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Applied Surface Science 357 (2015) 1765–1775

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Applied Surface Science
journal homepage: www.elsevier.com/locate/apsusc

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 Química, Universidade Federal de Vic¸osa, Av. PH Holfs, s/n, 36571-000 Vic¸osa, Minas Gerais, Brazil
Departamento de Engenharia Civil, Universidade Federal de Vic¸osa, Av. PH Holfs, s/n, 36571-000 Vic¸osa, Minas Gerais, Brazil
c
Departamento de Física, Universidade Federal de Vic¸osa, Av. PH Holfs, s/n, 36571-000 Vic¸osa, 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 significant enhancement of TiO2 /MgZnAl photocatalytic activity. Composite photocatalysts were characterized by ICP-MS, N2 adsorption-desorption, XRD, SEM, EDS, IR and UV–vis DRS.
Phenol in aqueous solution (50 mg/L) was used as a model compound for evaluation of UV–vis (filter
cut-off for  > 300 nm) photocatalytic activity. The most efficient photocatalyst composite was obtained
at a 5% Zn2+ /Mg2+ molar ratio, in the catalyst identified 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 efficiency after five 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 4–5% of the
solar spectrum [2–4]. TiO2 also suffers from electron recombination
that can decrease its photocatalytic efficiency [2]. However, TiO2
photocatalytic efficiency 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 efficiency [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 1−x−y M y M3+
x (OH)2 ]
2+ 

2+ 

2+

2+

x+

[(An− )x/n · mH2 O]

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 [13–15]. 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−

According to this scheme the composites were denominated TiO2 /MgZnAl-1 (TiO2 /Mg0. Reagents and materials TiO2 used was the P25 acquired from Degussa. 2. TiO2 /MgZnAl-CO3 -1. The gelatinous precipitate containing TiO2 were stirred at room temperature for a further 140 min after which the pH was adjusted to 10–10. respectively. Textural properties of the samples were analyzed by their N2 adsorption–desorption isotherms using a surface area and pore size analyzer (NOVA 2200e Quantachrome Instruments. Al(NO3 )3 ·9H2 O.0051 Al) and TiO2 /MgZnAl-15 (TiO2 /Mg0. TiO2 /MgZnAl-5 (TiO2 /Mg0. respectively. While Tzompantzi et al.0484 Zn0. The reactor consisted of a Pyrex glass cylinder (40. relatively low cost and are easily and reused [19].F. facilitating their removal by physical processes [21].1541 nm) with an angular variation of 5–80◦ angle (2) and 0. For this. 10% or 15%).0433 Zn0.3.0255 mol Ti). X-ray diffraction (XRD) was measured by –2 scans using a Bruker model D8 Discover diffractometer using Cu K␣ radiation ( = 0.2. The chemical formulae in parentheses represent the initial composition of preparation. TiO2 /LDH composite photocatalysts have much higher sedimentation velocities than TiO2 nanoparticles.0076 Al). LDHs are interesting alternatives for dispersal and support of TiO2 nanoparticles since they do not harm semiconductor characteristics [12. These mixed oxides semiconductors have a high surface area. Experimental 2. and consists of 70% anatase and 30% rutile. basic properties in an aqueous medium. Combined ZnO–TiO2 photocatalysts have been described in the literature [15.45 mol/L) and the anion to be intercalated Na2 CO3 (1. The calcined photocatalyst composite were designated using the formula TiO2 /MgZnAl-R.4.0005 Al). 5%. Prior to measurement.200 W. NaOH. The SEM equipment was equipped with an energy dispersive spectrometry system (EDS) for analysis of sample chemical composition. Furthermore. Zn(NO3 )2 ·6H2 O. where R represents the approximate percent molar ratio of Zn2+ to Mg2+ (1%. filter cut-off for  > 300 nm) with a 125 W mercury vapor lamp (HQL. The novel TiO2 /MgZnAl photocatalysts with potential for phenol photodegradation prepared in this work at different Zn2+ /Mg2+ molar ratios (1%. FL. TiO2 /MgZnAl-10 (TiO2 / Mg0. Zn and Al) impregnated with TiO2 nanoparticles (TiO2 /MgZnAl).0 cm internal diameter.05◦ s−1 scan rate. MA. 5%. 2.1541 nm). Subsequently. de Almeida et al. 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. Surface areas were estimated by the Brunauer–Emmett–Teller (BET) method and pore volumes were determined by the Horváth–Kawasoe (HK) method applied to the desorption branch. Osram without the bulb protector) at its center within a concentric glass cylinder (7 cm diameter.5 and the mixtures were transferred to a porcelain crucible and placed in an oven at 60 ◦ C for 18 h. All solutions were prepared with analytical grade reagents and high purity deionized water produced by a Milli-Q® system (Millipore.1766 M. 4. MgAl-CO3 (Mg0. Na2 CO3 and phenol were obtained from Sigma–Aldrich and used as received. 60 cm height. and  is the diffraction angle [18]. Al(NO3 )3 ·9H2 O and Zn(NO3 )2 ·6H2 O were added dropwise at a rate of 60 mL/h. Infrared spectroscopy (IR) were obtained using a VARIAN 660-IR spectrophotometer equipped with an attenuated reflectance accessory PIKE GladiATR in the region of 400–4000 cm−1 . to the best of our knowledge. / Applied Surface Science 357 (2015) 1765–1775 for photocatalytic degradation of Orange G dye [18]. all desirable properties for photocatalysts. where x and y stands for the content of magnesium and zinc. USA). 1000 mL total capacity) surrounded by a recirculating water bath maintained at 30 ± 2 ◦ C.0459 Zn0. TiO2 /MgZnAl-CO3 -10 and TiO2 /MgZnAl-CO3 -15.0 cm long. 2.20]. The digested samples were diluted and metals concentrations were determined by ICP-MS. to 100 mL of an alkaline solution containing a fixed proportion of TiO2 nanoparticles (0. thermal and structural stabilities.1. Diffuse reflectance spectra (RD) were acquired (reference BaSO4 ) in a dual beam spectrophotometer model GBC 20 CINTRA at 0.0025 Al).0025 Al-CO3 -5) LDHs were prepared by the procedure previously described but without incorporation of TiO2 .5 nm intervals at a scan speed of 10 nm/min with a 2. 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. 1. We therefore studied the effect of varying Zn2+ /Mg2+ molar ratios in TiO2 /MgZnAl composites on phenol photodegradation under UV–vis irradiation (filter cut-off for  > 300 nm). the samples were degassed at 110 ◦ C for 4 h. ZnO formed by calcination of TiO2 /MgZnAl composite may interact synergistically with TiO2 leading to more efficient photodegradation of organic compounds.19. The commercial reagents Mg(NO3 )2 ·6H2 O. . 2.0 mm gap width. Bedford. 100 mL of solution containing Mg(NO3 )2 ·6H2 O. TiO2 /MgZnAl-CO3 -5. Perkin-Elmer model NexION 300D. Scanning electron microscopy (SEM) images were obtained after sample mettalization with gold using a JEOL JSM-6010/LA microscope. The hydrotalcite calcined at 500 ◦ C was denominated MgAl (Mg0.23 mol/L) under vigorous stirring at room temperature. been reported in literature. USA).0510 Al).100 g of each sample with 4 mL HNO3 (65%). synthesized lamellar double hydroxides of ZnAlLa and applied them for removal of phenol [16].0510 Al-CO3 ) and MgZnAl-CO3 -5 The (Mg0. 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 adsorption–desorption equilibrium and then exposed to UV–vis radiation for 360 min.0510 Al) and the non-calcined composites as TiO2 /MgAl-CO3 . NaOH (2. 10% and 15%) have not yet.0505 Zn0. International Center for Diffraction Data) was used to identify crystalline phases. The Powder Diffraction File (PDF) database (JCPDS.22–25] 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. 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 muffle furnace at 500 ◦ C for 4 h. 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 . Photocatalyst characterization Determination of the final photocatalyst chemical compositions was made by mixing 0. Boynton Beach. The calcined composite without zinc was designated as TiO2 /MgAl (TiO2 /Mg0.0484 Zn0. 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.

