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Author(s): Florica Manea
Article title: TiO2 nanostructured carbon composite sorbent/photocatalyst for humic acid removal from
water
Article no: TDWT 1062433
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1 Corina Orha
2 Florica Manea
3 Aniela Pop
4 Cornelia Bandas
5 Carmen Lazau
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AQ1 Please provide department for affiliation for b.


AQ2 Would you consider changing the title TiO2 nanostructured carbon composite sor-
bent/photocatalyst for humic acid removal from water to TiO2-nanostructured carbon
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correct if necessary.
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in-text citation or provide full reference details.
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TDWT 1062433 CE: HN QA: AM
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Desalination and Water Treatment XX (2015) XXXX


www.deswater.com XXXX

doi: 10.1080/19443994.2015.1062433

TiO2 nanostructured carbon composite sorbent/photocatalyst for humic acid


AQ2 removal from water

Corina Orhaa, Florica Maneab,*, Aniela Popb, Cornelia Bandasa, Carmen Lazaua
a
Condensed Matter Department, National Institute for Research and Development in Electrochemistry and Condensed Matter,
5 Timisoara, P. Andronescu no. 1, 300254 Timisoara, Romania, emails: haiduccorina@yahoo.com (C. Orha),
cornelia.bandas@gmail.com (C. Bandas), carmen.lazau@gmail.com (C. Lazau)
b
Politehnica University of Timisoara, V. Parvan Bd., no. 6, Timisoara 300223, Romania, Tel. +40 256/403071;
AQ1 Fax: +40 256/403069; emails: florica.manea@upt.ro (F. Manea), aniela.pop@upt.ro (A. Pop)
Received 3 March 2015; Accepted 9 June 2015

10

ABSTRACT

In this study, two types of nanostructured carbonTiO2 within epoxy matrix, i.e. carbon nan-
15 otubes-TiO2-Epoxy (CNT-TiO2-Epoxy) and carbon nanofiber-TiO2-Epoxy (CNF-TiO2-Epoxy)
have been prepared, characterized and tested as sorbent and photocatalysts for humic acids
(HAs) removal from water envisaging advanced drinking water treatment. The HA adsorp-
tion capacities of CNT-TiO2-Epoxy of 8.68 mg g1 and CNF-TiO2-Epoxy of 7.14 mg g1 were
determined using Freundlich isotherm and pseudo-second-order kinetics model. Also, the
20 photocatalytic activities of both composites were assessed in terms of HA degradation effi-
ciency and rate constant and an enhancement effect was found for CNT-TiO2-Epoxy com-
posite for HA removal. CNF-TiO2-Epoxy photocatalytic performance was worse vs. simple
TiO2 traditional catalyst in terms of degradation efficiency, but five times faster from the
kinetics point of view. The lifetime and the regeneration pathway by the photocatalysis
25 were assessed for CNT-TiO2-Epoxy composite system in comparison with the sorption
applications. A HA removal efficiency of 43.8% was found by photocatalysis vs. 30.2%
reached by the sorption after successive five running. A regeneration degree of about 25%
was achieved under the similar conditions of photocatalysis without HA presence.

Keywords: Carbon materials; Titanium dioxide; Humic acid; Sorption; Photocatalysis


30

1. Introduction treatment due to their diverse reactivity and abun-


dance in natural waters [3]. 40
Natural organic matters (NOM) in the surface
Chlorination, the most widely used disinfection
water derived from the degradation of plants and
technique to destroy pathogens in drinking water
35 micro-organisms. Humic acids (HAs) represent a large
could lead to the formation of trihalomethanes and
portion of NOM present in most surface water used
other toxic by-products in the presence of NOM, and
for drinking [1] and also, in sediments and soils [2].
this aspect represents one of most important reason 45
Removal of HAs has long been of concern in water
for NOM removal from water [4]. Also, presence of
NOM in drinking water source is responsible for
membrane fouling in ultra- or nano-filtration steps of
*Corresponding author.

1944-3994/1944-3986 2015 Balaban Desalination Publications. All rights reserved.


