Applied Surface Science 357 (2015) 17651775

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Applied Surface Science

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Enhanced photocatalytic activity of TiO2 -impregnated with

MgZnAl mixed oxides obtained from layered double
hydroxides for phenol degradation
Marciano Fabiano de Almeida a , Carlos Roberto Bellato a, , Ann Honor Mounteer b ,
Sukarno Olavo Ferreira c , Jaderson Lopes Milagres a , Liany Divina Lima Miranda a
a

Departamento de Qumica, Universidade Federal de Vicosa, Av. PH Holfs, s/n, 36571-000 Vicosa, Minas Gerais, Brazil
Departamento de Engenharia Civil, Universidade Federal de Vicosa, Av. PH Holfs, s/n, 36571-000 Vicosa, Minas Gerais, Brazil
c
Departamento de Fsica, Universidade Federal de Vicosa, Av. PH Holfs, s/n, 36571-000 Vicosa, Minas Gerais, Brazil
b

a r t i c l e

i n f o

Article history:
Received 9 June 2015
Received in revised form 8 September 2015
Accepted 3 October 2015
Available online 9 October 2015
Keywords:
TiO2 photocatalysis
Layered double hydroxide
Phenol degradation
Semiconductor composite

a b s t r a c t
A series of TiO2 /MgZnAl photocatalysts were successfully synthesized from ternary (Mg, Zn and Al) layered double hydroxides impregnated with TiO2 nanoparticles by the co-precipitation method at variable
pH with different Zn2+ /Mg2+ molar ratios. The composite photocatalysts were calcined at 500 C resulting in the incorporation of oxide zinc, in the calcined MgZnAl LDH structure. Synergistic effect between
ZnO and TiO2 lead to signicant enhancement of TiO2 /MgZnAl photocatalytic activity. Composite photocatalysts were characterized by ICP-MS, N2 adsorption-desorption, XRD, SEM, EDS, IR and UVvis DRS.
Phenol in aqueous solution (50 mg/L) was used as a model compound for evaluation of UVvis (lter
cut-off for  > 300 nm) photocatalytic activity. The most efcient photocatalyst composite was obtained
at a 5% Zn2+ /Mg2+ molar ratio, in the catalyst identied as TiO2 /MgZnAl-5. This composite catalyst had
high photocatalytic activity, completely destroying phenol and removing 80% of total organic carbon in
solution after 360 min. The TiO2 /MgZnAl-5 catalyst remained relatively stable, presenting a 15% decrease
in phenol degradation efciency after ve consecutive photocatalytic cycles.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Titanium dioxide (TiO2 ) is a commonly used photocatalyst
because of its high oxidation potential, photostability, non-toxicity
and low cost [1]. However, the relatively high band-gap energy of its
more common anatase crystalline form (3.2 eV) limits its photocatalytic activity to the UV region, which represents only 45% of the
solar spectrum [24]. TiO2 also suffers from electron recombination
that can decrease its photocatalytic efciency [2]. However, TiO2
photocatalytic efciency can be improved by combining TiO2 with
other semiconductors [2,5,6] resulting in reduced electron recombination and a shift in maximum TiO2 absorption to the visible
region, improving photocatalytic process efciency [2]. Zinc oxide
(ZnO) has been combined with TiO2 , for this purpose because of
its photosensitivity, non-toxicity, ready availability, and low cost
[6,7].

Corresponding author. Tel.: +55 31 3899 3076; fax: +55 31 3899 3065.
E-mail address: bellato@ufv.br (C.R. Bellato).
http://dx.doi.org/10.1016/j.apsusc.2015.10.009
0169-4332/ 2015 Elsevier B.V. All rights reserved.

Layered double hydroxides (LDHs) or hydrotalcite-like anionic

mineral clays have an octahedral structure derived from the mineral brucite (Mg(OH)2 ) [8,9]. The general formula for ternary
LDHs is [M 1xy M y M3+
x (OH)2 ]
2+

 2+

 2+

2+

x+

[(An )x/n mH2 O]

, in which

M
and M
are different divalent cations,
is an n charged
3+
3+
anion and x and y are molar ratios x = M /(M + M2+ + M2+ );
y = M2+ /(M3+ + M2+ + M2+ ) [10]. The divalent and trivalent cations
are from the third and fourth periods of the periodic table of elements, that have ionic radii similar to Mg2+ (0.072 nm) and that
can occupy the octahedral interstices of crystal lattices similar to
those found in brucite. It is possible to introduce three or even four
metallic cations such as Zn2+ (0.074 nm) and Al3+ (0.054 nm) in the
brucite layers [11,12].
LDHs have recently been studied as photocatalysts and supports
for photocatalysts [1315]. Controlled thermal decomposition (calcination) of LDHs leads to collapse of layered structure and
formation of mixed oxides M2+ (M3+ )O [12,16,17]. In the work of
Prince et al. [12] zinc oxide was obtained by the calcination of LDH
of Zn(Ga)Al, which was applied in the photodegradation of phenol. Wang et al. obtained ZnO by the calcination of LDH of NiZnAl
An

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for photocatalytic degradation of Orange G dye [18]. While Tzompantzi et al. synthesized lamellar double hydroxides of ZnAlLa and
applied them for removal of phenol [16]. These mixed oxides semiconductors have a high surface area, basic properties in an aqueous
medium, thermal and structural stabilities, relatively low cost and
are easily and reused [19], all desirable properties for photocatalysts.
LDHs are interesting alternatives for dispersal and support
of TiO2 nanoparticles since they do not harm semiconductor characteristics [12,19,20]. Furthermore, TiO2 /LDH composite
photocatalysts have much higher sedimentation velocities than
TiO2 nanoparticles, facilitating their removal by physical processes
[21].
Combined ZnOTiO2 photocatalysts have been described in the
literature [15,2225] but no mention has been made to date of
photocatalysts synthesized with ZnO obtained by calcination of
double hydroxides layer by calcining the double ternary layer (Mg,
Zn and Al) impregnated with TiO2 nanoparticles (TiO2 /MgZnAl).
ZnO formed by calcination of TiO2 /MgZnAl composite may interact
synergistically with TiO2 leading to more efcient photodegradation of organic compounds. We therefore studied the effect of
varying Zn2+ /Mg2+ molar ratios in TiO2 /MgZnAl composites on phenol photodegradation under UVvis irradiation (lter cut-off for
 > 300 nm). The novel TiO2 /MgZnAl photocatalysts with potential for phenol photodegradation prepared in this work at different
Zn2+ /Mg2+ molar ratios (1%, 5%, 10% and 15%) have not yet, to the
best of our knowledge, been reported in literature.

