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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.
2+
2+
2+
x+
, 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
1766
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).
1767
G
F
E
D
C
B
A
0.0
0.2
0.4
0.6
0.8
1.0
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
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+
1.91
1.78
1.80
1.91
1.82
1.77
1.75
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
1768
(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.
1769
Fig. 5. SEM image of the composite TiO2 /MgZnAl-CO3 -5 (A) and TiO2 /MgZnAl-5 (B).
D
1632
Transmittance (%)
3451
1639
1371
1639
1364
3430
825 778
3444
1632
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
1770
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)
TiO2/MgZnAl-10
1/2
[F(R)h]
TiO2/MgZnAl-15
TiO2/MgZnAl-5
TiO2/MgZnAl-1
TiO2/MgAl
TiO2
3
2
1
0
2.0
2.5
3.0
3.5
4.0
Eg (eV)
Fig. 9. Determination of band-gap values (Eg ) for photocatalysts.
(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
1.1
1.0
0.9
0.8
TOC/TOC0
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.
(4)
(h+ )
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
(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)
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
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
Experimental condition
Dose (g/L)
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
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
t1/2 =
r=
dC
kr Kad C
=
1 + Kad C
dt
(17)
C0
= Kapp t
C
(18)
(19)
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
50
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.
1774
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.
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