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Efficiency of Cu/TiO2 to remove salicylic acid
by photocatalytic decomposition: kinetic
modelling
A. Peter*1, L. Mihaly-Cozmuta1, A. Mihaly-Cozmuta1, C. Nicula1, L. B. Tudoran2
and L. Baia3
Titanium dioxide has waste applications as photocatalyst, as antimicrobial material and in
biomedical field. By modifying the surface of TiO2 with noble metals its photoactivity will be
enhanced. This paper aims to explain the role of the copper particles deposited on titania surface
during the photodecomposition of salicylic acid and to provide evidence about which kinetic
model describes best the photocatalysis. The research explains why the photodecomposition rate
of salicylic acid is higher in Cu/TiO2 composite as compared to in TiO2. It consists in kinetic
approach of the photocatalytic behaviour of Cu–TiO2 and TiO2, thus being possible to discuss
the photodecomposition mechanism. This research will allow improvement of the techniques
to remove salicylic acid from synthetic solution. This could be extended to other organic
pollutants.
Keywords: Cu–TiO2, Photoactivity, XRD, TEM, FTIR, Kinetics, Diffusion model

Introduction activity of TiO2. Cu2O can cover the surface of TiO2 when
the concentration of Cu is high (.0?06 mol.-%), making
Because of its photochemical stability, low toxicity and the photocatalytic activity slow down.
low price, titanium dioxide presents waste applications as Arana et al.13 have documented that Cu–TiO2
photocatalyst,1,24,31,33 as antimicrobial material26–28,30,32 behaved in different ways when used for the decom-
and in biomedical field.23–25,29 However, using TiO2 as position of three different dihydroxybenzenes. The
photocatalyst incurs two significant disadvantages: (i) catalytic activity slows down when a covalent bond is
high recombination rate of the charge carriers (electrons formed between the organic compound to be degraded
and holes), thus reducing the quantum efficiency of the and the catalyst surface.
photocatalytic process and (2) limited absorption capa- The photocatalytic process is faster if hydrogen bonds
city in the visible (Vis) region. To overcome these are established.
problems, the surface of TiO2 can be modified with noble A Cu–TiO2 composite film with y1?5 at-%Cu proved
metals,1–10 non-metals11 and metal oxides.12 The compo- to be a strong Escherichia coli destroyer, as demon-
sites thus obtained allow for the formation of a doping strated by Ondok et al.14
energy level between the conduction band and the valence This study explains the role of the copper particles in
band of TiO2, subsequently extending the adsorption photodecomposition, when deposited on the surface of
capacity in the Vis region. Moreover, the electrons from TiO2, and provides evidence about which kinetic model
the conduction band are transferred on the metal particle, describes best the photodegradation process of salicylic
thus increasing the lifetime of the charge carriers and acid (SA).
reducing the recombination rate.
Xin et al.1 have demonstrated that Cu–TiO2 with the Experimental methods
appropriate content of Cu becomes a strong trap for
electrons, thus inhibiting the recombination of photo- Preparation and characterisation of Cu–TiO2
induced charge carriers and improving the photocatalytic TiO2 sols were prepared via the sol–gel method, by mixing
titanium tetraisopropoxide (TIP) (Merck, Darmstadt,
1
Germany) with ultrapure water obtained using the
Technical University Cluj Napoca, North University Center of Baia Mare,
Department of Chemistry and Biology, Victor Babes 76, 430083, Baia
Thermo Scientific device, ethanol (Chemical Company,
Mare, Romania Iasi, Romania) and 65% nitric acid (Lachner, Brno,
2
Babes-Bolyai University, Faculty of Biology & Geology, Clinicilor 5-7, Czech Republic). The molar ratio of the reactants used is
400006 Cluj-Napoca, Romania
3
Babes-Bolyai University, Faculty of Physics and Institute for Interdis- as follows: TIP/H2O/C2H5OH/HNO351 : 3?675 : 21 : 0?08.
ciplinarity Research on Bio-Nano-Sciences, M. Kogalniceanu 1, 400084 The TiO2 gels were allowed to age 4 weeks and then
Cluj-Napoca, Romania were immersed (0?4 mg gel/mL solution) in a 0?005M
*Corresponding author, email [email protected] CuSO4 solution (Silal Trading, Bucharest, Romania).

ß 2014 W. S. Maney & Son Ltd.