2. Experimental
2.1. Reagents and materials
TiO2 used was the P25 acquired from Degussa, and consists of 70% anatase and 30% rutile. The commercial reagents
Mg(NO3 )2 6H2 O, Al(NO3 )3 9H2 O, Zn(NO3 )2 6H2 O, NaOH, Na2 CO3
and phenol were obtained from SigmaAldrich and used as
received. All solutions were prepared with analytical grade
reagents and high purity deionized water produced by a Milli-Q
system (Millipore, Bedford, MA, USA).

2.2. Preparation of TiO2 /MgZnAl

MgZnAl LDH with TiO2 nanoparticles was prepared at molar
ratio (Zn2+ + Mg2+ ):Al3+ :Ti4+ equal to 2:1:1 in the presence of
NaOH and Na2 CO3 . For this, 100 mL of solution containing
Mg(NO3 )2 6H2 O, Al(NO3 )3 9H2 O and Zn(NO3 )2 6H2 O were added
dropwise at a rate of 60 mL/h, to 100 mL of an alkaline solution
containing a xed proportion of TiO2 nanoparticles (0.0255 mol
Ti), NaOH (2.45 mol/L) and the anion to be intercalated Na2 CO3
(1.23 mol/L) under vigorous stirring at room temperature. The
gelatinous precipitate containing TiO2 were stirred at room temperature for a further 140 min after which the pH was adjusted to
1010.5 and the mixtures were transferred to a porcelain crucible
and placed in an oven at 60 C for 18 h. Subsequently, the suspensions were washed with deionized water until reaching pH 7 and
the precipitates obtained were dried at 80 C for 16 h and then
calcined in a mufe furnace at 500 C for 4 h. The calcined photocatalyst composite were designated using the formula TiO2 /MgZnAl-R,
where R represents the approximate percent molar ratio of Zn2+ to
Mg2+ (1%, 5%, 10% or 15%). According to this scheme the composites were denominated TiO2 /MgZnAl-1 (TiO2 /Mg0.0505 Zn0.0005 Al),
TiO2 /MgZnAl-5 (TiO2 /Mg0.0484 Zn0.0025 Al), TiO2 /MgZnAl-10 (TiO2 /
Mg0.0459 Zn0.0051 Al) and TiO2 /MgZnAl-15 (TiO2 /Mg0.0433 Zn0.0076 Al),
respectively. The chemical formulae in parentheses represent the

initial composition of preparation, where x and y stands for the

content of magnesium and zinc, respectively.
The calcined composite without zinc was designated as
TiO2 /MgAl (TiO2 /Mg0.0510 Al) and the non-calcined composites as TiO2 /MgAl-CO3 , TiO2 /MgZnAl-CO3 -1, TiO2 /MgZnAl-CO3 -5,
TiO2 /MgZnAl-CO3 -10 and TiO2 /MgZnAl-CO3 -15.
MgAl-CO3
(Mg0.0510 Al-CO3 )
and
MgZnAl-CO3 -5
The
(Mg0.0484 Zn0.0025 Al-CO3 -5) LDHs were prepared by the procedure previously described but without incorporation of TiO2 .
The hydrotalcite calcined at 500 C was denominated MgAl
(Mg0.0510 Al).
2.3. Photocatalyst characterization
Determination of the nal photocatalyst chemical compositions
was made by mixing 0.100 g of each sample with 4 mL HNO3 (65%),
4 mL HCl (37%) and 1 mL HF (40%) followed by digestion in an industrial microwave oven (Milestone ETHOS) by heating to 230 C in
15 min and maintaining this temperature for 25 min at 1.200 W.
The digested samples were diluted and metals concentrations were
determined by ICP-MS, Perkin-Elmer model NexION 300D.
Textural properties of the samples were analyzed by their N2
adsorptiondesorption isotherms using a surface area and pore
size analyzer (NOVA 2200e Quantachrome Instruments, Boynton Beach, FL, USA). Prior to measurement, the samples were
degassed at 110 C for 4 h. Surface areas were estimated by the
BrunauerEmmettTeller (BET) method and pore volumes were
determined by the HorvthKawasoe (HK) method applied to the
desorption branch.
X-ray diffraction (XRD) was measured by 2 scans using
a Bruker model D8 Discover diffractometer using Cu K radiation ( = 0.1541 nm) with an angular variation of 580 angle
(2) and 0.05 s1 scan rate. The Powder Diffraction File (PDF)
database (JCPDS, International Center for Diffraction Data) was
used to identify crystalline phases. Network parameters (dh k l ) of
the composites were calculated according to the Bragg equation:
 = 2d sen  where  is the wavelength of X-rays ( = 0.1541 nm),
and  is the diffraction angle [18].
Scanning electron microscopy (SEM) images were obtained after
sample mettalization with gold using a JEOL JSM-6010/LA microscope. The SEM equipment was equipped with an energy dispersive
spectrometry system (EDS) for analysis of sample chemical composition.
Infrared spectroscopy (IR) were obtained using a VARIAN 660-IR
spectrophotometer equipped with an attenuated reectance accessory PIKE GladiATR in the region of 4004000 cm1 .
Diffuse reectance spectra (RD) were acquired (reference
BaSO4 ) in a dual beam spectrophotometer model GBC 20 CINTRA
at 0.5 nm intervals at a scan speed of 10 nm/min with a 2.0 mm gap
width.
2.4. Photocatalytic activity
Photocatalytic activity of the composites with different molar
ratios of Zn2+ /Mg2+ was assessed by photodegradation of a phenol solution in an annular photoreactor shown schematically in
Fig. 1. The reactor consisted of a Pyrex glass cylinder (40.0 cm long,
4.0 cm internal diameter, lter cut-off for  > 300 nm) with a 125 W
mercury vapor lamp (HQL, Osram without the bulb protector) at
its center within a concentric glass cylinder (7 cm diameter, 60 cm
height, 1000 mL total capacity) surrounded by a recirculating water
bath maintained at 30 2 C. Reactions were run with 300 mL of a
50 mg/L phenol solution and 300 mg of catalyst magnetically stirred
in the dark for 60 min to establish adsorptiondesorption equilibrium and then exposed to UVvis radiation for 360 min.

M.F. de Almeida et al. / Applied Surface Science 357 (2015) 17651775

1767

Volume adsorbed (a.u.)

G
F
E

D
C
B
A

0.0

0.2

0.4

0.6

0.8

1.0

Relative Pressure (P/P0)

Fig. 2. N2 adsorptiondesorption isoterms of photocatalyst samples: TiO2 (A),
MgAl (B), TiO2 /MgAl (C), MgZnAl-5 (D), TiO2 /MgZnAl-1 (E), TiO2 /MgZnAl-5 (F),
TiO2 /MgZnAl-10 (G) and TiO2 /MgZnAl-15 (H).