1.0 79. TiO2 /MgAl (C). de Almeida et al. The prepared materials present type IV isotherms according to the IUPAC classification that correspond to mesoporous materials [17].75 b SBET (m2 /g) Pore volume (cm3 /g) 48.0041 Al0. In either case. reversed-phase Zorbax Eclipse Plus® C18 (4.6 0. column temperature of 30 ◦ C and a flow of mobile phase methanol:water (55:45.4 160. Photocatalyst characterization 3.82 1.Ti4+ /Al3+ and Zn2+ /Mg2+ molar ratios found were lower than theoretically predicted.0496 Zn0.75 – 0.5. isocratic mode. Three milliliters of the reaction solution were removed using a syringe every 60 min for 360 min and filtered through a 0.M.1 123.3 100. MgZnAl-5 (D).1.0 Relative Pressure (P/P0) Fig.18.80 1.0484 Zn0.0433 Zn0.0255) /Mg0. v/v) at 1.0459 Zn0. initial pH 5.0484 Zn0.0255) /Mg0.0025 Al0.0221 TiO2(0.0307 Ti4+ /Al3+ – – – 0.0255 TiO2(0.73 . Chemical composition and textural analyses Table 1 presents the final metal composition of the synthesized photocatalysts in which final (Zn2+ + Mg2+ )/Al3+ . 300 mg of sample were added to 300 mL of phenol solution (50 mg/L.9 0.77 1.6 mm × 150 mm.0 ␮m) column. The photocatalysts were characterized by X-ray diffraction techniques and infrared spectroscopy before and after each photodegradation cycle to verify its stability.0510 Al0.0005 Al0.0255 TiO2(0.8 1.74 0.71 0.0442 Zn0. 5.30 Zn2+ /Mg2+ molar ratios in percent.0398 0.26]. final molar ratio and textural analysis of synthesized photocatalysts.0255) /Mg0. Zn2+ /Mg2+ b (Zn2+ + Mg2+ )/Al3+ – 1.0255 Mg0. Sample TiO2 MgAl MgZnAl–5 TiO2 /MgAl TiO2 /MgZnAl-1 TiO2 /MgZnAl-5 TiO2 /MgZnAl-10 TiO2 /MgZnAl-15 a b Chemical composition Molar ratio (final) Initial Final a – Mg0. / Applied Surface Science 357 (2015) 1765–1775 1767 H Volume adsorbed (a.0324 – – 4. the molar ratios obtained for the photocatalysts proved that the calcination process caused no significant loss of metal elements.0418 Zn0.0193) /Mg0.2) without UV–vis radiation.69 0.0321 0. All studies were performed in triplicate.5 99. Table 1 Initial and final chemical composition.1.0281 TiO2(0.0022 Al0.0428 0. TiO2 /MgZnAl-5 (F).2) under UV–vis radiation without catalyst. The (Zn2+ + Mg2+ )/Al3+ and Ti4+ /Al3+ molar ratios were kept constant.7 85.0236) /Mg0.2 0. Total organic carbon was quantified using a TOC-5000A analyzer from Shimadzu. TiO2 /MgZnAl-10 (G) and TiO2 /MgZnAl-15 (H).92 4.0255 – Mg0. 1.0406 0.68 9.0187) /Mg0.0 mL/min.45 ␮M membrane (Millipore) for phenol and total organic carbon (TOC) quantification.0076 Al0.0505 Zn0.0255) /Mg0. 3.u.0402 Al0.0255 TiO2(0.0504 Al0.75 0. 2.) G F E D C B A 0.0051 Al0.0255) /Mg0. injected volume 10 ␮L.0270 TiO2(0.0021 Al0. N2 adsorption–desorption isoterms of photocatalyst samples: TiO2 (A). TiO2 /MgZnAl-1 (E).0269 TiO2(0. The N2 adsorption–desorption isotherms are shown in Fig. Photolysis was evaluated using 300 mL of phenol solution (50 mg/L.0071 Al0. initial pH 5. Illustration of the annular photoreactor.0260 TiO2(0.0166) /Mg0.4 0.0208) /Mg0.0255 TiO2(0.0255 TiO2(0. Photolysis and adsorption studies were also run for 360 min and 3 mL were removed at 60 min intervals for phenol quantification by HPLC-DAD.0210 Mg0.0178 0.78 1.0495 0. 2. MgAl (B). These differences may have been caused by incomplete incorporation of cations inside the lamellar of LDH or preferential precipitation of cations as hydroxide [12.0470 Zn0. Results and discussions 3.0436 Zn0.0353 0.0004 Al0.0 0. The monitoring of the remaining phenol concentrations were carried out by High Performance Liquid Chromatography using a 1260 Infinity system (Agilent Technologies) with a linear photodiode array detector (HPLC-DAD) at 270 nm.4 89.41 14.91 1.F.0025 Al0. Reuse assays Photocatalysts were washed with deionized water and dried before reuse.91 1.0510 Al0. For adsorption tests. Fig. 2.