Received 23 November 2013; accepted 4 December 2013
DOI 10.1179/1753555713Y.0000000121 Materials Technology: Advanced Performance Materials 2014 VOL 29 NO 3 129
Peter et al. Efficiency of Cu/TiO 2 to remove SA by photocatalytic decomposition

The mixture was shaken 24 h (160 rev min21) using a After integration between boundary conditions (from
Heidolph Unimax 1010 Stirrer. The impregnated gel was t50 to t and from qt50 to qe), the equation becomes15
washed with a mixture of ultrapure water–ethanol (1 : 1
k1 t
v/v) to remove the non-reacted TIP and the residual logðqe {qt Þ~log qe { : (2)
copper ions. 2 303
Then the washed gels were dried for 24 h at 80uC in a
Binder oven and were thermally treated at 500uC for 2 h, The parameters qe and k1 were established from
in a Caloris furnace (heating rate: 4uC min21) to allow the intercept and slope of the representation
the reduction of the metal ions on the TiO2’s surface and log (qe2qt)5f(t).
the crystallisation of the titania structure.
Pseudo-second order kinetic model
The phase content and crystallites dimensions were
determined from the X-ray diffraction (XRD) patterns Pseudo-second order kinetic model is based on the
recorded with a Shimadzu XRD-6000 diffractometer, photodecomposition or adsorption capacity of the
using Cu Ka radiation (l51?5418 Å), with Ni filter. composite and is expressed as
A JEOL JEM1010 (JEOL, Tokyo, Japan) transmission dqt
electronic microscope (TEM) operating at an accelerating ~k2 ðqe {qt Þ2 (3)
dt
voltage of 80 kV, coupled with an images acquisition
system MegaView III CCD Camera (1?2 Mp) Soft where k2 (kg mol21 min21) is the apparent rate constant
Imaging Solutions (Olympus, Munster, Germany), was of the second-order model.16
used to obtain TEM images. For boundary conditions (from t50 to t and from
The concentration of Cu in the composite, 0?143% qt50 to qe), the equation becomes
(mass-%¡0?01), was established using the Atomic t 1 1
Absorption Spectrometer AAS 800 PerkinElmer. ~ z t (4)
qt k2 q2e qe
Photodegradation experiments
The photocatalytic experiments occurred in a glass reactor The plot of t/qt versus t should give a straight line, if
(approximately 300 mL). The initial concentrations of the the pseudo-second-order kinetic model is applicable,
SA (Utchim, Ramnicu Valcea, Romania) in solution were and qe and k2 can be determined from the slope and
700, 600, 500, 400, 300 and 200 mM. The mass of the intercept of the plot respectively.
composite was 10 g L21. The pH of the solution was 5?5
Diffusion through particle surface
as determined with a WTW Inolab pH 730 device. The
solution was illuminated with the ultraviolet (UV) light The diffusion through the particle surface can be
emitted by a tungsten lamp (160 W), as well as with solar expressed by equations (5) and (6)
light, under continuous stirring (at 120 rev min21). At  1=2
D
different time intervals, samples of 1 mL solution were at ~Az 2 t1=2 (5)
r
taken and the remaining concentration of SA was
determined using the Molecular Absorption Spectro-
C0 {CT
meter PerkinElmer Lambda 35. Before the photocatalytic at ~ (6)
experiment, the suspension was stirred in the dark to C0 {CE
achieve the adsorption–desorption equilibrium to dis- where C0, Ce and Ct are the concentrations initially, at
count the adsorption of the substrate on the composite. equilibrium and at moment t in time (expressed in min),
For reference, adsorption experiments were performed, D is the diffusion coefficient (m2 min21), and r is the
all parameters being identical except irradiation. mean diameter of the particles (m) and was determined
The results were compared with those obtained when from XRD analyses as being 761029 m. The plot of at
reference TiO2 (Carlo Erba, Italy) was used as catalyst, versus t1/2 should give a straight line, and the slope of the
both in UV and Vis light. linear part of the curve (D/r2)1/2 is proportional to the
initial rate of sorption. The intercept a is proportional to
Kinetic modelling of photodecomposition and the thickness of the boundary sorption layer. Using the
adsorption slope, it is possible to calculate the diffusion coefficient.
The results for photodegradation and adsorption were An order of magnitude of D between 1026 and 1028
fitted on the kinetic models to establish the mechanism means that the rate limiting step is the diffusion through
of photodegradation of SA on the Cu–TiO2 composite. the film on the surface of particles, while an order of
magnitude between 10211 and 10213 would be the proof
Pseudo-first order kinetic model that the rate limiting step is the diffusion through
The equation used in the pseudo-first order kinetic pores.17
model has the following expression
dqt Results and discussion
~k1 ðqe {qt Þ (1)
dt Characterisation of Cu–TiO2 composite
where qt (mmol g21) is the amount of adsorbed/photo- The XRD diffraction profile (Fig. 1) demonstrates the
decomposed SA at time t (min), qe (mmol g21) is the presence of a crystalline structure (anatase and rutile)
amount adsorbed/photodecomposed SA at equilibrium of the Cu–TiO2 composite. The peaks at 2h525, 37?5,
and k1 (min21) is the apparent rate constant of the 47?5 and 62?5u are attributable to the anatase phase.
pseudo-first order reaction. At time t50, qt50 and the The small peak at 2h553u is assigned to the rutile
process rate becomes k16qe. phase.18 The average size for the anatase particle of TiO2