Fig. 1. Illustration of the annular photoreactor.

Three milliliters of the reaction solution were removed using a

syringe every 60 min for 360 min and ltered through a 0.45 M
membrane (Millipore) for phenol and total organic carbon (TOC)
quantication.
The monitoring of the remaining phenol concentrations were
carried out by High Performance Liquid Chromatography using a
1260 Innity system (Agilent Technologies) with a linear photodiode array detector (HPLC-DAD) at 270 nm, isocratic mode,
reversed-phase Zorbax Eclipse Plus C18 (4.6 mm 150 mm,
5.0 m) column, injected volume 10 L, column temperature of
30 C and a ow of mobile phase methanol:water (55:45, v/v) at
1.0 mL/min. Total organic carbon was quantied using a TOC-5000A
analyzer from Shimadzu.
Photolysis was evaluated using 300 mL of phenol solution
(50 mg/L, initial pH 5.2) under UVvis radiation without catalyst.
For adsorption tests, 300 mg of sample were added to 300 mL of
phenol solution (50 mg/L, initial pH 5.2) without UVvis radiation.
Photolysis and adsorption studies were also run for 360 min and
3 mL were removed at 60 min intervals for phenol quantication
by HPLC-DAD. All studies were performed in triplicate.

2.5. Reuse assays

Photocatalysts were washed with deionized water and dried
before reuse. The photocatalysts were characterized by X-ray
diffraction techniques and infrared spectroscopy before and after
each photodegradation cycle to verify its stability.
3. Results and discussions
3.1. Photocatalyst characterization
3.1.1. Chemical composition and textural analyses
Table 1 presents the nal metal composition of the synthesized photocatalysts in which nal (Zn2+ + Mg2+ )/Al3+ ,Ti4+ /Al3+ and
Zn2+ /Mg2+ molar ratios found were lower than theoretically predicted. These differences may have been caused by incomplete
incorporation of cations inside the lamellar of LDH or preferential precipitation of cations as hydroxide [12,18,26]. In either case,
the molar ratios obtained for the photocatalysts proved that the
calcination process caused no signicant loss of metal elements.
The N2 adsorptiondesorption isotherms are shown in Fig. 2.
The prepared materials present type IV isotherms according to the
IUPAC classication that correspond to mesoporous materials [17].

Table 1
Initial and nal chemical composition, nal molar ratio and textural analysis of synthesized photocatalysts.
Sample

TiO2
MgAl
MgZnAl5
TiO2 /MgAl
TiO2 /MgZnAl-1
TiO2 /MgZnAl-5
TiO2 /MgZnAl-10
TiO2 /MgZnAl-15
a
b

Chemical composition

Molar ratio (nal)

Initial

Final

Mg0.0510 Al0.0255
Mg0.0484 Zn0.0025 Al0.0255
TiO2(0.0255) /Mg0.0510 Al0.0255
TiO2(0.0255) /Mg0.0505 Zn0.0005 Al0.0255
TiO2(0.0255) /Mg0.0484 Zn0.0025 Al0.0255
TiO2(0.0255) /Mg0.0459 Zn0.0051 Al0.0255
TiO2(0.0255) /Mg0.0433 Zn0.0076 Al0.0255

Mg0.0402 Al0.0210
Mg0.0442 Zn0.0021 Al0.0260
TiO2(0.0208) /Mg0.0504 Al0.0281
TiO2(0.0166) /Mg0.0418 Zn0.0004 Al0.0221
TiO2(0.0193) /Mg0.0470 Zn0.0022 Al0.0270
TiO2(0.0187) /Mg0.0436 Zn0.0041 Al0.0269
TiO2(0.0236) /Mg0.0496 Zn0.0071 Al0.0324

4.75

0.92
4.68
9.41
14.30

Zn2+ /Mg2+ molar ratios in percent.

The (Zn2+ + Mg2+ )/Al3+ and Ti4+ /Al3+ molar ratios were kept constant.

Zn2+ /Mg2+

(Zn2+ + Mg2+ )/Al3+

1.91
1.78
1.80
1.91
1.82
1.77
1.75

SBET (m2 /g)

Pore volume
(cm3 /g)

48.4
160.1
123.3
100.5
99.4
89.7
85.0
79.9

0.0178
0.0428
0.0495
0.0321
0.0398
0.0406
0.0353
0.0307

Ti4+ /Al3+

0.74
0.75
0.71
0.69
0.73

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M.F. de Almeida et al. / Applied Surface Science 357 (2015) 17651775

(003)

H
(003)

(003)
(006)

Intensity (a.u.)

A(101)
(113)
R(110) (009) A(200) (110)

(003)

E
(006) (009)

(003)

(015) (018)

(110)

A(200)
(003) A(101) (009)
(110)
(006) R(110) R(110)

(003)

(006)

A
10

20

A(204)

(110) (113)
(009)

B
A(101)

(113)
(116)

(015) (018)

(116)

A(105)
R(110) A(004) A(200) A(211) A(116) A(220)
A(204)
A(216)
R(110) R(111)

30

40

50

60

70

80

2
Fig. 3. X-ray diffraction spectra of the non-calcined samples: TiO2 (A), MgAl-CO3
(B), TiO2 /MgAl-CO3 (C), MgZnAl-CO3 -5 (D), TiO2 /MgZnAl-CO3 -1 (E), TiO2 /MgZnAlCO3 -5 (F), TiO2 /MgZnAl-CO3 -10 (G) and TiO2 /MgZnAl-CO3 -15 (H). A, anatase; R,
rutile.