The peaks (0 0 3) and (0 0 6) are basal peaks that confirm the solid obtained has a double layer structure. and agree the crystallographic standards found in the literature [30–32].69 (MgAl-CO3 ) to 7.17.52 A˚ (1 1 0). 2.49 A˚ (1 1 3) and 1. X-ray diffraction spectra of the non-calcined samples: TiO2 (A).2. 3D) showed interplanar Fig. The textural properties determined for MgAl and TiO2 were in agreement with values reported in the literature [19.37].27].6. 2.66 A˚ for TiO2 /MgZnAl-CO3 -1. 1. 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. TiO2 /MgZnAl-10 (F) and TiO2 /MgZnAl-15 (G).30. 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. TiO2 /MgZnAl-1 (D). resulting in a decrease in BET surface area of hydrotalcite (MgAl) [28].79 A˚ (0 0 6). respectively. However. 4B) shows intense peaks related to ZnO and also MgO (periclase) similar to crystallographic descriptions in the literature [7. After calcination.7 and 62) and for the TiO2 in its anatase and rutile phase.29]. anatase.72.69 A˚ (0 0 3).38].1768 M. R. rutile. The ternary LDH of the MgZnAl-CO3 -5 (Fig. These nanoparticles were previously shown to partially block supporter pores. 3.59 A˚ (0 0 9). 2. 3A shows the main peaks for TiO2 . A. 1. In the synthesized composite impregnated with TiO2 nanoparticles in the LDH (Fig. 2. similar to the peaks in the literature [29]. 1. X-ray diffraction The XRD spectra obtained for the non-calcined samples are shown in Fig. TiO2 /MgAl (C). 3C and Fig. One can also observe an increase in the (0 0 3) inter-layer distance from 7.36. TiO2 /MgZnAl-5 presented the highest surface area and pore volume of the zinc-containing composites (Table 1).33 A˚ (0 1 5).1. MgAl-CO3 (Fig. 1. for TiO2 /MgAl-CO3 photocatalyst to 7. there is a collapse of LDH structure forming mixed oxides of metals (Fig. 4D–G). Combined TiO2 /MgAl had a much larger specific surface area than pure TiO2 because of the presence of MgAl LDH. from 7.F.72 A˚ (TiO2 /MgAl-CO3 ) and from 7. 3. with a high degree of crystallinity. The difference between TiO2 /MgAl and MgAl surface areas was caused by TiO2 nanoparticle blockage. there is a decrease in the intensity of the reflection peaks.59 A˚ (0 0 3). related to the LDH.36].u. MgAl-CO3 (B). 3B) exhibited diffraction peaks with interplanar distances of 7. On the other hand. TiO2 /MgZnAlCO3 -5 (F). Peaks related to TiO2 and magnesium oxide were observed in the TiO2 /MgAl composite (Fig. A. TiO2 /MgAl-CO3 (C).59 A˚ (0 0 9). 23.90 A˚ (0 1 8). 4) [29.41 A˚ (1 1 6).59 A˚ in MgZnAl-CO3 -5 to 7. in agreement with other studies [8.21. ˚ and TiO2 /MgZnAl-CO3 -15 (7. 34. 3. indicating the presence of asymmetric pores (non-uniform size and shape) created by the collapse of LDH lamella upon calcination [19]. TiO2 (B).62 A). The highest surface area was found for MgAl and the lowest for TiO2 . also agreeing with the values cited in the literature [33–35]. distances of 7. MgZnAl-CO3 -5 (D). 3. R.9◦ ) . X-ray diffraction spectra of the calcined samples: MgZnAl-5 (A). Incorporation of a cation with a greater electronegativity increased the forces of attraction and decreased the interlayer distance between the hydrotalcite layers [29].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]. 3. a peak related to the ZnO (2 = 34. Hysteresis loops were of type H3. As shown in Table 1. rutile. 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.) F A(101) (113) R(110) (009) A(200) (110) (003) E (006) (009) (003) D (015) (018) (110) A(200) (003) A(101) (009) (110) (006) R(110) R(110) C (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 2θ Fig. 4. The calcined MgZnAl5 (Fig. 60. which corresponds to hydrotalcite-like material (JCPDS # 22-0700) [35]. The textural properties of all samples are listed in Table 1. there is a decrease in the interlayer distance. In the composite containing zinc (Fig. TiO2 /MgZnAl-CO3 -10 (G) and TiO2 /MgZnAl-CO3 -15 (H).6. 1. / Applied Surface Science 357 (2015) 1765–1775 (003) H (003) G (003) (006) Intensity (a. ˚ This behavior CO3 -10 (7. de Almeida et al.80 A˚ (0 0 6). the substitution of Mg2+ by Zn2+ . TiO2 /MgZnAl-R composite surface areas decreased gradually with the increase in zinc (Zn2+ /Mg2+ ) content.62 A˚ in TiO2 /MgZnAl-CO3 -5 caused by TiO2 incorporation.4. TiO2 /MgZnAl-5 (E).56 A).49 A˚ (1 1 3).52 A˚ (1 1 0) and 1. 3E–H) one can observe the diffraction peaks for LDH (2 = 11. TiO2 /MgZnAl-CO3 -1 (E). 4C).32 A˚ (0 1 5).8. anatase.90 A˚ (0 1 2). Fig.