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2 C. Orha et al. / Desalination and Water Treatment XX (2015) XXXXXX

the drinking water treatment technology. For this rea- Even if much progress has been made recently, in
5 son, numerous approaches have been investigated for adsorption and photocatalysis applications of CNTs
the development of cheaper and more effective materi- and CNT-TiO2 [11], however, there is still a lot of 60
als characterized by advanced properties suitable for works to do to enhance its performance in water treat-
the adsorption and photocatalysis applications in the ment. Several drawbacks must be taken into con-
water treatment. Various carbonaceous materials, e.g. siderations: (a) the aggregation of CNTs in aqueous
10 activated carbon [5], carbon nanotubes (CNTs) [6] and solution limits the available sites for the adsorption of
carbon nanofibers (CNFs) [7] have been intensively the pollutants; (b) the small size of CNTs makes them 65
tested as sorbents, composite filters, antifouling mem- to be difficult to separate from aqueous solutions and
branes and photocalysis processes [810]. Moreover, energy-consuming methods are required, e.g. ultracen-
CNTs have been demonstrated as excellent catalyst trifugation and membrane filtration. In this context,
15 support and as building block in hybrid catalyst to CNFs are considered as alternative for CNTs because
improve the photocatalysis performance of the they possess similar adsorptive and electron proper- 70
traditional photocatalyst, such as TiO2 [11]. ties and are cheaper and easier to manipulate [32].
Carbon nanomaterials have been used as a support The aim of this work is to investigate compara-
for the dispersion of the functional materials in order tively the performances of two types of compos-
20 to give them additional functional properties, such as: ite materials, e.g. carbon nanofiber-TiO2-Epoxy (CNF-
structure, surface area, activity and conductivity. Car- TiO2-Epoxy) and carbon nanotubes-TiO2-Epoxy 75
bon particles have been used for the photocatalytic (CNT-TiO2-Epoxy) for adsorption and photocatalytic
composite for many purposes, e.g. adsorbent agents, degradation of HAs from water envisaging drinking
dispersants for avoiding photocatalyst agglomeration water treatment improvement. The main idea is to use
25 and increment of the effective surface area [12,13]. a simple, cheap and efficient method for the prepara-
Nanostructured carbon composite materials are used tion of a composite system that achieves a good disper- 80
for interesting applications in many fields due to their sion of nanostructured carbon and TiO2 nanoparticles
unique properties compared to bulk material and have allowing their easy separation after the practical
been the subjects of numerous studies [1416]. application in water treatment technology. Two
30 Composite materials containing carbon and TiO2 approaches regarding CNT/CNF-TiO2 composite are
have been tested for many applications, e.g. treatment considered, the first is linked to the effect of TiO2 on 85
of contaminated water and air by the heterogeneous adsorption process of HA involving the regeneration
photocatalysis, hydrogen evolution, CO2 photoreduc- of fouled adsorbent. The second approach is regarded
tion, dye sensitized solar cells and sensor devices [17], to the photocatalytic activity of these composites that
35 exhibiting cooperative and synergetic effects between should be enhanced vs. TiO2 because of the potential
the metal oxides and carbon phases. Some recent effect of CNT/CNF to retard the electronhole pair 90
works have emphasized on the preparation of these recombination [33]. A potential synergic effect
new hybrid materials and a few examples are reported between nanostructured carbon and TiO2 related to the
[1821]. These composite materials have been fabri- photocatalytic activity is confirmed in this study.
40 cated by a range of different methods, including
mechanical mixing of TiO2 and carbon materials [22],
solgel synthesis of TiO2 in the presence of carbon 2. Experimental
AQ3 [23], electro-spinning methods [24,25], electrophoretic
2.1. Materials and composite materials preparation 95
deposition [26] and chemical vapour deposition [27].
45 Titanium dioxide is a traditional inexpensive photo- Multiwall CNTs and CNF were purchased from
catalyst material using UV irradiation to degrade envi- Nanocyl, Belgium (Belgium Nanocyl, Sambreville,
ronmental pollutants from industrial wastewater Belgium) and respective, from Sigma-Aldrich, St.
owing to its ability to convert them into innocuous Louis, USA. CNT are characterized by high specific
end products such as CO2 [12,2830]. surface area of 500 m2 g1 vs. 6575 m2 g1 for CNF. 100
50 The mixture of titanium dioxide and carbon Titanium dioxide TiO2 nanocrystals were synthesized
materials provides an effective surface area, where by solgel method [34].
pollutants (organic or inorganic compounds) can be For the synthesis process of the composite materi-
adsorbed and destroyed photocatalytically. Adsorp- als consisted of CNTs or CNFs mixed with TiO2
tion is a key process in the photocatalytic destruction particles within epoxy matrix, the two-roll mill tech- 105
55 of the pollutants and TiO2-carbon particles compos- nique was applied. The composite materials were
ites are able to achieve enhanced photocatalytic prepared by dispersion of CNTs and CNFs in tetrahy-
activities [31]. drofuran 99.9% (THF, Sigma-Aldrich, Germany) and
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epoxy resin (AralditeLY5052, Huntsman Advanced same photocatalytic reactor without UV irradiation
5 Materials, Basel, Switzerland) by ultrasonication for to achieve the same hydrodynamic conditions. After
20 min, followed by the homogenization of the result- irradiation time of 3 h, the suspension was sampled 55
ing paste with the TiO2 particles and also, with the and filtered through a 0.2 mm membrane filter. The
hardener using a two-roll mill to obtain a high level of concentration of HA was measured in terms of
dispersion and homogeneous distribution of the absorbance at 254 nm (A254) with a Carry 100 Varian
10 components in the epoxy matrix. The ratios were spectrophotometer. AQ4
chosen to reach 20% (wt.) carbon, 20% (wt.) TiO2 and For all studied processes, the HA removal 60
respective, 60% (wt.) epoxy. efficiency was calculated using the following equation:
For adsorption and photocatalysis application, the
composite material was crushed and sieved and the C0  Ct
15 composite size between 1 and 2 mm was used. The Removal efficiency  100 % (1)
C0
HA was obtained from Sigma Aldrich, Switzerland,
and 100-mg L1 stock solution of HA was prepared by
where C0 and Ct are the concentrations of HA in
dissolving 0.1 g of HA in 1,000 ml of distilled water.
aqueous solution at initial time and at any time t,
All experiments were performed at pH of 6.5.
respectively, (mg L1). 65
Kinetics data were fitting with the pseudo-second-
order kinetic model [35] expressed as (Eq. (2)):
20 2.2. Characterization of the composite material
A scanning electron microscopy (SEM) using t 1 t
Inspect S PANalytical model coupled with the energy 2
(2)
qt k2 qe qe
dispersive X-ray analysis detector was used to charac-
terize the morphology of the composite materials,
where k2 is the rate constant of the pseudo-second-
25 using catalyst powder supported on carbon tape. The
order adsorption kinetics (g mg1 min1); qethe 70
light absorption properties of the composite materials
equilibrium adsorption capacity (mg g1).
were studied by UVVIS Diffuse Reflectance Spec-
From the kinetics point of view, for the heteroge-
troscopy (DRUVVIS), performed under ambient
neous photocatalytic processes, the dependencies of
conditions using Lambda 950 PerkinElmer device in
the HA degradation rate on the irradiation time have
30 the wavelength range of 200650 nm.
been described by the LangmuirHinshelwood kinetic 75
Zeta potential measurements were carried out by a
model [36] (Eq. (4)), which can be simplified to a
Zeta Metre 3.0+ for suspensions of 1 g L1 composite
pseudo-first-order equation (Eq. (3)):
material in distilled water at pH of 6.5.

