Journal of Photochemistry and Photobiology A: Chemistry 277 (2014) 8289

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Journal of Photochemistry and Photobiology A:

Chemistry
journal homepage: www.elsevier.com/locate/jphotochem

Photodegradation of sodium naproxen and oxytetracycline

hydrochloride in aqueous medium using as photocatalysts Mg-Al
calcined hydrotalcites
G. Jcome-Acatitla a, , F. Tzompantzi a , R. Lpez-Gonzlez b , C. Garca-Mendoza a ,
J.M. Alvaro a , R. Gmez a
a

Universidad Autnoma Metropolitana-Iztapalapa, Depto. de Qumica, Av. San Rafael Atlixco No. 189, Mxico, D.F. CP. 09430, Mexico
Universidad Jurez Autnoma de Tabasco, Divisin Acadmica de Ingeniera y Arquitectura, Carretera Cunduacn-Jalpa Km. 1, Col. La Esmeralda, CP.
86690 Cunduacn, Tabasco, Mexico
b

a r t i c l e

i n f o

Article history:
Received 8 October 2013
Received in revised form 7 December 2013
Accepted 9 December 2013
Available online 25 December 2013
Keywords:
MgAl calcined LDHs
Sodium naproxen photodegradation
Oxytetracycline hydrochloride
photodegradation
Sodium naproxen TOC analysis
Oxytetracycline TOC analysis
Fluorescence probe

a b s t r a c t
Layered double hydroxides (LDH) MgAl with different MII /MIII ratios were synthesized by the coprecipitation method. The materials were calcined at 723 K and characterized by XRD, nitrogen
adsorption, UVvis DRS and FTIR. The catalytic activity of the calcined solids was tested in the photodegradation of two water soluble pharmaceuticals: sodium naproxen, a non-steroidal anti-inflammatory, and
oxytetracycline hydrochloride, a tetracycline family antibiotic. The synthesized solids mineralize rapidly
both pharmaceuticals using UV as light source and after 5 h of reaction, about 90% of sodium naproxen
and 70% of oxytetracycline hydrochloride were degraded by the catalyst with the higher photoactivity.
Comparative studies were performed with TiO2 P25 commercial semiconductor. The results showed that
the MgAl calcined hydrotalcites have a greater photoactivity in the degradation of the target molecules
than TiO2 . Fluorescence spectroscopy study suggests the generation of hydroxyl radicals as the oxidative
species of the target molecules when MgAl calcined hydrotalcites are irradiated.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Pharmaceuticals are a large and diverse group of organic compounds widely used in the world. In recent years and with the
development of new advanced analytic techniques, many of them
have been detected in waste, surface, ground and drinking water.
Although, pharmaceuticals are designed to have physiological
effect on humans, they can be seriously dangerous for a large number of living organisms.
Pharmaceuticals move in wastewaters after they are excreted
by human and animals via urine and feces. Because of their high
stability, a large amount of them cannot be biologically degraded
or eliminated in treatment plants, ending up in effluents of lakes
and rivers [14]. Although pharmaceuticals have been found in low
concentration, diverse researches have suggested a link between
their presence in aquatic media and alterations on the endocrine
system of non-target organisms [5,6].

Corresponding author. Tel.: +52 58044669.

E-mail address: jacomeg82@yahoo.com.mx (G. Jcome-Acatitla).
1010-6030/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jphotochem.2013.12.014