the wide absorption band at 3444 cm−1 is attributed to vibratory stretching of the O–H (O–H) groups of inter-layer water 3439 4000 3500 3000 2500 2000 1500 1000 500 -1 Wavenumber (cm ) Fig. D 1632 Fig.41]. MgZnAl-CO3 -5 (B). further increasing the heterogeneity of the surface.1. 8 shows the absorption spectra of photocatalyst obtained by the UV–vis diffuse reflectance. 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. In Fig. 7D). 7B. 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. 5B).86% Ti. The absorption band at 1632 cm−1 due to the presence of the bending vibration of the O–H due to re-absorption of water from the atmosphere through the TiO2 nanoparticles (Ti-OH) [42]. 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]. According to the literature these bands centered at 778 cm−1 and 825 cm−1 are assigned to the LDH MgAl and ZnAl. Determination of band-gap values Fig. where there is an absorption band in the low frequency region 400–800 cm−1 associated with Ti–O–Ti. The presence of TiO2 in the calcined composite TiO2 /MgZnAl-5 can be evidenced by the lead shoulder O–Ti–O at 400–800 cm−1 . After the calcination (Fig.8◦ . respectively [18.3. According to Fig. the lamellar structure collapses and a solid solution of mixed oxides with some large particles are formed.1. Maximum absorption shifted to longer wavelengths in the calcined composites with higher Zn2+ /Mg2+ molar ratios indicating . The molar ratio found by EDS agreed with the molar ratio used to synthesize the composite (2:1:1) and confirmed by ICP-MS (Table 1).F. This can probably be attributed to the collapse of the lamellar structure. Infrared spectra: TiO2 (A). corresponding to a Zn:Mg:Al:Ti ratio of 2. 7. because there is still the presence of bands at 825 and 778 cm−1 . Transmittance (%) C B A 3451 1639 1371 1639 1364 3430 825 778 3444 1632 was formed by zinc in the hydratalcite layers [39]. 6) confirmed the expected metals composition in the TiO2 /MgZnAl-5 composite of 15. we can see a decrease in the bands related to the hydroxyls (3451 cm−1 ) and carbonates (1371 cm−1 ) indicating the loss of water and CO2 . TiO2 /MgZnAl-CO3 -5 (C) and TiO2 /MgZnAl-5 (D).01:1:1. 3.1. 7. 6.40]. Infrared spectroscopy analysis Fig.2◦ and 62. it is clear that the incorporation of TiO2 to the calcined MgZnAl-5 LDH did not impair the lamellar formation. 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].52% Al and 7. Energy dispersive spectroscopy (EDS) results (Fig. de Almeida et al. 3. 3. 5. However. molecules and also of the layers of metal hydroxides in the layers MgZnAl-CO3 -5 [18]. After the heat treatment at 500 ◦ C (Fig. / Applied Surface Science 357 (2015) 1765–1775 1769 Fig. Scanning electron microscopy and energy dispersive spectroscopy Fig.5. SEM image of the composite TiO2 /MgZnAl-CO3 -5 (A) and TiO2 /MgZnAl-5 (B).71% Zn.04 and a Zn2+ /Mg2+ ratio of 4. 0.4.M.68%. 7A shows the spectrum obtained for the TiO2 nanoparticles. A decrease in the MgO peak was also observed after increasing the molar proportion of zinc in a calcined MgZnIn LDH [8. as expected. 7C. The change of Zn2+ /Mg2+ molar ratio has not introduced any significant differences in the infrared spectra. which are responsible by increasing the heterogeneity of the surface of the photocatalysts [37.43].2% Mg. The weak band near 1632 cm−1 is assigned for to bending mode of water molecules. absorption bands below 1000 cm−1 are mainly corresponding to metal–oxygen vibration and metal–oxygen–metal layers of the brucite type. In addition. Energy dispersive spectra (EDS) for TiO2 /MgZnAl-5. A band at 1364 cm−1 is attributed to the symmetric stretching of carbonate ions.