Hysteresis loops were of type H3, indicating the presence of asymmetric pores (non-uniform size and shape) created by the collapse
of LDH lamella upon calcination [19]. The textural properties of all
samples are listed in Table 1. The highest surface area was found for
MgAl and the lowest for TiO2 . The textural properties determined
for MgAl and TiO2 were in agreement with values reported in the
literature [19,27]. Combined TiO2 /MgAl had a much larger specic
surface area than pure TiO2 because of the presence of MgAl LDH.
The difference between TiO2 /MgAl and MgAl surface areas was
caused by TiO2 nanoparticle blockage. These nanoparticles were
previously shown to partially block supporter pores, resulting in a
decrease in BET surface area of hydrotalcite (MgAl) [28]. As shown
in Table 1, TiO2 /MgZnAl-R composite surface areas decreased gradually with the increase in zinc (Zn2+ /Mg2+ ) content, in agreement
with other studies [8,17,29]. TiO2 /MgZnAl-5 presented the highest
surface area and pore volume of the zinc-containing composites
(Table 1).
3.1.2. X-ray diffraction
The XRD spectra obtained for the non-calcined samples are
shown in Fig. 3. Fig. 3A shows the main peaks for TiO2 . The peaks
are labeled A(h k l) or R(h k l) relating to the anatase (JCPDS #211272)) or rutile (JCPDS #21-1276) phases, respectively, and agree
the crystallographic standards found in the literature [3032].
MgAl-CO3 (Fig. 3B) exhibited diffraction peaks with interplanar
distances of 7.69 A (0 0 3), 3.79 A (0 0 6), 2.59 A (0 0 9), 2.32 A (0 1 5),
1.90 A (0 1 8), 1.52 A (1 1 0), 1.49 A (1 1 3) and 1.41 A (1 1 6), also
agreeing with the values cited in the literature [3335]. The peaks
(0 0 3) and (0 0 6) are basal peaks that conrm the solid obtained has
a double layer structure, with a high degree of crystallinity, which
corresponds to hydrotalcite-like material (JCPDS # 22-0700) [35].
The ternary LDH of the MgZnAl-CO3 -5 (Fig. 3D) showed interplanar

Fig. 4. X-ray diffraction spectra of the calcined samples: MgZnAl-5 (A), TiO2 (B),
TiO2 /MgAl (C), TiO2 /MgZnAl-1 (D), TiO2 /MgZnAl-5 (E), TiO2 /MgZnAl-10 (F) and
TiO2 /MgZnAl-15 (G). A, anatase; R, rutile.

distances of 7.59 A (0 0 3), 3.80 A (0 0 6), 2.59 A (0 0 9), 2.33 A (0 1 5),

1.90 A (0 1 2), 1.52 A (1 1 0) and 1.49 A (1 1 3), similar to the peaks
in the literature [29].
In the synthesized composite impregnated with TiO2 nanoparticles in the LDH (Fig. 3C and Fig. 3EH) one can observe the
diffraction peaks for LDH (2 = 11.6, 23.4, 34.6, 60.7 and 62) and for
the TiO2 in its anatase and rutile phase. However, there is a decrease
in the intensity of the reection peaks, related to the LDH. This is
probably due to the disorder caused by the random incorporation
of TiO2 nanoparticles inside the LDH lamellar structure can lead to
broad peaks and a low intensity [20,21,36,37]. One can also observe
an increase in the (0 0 3) inter-layer distance from 7.69 (MgAl-CO3 )
to 7.72 A (TiO2 /MgAl-CO3 ) and from 7.59 A in MgZnAl-CO3 -5 to
7.62 A in TiO2 /MgZnAl-CO3 -5 caused by TiO2 incorporation.
On the other hand, the substitution of Mg2+ by Zn2+ , there is a
decrease in the interlayer distance, from 7.72, for TiO2 /MgAl-CO3
photocatalyst to 7.66 A for TiO2 /MgZnAl-CO3 -1. This decrease in
interlayer distance continues with the increase in Zn+2 /Mg+2 molar
TiO2 /MgZnAlratio in the composites TiO2 /MgZnAl-CO3 -5 (7.62 A),
and TiO2 /MgZnAl-CO3 -15 (7.56 A).
This behavior
CO3 -10 (7.60 A)
can be explained by an increase in the charge density in the layer
because of the higher electronegativity of zinc compared to the
magnesium [29]. Incorporation of a cation with a greater electronegativity increased the forces of attraction and decreased the
interlayer distance between the hydrotalcite layers [29].
After calcination, there is a collapse of LDH structure forming
mixed oxides of metals (Fig. 4) [29,38]. The calcined MgZnAl5 (Fig. 4B) shows intense peaks related to ZnO and also MgO
(periclase) similar to crystallographic descriptions in the literature [7,8,30,36]. Peaks related to TiO2 and magnesium oxide were
observed in the TiO2 /MgAl composite (Fig. 4C). In the composite
containing zinc (Fig. 4DG), a peak related to the ZnO (2 = 34.9 )

M.F. de Almeida et al. / Applied Surface Science 357 (2015) 17651775

1769

Fig. 5. SEM image of the composite TiO2 /MgZnAl-CO3 -5 (A) and TiO2 /MgZnAl-5 (B).

D
1632

Fig. 6. Energy dispersive spectra (EDS) for TiO2 /MgZnAl-5.

Transmittance (%)

3451
1639

1371

1639

1364

3430

825 778

3444
1632

was formed by zinc in the hydratalcite layers [39]. However, there

was a slight decrease in the peak related to the MgO because of the
increased molar ratio of zinc in the MgAl LDH structure at 2 equal
to 43.2 and 62.8 . A decrease in the MgO peak was also observed
after increasing the molar proportion of zinc in a calcined MgZnIn
LDH [8,40].
3.1.3. Scanning electron microscopy and energy dispersive
spectroscopy
Fig. 5A shows the micrograph of the non-calcined photocatalyst TiO2 /MgZnAl-CO3 -5 where there is a random coating of the
LDH layers of the MgZnAl-5 by the nanoparticles of TiO2 forming
agglomerates with a spongy appearance, which are responsible by
increasing the heterogeneity of the surface of the photocatalysts
[37,41]. After the calcination (Fig. 5B), the lamellar structure collapses and a solid solution of mixed oxides with some large particles
are formed, further increasing the heterogeneity of the surface. This
can probably be attributed to the collapse of the lamellar structure,
which occurs during the calcination stage [26] as can be observed
by the absence of the (0 0 3) and (0 0 6) peaks in the XRD data [37].
Energy dispersive spectroscopy (EDS) results (Fig. 6) conrmed
the expected metals composition in the TiO2 /MgZnAl-5 composite of 15.2% Mg, 0.71% Zn, 7.52% Al and 7.86% Ti, corresponding to a
Zn:Mg:Al:Ti ratio of 2.01:1:1.04 and a Zn2+ /Mg2+ ratio of 4.68%. The
molar ratio found by EDS agreed with the molar ratio used to synthesize the composite (2:1:1) and conrmed by ICP-MS (Table 1).
3.1.4. Infrared spectroscopy analysis
Fig. 7A shows the spectrum obtained for the TiO2 nanoparticles,
where there is an absorption band in the low frequency region
400800 cm1 associated with TiOTi. The absorption band at
1632 cm1 due to the presence of the bending vibration of the OH
due to re-absorption of water from the atmosphere through the
TiO2 nanoparticles (Ti-OH) [42].
In Fig. 7B, the wide absorption band at 3444 cm1 is attributed to
vibratory stretching of the OH (OH) groups of inter-layer water

