4. Conclusion

A supported nano-catalyst has been prepared by the buildup of


TiO2 nanoparticles on the cenospheres and bulk surfaces of the FA
(with an optimum value of 88%). This material shows bifunctional
properties with adsorption capability in addition to photocat-
alytic activity. Enhanced adsorption of MO and water vapor on
the supported catalysts are detected. By extensive characteriza-
tion techniques, the pronounced performance was attributed to
the transformation of FA to a mesoporous structure. Improved
photocatalytic efciencies were obtained by the application of the
supported nano-catalysts. Combined with the water vapor adsorp-
tion and the utilization of the IR part of the solar spectrum open
up new opportunities and widens the application prospects of the
prepared nanocatalysts.

Acknowledgements

This study was supported by the framework of the Joint


Research and Technology Programmes 20112013 between Greece
(General Secretariat for Research and Technology and European
Regional Development Fund, GSRT 10 TUR/1-25-1) and Turkey
(TUBITAK, 209T109) and also Bogazici University Research Foun-
dation (Project No. 11B05P4).

Appendix A. Supplementary data

Supplementary material related to this article can be found,


in the online version, at http://dx.doi.org/10.1016/j.cattod.
2014.01.031.

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