The pharmaceuticals identified in polluted water, included a

wide variety of compounds [7,8], among them sodium naproxen
and oxytetracycline hydrochloride. Sodium naproxen (chemical
formula C14 H14 O3 Na) is one of the most commonly nonsteroidal
anti-inflammatory drug, use for the reduction of pain, fever,
inflammation and stiffness. It has been found in wastewater at
concentration up to 0.5 7.84 !g/L [9,10]. On the other hand, the
oxytetracycline hydrochloride (chemical formula C22 H24 N2 O9 HCl)
is a broad-spectrum antibiotic, frequently used in medicine and
agriculture. It has been reported that the occurrence of this compound in some treatment plants of USA is in the range 4.2 0.4 !g/L
[6].
Adsorption on diverse materials and advanced oxidation processes (AOP), have been applied for the removal of pharmaceuticals
from aqueous systems [514]. AOP provides the advantage of
mineralize the drugs and its metabolites. Although, AOP include
electrolysis, ozonation, Fenton oxidation and photolysis, heterogeneous photocatalysis is a promising technique for the elimination
of pharmaceuticals, and TiO2 the material commonly employed.
Besides titanium oxide, few photocatalysts, such as ZnO, CdS and
SnO2 , have been proved in AOP process [11]. However, in recent

G. Jcome-Acatitla et al. / Journal of Photochemistry and Photobiology A: Chemistry 277 (2014) 8289

years in the search of affordable and environmentally-friendly new

materials, the layered double hydroxides have been attracting considerable attention as a good alternative for the photodegradation
of organic compounds.
Layered double hydroxides (LDH) are anionic clays which
structure consists of positive charge brucite-like layers where
the divalent cation has been partially substituted by a trivalent
metal ion. The positive charge is compensated by anions that are
located in the interlayer space. The general formula of LDHs is
[M(1x) II Mx III (OH)2 ]Ax/n n mH2 O where MII and MIII represent the
divalent and trivalent metal ions respectively and An is the interlayer anion, being CO3 2 the most common.
The LDHs have been used in a wide range of technological
applications such as adsorbents, anti-acid agents, hybrid composites, flame retardants and PVC additives [12]. The mixed oxides
obtained by the thermal decomposition of hydrotalcite-like materials, have been frequently employed as catalysts and catalyst
supports due to their high specific surface area, basic properties
and structural stability. However, the photochemical applications
of LDH-derived oxides have not been enough investigated. A limited
number of studies have reported the physicochemical behavior of
these solids in the photodegradation of 2,4-dichlorophenoxiacetic
acid [15], organic molecules such as colorants [16,17] and phenolic compounds [18,19], but no research studies have been done
about the use of these materials in the elimination of pharmaceuticals.
In the present work three layered double hydroxides Mg-Al
with different MII /MIII molar ratio, were synthesized by the coprecipitation method. The obtained materials were characterized
by X-ray diffraction (XRD), nitrogen adsorption, thermogravimetric analysis, infrared (FTIR) and UVvis spectroscopy. In order to
examine the catalytic behavior of the calcined LDHs, photodegradation studies of two commonly used pharmaceuticals, sodium
naproxen and oxytetracycline hydrochloride, were performed. The
concentration of the target molecules at different reaction times
were followed by UVvis spectroscopy and total organic carbon
(TOC).
2. Experimental
2.1. Synthesis
LDHs Mg-Al with three different MII /MIII molar ratio were
synthesized by the co-precipitation method [15,18,19]. Aqueous
solutions of Mg(NO3 )2 6H2 O (Reasol, 98%) and Al(NO3 )3 9H2 O
(Reasol, 98%) precursors were added to a glass reactor in required
amounts to obtain MII /MIII molar ratio of 2.0, 2.5, 3.0. After, a solution of K2 CO3 and KOH (1 M) was used to fix the pH system at
9 0.5. The precipitate obtained was kept under vigorous mechanical stirring at a temperature of 353 K for 18 h. The obtained solids
were filtered, thoroughly washed with deionized water and dried
at 373 K for 24 h. Finally the materials were calcined at 723 K for
12 h before the degradation studies were performed. Samples were
named MgAl2.0, MgAl2.5 and MgAl3.0 where the number denotes
the Mg/Al molar ratio.
2.2. Characterization
2.2.1. X-Ray diffraction
The X-ray diffraction patterns were collected on a Siemens D500
diffractometer with Cu K" radiation, a crystal graphite monochromator and with a 2! step of 0.02 s1 . Assuming a hexagonal packing,
the cell parameters were calculated with the equations c = 3d003
and a = 2d110 [15,19]. Crystal sizes were obtained using the Scherrer
equation.