r dC=dt kKC=1 KC (3)


2.3. Adsorption and photocatalysis experiments
lnC0 =Ct kKt kapp t (4)
35 Both TiO2-carbon composite materials, i.e. carbon
nanotubes-titanium dioxide-epoxy (CNT-TiO2-Epoxy)
where r is the rate of HA degradation and discol- 80
and carbon nanofibers-titanium dioxide-epoxy (CNF-
oration (mg L1 min1); C0 is the the initial HA con-
TiO2-Epoxy) were tested as adsorbents and photocata-
centration (mg L1); Ct is the concentration of the HA
lysts in advanced water treatment processes for the
at time t (mg L1); t is the irradiation time (min); k is
40 removal of HAs from water.
the reaction rate constant (min1).
To study HA sorption and photocatalytic activity,
The apparent rate constant, kapp, was calculated 85
an accurate weight of 0.3 g of composite materials
from the intercept of the plot of lnC0 =Ct vs. time, t.
were shaken with 300 mL of 10, 15, 20 and 25 mg L1
For equilibrium study regarding HA adsorption on
HA solutions for 180 min at pH of 6.5. The experimen-
the composite materials, three models presented below
45 tal solution was prepared by diluting the HA stock
were applied to assess the adsorption isotherm:
solution with distilled water.
The linear form of the Langmuir isotherm can be 90
The photocatalytic experiments were carried out
represented by the following Eq. (5):
under magnetic stirring at 20C into a RS-1 photo-
catalytic reactor (Heraeus, Germany), which con-  
50 sisted of a submerged UV lamp surrounded by a 1