3439
4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )
Fig. 7. Infrared spectra: TiO2 (A), MgZnAl-CO3 -5 (B), TiO2 /MgZnAl-CO3 -5 (C) and
TiO2 /MgZnAl-5 (D).

molecules and also of the layers of metal hydroxides in the layers MgZnAl-CO3 -5 [18]. The weak band near 1632 cm1 is assigned
for to bending mode of water molecules. A band at 1364 cm1 is
attributed to the symmetric stretching of carbonate ions. In addition, absorption bands below 1000 cm1 are mainly corresponding
to metaloxygen vibration and metaloxygenmetal layers of the
brucite type. According to the literature these bands centered at
778 cm1 and 825 cm1 are assigned to the LDH MgAl and ZnAl,
respectively [18,43].
According to Fig. 7C, it is clear that the incorporation of TiO2 to
the calcined MgZnAl-5 LDH did not impair the lamellar formation,
because there is still the presence of bands at 825 and 778 cm1 .
After the heat treatment at 500 C (Fig. 7D), we can see a decrease
in the bands related to the hydroxyls (3451 cm1 ) and carbonates
(1371 cm1 ) indicating the loss of water and CO2 , as expected. The
presence of TiO2 in the calcined composite TiO2 /MgZnAl-5 can
be evidenced by the lead shoulder OTiO at 400800 cm1 . The
change of Zn2+ /Mg2+ molar ratio has not introduced any signicant
differences in the infrared spectra.
3.1.5. Determination of band-gap values
Fig. 8 shows the absorption spectra of photocatalyst obtained by
the UVvis diffuse reectance. TiO2 showed an intense absorption
band in the UV region below 385 nm that originated from charge
transfer that occurs between the 2p orbital of the oxygen atom to
the 3d of the Ti [44].
Maximum absorption shifted to longer wavelengths in the calcined composites with higher Zn2+ /Mg2+ molar ratios indicating

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M.F. de Almeida et al. / Applied Surface Science 357 (2015) 17651775

1.6

0.9

TiO2/MgZnAl-10

1.2

TiO2/MgZnAl-5

1.0

TiO2/MgZnAl-1

0.8
0.7

C/C0

Absorbance

1.0

TiO2/MgZnAl-15

1.4

TiO2/MgAl

0.8

TiO2

0.6

TiO2

0.5

TiO2/MgAl

0.3

Photolysis
MgZnAl-5
TiO2/MgZnAl-1

0.4

0.2

TiO2/MgZnAl-5

0.2

0.1

0.6

0.4

0.0

0.0

-50

TiO2/MgZnAl-10
TiO2/MgZnAl-15
Adsorption (TiO2/MgZnAl-5)

50

-0.2

100

150

200

250

300

350

Time (min)

300

400

500

600

700

Wavelenght (nm)

Fig. 10. Phenol concentration as a function of time in different photocatalytic

treatments. Reaction conditions: initial phenol concentration of 50 mg/L, 300 mg
photocatalyst, reaction temperature 30 2 C and initial pH 5.2.

Fig. 8. UVvis absorption spectrum of the photocatalysts.

TiO2/MgZnAl-10

1/2

[F(R)h]

calcination of the composites, since this oxide has a band-gap of

about 3.0 eV and when combined with the TiO2 (3.2 eV) it decreased
band-gap [6,49]. Thus, it is observed that the increase in composite
Zn2+ /Mg2+ molar ratio decreases the band-gap energy from 3.12 eV
in TiO2 /MgAl to 3.08 eV in TiO2 /MgZnAl-1, 3.06 eV in TiO2 /MgZnAl5, 3.04 eV in TiO2 /MgZnAl-10 and 3.00 eV in TiO2 /MgZnAl-15. Other
studies have also reported that an increase in the molar ratio of Zn
reduced band-gap values [17,29].

TiO2/MgZnAl-15

TiO2/MgZnAl-5
TiO2/MgZnAl-1

TiO2/MgAl

TiO2

3
2

3.2. Photocatalytic activity

1
0
2.0

2.5

3.0

3.5

4.0

Eg (eV)
Fig. 9. Determination of band-gap values (Eg ) for photocatalysts.

that less energy would be necessary for photocatalytic activity. This

shift was purportedly due to electronic interaction of molecular
orbitals between Zn, Mg, Al, with TiO2 building a new molecular orbit and thus, reducing the difference in the band of energy.
Similar phenomenon was observed for TiO2 in associated with
other compounds such as zinc oxide [45] graphene oxide [46],
carbon graphene nanotubes [47] and lamellar double hydroxidehydrophobic MgAl [37].
The band-gap energy (Eg ) was determined by the Tauc relation
using the transformed KulbelkaMunk function according to the
following equations [48]:
h = A(h Eg )
n

(1)

[F(R)h] = A(h Eg )

(2)

(1 R)2
2R

(3)

F(R) =

where h is Plancks constant,  is the frequency of vibration, coefcient A is a constant, Eg is the band-gap value, R is the diffuse
reectance, value n is equal to 1/2 for direct transitions. The determination of band-gap energy for photocatalysts were calculated
by extrapolating the linear region to the x-axis, plotting the transformed KulbelkaMunk equation [F(R)h]1/2 versus the energy
band-gap (h) as shown in Fig. 9. It can be seen that the energy
band-gap decreased from 3.2 eV for TiO2 to 3.12 eV for the composite TiO2 /MgAl. However, after substitution of Mg by Zn cations in
the hydrotalcite structure, the band-gap energy shifted to the visible region. This was attributed to the formation of zinc oxide during

In the studies on the absence of UVvis the removal of the

phenol was evaluated by means of adsorption. According to
Fig. 10, the TiO2 /MgZnAl-5 photocatalyst adsorbed 3% of the
phenol after 360 min in the absence of UVvis radiation. In all
(photo)degradation assays the phenol solution pH increased from
5.2 to 9.7 after 30 min and then gradually increased to 10.6
over 360 min. The increase in the pH value during the experiments provides evidence for the lamellar reconstruction of calcined
hydrotalcite that also observed in other studies [29,34]. According
to Chen et al. [50], during the lamellar reconstruction of hydrotalcite the interleaving with the phenol molecule is reduced. The
benzyl ring phenol at pH 10.7 is hydrophobic and bulky and so does
not provide any electrostatic interaction with the layers of hydroxides present in the layers of the composite; and also has a weak
afnity for the phenolate anion. These authors suggest that the
afnity of phenolate for LDH should be much weaker than hydroxyl
ion ( OH). Although more than 60% of phenol can dissociate to phenolate anion at pH 1011 (pKa = 9.8), the degree of interleaving of
the phenolate is low, most of the aqueous phase remains [50]. Allied
to this, there is a preference in the reconstruction of the LDH by the
CO3 2 , principally under basic conditions, thus reducing the possibility of merging with the phenol molecule [50]. The presence of
carbonate in the TiO2 /MgZnAl-5 photocatalyst was conrmed by
its adsorption band at 1380 cm1 in the IR spectrum of the reused
material (Fig. 15C).
UVvis photolysis alone degraded 14% of the initial phenol
while the addition of photocatalysts increased phenol degradation. The TiO2 /MgAl catalyst removed 60% of the phenol whereas
the photocatalysts containing zinc produced greater phenol photodegradation. As shown in Fig. 10, it can be seen that with the
increase in the Zn2+ /Mg2+ molar ratio from 1% to 5% increased phenol photodegradation 88 to approximately 100%. The increase in
molar ratio of Zn to 10% and 15% provided a decrease in the amount
of phenol removed of 93% and 82%, respectively. These results may
be due to the large surface area, pore volume (Table 1) and the