130 Materials Technology: Advanced Performance Materials 2014 VOL 29 NO 3

 Peter et al. Efficiency of Cu/TiO 2 to remove SA by photocatalytic decomposition

2 TEM image of Cu–TiO2 composite

It can be seen that the amount of photodecomposed

SA increases as the initial concentration of SA increases
1 XRD profile of Cu–TiO2 composite
from 400 to 500 mM. In contrast, low values for qt were
obtained for the extremely concentrations used (700, 300
in Cu–TiO2 composite is 14 nm and in reference TiO2, it is and 200 mM respectively).
9?6 nm. No peak corresponding to various Cu species The results were also fitted on the pseudo-first and
were detected, suggesting its low content in the composite. pseudo-second kinetic models (Table 1) and the values
The TEM image of the Cu–TiO2 composite (Fig. 2) of the correlation coefficients (0?97–0?99 for pseudo-first
illustrates a homogeneous dispersion of the titania kinetic model and 0?1–0?95 for pseudo-second kinetic
particles with well defined geometric shape, thus model; data not shown) demonstrated that the adsorp-
demonstrating its crystalline structure. The copper tion and photodecomposition of SA on Cu–TiO2 follows
particles (dark points) are heterogeneously dispersed in the pseudo-first kinetic model, meaning that the amount
the titania network. In some areas, the particles are of adsorbed/photodecomposed SA increases linearly
agglomerated in clusters and in other areas, they are with time.
isolated (Fig. 3). A similar morphology of the metal– The values of the process rate (k16qe) can be
TiO2 compound is mentioned in the literature.19,20 correlated with the values of qe in Fig. 3. Thus, the
higher rate was obtained for UV 500, UV 400 and UV
Adsorption and photodegradation of SA 600 processes (marked with * in Table 1).
Figure 3 shows how qt changes in time during the The order of magnitude for the diffusion through
adsorption and photodecomposition process of the particle surface coefficient (Table 1) is 10212, suggesting
molecules of SA, starting from different concentrations that the diffusion of the SA molecules through the pores
of the initial solution. There is very little salicylic acid of Cu–TiO2 is the rate limiting step. Thus, the
adsorbed on Cu–TiO2 as compared to the quantity of adsorption of the SA molecules on the TiO2 surface
photodecomposed SA. occurs more rapidly than the diffusion through the pores
However, there is a bigger amount of SA photo- of the composite.
decomposed in UV light than the amount photodecom-
posed in Vis light; therefore, the efficiency of Cu–TiO2 is
higher when excited by UV light than under the effect of
Vis light. On the other hand, the quantity of SA
decomposed on Cu–TiO2 is higher as compared with
that decomposed on reference TiO2, both in UV and Vis
light, suggesting the positive role of Cu on the
photocatalytic activity of the composite.
Xin et al.1 demonstrated that the copper on the
surface of TiO2 may exist in multiple oxidation states
such as Cu2O and CuO, p-type semiconductors with a
small band gap of 2?1 and 1?7 eV respectively.21,22 The
adsorption in the Vis light region from 400 to 700 nm is
attributed to the adsorption of Cu2O and CuO on the
TiO2 surface.1
The low photocatalytic activity in our study in the
presence of Vis light may be attributed to the fact that
CuO2 and CuO species do not exist on the surface of
TiO2 or their concentration on the surface of TiO2 is
relatively small. 3 Variation of adsorbed/photodecomposed salicylic acid
At an initial concentration of the SA of 500 mM, in time (UV: photodecomposition in presence of UV
under the effect of UV light, the quantity of acid light; Vis: photodecomposition in presence of visible
decomposed is the biggest, being followed by the light) at different concentrations of initial solution of
quantity of that decomposed when the initial concentrations salicylic acid: 200 mM (2), 300 mM (3), 400 mM (4),
were 400 and 600 mM respectively, as shown in Fig. 3. 500 mM (5), 600 mM (6) and 700 mM (7)