83

2.2.2. Chemical analysis

The chemical composition of the synthesized solids was
obtained by EDS technique, using a Zeiss EM-910 TEM microscope
with a 0.34 nm resolution, voltage of 120 kV and a Noran detector.
2.2.3. Textural analysis
The textural properties of the calcined solids were analyzed
by N2 adsorptiondesorption isotherms using a Quantachrome
Autosorb-3B equipment. The samples were out-gassed in vacuum
(105 Torr) at 673 K for 12 h before the analysis. The specific surface
areas were calculated using the BrunauerEmmettTeller (BET)
equation.
2.2.4. Band gap energy
The band gap energies (Eg) were obtained by diffuse reflectance
measurements, using a Cary 100 spectrophotometer with an integration sphere. The KubelkaMunk equation
F(R) =

(1 R)2
2R

where R is the reflectance (%), was employed to calculated the values of the band gap of the samples, considering in all the cases
indirect transitions. The method consists in plotting the square roof
of the KulbelkaMunk function multiplied by photon energy versus
photon energy. The Eg value is obtained by extrapolating the linear
part of the graph to the abscissa axis [15,20,21].
2.3. Photodegradation activity
As it was mentioned in the introduction, due to particular characteristics of the LDH-derived mixed oxides, such as high surface
area, basic properties and structural stability, the synthesized LDHs
were calcined at 723 K for 12 h to obtain the respective mixed
oxides and consecutively performing the photocatalytic tests.
Photodegradation of sodium naproxen (Sigma, 98%) and oxytetracycline hydrochloride (Sigma, 95%) was carried out preparing
solutions containing 50 ppm of the compound in distillated water.
200 mL of the solutions were put in contact with 0.1 g of the catalysts at room temperature and without adjusting the pH at any
moment. The reaction systems were kept under mechanical stirring
and UV irradiation, using a Pen Ray Power Supply lamp (2.16 W,
18 mA and " = 254 nm) for 6 h. During the reaction, aliquots of
3 mL were taken in different periods of time using nylon filters.
For comparative analysis, photolysis and photodegradation studies employing TiO2 P25 were performed under the same conditions
imposed for the synthesized catalysts.
The evolution of the concentration of the target molecules as
a function of time, was monitored by UVvis spectroscopy, using
a Cary-100 spectrophotometer following the absorption band at
271 nm for sodium naproxen and at 275 nm for oxytetracycline
hydrochloride. Total organic carbon analysis of the irradiated samples, was made employing a Shimadzu TOCV CSH.
In order to discard the retention of the target molecules or any
intermediate on the synthesized catalysts, after the photocatalytic
test, the powders were removed, dried for 12 h and analyzed by
FTIR using a Perkin-Elmer FT1730 spectrophotometer.
2.3.1. Fluorescence probes
The generation of OH radicals by the synthesized materials, was
followed by fluorescence probes according to the method described
in [22,23]. In brief: Coumarin (Aldrich) was dissolved in a dilute
NaOH (1 103 M). 100 mg of the most active catalyst was added
to 200 mL of the coumarin solution. Under continuous stirring, the
reaction system was irradiated with UV-light for 1 h. The fluorescence emission spectra of 7-hydroxycoumarin at different times
of reaction, were measured in a K2 spectrofluorometer (ISS Inc.,

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G. Jcome-Acatitla et al. / Journal of Photochemistry and Photobiology A: Chemistry 277 (2014) 8289

MgAl2.5

MgAl2.0

15

30

45

60

Fig. 1. X-ray diffraction patters for LDHs with different Mg/Al molar ratio.