Other studies have also reported that an increase in the molar ratio of Zn reduced band-gap values [17.06 eV in TiO2 /MgZnAl5. Eg is the band-gap value.2 eV for TiO2 to 3. These results may be due to the large surface area.34]. [50].12 eV for the composite TiO2 /MgAl.5 TiO2/MgAl 0.9 TiO2/MgZnAl-10 1. The band-gap energy (Eg ) was determined by the Tauc relation using the transformed Kulbelka–Munk function according to the following equations [48]: ˛h = A(h − Eg ) n n (1) [F(R)h] = A(h − Eg ) (2) (1 − R)2 2R (3) F(R) = where h is Planck’s constant. 9.2 100 150 200 250 300 350 Time (min) 300 400 500 600 700 Wavelenght (nm) Fig. most of the aqueous phase remains [50]. The determination of band-gap energy for photocatalysts were calculated by extrapolating the linear region to the x-axis. Fig. According to Chen et al.6 over 360 min. 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%. Mg. R is the diffuse reflectance.  is the frequency of vibration. Reaction conditions: initial phenol concentration of 50 mg/L.0 3.2 to 9. In all (photo)degradation assays the phenol solution pH increased from 5.0 Eg (eV) Fig. it is observed that the increase in composite Zn2+ /Mg2+ molar ratio decreases the band-gap energy from 3.8 0.1 0. However. reaction temperature 30 ± 2 ◦ C and initial pH 5.0 TiO2/MgZnAl-1 0.2 eV) it decreased band-gap [6. 9.04 eV in TiO2 /MgZnAl-10 and 3. Al. principally under basic conditions. The TiO2 /MgAl catalyst removed 60% of the phenol whereas the photocatalysts containing zinc produced greater phenol photodegradation. since this oxide has a band-gap of about 3. coefficient A is a constant. TiO2/MgZnAl-10 1/2 6 [F(R)hν] calcination of the composites. Determination of band-gap values (Eg ) for photocatalysts. respectively.2. UV–vis absorption spectrum of the photocatalysts.6 TiO2 0. The presence of carbonate in the TiO2 /MgZnAl-5 photocatalyst was confirmed by its adsorption band at 1380 cm−1 in the IR spectrum of the reused material (Fig.6 0. 3. plotting the transformed Kulbelka–Munk equation [F(R)h]1/2 versus the energy band-gap (h) as shown in Fig. carbon graphene nanotubes [47] and lamellar double hydroxidehydrophobic MgAl [37].49].2. the TiO2 /MgZnAl-5 photocatalyst adsorbed 3% of the phenol after 360 min in the absence of UV–vis radiation. value n is equal to 1/2 for direct transitions.2 0.29].2 TiO2/MgZnAl-5 1. 300 mg photocatalyst. Phenol concentration as a function of time in different photocatalytic treatments.0 -50 TiO2/MgZnAl-10 TiO2/MgZnAl-15 Adsorption (TiO2/MgZnAl-5) 0 50 -0. that less energy would be necessary for photocatalytic activity. Allied to this. / Applied Surface Science 357 (2015) 1765–1775 1. Although more than 60% of phenol can dissociate to phenolate anion at pH 10–11 (pKa = 9.8 TiO2 0.5 3.7 is hydrophobic and bulky and so does not provide any electrostatic interaction with the layers of hydroxides present in the layers of the composite.0 0.4 TiO2/MgAl 0.00 eV in TiO2 /MgZnAl-15. UV–vis photolysis alone degraded 14% of the initial phenol while the addition of photocatalysts increased phenol degradation. 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. 10.7 C/C0 Absorbance 1. 3.6 0.4 0. The benzyl ring phenol at pH 10. pore volume (Table 1) and the .08 eV in TiO2 /MgZnAl-1. Thus. during the lamellar reconstruction of hydrotalcite the interleaving with the phenol molecule is reduced. 10. thus reducing the possibility of merging with the phenol molecule [50].4 0. It can be seen that the energy band-gap decreased from 3. the degree of interleaving of the phenolate is low. reducing the difference in the band of energy. with TiO2 building a new molecular orbit and thus.8). This shift was purportedly due to electronic interaction of molecular orbitals between Zn. there is a preference in the reconstruction of the LDH by the CO3 2− . According to Fig. the band-gap energy shifted to the visible region. and also has a weak affinity for the phenolate anion. These authors suggest that the affinity of phenolate for LDH should be much weaker than hydroxyl ion (− OH). after substitution of Mg by Zn cations in the hydrotalcite structure.1770 M.3 Photolysis MgZnAl-5 TiO2/MgZnAl-1 0. de Almeida et al.F. 15C).7 after 30 min and then gradually increased to 10. Similar phenomenon was observed for TiO2 in associated with other compounds such as zinc oxide [45] graphene oxide [46].0 2. TiO2/MgZnAl-15 7 TiO2/MgZnAl-5 TiO2/MgZnAl-1 5 TiO2/MgAl 4 TiO2 3 2 3.12 eV in TiO2 /MgAl to 3. 8.2 TiO2/MgZnAl-5 0.0 eV and when combined with the TiO2 (3. This was attributed to the formation of zinc oxide during In the studies on the absence of UV–vis the removal of the phenol was evaluated by means of adsorption. Photocatalytic activity 1 0 2. 10.5 4. The increase in molar ratio of Zn to 10% and 15% provided a decrease in the amount of phenol removed of 93% and 82%. As shown in Fig.0 TiO2/MgZnAl-15 1.

