Accepted Manuscript

Title: Photocatalytic degradation of caffeine as a model

pharmaceutical pollutant Mg doped ZnO-Al2 O3
heterostructure

Authors: A. Elhalil, R. Elmoubarki, M. Farnane, A.

Machrouhi, F.Z. Mahjoubi, M. Sadiq, S. Qourzal, N. Barka

PII: S2215-1532(17)30249-0
DOI: https://doi.org/10.1016/j.enmm.2018.02.002
Reference: ENMM 137

To appear in:

Received date: 22-10-2017

Revised date: 3-2-2018
Accepted date: 28-2-2018

Please cite this article as: A.Elhalil, R.Elmoubarki, M.Farnane, A.Machrouhi,

F.Z.Mahjoubi, M.Sadiq, S.Qourzal, N.Barka, Photocatalytic degradation
of caffeine as a model pharmaceutical pollutant Mg doped ZnO-
Al2O3 heterostructure, Environmental Nanotechnology, Monitoring and
Management https://doi.org/10.1016/j.enmm.2018.02.002

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 Photocatalytic degradation of caffeine as a model pharmaceutical pollutant Mg doped

ZnO-Al2O3 heterostructure

A. Elhalil1, R. Elmoubarki1, M. Farnane1, A. Machrouhi1, F.Z. Mahjoubi1, M. Sadiq1, S.

Qourzal2, N. Barka1,*
1
Laboratoire des Sciences des Matériaux, des Milieux et de la Modélisation (LS3M), FPK,

Univ Hassan 1, B.P. 145, 25000 Khouribga, Morocco.

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2
Equipe de Catalyse et Environnement, Département de Chimie, Faculté des Sciences,

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Université Ibn Zohr, B.P.8106 Cité Dakhla, Agadir, Morocco.

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* Corresponding author: E-mail: barkanoureddine@yahoo.fr; Tel: +212 661 66 66 22; fax:

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+212 523 49 03 54

Highlights

 U
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Mg-ZnO-ZnAl2O4 mixed phases derived from Mg doped LDH structure.
 Remarkable photocatalytic degradation performance of caffeine in aqueous solution.

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Crystallinity, adsorption and dispersion of active ZnO were the important factors.

Abstract
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In this work, Mg-doped ZnO-Al2O3 heterostructure photocatalyst with different content

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of Mg (1, 3 and 5 wt%) was prepared from Zn-Al-CO3 layered double hydroxides precursors

using ceramic process. The synthesized catalysts were characterized by X-ray diffraction
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(XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope

(SEM) coupled energy dispersive X-ray analysis (EDX). The photocatalytic activity of the
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CC

catalysts was evaluated for the degradation of caffeine as a model pharmaceutical pollutant in

aqueous solutions under UV irradiation. Detailed photocatalytic experiments based on the

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effects of dopant amount, irradiation time, catalyst dose, initial solution pH, caffeine

concentration and reuse were performed and discussed in this study. The 1%Mg-ZnO-Al2O3

sample with high adsorption capacity showed the highest photocatalytic activity with a

degradation efficiency of 98.9 % after 70 min of irradiation. It showed a significantly higher

1
rate of degradation compared to undoped, pure ZnO and standard Degussa P-25 titanium

dioxide. The photocatalyst showed high stability after three regeneration cycles.

Keywords: Mg-doped ZnO-Al2O3; Mixed metal oxides; Photocatalytic activity; Caffeine

degradation.

1. Introduction

Occurrence of pharmaceuticals in the aquatic environment has received increasing

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attention as environmental issue. It is caused by discharges of industrial, hospital and

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wastewater or household activities. These contaminants can cause severe adverse effects in

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human and wildlife and their removal is of a great concern on environmental and health risk

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management (Barceló and Petrovic, 2008; Halling-Sorensen et al., 1998). Most of these

compounds are not easily biodegradable, so they become persistent in the aquatic environment
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(Fathinia et al., 2015). The literature shows that pharmaceutical residues metabolized or not,
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produce unfavorable effects in both humans and ecosystems (Khataee et al., 2013). One of such
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undegradable and very stable pharmaceuticals products is caffeine.