1 1

1
(5)
quartz shield. The adsorption of HA on composite qe KL qm Ce qm
materials was studied using batch method in the
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4 C. Orha et al. / Desalination and Water Treatment XX (2015) XXXXXX

where Ce is the equilibrium HA concentration at 3.2. DRUVvis spectroscopy 30


30 min adsorption time (mg L1); qm is the maximum
The diffuse reflectance UVvis spectra of
5 adsorption capacity (mg dye/g zeolite); KL is the
CNT-TiO2-Epoxy and CNF-TiO2-Epoxy in comparison
Langmuir isotherm constant (L g1).
with of CNT-Epoxy, CNF-Epoxy and TiO2 are pre-
The Freundlich equation for a linear plot is described
sented in Fig. 2, expressed in terms of Kubelka-Munk
by the following Eq. (6):
equivalent absorption units. It is observed for both 35
CNTs and CNFs an increased absorption in VIS wave-
ln qe ln KF n ln Ce (6) length range in comparison with single TiO2 that
absorb only in UV wavelength range, which informs
10 where KF is the Freundlich constant (L g1); n is the about the potential of CNTs- and CNFs-based materials
heterogeneity factor. to be used in VIS-driven photocatalysis applications. 40
The D-R equation is expressed in a linear form as However, the absorption intensity at VIS wavelength
(Eq. (7)): is lower towards UV absorption, and VIS-driven

ln qe ln qm  KDR e2 (7)

15 where qm is the monolayer capacity (mol kg1); is the


Polanyi potential equal to RT ln(1 + 1/Ce); R is the gas
constant (J mol1 K1); T is the absolute temperature
(K); KDR is the constant of the adsorption energy
(mol2 J K1).

20 3. Results and discussion


3.1. Scanning electron microscopy (SEM)
Fig. 1(a) and (b) shows the SEM images of CNT-
TiO2-Epoxy and CNF-TiO2-Epoxy composite material.
It can be noticed that part of TiO2 nanoparticles was
25 attached on CNT/CNF surface and also, a well dis-
persion of nanostructured carbon and TiO2
nanoparticles within epoxy matrix is noticed. A
more uniform distribution of TiO2 nanoparticles Fig. 2. DRUVvis spectra of composite materials (1)
CNF-TiO2-Epoxy, (2) CNT-TiO2-Epoxy, (3) CNF-Epoxy, (4)
seems to appear for CNF in comparison with CNT.
CNT-Epoxy and (5) TiO2.

Fig. 1. SEM image of (a) CNT-TiO2-Epoxy and (b) CNF-TiO2-Epoxy.


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applications are beyond our aim. No significant Table 1


enhancement of absorption intensity in UV wavelength Results of fitting experimental data to pseudo-second-
5 is noticed on CNT-TiO2-Epoxy and CNF-TiO2-Epoxy in order kinetic model for 10 mg L1 HA concentration
comparison with TiO2. However, the adsorption stage Parameters
that represents the key for the photocatalytic applica-
tion performance should be improved in the presence Composite type qe (mg g1) k2 (g mg1 min1) R2
of the nanostructured carbon. CNT-TiO2-Epoxy 8.6850 0.00963 0.9998
CNF-TiO2-Epoxy 7.14438 0.00897 0.99175