Champaign IL) using an excitation wavelength of 332 nm. As a

control test, fluorescence measurements of the coumarin solution
irradiated with UV light in absence of photocatalyst were made.
3. Results and discussion
3.1. Photocatalyst characterization
3.1.1. X-ray diffraction
X-ray diffractions patterns of the dried solids are shown in
Fig. 1. The three materials showed pure hydrotalcite-like phase
[15,19,24]. The (0 0 l) reflections present a relatively symmetrical
sequence, indicating a high order in the stacking of the brucite-like
layers [21]. Characteristic reflections (0 0 3) and (1 1 0) at 2! = 11.8
and 60.8 respectively, correspond to basal and in-plane spacing
[15,25,26]. Using the Braggs law and assuming a hexagonal stacking, the cell parameters can be calculated by the equations c = 3d003
and a = 2d110 (Table 1).
The cell parameter a, which indicates the distance between two
adjacent cations within the hydroxylated sheets, decreases as the
amount of Al3+ increases (MgAl2.0), due to the trivalent cation
radius is smaller than Mg2+ . On the other hand, the c parameter
diminishes at low MgII /MIII molar ratio. This fact could be due to an
increasing in the layer charge density with the Al3+ addition. As for
the cell parameters, the crystallite size of the synthesized materials (Table 1) is directly proportional to the MII /MIII molar ratio;
thus a decrease of the amount of Al3+ in the sample, diminishes the
crystallite size.
3.1.2. Chemical and textural analysis
The EDS analysis, indicate that the obtained solids have only
LDH phases (Table 2), since pure hydrotalcite-type structures can
be formed just for MII /MIII molar ratios in the range of 24 [26].
The experimental nominal ratios are very close to those previously
calculated for the synthesis of the materials, which evidenced that
the co-precipitation was nearly complete.
The N2 adsorptiondesorption isotherms are shown in Fig. 2.
According to the IUPAC classification, the synthesized materials
Table 1
Cell parameters and crystallite size of the MgAl materials.
Sample

MgAl2.0
MgAl2.5
MgAl3.0

Unit cell parameters (A)

Crystallite size

L003 (A)

22.336
22.504
22.566

3.041
3.043
3.045

90.139
84.959
80.034

Experimental
MII /MIII

SBET (m2 /g)

Eg (eV)

MgAl2.0
MgAl2.5
MgAl3.0

2.1
2.3
2.8

277
251
237

3.083
3.054
3.077

present type IV isotherms which correspond to mesoporous materials. The H3 hysteresis loop exhibited by all the samples indicates
the presence of asymmetry pores (non-uniform size and shape)
[15,24].
The specific surface area (SSA) decreases upon reducing the aluminum amount in the samples (Table 2). When the synthesized
solids are calcined, the lamellar structure collapses, given rise to
the formation of periclase and Mg-Al mixed oxide [27]. Diverse
researches have reported specific surface areas of MgO and Al2 O3 ,
synthesized by precipitation, of 100300 m2 /g and 250460 m2 /g,
respectively [2830]. According to these data, the aluminum oxide
has a larger SSA than MgO, therefore, the specific surface area of
the synthesized materials presents a tendency to decrease as the
amount of aluminum in the samples diminishes.
3.1.3. Band gap energy
The band gap energies of the synthesized materials were
obtained by diffuse reflectance measurements (Fig. 3). Although,
the variation in the band gap values as a function of MII /MIII molar
ratio was small (Table 2), a minimum value was observed for the
catalyst MgAl2.5. The shift in the Eg of the material MgAl3.0 to

MgAl3.0
MgAl2.5
MgAl2.0
0.0

0.2

0.4

0.6

0.8

1.0

Relative Pressure (P/Po)

Fig. 2. N2 adsorptiondesorption isotherms of the calcined materials.

(F(R)*E)1/2 (a. u.)

MgAl3.0

Sample

Volume adsorbed (a.u.)