simultaneous generation of a hole in the valence band (h+ ) and excess electrons in the conduction band (e− ) (Eq.4 0. 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). Several studies have shown that the increase in the ratio of Zn with respect to TiO2 did not result in increased in photocatalytic efficiency [6.2 TiO2/MgZnAl-15 0.1 0 50 100 150 200 250 300 350 Time (min) Fig.18]. The increased efficiency was caused by increased hydroxyl radical (䊉 OH) generation because of the greater number of electron–hole pairs generated upon radiation of the TiO2 -containing photocatalyst. 11.7.3 TiO2/MgZnAl-5 TiO2/MgZnAl-10 0. Huang et al.F. Thus. 10) also resulted in the highest TOC reduction. which act as electron traps and thus slow the electronic transfers.  − Oxide−→Oxide(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 . (6)) that can subsequently oxidize the organic pollutant (Eqs. and thereby promote the production of 䊉 OH [37.072 nm) [11. Presence of Mg in the composite probably improved photocatalyst stability. thereby reducing photocatalytic activity [57]. / Applied Surface Science 357 (2015) 1765–1775 1. Tzompantzi et al.58–60]. Hydroxyl radical can be reduced by the electrons in the conduction band and thereby promote the reconstruction of oxide with the re-hydroxylation (Eq. Therefore. This behavior was evident in the composites synthesized in our work. the hydroxyl groups present in the LDH structure can react with the photogenerated hole in the VB of TiO2 . TiO2 /MgZnAl-5(e− ) + O2 → • O− 2 CB • • − O2 + Phen → Phen-OO • − O2 + HO•2 (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 influence generation of the hydroxyl radical (Eqs. (15)) [17. observed in this study) to replace the Mg. [49] found that a Zn/Al molar ratio of 1. The presence of oxygen in the CB can generate a super-peroxide anion (Eq. Al and TiO2 in order to achieve efficient photocatalytic degradation of phenol.0 0. The results obtained in this study are consistent with those of Valente et al.67 and 3.47 resulted in higher photocatalytic efficiency than molar ratios of 1. Reaction conditions: initial phenol concentration of 50 mg/L.5 Photolysis MgZnAl-5 TiO2/MgZnAl-1 0.58. 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].9 0.41. resulting in ∼100% photodegradation efficiency.074 nm) and Mg (0. (12)) [16. (4)) [58]. indicated an enhanced stress in the hydrotalcite crystal structure because of the differences between the ionic radii of Zn (0. Furthermore.6 TiO2/MgAl 0. similar to other ternary LDHs [8. TOC removal was also quantified (Fig. Alanis et al. The proposed scheme for phenol degradation by TiO2 /MgZnAl-5 presented in Fig.1 1. Large surface areas of the composite photocatalysts produce more electron–hole pairs and thus increase the hydroxyl radical formation to photodegradation of phenol [51].54] and contributed to dispersion of ZnO on the surface of calcined samples [8]. (7) and (8)) [16. studied methylene blue photodegradation using Mg–Zn–In ternary LDH and found that adjusting the Mg2+ /Zn2+ molar ratio to obtain a maximum surface area resulted in higher photocatalytic efficiency [8]. Less Mg in the hydrotalcite structure could lead to a smaller surface area. According to Zhao et al.81.59] + • 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. Mg. de Almeida et al. leading to the 1771 0. Therefore. (10)) and hydrogen peroxide (Eq. (9)).. TOC removal during photodegradation of a phenol solution. which can produce organic peroxide (Eq.2. which imply a larger number of sites available for interaction with the TiO2 and enhancement of photocatalytic properties. (5)) or from hydroxyl ions (Eq. since the distribution of a second divalent cation is non-uniform after the reconstruction the calcined LDH. The MgZnAl-5 photocatalyst produced 73% phenol removal while its combination with TiO2 (TiO2 /MgZnAl-5) increased removal by 27%.56]. (11)) that also generate 䊉 OH radicals (Eq. [29] who observed that increasing zinc content above 5% (m/m) in Mg–Zn–Al LDH photocatalysts decreased efficiency of photodegradation of 2. [17] and Sánchez-Cantú et al. [53].7 TiO2 0.M.52]. reaction temperature 30 ± 2 ◦ C and initial pH 5. 300 mg photocatalyst. it is necessary to have an appropriate molar ratio of Zn.4-dichlorophenoxyacetic acid and phenol.59]. otherwise the structure will be damaged [8]. 11) to measure the degree of phenol mineralization. the incorporation of Zn into the stable layer structure is limited. 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. the excess Zn associated with TiO2 can lead to excessive formation of surface oxygen vacancy. reaching about 80% after 360 min. pore volume and an irregular distribution of the zinc as observed in this study (Table 1) and evidenced by Valente et al.8 TOC/TOC0 addition of optimum amount of the zinc oxide in the hydrotalcite layers in the composite TiO2 /MgZnAl-5. an excess of zinc present in the hydrotalcite structure impregnated with TiO2 (TiO2 /MgZnAl) would reduce the photocatalytic efficiency of TiO2 . h − TiO2 /MgZnAl-5−→TiO2 /MgZnAl-5(h+ VB ) + TiO2 /MgZnAl-5(eCB ) (4) (h+ ) These photogenerated holes possess sufficiently positive potential to generate 䊉 OH radicals from water molecules adsorbed on its the photocatalyst surface (Eq. On the other hand. [29]. (13) and (14)).55. the incorporation of an excess of the Zn (10% and 15% zinc. The TiO2 /MgZnAl-5 catalyst that produced the greatest phenol removal (Fig.