M.F. de Almeida et al. / Applied Surface Science 357 (2015) 17651775

1.1
1.0
0.9
0.8

TOC/TOC0

addition of optimum amount of the zinc oxide in the hydrotalcite

layers in the composite TiO2 /MgZnAl-5, which imply a larger number of sites available for interaction with the TiO2 and enhancement
of photocatalytic properties. Large surface areas of the composite
photocatalysts produce more electronhole pairs and thus increase
the hydroxyl radical formation to photodegradation of phenol [51].
Furthermore, in the composite prepared with a lower molar ratio
of zinc (1% and 5% versus 10% and 15%) this element is probably more uniformly distributed along the hydrotalcite layers [29].
On the other hand, the incorporation of an excess of the Zn (10%
and 15% zinc, observed in this study) to replace the Mg, indicated
an enhanced stress in the hydrotalcite crystal structure because
of the differences between the ionic radii of Zn (0.074 nm) and
Mg (0.072 nm) [11,52]. Therefore, the incorporation of Zn into the
stable layer structure is limited, otherwise the structure will be
damaged [8].
Less Mg in the hydrotalcite structure could lead to a smaller
surface area, pore volume and an irregular distribution of the zinc
as observed in this study (Table 1) and evidenced by Valente et al.
[29], Alanis et al. [17] and Snchez-Cant et al. [53]. Presence of Mg
in the composite probably improved photocatalyst stability, similar
to other ternary LDHs [8,54] and contributed to dispersion of ZnO
on the surface of calcined samples [8].
The results obtained in this study are consistent with those
of Valente et al. [29] who observed that increasing zinc content
above 5% (m/m) in MgZnAl LDH photocatalysts decreased efciency of photodegradation of 2,4-dichlorophenoxyacetic acid and
phenol. According to the authors the superiority of hydrotalcite
with 5% Zn was due to the increase in catalytically active sites
and improved distribution of the ZnO along the layers of brookite,
since the distribution of a second divalent cation is non-uniform
after the reconstruction the calcined LDH. Huang et al. studied
methylene blue photodegradation using MgZnIn ternary LDH
and found that adjusting the Mg2+ /Zn2+ molar ratio to obtain a
maximum surface area resulted in higher photocatalytic efciency
[8].
Tzompantzi et al. [49] found that a Zn/Al molar ratio of 1.47
resulted in higher photocatalytic efciency than molar ratios of 1.67
and 3.81. This behavior was evident in the composites synthesized
in our work. Several studies have shown that the increase in the
ratio of Zn with respect to TiO2 did not result in increased in photocatalytic efciency [6,7,55,56]. According to Zhao et al., the excess
Zn associated with TiO2 can lead to excessive formation of surface oxygen vacancy, which act as electron traps and thus slow the
electronic transfers, thereby reducing photocatalytic activity [57].
Thus, an excess of zinc present in the hydrotalcite structure impregnated with TiO2 (TiO2 /MgZnAl) would reduce the photocatalytic
efciency of TiO2 .
The MgZnAl-5 photocatalyst produced 73% phenol removal
while its combination with TiO2 (TiO2 /MgZnAl-5) increased
removal by 27%, resulting in 100% photodegradation efciency.
The increased efciency was caused by increased hydroxyl radical
( OH) generation because of the greater number of electronhole
pairs generated upon radiation of the TiO2 -containing photocatalyst. Therefore, it is necessary to have an appropriate molar ratio
of Zn, Mg, Al and TiO2 in order to achieve efcient photocatalytic
degradation of phenol.
TOC removal was also quantied (Fig. 11) to measure the degree
of phenol mineralization. The TiO2 /MgZnAl-5 catalyst that produced the greatest phenol removal (Fig. 10) also resulted in the
highest TOC reduction, reaching about 80% after 360 min.
The proposed scheme for phenol degradation by TiO2 /MgZnAl-5
presented in Fig. 12 can be summarized as follows: when a photon
(h) of energy equal to or greater than the band-gap energy hits the
particles of the photocatalyst TiO2 /MgZnAl-5 an electron valence
band (VB) is promoted to the conduction band (CB), leading to the

1771

0.7
TiO2

0.6

TiO2/MgAl

0.5

Photolysis
MgZnAl-5
TiO2/MgZnAl-1

0.4
0.3

TiO2/MgZnAl-5
TiO2/MgZnAl-10

0.2

TiO2/MgZnAl-15

0.1
0

50

100

150

200

250

300

350

Time (min)
Fig. 11. TOC removal during photodegradation of a phenol solution. Reaction conditions: initial phenol concentration of 50 mg/L, 300 mg photocatalyst, reaction
temperature 30 2 C and initial pH 5.2.

simultaneous generation of a hole in the valence band (h+ ) and

excess electrons in the conduction band (e ) (Eq. (4)) [58].
h

TiO2 /MgZnAl-5TiO2 /MgZnAl-5(h+

VB ) + TiO2 /MgZnAl-5(eCB )

(4)
(h+ )

These photogenerated holes

possess sufciently positive
potential to generate OH radicals from water molecules adsorbed
on its the photocatalyst surface (Eq. (5)) or from hydroxyl ions (Eq.
(6)) that can subsequently oxidize the organic pollutant (Eqs. (7)
and (8)) [16,58,59]
+

TiO2 /MgZnAl-5(h+
VB ) + H2 Oads OH + H

(5)

TiO2 /MgZnAl-5(h+
VB ) + OH

(6)

oxidation of phenol

(7)

OH

TiO2 /MgZnAl-5(h+
VB ) + phenol

OH + phenol degradation of phenol

(8)

Allied to this, the hydroxyl groups present in the LDH structure can react with the photogenerated hole in the VB of TiO2 , and
thereby promote the production of OH [37,41,59].
The presence of oxygen in the CB can generate a super-peroxide
anion (Eq. (9)), which can produce organic peroxide (Eq. (10)) and
hydrogen peroxide (Eq. (11)) that also generate OH radicals (Eq.
(12)) [16,5860].
TiO2 /MgZnAl-5(e
) + O2 O
2
CB

O2

+ Phen Phen-OO

O2

+ HO2

(10)

+ H H2 O2 + O2

TiO2 /MgZnAl-5(e
) + H2 O2
CB

(9)

(11)

OH

(12)

The presence of oxides formed during LDH calcination can

inuence generation of the hydroxyl radical (Eqs. (13) and (14)).
Hydroxyl radical can be reduced by the electrons in the conduction band and thereby promote the reconstruction of oxide with
the re-hydroxylation (Eq. (15)) [17,18].