(110)

(006)

Intensity (a. u.)

(003)

Table 2
Chemical composition, surface area and band gap energies of the MgAl materials.

MgAl3.0
MgAl2.5
MgAl2.0
2

Energy (eV)
Fig. 3. UVvisKM spectra for the MgAl calcined hydrotalcites with different Mg/Al
molar ratio.

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G. Jcome-Acatitla et al. / Journal of Photochemistry and Photobiology A: Chemistry 277 (2014) 8289

Adsorption
MgAl2.0
MgAl2.5
MgAl3.0

1.0

0.6
Degradation
MgAl2.0
MgAl2.5
MgAl3.0

0.4
0

0.8

-Ln(C/Co)

C/Co

0.8
Degradation
Photolysis
TiO 2 P25

0.4

0.0

30

60

90

120

Time (min)

Fig. 4. Adsorption and photodegradation of sodium naproxen in aqueous solution

by MgAl calcined hydrotalcites with different Mg/Al molar ratio, photodegradation
by TiO2 and photolysis.

higher energy could be attributed to its crystallite size [20,21,31].

According to the values obtained, the MgAl3.0 catalyst has a slightly
smaller crystallite size than MgAl2.5 (Table 1), in which the band
gap energy increases.
3.2. Photodegradation test and fluorescence probes
Experiments of dark adsorption of the pharmaceuticals on the
MgAl calcined LDHs were carried out 2 h before the reaction system
was irradiated with UV light. No variation in the concentration of
the target molecules before irradiation, indicates that pharmaceuticals are not adsorbed on the calcined materials.
UVvis spectra of sodium naproxen and oxytetracycline
hydrochloride (not shown) were obtained at different reaction
time. For the three synthesized materials, it was observed that after
2 h of irradiation, the spectrum of sodium naproxen changes considerably indicating that the target molecule is rapidly modified
by the catalysts. A quantitative study of the drug degradation by
UVvis spectroscopy as a function of time, is not possible due to
the complexity of the spectra, thus we prefer to follow the photodegradation by determining the mineralization of the molecule
by means of TOC analysis (Fig. 4).
As for the sodium naproxen, the oxytetracycline hydrochloride
molecule is modified rapidly by the MgAl calcined hydrotalcites,
hence the photodegradation of the drug as a function of time was
monitored by TOC analysis (Fig. 5). The oxytetracycline hydrochloride photodegradation was slower than that obtained for sodium
naproxen. It can be then concluded that sodium naproxen can be
degraded more effectively by the synthesized materials than the
oxytetracycline hydrochloride. In both figures it can be seen that

30

60

90

120

150

Time (min)
Fig. 5. Adsorption and photodegradation of oxytetracycline by MgAl calcined
hydrotalcites with different Mg/Al molar ratio, photodegradation by TiO2 and
photolysis.

60

80

100

120

Table 3
Apparent rate constant, half-life time and TOC analysis for sodium naproxen
photodegradation.
Sample

Kapp (h1 )

t1/2 (h)

% degradation (5 h)

MgAl2.0
MgAl2.5
MgAl3.0
Photolysis
TiO2

0.45
0.656
0.551
0.125
0.142

1.54
1.06
1.26
5.53
4.87

70.37
87.90
81.13
10.82
32.54

the MgAl2.5 sample exhibits the higher activity in drug photodegradation (TOC analysis).
The sodium naproxen photodegradation follows a pseudo-first
order kinetics (Fig. 6). Plotting Ln(C/Co) versus reaction time yields
a straight line where the slope is the apparent rate constant
[8,15,19,32]. Sodium naproxen half-life, apparent rate constants
and the percentage of degradation after 5 h of irradiation are summarized in Table 3. It can be observed that the synthesized catalysts
can mineralize 50% of the sodium naproxen in just over 1 h. Catalyst MgAl2.5 showed the highest activity with a kapp = 0.656 h1 and
nearly 90% of the target molecule degraded after 5 h.
As for sodium naproxen, the oxytetracycline hydrochloride
photodegradation follows a pseudo-first order kinetics (Fig. 7).
Although the rate constants and the amount of pharmaceutical
degraded after 5 h of reaction are similar for the three synthesized
materials (Table 4), the MgAl2.5 calcined LDH shown slightly higher
photoactivity.
For comparison purposes, photolysis and photodegradation
studies using TiO2 Sodium naproxen exhibits low mineralization
without catalyst (Fig. 5): only 11% of the molecule was degraded