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Caffeine is the most consumed psychoactive drugs worldwide (Lovett, 2005). It is found
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in various consumer products as coca nuts, coffee and tea leaves (Miners and Birkett, 1996)

and other plants. Caffeine has a high water solubility (Ks value is more than 10,000 mg/L).
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However, intense use of caffeine over time can lead to irritability, mutation effects such as

inhibition of DNA, anxiety and tremors, among other side effects (Zhang et al., 2011). It can
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mobilize calcium from cells which leads to bone mass loss and is considered as a risk factor for

cardiovascular diseases (Ali et al., 2012; Torres et al., 2014). The presence of caffeine in water
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will produce negative effects on the aquatic organism and ecological environment due to their

resistance to natural degradation and potential toxicity to aquatic organism and human life. In

moderate doses, it can increase alertness, reduce fine motor coordination, cause insomnia,

headaches, nervousness and dizziness (Aly, 2013; Guo et al., 2011; Habibi et al., 2012).

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 Heterogeneous photocatalysis, one of the advanced oxidation processes (AOPs), is an

effective process for the degradation of persistent pollutants (Abdennouri et al., 2015; Zhou et

al., 2017). Photocatalytic reactions occurring on the surface of a semiconductor catalyst proceed

through the photo-production of electron/hole (e-/h+) pairs after absorption of photons with

energy equal to or greater than the semiconductor band gap. This is followed by space/charge

separation by the traps available on the semiconductor surface and by charge transfer processes

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involving the separated electrons and holes (Bahnemann et al., 1997; Fujishima et al., 2008).

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The resulting electrons-holes can then further react with oxygen (O2) and water (H2O) to form

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hydroxyl radical (°OH) (Feng et al., 2014). Hydroxyl radicals are able to destroy the most

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persistent organic molecules and break them down into relatively less persistent organics and

end products such as CO2, H2O and mineral salts (Diaz-Uribe et al., 2014).
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Up to now, a large number of oxides semiconductors have been developed, such as TiO2
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(Xu et al., 2014), ZnO (Alvi et al., 2017), WO3 (Zhang et al., 2014), ZrO2 (Zinatloo-Ajabshir
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and Salavati-Niasar, 2016), Bi2O3 (Iyyapushpam et al., 2014), and Bi2WO6 (Yang, 2017), etc.
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Among theme, ZnO a multifunctional semiconductor photocatlyst, has been widely

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investigated due to its thermal conductivity, chemical stability and good UV absorption

properties (Gratzel, 1995). Nevertheless, it is noteworthy that ZnO has some shortcomings,
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including fast recombination rate of photogenerated electron/hole pairs and a low quantum yield

of the photocatalytic reactions in aqueous solution, which obstruct its full scale application as
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photocatalysts (Osman et al., 2016; Lee et al., 2016). Therefore, several efforts have been made

to reduce the e-/h+ recombination rate of ZnO by modification or by doping with several
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elements such as transition metal (Bousslama et al., 2017), non-metal (Perillo and Atia, 2017)

and noble metal (Yu et al., 2013), or by alkaline earth metals (Wang et al., 2015). Mg doped

ZnO is one of the most intriguing candidates for the replacement of traditional semiconductors

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materials, due to its relative abundance, low fabrication cost, and high thermal stability (Saikia

et al., 2015).