10 3.3. Testing carbon-TiO2 composite materials in adsorption


and photocatalysis processes for HA removal from water
kinetic model that predicts an exponential decay of
The adsorption process for HA removal using all
concentrations as a function of time. There are many
composite materials was characterized through
experimental parameters, e.g. targeted organic com-
kinetics and equilibrium studies.
pounds-type and concentration, catalyst dose and pH
that control the reaction rate and kinetics. 35
15 3.3.1. Adsorption-kinetics studies Table 1 presents the kinetic parameters resulted by
fitting the pseudo-second-order equation to the experi-
Zero, first and pseudo-second-order kinetics mental data recorded for 10 mg L1 HA, and it can be
models were tested for fitting the experimental data. If noticed that even if CNT-TiO2-Epoxy exhibited higher
the pseudo-second-order kinetics fitted well in the equilibrium adsorption capacity (qe) and also, the 40
experimental data, the plot of t/qt vs. t should show a adsorption rate is slightly faster in comparison with
20 linear relationship. Zero and first-order kinetics CNF-TiO2-Epoxy composite material.
models were not appropriate for fitting the experimen-
tal data.
The linear plots of t/qt vs. t (Fig. 3) show that the 3.3.2. Adsorptionequilibrium studies
experimental data agree with the pseudo-second-order
The results of adsorption isotherm fitting using the
25 kinetic model for the HA adsorption. The calculated qe
three models showed that the Freundlich model fitted 45
values agree very well with the experimental data and
best in the adsorption data with good correlation
the correlation coefficients for the second-order kinetic
coefficient (R2 > 0.99). The results of Freundlich model
model are higher than 0.99 in almost all cases. These
fitting are presented in Fig. 4. The correlation coeffi-
indicate that the adsorption of HA from water onto
cient values of R2 = 0.9518 obtained for Langmuir and
30 composite materials obeys the pseudo-second-order
of R2 = 0.81 for D-R model led to choose Freundlich 50

Fig. 3. The pseudo-second-order adsorption kinetic model Fig. 4. Freundlich isotherm plot for the adsorption of HA
for CNT-TiO2-Epoxy and CNF-TiO2-Epoxy. on (1) CNT-TiO2-Epoxy and (2) CNF-TiO2-Epoxy.
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6 C. Orha et al. / Desalination and Water Treatment XX (2015) XXXXXX

model (Fig. 4) to describe the adsorption process. This isoelectric point, which means that the repulsion
model is an empirical one and applicable to the phenomenon is favoured; however, HA adsorption
adsorption on heterogeneous surface. The first avail- occurred the best for CNT-TiO2-Epoxy and CNF-TiO2- 35
able sorption sites are occupied and characterized by Epoxy.
5 the strong bindings that are weaker with increasing The different adsorption capacity for HA of CNT-
degree of sites occupation [11]. Based on the results TiO2-Epoxy and CNF-TiO2-Epoxy could due to the
presented in Table 2, it can be seen that the adsorption morphology difference that may result in a difference
capacity was higher for CNT-TiO2-Epoxy than for in their aggregation tendency, which may further 40
CNF-TiO2-Epoxy. The Freundlich n values were impact their adsorption ability by the less available
10 similar for both sorbents suggesting the same adsorp- active sites. Also, the adsorption capacity is influenced
tion affinities for HA. by the different porous structures and the more uni-
In general, the adsorption mechanism on carbon- form pore structure favoured the diffusion of the
based adsorbents is considered to be complex based pollutants in inner pores [11]. These peculiarities are 45
on the hydrophobic effect, electrostatic interactions, reflected also in the specific surface area that is much
15 hydrogen bonding and bonds [11]. Both CNTs higher for CNT vs. CNF. Ren et al. [38] reviewed the
and CNFs provide hydrophobic regions that interact factors affecting the adsorptive interactions between
strongly with hydrophobic fraction of HA, this can organic pollutants and CNTs, as (i) nanostructured
be considered as one of the important mechanism. carbon peculiarities in relation with the surface area, 50
Nevertheless, it has been proved that no hydrophobic size, shape pore diameter and volume, morphology,
20 effect was the dominant mechanism even under the functional groups and impurity, (ii) organic molecule
conditions of strong affinity of CNT to organic properties of hydrophobicity, polarity, size and func-
chemicals [37]. To assess the electrostatic interactions, tional group and (iii) operational conditions (pH, ionic
the electrokinetic Zeta potential () for each material strength). 55
at pH 6.5 was determined and the values are gath- To evidence more detailed the adsorption perfor-
25 ered in Table 3. mances of both CNT-TiO2-Epoxy and CNF-TiO2-
By corroboration the kinetics and equilibrium Epoxy the comparative adsorption studies vs. TiO2,
adsorption results with the Zeta potential values, it is CNT-Epoxy and respective, CNF-Epoxy was per-
noticed that no electrostatic interaction was a signifi- formed for the adsorption of 25 mg L1 HA. Fig. 5 60
cant mechanism for HA adsorption. Even if the Zeta shows the adsorption efficiency expressed in terms of
30 potential for all tested materials including HA is efficiency degree (%). It is obviously that CNTs-based
characterized by the negative value at this neutral composite material exhibited higher adsorption ability
pH of 6.5, except TiO2 that is characterized by the for HA in comparison with CNFs-based composite