MgAl2.0
MgAl2.5
MgAl3.0

0.9

-Ln (C/Co)

C/Co
0.4

Degradation
TiO 2 P25

Degradation
MgAl2.0
MgAl2.5
MgAl3.0

40

Fig. 6. Pseudo-first order kinetics of sodium naproxen degradation by MgAl calcined

hydrotalcites with different Mg/Al molar ratio.

Photolysis

0.8

20

Time (min)

Adsorption
MgAl2.0
MgAl2.5
MgAl3.0

1.0

0.6

MgAl2.0
MgAl2.5
MgAl3.0

1.2

0.6

0.3

0.0

30

60

90

120

150

Time (min)
Fig. 7. Pseudo first order kinetics of oxytetracycline photodegradation by MgAl
calcined hydrotalcites with different Mg/Al molar ratio.

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G. Jcome-Acatitla et al. / Journal of Photochemistry and Photobiology A: Chemistry 277 (2014) 8289

Table 4
Apparent rate constant, half-time time and TOC analysis for oxytetracycline
photodegradation.

2.41
1.87
1.92
11.33
4.48

59.32
65.82
63.87
20.14
48.13

1483
1390
1251
1213
1161
1029
924
812

1585

2959
2907

3449

% Transmittance (a. u.)

Sodium naproxen/KBr

MgAl2.0
MgAl2.5
MgAl3.0
3500

3000

2500

Wavenumber

MgAl2.0

1500

1000

(cm -1)

Fig. 9. FTIR analysis of the MgAl calcined hydrotalcites with different Mg/Al molar
ratio after the photodegradation of oxytetracycline (50 ppm).

MgAl2.5
MgAl3.0

3500

1240
1179
1132
1009
945
841

0.288
0.370
0.362
0.061
0.155

1630
1581
1454

% degradation (5 h)

MgAl-2.0
MgAl-2.5
MgAl-3.0
Photolysis
TiO2 P25

3001

t1/2 (h1 )

3354

Kapp (h1 )

% Transmittance (a. u.)

Sample

Oxitetracycline/KBr

3000

2500

1500

1000

-1

Wavenumber (cm )
Fig. 8. FTIR spectra of the MgAl calcined hydrotalcites with different Mg/Al molar
ratio after the photodegradation of sodium naproxen (50 ppm).

in 5 h, while employing TiO2 the mineralization of the molecule

reaches 32.5%. For oxytetracycline hydrochloride, 20.1% of the drug
was mineralized after 5 h under irradiation via photolysis and 48%
was reached in the presence of TiO2 (Fig. 5).
Figs. 8 and 9 show the FTIR spectra of the target molecules
and of the recovered solid after the reaction. The spectrum of
sodium naproxen presents four main regions. The first one is
in the range 34502900 cm1 and is generated by stretching

Fig. 10. Schematic representation of the photodegradation of pharmaceuticals by MgAl calcined hydrotalcites.