OxideOxide(h+
VB + eCB )

(13)

Oxide(h+
VB ) + H2 Oads Oxide + OHads + H

Oxide(e
)+ OHads
CB

Oxide +

OH
ads

(14)
(15)

Combination of the ZnO semiconductor obtained by the calcining LDH with TiO2 made it possible to visible radiation for

1772

M.F. de Almeida et al. / Applied Surface Science 357 (2015) 17651775

Fig. 12. Schematic diagram of the photocatalytic processes occurring on the surface of the TiO2 /MgZnAl-5.
Table 2
Comparison of different photocatalysts used in phenol photodegradation.
Photocatalyst

Initial concentration (mg/L)

Experimental condition

Dose (g/L)

Rate (%) of degradation

Ref.

Fe-TiO2
N-Si co-doping TiO2
ZnO/La2 O3 (doped with K)
CeO2 -ZnTi-LDHs
ZnAlLa
CeO2 -TiO2 /SiO2
TiO2 /MgZnAl-5

33.5
10
20
50
40
30
50

High-pressure lamp 125 W; UVvis

500 W Xenon lamp; UVvis
300 W halogen lamp; UVvis
Mercury lamp; 300 W
Mercury lamp, 300 W; UVvis radiation
350 W; radiation 3002500 nm
Hg vapor lamp 125 W; radiation > 300 nm

1.0
1.0
1.0
1.0
1.0
2.0
1.0

8 h of radiation: 66
8 h of radiation: 99
2.5 h radiation: 98.5
After 7 h of radiation: 90
5 h radiation: 100
3 h radiation: 96.2
After 6 h of radiation: 100

[63]
[64]
[65]
[66]
[16]
[67]
This study

photocatalysis (Fig. 8) [61]. Electron created in ZnO CB, after irradiation can migrate to the CB of TiO2 , and promote catalytic process
(Eq. (16)) [57,62].
ZnO(e
) TiO2 (e
)
CB
CB

(16)

Table 2 presents a summary of photocatalytic phenol degradation studies published in the literature. It can be seen that phenol
degradation by TiO2 /MgZnAl-5 showed satisfactory performance
compared to other catalysts previously reported.

where
C0
is
the
initial
phenol
concentration
at
adsorptiondesorption equilibrium at t = 0 min and Kapp is the
apparent rate constant (Kapp = kr Kad ) [70]. In this model, the slope
of the ln(C0 /C) versus time (t) plot is the apparent rate constant
(Kapp ).
Fig. 13 presents results of the phenol photodegradation kinetic
studies that were used to determine apparent rate constants (Kapp )
and phenol half-lives (t1/2 ). Half-life time (t1/2 ), the time at which
C = 0.5C0 , is one of the most useful values to compare pseudo-rstorder reaction rates (Eq. (19)) [48],
ln(2)
Kapp

3.3. Kinetics of phenol photodegradation

t1/2 =

The LangmuirHinshelwood is commonly used to describe the

kinetics of pseudo-rst-order degradation of organic pollutants,
which occur at the solidliquid interface [18]. This model relates
the degradation rate r (mg/L min), reaction time t (min) and the
concentration of the organic compound C (mg/L), as expressed in
Eq. (17) [68]

Phenol (Fig. 13A) and TOC (Fig. 13B) photodegradation results

adjusted well to the pseudo-rst-order kinetic model, with
coefcients of determination, R2 > 0.98 (Fig. 13). Apparent rate
constants (Kapp ), half-lifes time (t1/2 ), and the coefcients of determination (R2 ) are summarized in Table 3.
Half-lives of 248.4 min (phenol by HPLC-DAD) and 545.8 min
(TOC) were found for photodegradation with the TiO2 /MgAl composite. Incorporation of Zn into the hydrotalcite layers increased
the reaction rate, with TiO2 /MgZnAl-5 reducing half-lives to
60.8 min (phenol by HPLC-DAD) and 248.4 min (TOC), corresponding to Kapp = 0.0114 min1 (phenol by HPLC-DAD) and 0.0040 min1
(TOC). In comparison, Valente et al. [29] reported phenol degradation by a MgZnAl LDH of about 70% (initial concentration
40 mg/L) after 6 h, with Kapp = 0.0033 min1 and t1/2 = 208.2 min.
Prince et al. obtained nearly 80% phenol degradation by LDH3ZnAl-c after 6 h for the same initial phenol concentration

r=

dC
kr Kad C
=
1 + Kad C
dt

(17)

where kr is the intrinsic rate constant and Kad is the adsorption

equilibrium constant. At low initial organic compound concentration Kad C is negligible [29,69] and the model reduces to Eq. (18)
that describes pseudo-rst-order kinetics over the interval [C, C0 ].
ln

C0
= Kapp t
C

(18)

(19)

M.F. de Almeida et al. / Applied Surface Science 357 (2015) 17651775

Photolysis
MgZnAl-5
TiO2

1.4

TiO2/MgAl
TiO2/MgZnAl-1

TiO2/MgZnAl-5
TiO2/MgZnAl-10

Photolysis
MgZnAl-5
TiO2

1.6

-ln(TOC/TOC0)

-ln(C/C0)

TiO2/MgZnAl-15

1773

TiO2/MgAl

1.2

TiO2/MgZnAl-1
TiO2/MgZnAl-5

1.0

TiO2/MgZnAl-10

0.8

TiO2/MgZnAl-15

0.6
0.4

0.2

0.0
0

50

100 150 200 250 300 350

50

100 150 200 250 300 350

Time (min)

Time (min)

Fig. 13. Pseudo-rst-order degradation kinetics for phenol with different photocatalysts, used to estimate LangmuirHinshelwood coefcients. Phenol measured by HPLCDAD (A) and TOC (B) removals. Reaction conditions: initial phenol concentration of 50 mg/L, 300 mg photocatalyst, reaction temperature 30 2 C and initial pH 5.2.
Table 3
LangmuirHinshelwood apparent rate constants (Kapp ), half-lifes (t1/2 ) and coefcients of determination (R2 ) for the photodegradation of phenol measured by HPLC-DAD
and TOC.
Phenol (HPLC-DAD)