Table 2
Freundlich isotherm parameters of HA adsorption on
CNT-TiO2-Epoxy (1) and CNF-TiO2-Epoxy (2)

Material KF (L g1) n R2
CNT-TiO2-Epoxy 0.24103 0.40675 0.9901
CNF-TiO2-Epoxy 0.29171 0.38528 0.9985

Table 3
Zeta potential ()

Material potential/mV
CNF-Epoxy 26.585
CNF-TiO2-Epoxy 32.314
CNT-Epoxy 10,334
CNT-TiO2-Epoxy 22.655
TiO2 0 Fig. 5. Evolution of HA removal efficiency in time by
Humic acid solution (25 mg L1) 32.5 adsorption on CNT-TiO2-Epoxy (1); CNT-Epoxy (2);
CNF-TiO2-Epoxy (3); CNF-Epoxy (4); TiO2 (5).
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5 material, which is expected in relation with the higher in the first stage of photocatalysis process. However,
specific surface area for CNT. Different adsorption after 1,80 min of irradiation, HA degraded in the 25
behaviour is evidenced for CNTs that reached the presence of CNT-TiO2-Epoxy composite is slightly
equilibrium after longer time in comparison with better than in the presence of TiO2. Similar beha-
CNFs composite and TiO2. This behaviour should be viour was shown for CNFs-based composite materi-
10 explained by more porous structure for CNTs. als, for which photocatalysis performance was worse
The presence of TiO2 gave its contribution to the in comparison with CNTs. This behaviour informed 30
adsorption of HA onto composite system. about a possible self-photocatalytic activity of car-
bonaceous in according with the literature data [39].
Also, as we mentioned previously the adsorption
3.3.3. Photocatalytic activity of the composite materials stage that represents the key of adsorption process
The photocatalytic activities of the composite was improved. 35
15 materials were assessed for the degradation of HA The kinetics results determined by the Langmuir
for comparison with the sorption performances. The Hinshelwood kinetic model expressed as the apparent
photocatalysis results expressed in terms of HA first-order rate constant (kapp) [40] are gathered in
amount removed per unit of TiO2 are shown in Table 4, and it can be seen that the fastest rate of HA
Fig. 6. It must be mentioned that the photocatalysis degradation by photocatalysis under UV irradiation 40
20 component is assessed by subtracting adsorption was achieved for CNT-TiO2-Epoxy composite
results from overall photocatalysis process. It can be material.
noticed that the best photocatalysis results are To assess if the photocatalytic activity of the com-
achieved for CNT-TiO2-Epoxy composite, especially posite is enhanced should compare with a standard
that is TiO2 unit. The effect can be quantified in terms 45
of the enhancement factor (R) defined by Eq. (8):

k0app composite
R (8)
k0TiO2

where k0app is apparent first-order rate constant normal-


ized per TiO2 unit. 50
he enhancement factor of about 10 was achieved
for CNT-TiO2-Epoxy and about 5 for CNF-TiO2-Epoxy
composite. Based on these results, it can be concluded
about the enhanced performance of the nanostruc-
tured carbon-TiO2-epoxy system in special for CNTs. 55
Taking into account the morpho-structural aspects of
the composite and the literature data reported for car-
bon nanotube-TiO2 composite [31], the photocatalysis
mechanism is very complex. Nanostructured carbon
Fig. 6. Evolution of HA removed by photocatalysis under and TiO2 particles are distributed as small islands 60
UV irradiation normalized per TiO2 unit vs. time using (1) within insulating matrix, part of them being attached
CNT-TiO2-Epoxy, (2) TiO2 and (3) CNF-TiO2-Epoxy. one by other. Thus, part of them should acts as

Table 4
Apparent rate constants for photocatalytic degradation of 25 mg L1 HA solution by UV irradiation