1772 M. with Kapp = 0. where C0 is the initial phenol concentration at adsorption–desorption equilibrium at t = 0 min and Kapp is the apparent rate constant (Kapp = kr Kad ) [70]. 13A) and TOC (Fig. (16)) [57. Electron created in ZnO CB. 13 presents results of the phenol photodegradation kinetic studies that were used to determine apparent rate constants (Kapp ) and phenol half-lives (t1/2 ).0033 min−1 and t1/2 = 208. with TiO2 /MgZnAl-5 reducing half-lives to 60. (18) that describes pseudo-first-order kinetics over the interval [C. radiation > 300 nm 1.0 1. Incorporation of Zn into the hydrotalcite layers increased the reaction rate. the time at which C = 0. radiation 300–2500 nm Hg vapor lamp 125 W. In this model.0 2. Prince et al. the slope of the ln(C0 /C) versus time (t) plot is the apparent rate constant (Kapp ). [29] reported phenol degradation by a Mg–Zn–Al LDH of about 70% (initial concentration 40 mg/L) after 6 h. UV–vis Mercury lamp.8 min (phenol by HPLC-DAD) and 248. Photocatalyst Initial concentration (mg/L) Experimental condition Dose (g/L) Rate (%) of degradation Ref.98 (Fig. reaction time t (min) and the concentration of the organic compound C (mg/L). and the coefficients of determination (R2 ) are summarized in Table 3.0040 min−1 (TOC). which occur at the solid–liquid interface [18]. (17) [68] Phenol (Fig. It can be seen that phenol degradation by TiO2 /MgZnAl-5 showed satisfactory performance compared to other catalysts previously reported. ln C0 = Kapp t C (18) (19) .0 1. 8) [61]. Fig. UV–vis 300 W halogen lamp.2 After 6 h of radiation: ∼100 [63] [64] [65] [66] [16] [67] This study photocatalysis (Fig. after irradiation can migrate to the CB of TiO2 .0 1.8 min (TOC) were found for photodegradation with the TiO2 /MgAl composite. and promote catalytic process (Eq. This model relates the degradation rate r (mg/L min). Fe-TiO2 N-Si co-doping TiO2 ZnO/La2 O3 (doped with K) CeO2 -ZnTi-LDHs ZnAlLa CeO2 -TiO2 /SiO2 TiO2 /MgZnAl-5 33.69] and the model reduces to Eq. UV–vis 500 W Xenon lamp.0114 min−1 (phenol by HPLC-DAD) and 0. Valente et al. Half-life time (t1/2 ).0 1. In comparison.2 min. R2 > 0.5 After 7 h of radiation: ∼90 5 h radiation: ∼100 3 h radiation: 96. C0 ]. 300 W.5 10 20 50 40 30 50 High-pressure lamp 125 W. de Almeida et al. corresponding to Kapp = 0. 12.F. At low initial organic compound concentration Kad C is negligible [29.0 8 h of radiation: ∼66 8 h of radiation: ∼99 2.4 min (TOC). UV–vis radiation 350 W. 13). half-lifes time (t1/2 ).0 1. 300 W Mercury lamp. Apparent rate constants (Kapp ). Schematic diagram of the photocatalytic processes occurring on the surface of the TiO2 /MgZnAl-5. is one of the most useful values to compare pseudo-firstorder reaction rates (Eq. (19)) [48]. as expressed in Eq.3. 13B) photodegradation results adjusted well to the pseudo-first-order kinetic model.5C0 . / Applied Surface Science 357 (2015) 1765–1775 Fig. with coefficients of determination. Table 2 Comparison of different photocatalysts used in phenol photodegradation.5 h radiation: 98.4 min (phenol by HPLC-DAD) and 545. ln(2) Kapp 3. 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. ZnO(e− ) → TiO2 (e− ) CB CB (16) Table 2 presents a summary of photocatalytic phenol degradation studies published in the literature.62]. Half-lives of 248. Kinetics of phenol photodegradation t1/2 = The Langmuir–Hinshelwood is commonly used to describe the kinetics of pseudo-first-order degradation of organic pollutants.