Different techniques have been used to elaborate ZnO semiconductor, such as sol–gel

technique (Astinchap, 2016), hydrothermal synthesis method (Liu and Zeng, 2003), chemical

vapor deposition (Liu and Liu, 2017), photo-chemical reduction processes (Oster and

Yamamoto, 1966), co-precipitation method (Akir et al., 2016), spray-pyrolysis method

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(Tharsika et al., 2015), ultrasound-assisted method (Carp et al., 2017), and microwave-assisted

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thermal decomposition (Solis-Pomar et al., 2016). By using layered double hydroxides (LDHs)

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as precursor for the preparation of ZnO it is possible to obtain a fine dispersion of active

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components on the surface of semiconductor, and as a consequence the formation of an intimate

contact at atomic level between the generated semiconductor phases. Moreover, Al in the
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structure has more advantages over ZnO photocatalyst owing to its high photocatalytic activity,
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morphology, particle size and good stability (Duan et al., 2015; Xing et al., 2016; Zhang et al.,
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2017).
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In this study, Mg-doped ZnO-Al2O3 heterostructure photocatalyst with different content

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of Mg (1, 3 and 5 wt%) was prepared from Zn-Al-CO3 layered double hydroxides precursors

using ceramic process. The photocatalysts were characterized by several physico-chemical

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techniques (XRD, FTIR and SEM/EDX). The photocatalytic property of prepared

photocatalysts was evaluated for the degradation of caffeine as model pollutant under UV
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irradiation. The effect of Mg doping concentration on the photocatalytic activity was

investigated in detail. A kinetic study was also carried out to determine the order of the caffeine
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degradation.

2. Experimental

2.1.Reagents

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 The starting chemicals; zinc nitrate (Zn(NO3)2.6H2O), aluminum nitrate

(Al(NO3)3.9H2O), magnesium nitrate (Mg(NO3)2.6H2O), sodium carbonate (Na2CO3), sodium

hydroxide (NaOH), hydrochloric acid, 37% (HCl) and standard Degussa P-25 titanium dioxide

have been acquired from Sigma-Aldrich (Germany). Degussa P-25 titanium dioxide has a

specific surface area of 50±5 m2/g and is composed of 80% anatase and 20% of rutile (Barka et

al., 2013), which was used in this study as a reference photocatalyst. Caffeine (C8H10N4O2) was

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a product of Sigma-Aldrich (China). All the used chemicals were of analytical grade and were

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used without further purification. Bidistilled water was used as the solvent throughout this

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study.

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2.2.Catalysts preparation

2.2.1. Synthesis of LDH precursor and ZnO-Al2O3 photocatalyst

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Zn-Al-CO3 layered double hydroxide material was prepared by co-precipitation method
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from metal salts. The molar cationic ratio r = Zn/Al was fixed to 3. A mixture solution of
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Zn(NO3)2.6H2O and Al(NO3)3.9H2O with a total concentration of metal ions of 2 mol/L and
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Na2CO3 (1 mol/L) was added drop-wise in a backer containing 50 mL of bidistilled water. The
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pH of the mixture was adjusted and kept constant at 8.5±0.2 during the synthesis by adding

suitable amounts of NaOH (2 M) solution. The formed gel was kept under constant magnetic
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stirring for 4 h. The final product was recuperated by filtration, washed several times with

bidistilled water until pH=7 and dried at 100 °C for 24 h. The mixed metal oxides photocatalysts
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were prepared by calcination of LDH precursor at 500 °C for 6 h in muffle furnace.

2.2.2. Solid state impregnation

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Desired amount of LDH precursor and Mg(NO3)2.6H2O were manually ground in an

agate mortar for 30 min. After that the homogeneously mixed powder was transferred into a

crucible and calcined in air at 500 °C for 6 h in muffle furnace. The entire process is free of

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solvent. The obtained samples were denoted as x%Mg-ZnO-Al2O3, where x% represent the

weight percentage of Mg in the mixture (1, 3, and 5 wt%).

2.2.3. Synthesis of pure ZnO

For comparison, pure ZnO oxide powder was prepared using precipitation method.

Firstly, Zn(NO3)2·6H2O was dissolved in distilled water under stirring to form a clear solution.

Subsequently, the pH of solution was adjusted to 8.5 with NaOH (2 M) added dropwise. After

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stirring for 4h, the mixture solution was transferred to a 500 mL flask and heated at 75 °C for

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16 h. After that, the precipitate is filtered, washed several times with deionized water and dried

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at 100 °C for 24 h. Finally, the product was calcined at 500 °C for 6 h to obtain the pure ZnO

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oxide.