Composite type kapp (min1) k0app (min1 g1 TiO2) R2


CNT-TiO2-Epoxy 0.01996 0.4990 0.98565
CNT-Epoxy 0.01152 0.94603
CNF-TiO2-Epoxy 0.0104 0.2600 0.98962
CNF-Epoxy 0.0077 0.8684
TiO2 0.00921 0.0460 0.92885
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8 C. Orha et al. / Desalination and Water Treatment XX (2015) XXXXXX

individual photocatalyst and other by the two mecha- potential application in water decontamination as next
nism described by Woan et al. [31], which suppose generation of self-cleaning filtering material.
5 both nanostructured carbon as sink for electron from
TiO2 conduction band avoiding electron-hole recom-
bination and the generation of electronhole pair in
4. Conclusions 35
nanostructured carbon that was proved by DRUVvis
AQ5 characterization. Two types of nanostructured carbon-TiO2 within
10 Because no pronounced enhanced HA, degradation epoxy matrix, i.e. carbon nanotubes-titanium dioxide-
in terms of efficiency was achieved by the photo- epoxy (CNT-TiO2-Epoxy) and carbon nanofibers-tita-
catalysis in comparison with the adsorption using nium dioxide-epoxy (CNF-TiO2-Epoxy) have been pre-
nanostructured carbon-based composite materials, the pared, characterized and tested as sorbent and 40
lifetime of the CNT-TiO2-Epoxy composite material as photocatlysts for HAs removal envisaging advanced
15 sorbent and as photocatalyst was assessed by repeti- drinking water treatment. The adsorption capacities of
tive five running in sorption and photocatalysis pro- CNT-TiO2-Epoxy of 8.68 mg g1 and CNF-TiO2-Epoxy
cesses. The HA removal efficiency after 1,80 min of 7.14 mg g1 for HA were determined using Fre-
reached by applying the adsorption and photocatalysis undlich isotherm. The different adsorption capacity 45
processes are presented in Fig. 7. It can be noticed that own the morphology and porosity difference between
20 by photocatalysis the material fouling is slowed in CNTs and CNFs, which is reflected in specific surface
comparison with its application in sorption process. In area and also, may affect their aggregation tendency
addition, a regeneration step of the material was that may further impact their adsorption ability. The
tested by applying the photocatalysis under the same presence of TiO2 into composite composition con- 50
conditions, but only in water without HA presence tributed to the adsorption process related to its dis-
25 and then, by further photocatalysis application for HA tribution within epoxy matrix or its attachment onto
degradation a better efficiency was achieved. How- nanostructured carbon surface. The photocatalytic
ever, no complete regeneration was achieved by this activities of both composite materials were assessed
method because HA degradation efficiency was about comparatively with TiO2 reference photocatalyst. 55
56.15% for regenerated material vs. 81.63% HA Besides the role of the nanostructured carbon in
30 degradation efficiency reached by the first utilization. adsorption step considered as the key for the photo-
This composite may provide a robust system catalysis performance, it was found that both CNTs
requiring little maintenance, which exhibits a great and CNFs exhibited photocatalytic properties. The
most enhanced photocatalytic performance for HA 60
degradation was achieved for CNT-TiO2-Epoxy com-
posite material, while for CNF-TiO2-Epoxy the photo-
catalytic performance was slightly worse in comparison
with TiO2, which should be explained by a potential
blockage of the photoactive centers in TiO2 after its 65
immobilization together CNFs within epoxy matrix.
The lifetime and the regeneration pathway by the
photocatalysis investigated for CNT-TiO2-Epoxy com-
posite system showed a HA removal efficiency of
43.8% achieved by photocatalysis vs. 30.2% reached by 70
the sorption after successive five running. A regenera-
tion degree of about 25% was achieved under the
similar conditions of photocatalysis without HA pres-
ence, which showed that the photocatalysis method is
suitable as regeneration step for application of CNT- 75
TiO2-Epoxy as sorbent and/or photocatalyst for HA
removal from water envisaging the advanced drinking
water treatment. For concrete practical application in
advanced drinking water treatment technology this
CNT-TiO2-Epoxy composite-based robust system 80
Fig. 7. Evolution of HA removal degree during successive
running of comparative photocatalytic and adsorption pro- should be used as attractive addition or alternative to
cess on CNT-TiO2-Epoxy for 25 mg L1 HA without/with the various oxidation/filtering techniques that are
regeneration. currently used.
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C. Orha et al. / Desalination and Water Treatment XX (2015) XXXXXX 9

Acknowledgements [12] D. Li, H. Haneda, Photocatalysis of sprayed nitrogen- 55


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