X-ray diffraction and infrared spectroscopy analysis were used to investigate the stability of TiO2 /MgZnAl-5.9873 0. one can notice the reappearance of peaks related to LDH at 2 equal to 11.4 A 0.9809 0. The results revealed that the composite TiO2 /MgZnAl-5 showed good photocatalytic activity after five successive cycles.2 248.4 0.0 min [12]. The appearance of these peaks shows the ability of the composite to partially or completely regenerate when placed in contact with water or solution.3 545.0044 min−1 and t1/2 = 156.0003 0. respectively.0 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 Time (min) Time (min) Fig.2. Reaction conditions: initial phenol concentration of 50 mg/L.0025 0. Reaction conditions: initial phenol concentration of 50 mg/L.4. While with the TOC analysis the yield of the first to fifth cycle was 77%. half-lifes (t1/2 ) and coefficients of determination (R2 ) for the photodegradation of phenol measured by HPLC-DAD and TOC. de Almeida et al. a Fig.0079 0. 14B). it is essential to evaluate the re-usability and stability of the photocatalyst.9956 0. 14A). In addition. In the study of Chwei-Huann et al.0051 1556. Table 3 Langmuir–Hinshelwood apparent rate constants (Kapp ). 13. 14B.0022 2539.05 mg/L) and using a 400 W UV lamp.6 0.0114 0.9880 0.2 0 B 0.0028 0. Therefore. 14. 70%.53◦ (0 0 3) and 23. X-ray diffraction spectra of TiO 2 /MgZnAl-5 photocatalyst before (A) and after (B) five reuse cycles. shows the presence of a broad band around 3455 cm−1 attributed to O–H stretching and at 1637 cm−1 of the bending mode of the water molecules adsorbed by contact with the aqueous solution of phenol.9969 0.9976 0.014 min−1 and t1/2 = 49.9930 0.0 min [12]. 15C). Reuse For the purpose of practical application.0005 0.0 362.9910 0.0009 0.8 88.F.0062 0.9950 0. Phenol measured by HPLCDAD (A) and TOC (B) removals.6 -ln(TOC/TOC0) -ln(C/C0) 4 TiO2/MgZnAl-15 1 1773 TiO2/MgAl 1. P25) but only after addition of H2 O2 (0.3 325. reaction temperature 30 ± 2 ◦ C and initial pH 5. 68% and 65%. used to estimate Langmuir–Hinshelwood coefficients.8 TiO2/MgZnAl-15 0.0036 0.0013 0. .9958 0.7 217. 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.9 0.0039 min−1 and t1/2 = 174. 88%. with Kapp = 0.2.8 433.8 275. The experiments were performed with the recovery of the material (300 mg) and reuse. respectively.9894 0. keeping all other parameters constant. 74%.0019 0.4 111.4 TiO2/MgAl TiO2/MgZnAl-1 3 TiO2/MgZnAl-5 TiO2/MgZnAl-10 2 Photolysis MgZnAl-5 TiO2 1. According to the DRX analysis shown in Fig. 300 mg photocatalyst.0032 0. reaction temperature 30 ± 2 ◦ C and initial pH 5.1 159.9940 0.9865 0. Pseudo-first-order degradation kinetics for phenol with different photocatalysts. The bands 1397. 90%.4◦ (0 0 6) relative to the calcined material (Fig. The yield for phenol degradation was 96%. 300 mg photocatalyst. 86% and 81% for the five tests.1 193.9918 0. 3.9903 with Kapp = 0.0 TiO2/MgZnAl-10 0. Phenol (HPLC-DAD) Photolysis MgZnAl-5 TiO2 TiO2 /MgAl TiO2 /MgZnAl-1 TiO2 /MgZnAl-5 TiO2 /MgZnAl-10 TiO2 /MgZnAl-15 TOC Kapp (min−1 ) t1/2 (min) R2 Kapp (min−1 ) t1/2 (min) R2 0. phenomenon known as the “memory effect” [19]. although at lower intensity (Fig. The IR spectrum of the reused photocatalyst (Fig.3 60. peaks related to zinc oxide and magnesium oxide remained after reuse.9 718.3 min using 1 g/L of TiO2 (Degussa. 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. / Applied Surface Science 357 (2015) 1765–1775 5 Photolysis MgZnAl-5 TiO2 1.9913 0.2 TiO2/MgZnAl-1 TiO2/MgZnAl-5 1. 1380 and 1376 cm−1 were attributed to symmetric stretching of carbonate ions intercalated in LDH.2 136.M.0016 0. [71] reported phenol (initial concentration of 50 mg/L) was degraded in 180 min with Kapp = 0.0040 0.

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