2.3.Characterization
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The XRD measurements were performed at room temperature on a D2 PHASER
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diffractometer, with the Bragg–Brentano geometry, using CuKα target (λ=0.15406 nm)
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operated at 30 KV and 10 mA. The XRD scans were recorded in the 2θ range 10–80° with step
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size 0.01° (0.5s/step). Fourier transform infrared (FTIR) spectra in KBr pellets were collected
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on a Perkin Elmer (FTIR-2000) spectrophotometer, in the range of 4000-400 cm-1. The external

surface of sample was analyzed by scanning electron microscopy coupled to the energy
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dispersive X-ray spectroscopy (SEM/EDX) using a FEI Quanta 200 model.

2.4.Photocatalytic measurements
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The photocatalytic performance of the photocatalysts was studied by degradation of

caffeine in water solution. The catalyst of 0.6 g/L was added into a 2 L of caffeine solution of
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20 mg/L. The reaction was carried out in a cylindrical Pyrex photoreactor with a capacity of 2

L and was initiated by a UV mercury lamp (400 W) placed in the center of the reactor. The

temperature was maintained at 25±2 °C by connecting the reactor to circulating water for

preventing the lamp from overheating. Before irradiation, the mixtures were vigorously stirred

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for 60 min under dark to establish an adsorption/desorption equilibrium on the surface of

catalysts. Subsequently the solution was stirred under UV light irradiation. At given time

intervals, 3 ml aliquots were sampled and filtered to remove the solid particles. The filtrates

were analyzed using a double-beam scanning spectrophotometer (Shimadzu

spectrophotometer, model biochrom) at maximum wavelength of 273 nm, characteristic to

caffeine. The percentage of degradation was calculated by C/C0, where C is the concentration

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of remaining caffeine solution at each irradiated time interval, while C0 is the initial

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concentration.

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3. Results and discussion

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3.1.Catalysts characterization

3.1.1. X-ray diffraction (XRD) study

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XRD patterns of LDH precursor before and after calcination, pure ZnO and Mg-doped
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ZnO-Al2O3 are shown in Fig.1. The figure exhibits the characteristic reflections of the LDH
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structure with planes (003), (006), (012), (015), (018), (110) and (113). No impurities from any
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residual Zn(OH)2 or Al(OH)3 were observed. Remarkable changes are observed after
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calcination at 500 °C. The lamellar structure collapsed and new peaks corresponding to ZnO

oxide appear. The characteristic XRD peaks of ZnO oxide started to appear indicated by the
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peaks at 2θ = 31.8°, 34.5°, 36.3°, 47.6°, 56.6°, 62.9°, 66.4°, 68° and 69.1°. These peaks

correspond to the reflections from (100), (002), (101), (102), (110), (103), (200), (112) and
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(201) planes, respectively, this is also confirmed by the JCPDS data (Card No. 36- 1451) (Sahoo

et al., 2015).
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Total dehydroxylation was observed at 500 °C and resulted in the transformation of

LDH structure to corresponding metal oxides ZnO and Al2O3. There is no detection of signals

corresponding to Al2O3 phase, implying that Al2O3 is amorphous (Zhang et al., 2016). The

characteristic diffraction peaks of synthesized pure ZnO match well with the standard card of

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ZnO oxide. For Mg-doped ZnO-Al2O3 precursor, the results clarify that the products possess

the only phase of wurtzite ZnO when the amount of Mg is fixed in the range from 0 to 3%.

Further, we did not observe any additional peaks of MgO, which suggests the complete

incorporation of Mg into the ZnO matrix and the doping concentration is under the solubility

limit of MgO into ZnO matrix. However, when the Mg ratio is up to 5%, besides the major

phase of wurtzite ZnO, a low intensity diffraction peak is detected at 2θ=42.834°, which

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responds to the (200) crystal face of cubic MgO (JCPDS Card No. 45-0946) (Li et al., 2015).