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G. Jcome-Acatitla et al. / Journal of Photochemistry and Photobiology A: Chemistry 277 (2014) 8289

catalyst MgAl2.5, which could explain its greater activity in the

degradation of both pharmaceuticals. The material with the larger
MII /MIII molar ratio has higher band gap energy, decreasing its
efficiency in the photodegradation process. The experimental data
show that the MgAl calcined LDHs have a greater photocatalytic
activity in the mineralization of the target molecules than TiO2 P25
commercial semiconductor.
The photodegradation of the pharmaceuticals can be explained
according to the model shown in Fig. 10. When the synthesized
materials are heated to 450 C, the interlayer anions decompose
to CO2 and the brucite-like layers are dehydroxylated, leading to
formation of MgAl calcined LDHs. Depending on the calcination
temperature, the mixed oxide is able to regenerate partially or completely its laminar structure by being exposed to aqueous media.
According to this, when the MgAl calcined hydrotalcites (450 C) are
placed in water, molecules of solvent interact with the solids causing the gradual hydroxylation of the material. Diverse researches,
have reported that the MgO and Al2 O3 have wide band gap energies. However, the synthesis of solids which contains both metal
cations, Mg2+ and Al3+ , result in to the obtaining of new materials
with semiconductor properties, whereby the irradiation of UV-light
to the reaction systems, provokes the generation of electronhole
pairs, where the electron is delocalized toward the charge electro deficient Al3+ [39] and the hole oxidize the hydroxyl groups

(a)
40 min
60 min
30 min
20 min
10 min
Coumarin (NaOH)

300000

Intensity (a. u.)

250000
200000
150000
100000
50000
0
375

450

525

600

675

Wavelength (nm)

(b)
500000

60 min
30 - 40 min
10 - 20 min
Coumarin (NaOH)

400000

Intensity (a. u.)

vibrations of the methylic groups. In the region 16001450 cm1 ,

appear the asymmetric (1585 cm1 ) and symmetric stretching
bands of the carboxylate anion in addition to the aromatic C C
stretch band. The in plane C H bending vibrations are in the range
12501000 cm1 while the out of plane C H stretching are in the
region 900750 cm1 . Unlike sodium naproxen, the spectrum of
oxytetracycline hydrochloride presents a broad intense band in the
range 36002500 cm1 , which is generated by stretching vibrations
of groups N H, O H and C H; annular C C and C O stretching
appear around at 1450 cm1 and 1581 cm1 , respectively. The short
band at 1630 cm1 can be attributed to bending vibration of N H.
In the spectra of the recovered solids, it can be observed, that
there are not peaks corresponding to sodium naproxen, oxytetracycline hydrochloride or any intermediate on the catalysts after
the photodegradation test, which suggested that target molecules
were mineralized. The bands at 1360 cm1 and around 3450 cm1 ,
attributed to stretching vibrations of C O and O H groups respectively, indicate that during the photocatalytic process, CO3 2 and
H2 O molecules were adsorbed by the MgAl calcined LDHs.
Although the target molecules can be degraded by the synthesized catalysts, sodium naproxen is mineralized with greater
efficiency than oxytetracycline hydrochloride. This fact could be
due to the chemical structure of the polycyclic pharmaceuticals.
In generally, to reach the transformation of high toxicity polycyclic pollutants into easier biodegradable compounds or even
more, achieve its mineralization to CO2 and H2 O, the organic compounds must undergo a series of reactions which finally include
the opening of the rings. It has been observed that if the polycyclic organic compound has various reactive substituents, the OH
radicals react with these groups before attack the cyclic structure
[33]. According to this, the photodegradation of sodium naproxen
could be faster than that of oxytetracycline due to the lower number of substituents and rings in the chemical structure of sodium
naproxen.
Diverse researches focused to the pathways of photodegradation of naproxen have found that OH radicals first react with
COOH group, leading to the formation of three main photoproducts in which the aromatic rings remain unchanged [9,34]. In
the other hand, the oxytetracycline molecule has several reactive
groups along its structure which could be attack by the OH radicals.
Studies done about the possible pathways of its photodegradation,
have suggested that the reactive oxygen species attack the cetoenol, amino, or amide groups or in some cases the double bonds of
the aromatic ring, generating many by-products that contained the
tetracycline nucleus (the four ring) [35,36]. The opening of the rings
may be effective for sodium naproxen than oxytetracycline, due to
the first one compound has two aromatic rings, rich in electrons,
which could react faster with the OH radicals.
The variation of the MII /MIII molar ratio in the synthesized catalysts has a direct effect on the band gap energies and therefore in
their photocatalytic activity. Several researches have shown that
the electronic properties of diverse photocatalysts are determined
by their band gap energy. The Eg value, which is the separation
between the energy of the lowest conduction band and that of the
highest valence band [21] defines the required energy of the incident light to be absorbed by the photocatalyst for the generation of
electronhole pair. The photoinduced holes react with hydroxide
ions or water molecules leading to the formation of high reactive
OH radicals, which subsequently oxidize organic pollutants. Thus,
the band gap value plays an important role in the photocatalytic
activity of the materials, since it determines the energy needed
to initiate the photocatalytic process. In general it has been found
that photocatalyst with small band gap values absorbed strongly
the light leading to an enhancement of the photocatalytic process [15,37,38]. The band gap energies of the tested photocatalysts
are modified with the addition of Al3+ , having a minimum in the