Photolysis
MgZnAl-5
TiO2
TiO2 /MgAl
TiO2 /MgZnAl-1
TiO2 /MgZnAl-5
TiO2 /MgZnAl-10
TiO2 /MgZnAl-15

TOC

Kapp (min1 )

t1/2 (min)

R2

Kapp (min1 )

t1/2 (min)

R2

0.0005
0.0036
0.0016
0.0028
0.0062
0.0114
0.0079
0.0051

1556.1
193.8
433.2
248.4
111.3
60.8
88.2
136.9

0.9865
0.9809
0.9969
0.9880
0.9940
0.9956
0.9918
0.9930

0.0003
0.0019
0.0009
0.0013
0.0025
0.0040
0.0032
0.0022

2539.0
362.9
718.3
545.8
275.1
159.7
217.3
325.4

0.9894
0.9950
0.9976
0.9958
0.9873
0.9910
0.9913
0.9903

with Kapp = 0.0044 min1 and t1/2 = 156.0 min [12]. These same
authors used a calcined LDH of Zn(Ga)Al-5c and obtained 60%
phenol removal (initial concentration of 80 mg/L) in 6 h, with
Kapp = 0.0039 min1 and t1/2 = 174.0 min [12]. In the study of
Chwei-Huann et al. [71] reported phenol (initial concentration of
50 mg/L) was degraded in 180 min with Kapp = 0.014 min1 and
t1/2 = 49.3 min using 1 g/L of TiO2 (Degussa, P25) but only after addition of H2 O2 (0.05 mg/L) and using a 400 W UV lamp. Therefore,
one can conclude that the TiO2 /MgZnAl-5 composite photocatalyst
showed a satisfactory performance kinetic with the potential to
eliminate the phenolic compounds in an aqueous medium.

3.4. Reuse
For the purpose of practical application, it is essential to evaluate
the re-usability and stability of the photocatalyst. The experiments
were performed with the recovery of the material (300 mg) and
reuse, keeping all other parameters constant. The results revealed
that the composite TiO2 /MgZnAl-5 showed good photocatalytic
activity after ve successive cycles. The yield for phenol degradation was 96%, 90%, 88%, 86% and 81% for the ve tests, respectively.
While with the TOC analysis the yield of the rst to fth cycle was
77%, 74%, 70%, 68% and 65%, respectively.
X-ray diffraction and infrared spectroscopy analysis were used
to investigate the stability of TiO2 /MgZnAl-5. According to the DRX
analysis shown in Fig. 14B, one can notice the reappearance of
peaks related to LDH at 2 equal to 11.53 (0 0 3) and 23.4 (0 0 6)
relative to the calcined material (Fig. 14A). The appearance of these
peaks shows the ability of the composite to partially or completely
regenerate when placed in contact with water or solution, a

Fig. 14. X-ray diffraction spectra of TiO 2 /MgZnAl-5 photocatalyst before (A) and
after (B) ve reuse cycles. Reaction conditions: initial phenol concentration of
50 mg/L, 300 mg photocatalyst, reaction temperature 30 2 C and initial pH 5.2.

phenomenon known as the memory effect [19]. In addition,

peaks related to zinc oxide and magnesium oxide remained after
reuse, although at lower intensity (Fig. 14B).
The IR spectrum of the reused photocatalyst (Fig. 15C), shows
the presence of a broad band around 3455 cm1 attributed to OH
stretching and at 1637 cm1 of the bending mode of the water
molecules adsorbed by contact with the aqueous solution of phenol.
The bands 1397, 1380 and 1376 cm1 were attributed to symmetric
stretching of carbonate ions intercalated in LDH.

1774

M.F. de Almeida et al. / Applied Surface Science 357 (2015) 17651775

Transmittance (%)

C
1637
B

1380

3455
1639
1376

3447
1632

1397

3451
4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )
Fig. 15. Infrared spectrum of the calcined TiO2 /MgZnAl-5 (A) photocatalyst,
hydrated TiO2 /MgZnAl-5 (B) and TiO2 /MgZnAl-5 (C) after ve reuse cycles. Reaction
conditions: initial phenol concentration of 50 mg/L, 300 mg photocatalyst, reaction
temperature 30 2 C and initial pH 5.2.

Analysis of the photocatalyst infrared spectrum in an aqueous

medium (hydrated) (Fig. 15B) and compared to the spectrum of
calcined material (Fig. 15C) shows no peaks corresponding to phenol or its possible intermediaries, been further evidence that the
phenol molecule was mineralized by the TiO2 /MgZnAl-5.
4. Conclusions
Novel composite photocatalysts containing zinc oxide obtained
by calcination of ternary (Mg, Zn and Al) layered double hydroxides
impregnated with TiO2 nanoparticles were successfully synthesized for the rst time. The TiO2 /MgZnAl photocatalysts were
used in UV-vis (lter cut-off for  > 300 nm) photodegradation
of phenol in aqueous solution and presented high photocatalytic
activity. Optimum catalyst Zn2+ /Mg2+ molar ratio was about 5% and
this TiO2 /MgZnAl-5 composite photocatalyst resulted in approximately 100% phenol and 80% TOC removal from an aqueous phenol
solution of initial concentration equal 50 mg/L after 360 min. The
TiO2 /MgZnAl-5 showed good stability after 5 cycles, thus showing a
promising potential for practical applications. Phenol removal with
the novel catalyst was greater than that obtained with commercial
TiO2 (Degussa P25) because of its smaller band-gap energy (3.06 eV
vs 3.20 eV) and lower electronhole pair recombination rate due to
the presence of zinc oxide. Since the TiO2 /MgZnAl-5 photocatalyst
shifted the light absorption to a higher wavelength, less energy was
required for the photocatalytic activity and phenol removal efciency increased. The new photocatalysts showed a synergy effect
of the hydrotalcite support, the presence of zinc oxide associated
with photoactivity of TiO2 , resulting in formation of a composite
with high photocatalytic capacity.
Acknowledgements
The authors acknowledge the nancial support of the Fundaco
de Amparo Pesquisa do Estado de Minas Gerais (FAPEMIG, Universal Demand, process number: APQ-00416-11) and the Conselho
Nacional de Desenvolvimento Cientco e Tecnolgico (CNPq) and
the Departamento de Solos, Universidade Federal de Vicosa, Laboratrio de Geoqumica for N2 adsorption isotherms (BET) analyses.
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