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As previously mentioned (Klubnuan et al., 2015; Wang et al., 2015), the solubility limit of MgO

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in ZnO is less than 4%, so this is in good agreement with the results obtain in this study.

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To investigate the effect of Mg on a crystallinity of the ZnO, crystallite size was

calculated by Scherrer’s formula:

Kλ U
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𝐷=
βcos⁡(θ)
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where D is a crystallite size (nm), k is a constant (0.9), λ is a wavelength used (0.15406 nm),
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β is the peak width at half maximum in radian along (101) plane and θ is a diffraction angle.
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The lattice parameters (a and c), cell volume and crystallite size of ZnO oxide in differents

samples are given in Table 1. The slight reduction of the lattice parameters (a and c) with
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increasing of Mg amount can be associated to the incorporation of smaller Mg instead of Zn

with ionic radius of 0.72 Å and 0.74 Å respectively, within ZnO structure. The crystallite size
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systematically increase, when Mg doping amount is increasing from 0 to 5%, which illustrates
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that a small amount of dopant have a great influence on the crystallite size.

3.1.2. Fourier transform infrared (FTIR) spectra

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Fig.2 shows the FTIR spectra of fresh LDH precursor, pure ZnO, undoped and Mg

doped ZnO-Al2O3. The spectrum of the fresh LDH precursor shows a broad band between 3600

and 3200 cm-1, which is attributed to the stretching vibration of the OH groups of physically

adsorbed and interlamellar water molecules (Mahjoubi et al., 2016). The band at 1617 cm-1 was

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due the O–H bending vibration of the interlayer water molecules. The band at 1364 cm -1 is

assigned to the stretching vibration of the CO32− groups in the LDH interlayer (Li et al., 2013).

This band rapidly disappears after calcination, which is attributed to the thermal decomposition

of carbonate ions. Bands around 700-400 cm-1 could be related to the lattice vibration modes

such as the translation vibrations by M-O (590 and 670 cm-1) and O-M-O (430 cm-1) (Mahjoubi

et al., 2017; Guo et al. 2012)]. The absorption band at ~541 cm-1 confirms the symmetric

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stretching of Mg-O bond (Sharma et al., 2017). This confirms the insertion of Mg in ZnO-Al2O3

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structure.

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3.1.3. SEM/EDX observation

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Fig.3 displays the surface morphology and crystallite structure of undoped and 1% Mg

doped ZnO-Al2O3. The images (Fig.3(a-c)) indicate obvious difference in morphology between
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undoped and Mg composite. It is clearly seen that photocatalysts has a heterogeneous surface
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with observable porosity. We can observe that 1% Mg-ZnO-Al2O3 powder exhibit slight
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increase in grain sizes compared with undoped material. This is in agreement with DRX results.
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This may be due to Mg doping which improves the crystallinity of materials. Energy dispersive
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X-ray spectrum (EDX) of undoped and Mg doped nanocomposite are shown in Fig.3(b-d). The

results confirm the presence of Zn, Al and O in the undoped sample. For 1% Mg-ZnO-Al2O3
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composite, the spectrum shows peaks corresponding to Mg along with the other constituent

elements (Zn, Al and O).

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3.2.Photocatalytic study

3.2.1. Effect of Mg doping

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The adsorption and photocatalytic performance of undoped and Mg doped ZnO-Al2O3

nanocomposite in comparaison with pure ZnO and P-25 titanium dioxide in the same

experimental conditions for caffeine degradation under UV light irradiation is presented in

Fig.4. In the same operating conditions for the photocatalytic degradation, the photolytic

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degradation (direct photolysis) without photocatalysts was studied. It could be seen that the

degradation of caffeine is very low in the absence of photocatalysts under UV light irradiation.