300000

200000

100000

0
375

450

525

600

675

Wavelength (nm)
Fig. 11. Fluorescence spectra using an excitation wavelength of 332 nm of (a)
coumarin irradiated with UV-light (absence of catalyst) and (b) coumarin-MgAl2.5UV light.

88

G. Jcome-Acatitla et al. / Journal of Photochemistry and Photobiology A: Chemistry 277 (2014) 8289

allowing the formation of OH radicals which subsequently attack

to the target drugs.
According to several investigations done about photodegradation reactions, the reactive oxygen species, specially OH
radicals, are key species in the photo-oxidation of organic pollutants. Although OH radicals are very active, their presence in
photocatalytic process have been detected by applied the fluorescence technique [22,23]. The formation of OH radicals in
the photodegradation of the sodium naproxen and oxytetracycline by MgAl calcined hydrotalcites, was detected by the reaction
between coumarin and hydroxyl radicals, following the formation of highly flourescent 7-hydroxycoumarine. Fig. 11 shows
the spectrum of fluorescence for the systems coumarin + UV-light
(a) and coumarin + MgAl2.5 (material with the highest photoactivity) with UV-light irradiation (b). It can see the generation of
7-hydroxycoumarin in both reaction systems but with marked differences. In the (a) system the OH radicals are generated very faster
but the amount of these reactive oxygen species is no increasing as
the reaction proceeds. In the case of the (b) system, the fluorescence intensity at the first minutes of irradiation is higher than the
maximum obtained for the (a) system in the whole reaction. It is
observed too, the increase of 7-hydroxycoumarine with the time
reaction, which is related with the gradual generation of OH radicals. Thus the generation of hydroxyl radicals by the synthesized
photocatalysts is proved and confirms the mechanism proposed.
4. Conclusions
The results presented in this work showed that the MgAl calcined hydrotalcites, obtained by the thermal decomposition of
the respective layered double hydroxides are promising materials
for the photodegradation of sodium naproxen and oxitetracycline
hydrochloride. The first target molecule was degraded more efficiently (above 80%) than oxitetracycline hydrochloride (around
60%), which could be due to the less complex chemical structure
of sodium naproxen. The generation of OH radicals, key species
in the photodegradation process, by the most active photocatalyst (MgAl2.5) was corroborated using the fluorescence technique.
The photocatalytic activity of the synthesized materials was greater
than that of the commercial TiO2 P25, which could be explained by
the Eg values obtained (3.0503.080). The addition of an optimum
amount of aluminum enhances the activity of the materials.
Acknowledgements
G. Jcome-Acatitla acknowledge the scholarship 240852 given
by CONACYT Mxico and the support given to the project SEPCONACYT 154994 Elimination of polluting molecules using laminar
oxides.
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