Materials Technology: Advanced Performance Materials 2014 VOL 29 NO 3 131

Peter et al. Efficiency of Cu/TiO 2 to remove SA by photocatalytic decomposition

4 Mechanism of adsorption/photodecomposition of salicylic acid

Mechanism of SA adsorption/ water adsorbed on the TiO2 and generating very reactive
photodecomposition hydroxyl radicals. These radical can, subsequently, oxi-
The mechanism of SA adsorption/photodecomposition dise the salicylic molecules. These are, finally, decom-
is schematised in Fig. 4. The TiO2 particle is excited by posed to CO2 and H2O.
the incident radiation, when the electrons ‘jump’ from The low degradation rate occurred during the process
the valence band (VB) into the conduction band (CB), using Vis light as compared with that calculated for
leaving in VB very active oxidising holes. the UV process demonstrated, again, that the role of the
The electrons from the CB are transferred on the Cu cooper particles from the titania surface is to reduce the
particles, thus becoming more active. This behaviour charge carriers recombination rate.
significantly reduces the recombination rate of the
charge carriers. From the Cu surface, the electrons Conclusions
subsequently reduce the molecules of oxygen to oxygen
radicals. The holes from the VB act in two routes: on the 1. The pattern by which the concentration of SA
one hand, oxidising SA molecules adsorbed on the TiO2 decreases during photodecomposition is best described
surface and on the other hand, oxidising the molecule of by the pseudo-first kinetic model.

Table 1 Parameters of kinetic and diffusion models for photodegradation of salicylic acid at different concentrations of
the initial solution and light sources (k1 and k2: apparent rate constants for pseudo-first and pseudo-second
kinetic models; qe: amount of adsorbed/photodegraded salicylic acid; r: correlation coefficient; k16qe: rate of
adsorption/photodegradation process; D: coefficient of diffusion through particle surface): values in parentheses
correspond to the processes when reference TiO2 was used as catalyst

Diffusion through
Pseudo-first kinetic model particle surface
Concentration
of the initial Process/ k16qe/ D, 61012
solution/mM light source k1/min21 qe/mmol g21 r mmol g21 min21 m2 min21 r

700 Adsorption 0.041 (0.039) 0.474 (0.452) 20.99 (20.98) 0.019 (0.017) 1.16 (1.02) 0.97 (0.98)
UV 0.024 (0.012) 13.31 (6.85) 20.99 (20.99) 0.322 (0.082) 0.93 (1.11) 0.93 (0.99)
Vis 0.045 (0.012) 3.43 (2.85) 20.99 (20.99) 0.156 (0.119) 1.14 (1.01) 0.98 (0.99)
600 Adsorption 0.03 (0.03) 0.05 (0.04) 20.99 (20.98) 0.002 (0.012) 1.03 (1.15) 0.95 (0.98)
UV 0.045 (0.020) 19.53 (15.47) 20.98 (20.99) 0.893* (0.464) 1.16 (1.57) 0.97 (0.99)
Vis 0.03 (0.009) 16.59 (6.87) 20.99 (20.99) 0.5 (0.123) 1.02 (1.98) 0.95 (0.99)
500 Adsorption 0.03 (0.34) 0.263 (0.358) 20.99 (20.99) 0.008 (0.121) 1.02 (2.42) 0.95 (0.99)
UV 0.058 (0.041) 30.99 (17.97) 20.98 (20.99) 1.811* (0.736) 1.33 (1.84) 0.97 (0.99)
Vis 0.039 (0.008) 7.58 (1.15) 20.99 (20.99) 0.298 (0.009) 1.09 (2.11) 0.97 (0.99)
400 Adsorption 0.03 (0.032) 0.569 (0.611) 20.99 (20.97) 0.017 (0.019) 1.02 (2.57) 0.95 (0.98)
UV 0.033 (0.017) 27.38 (15.87) 20.98 (20.99) 0.918* (0.269) 1.06 (1.01) 0.96 (0.98)
Vis 0.036 (0.007) 21.25 (9.87) 20.97 (20.99) 0.784 (0.069) 1.13 (2.04) 0.95 (0.98)
300 Adsorption 0.03 (0.018) 0.433 (0.117) 20.99 (20.98) 0.013 (0.002) 1.02 (2.54) 0.95 (0.99)
UV 0.027 (0.007) 15.76 5.47) 20.98 (20.98) 0.432 (0.038) 1.01 (1.57) 0.94 (0.98)
Vis 0.031 (0.002) 11.06 (2.54) 20.98 (20.99) 0.348 (0.005) 1.04 (2.87) 0.95 (0.98)
200 Adsorption 0.031 (0.03) 0.187 (0.172) 20.98 (20.99) 0.0059 (0.005) 1.03 (1.98) 0.95 (0.97)
UV 0.029 (0.002) 6.59 (1.15) 20.99 (20.97) 0.197 (0.002) 1.02 (2.74) 0.95 (0.99)
Vis 0.029 (0.002) 5.54 (0.98) 20.98 (20.99) 0.162 (0.0019) 1.00 (1.57) 0.95 (0.97)

132 Materials Technology: Advanced Performance Materials 2014 VOL 29 NO 3

 Peter et al. Efficiency of Cu/TiO 2 to remove SA by photocatalytic decomposition

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