In the adsorption phase, pure ZnO and P-25 titanium dioxide have hardly any adsorption of

caffeine after stirred for 60 min. The adsorption efficiencies of caffeine on ZnO-Al2O3, 1% Mg-

ZnO-Al2O3, 3% Mg-ZnO-Al2O3 and 5% Mg-ZnO-Al2O3 are 7%, 11.05%, 6.72 and 1.19%,

respectively. Clearly, 1% Mg-ZnO-Al2O3 exhibits much higher adsorptive ability than other

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catalysts. This may be attributed to the increase in surface area aroused by the introduction of

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1% of Mg agent in ZnO-Al2O3 mixed metal oxides. While the adsorption process decreases in

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the presence of 3% Mg-ZnO-Al2O3 and 5% Mg-ZnO-Al2O3 catalysts respectively, this could

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be attributed to the increase in the crystallinity of ZnO. From 3% of Mg, the crystallinity of

ZnO oxide strongly increase which will reduce the surface areas of catalyst (Wu et al., 2011).
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As it can be observed, there was an important decrease of the caffeine concentration
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during the irradiation in the presence of all the prepared photocatalysts in comparison to the
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photolysis. The pure ZnO exhibits moderate photocatalytic activity with the degradation
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percentage of 60.8%, while the ZnO-Al2O3 photocatalyst synthesized from layered double
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hydroxides precursor enhances greatly the photcatalytic activitie (89.18%). The photocatalytic

activity of Mg-doped ZnO-Al2O3 catalysts increased with the increase of Mg content until 1 %
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and then decreased when Mg content was higher than 3%. It was evident that the 1% Mg-ZnO-

Al2O3 nanocomposites showed the highest photocatalytic degradation, as this sample degraded
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the caffeine by about 98.9% within 70 min of irradiation.

As we know, many parameters such as adsorption process, particle shape and

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morphologies, crystallinity, affected the photocatalytic activity. The increase in the crystallite

size from 4.09 nm to 8.21 nm for undoped ZnO and 1% Mg-ZnO-Al2O3, respectively, led to a

significant improvement in the photocatalytic activity. When Mg amount was higher than 3%,

the photocatalytic activity starts to decrease. This may be due to fact that with increase in

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crystallite size, the number of active sites on the surface of the photocatalyst decrease.

Generally, the photocatalytic activities of catalysts increase initially with the increase of

crystallinity, and then decrease because of the reduction of the surface area (Wu et al., 2011).

The adsorption ability is very important during the photocatalytic process, very high

adsorptive efficiency will accelerate the degradation process. This behavior was confirmed by

the great correlation between adsorbed quantity and photocatalytic degradation rate of caffeine

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on 1%Mg-ZnO-Al2O3, 3%Mg-ZnO-Al2O3 and 5%Mg-ZnO-Al2O3 photocatalysts, as shown in

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Fig.5. The absorption rates of ZnO-Al2O3 and 3%Mg-ZnO-Al2O3 are comparable, whereas 3%

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Mg-ZnO-Al2O3 exhibits an important photocatalytic activity than ZnO-Al2O3. This could be

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attributed to synergic effect between Mg and ZnO-Al2O3 mixed metal oxides (Golzad-

Nonakaran et al., 2016). These results suggested that, the adsorption process, synergistic effect
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between Mg and ZnO-Al2O3 material and crystallinity of ZnO were benefit in the enhancement
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of the photocatalytic degradation of caffeine.
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3.2.2. Effect of photocatalyst dose

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In order to avoid excess catalyst and ensure total absorption of efficient photons, series
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of experiments was carried out to assess the optimum catalyst loading by varying the amount

of the best photocatalyst (1% Mg-ZnO-Al2O3) from 0.1 to 1.5 g/L. Experiments were done with
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20 mg/L caffeine aqueous solution at initial solution pH of 7.5. After 70 min of UV irradiation,

the photocatalytic degradation efficiency (%) was evaluated. Results given in Fig.6 showed that
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the increase in photocatalyst dose from 0.1 to 0.3 g/L resulted in an increase in the

photocatalytic degradation efficiency from 69.42 to 98.9%. Beyond this dose, a slight decrease
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with the rise of the dose was observed. This can be explained by the fact that excess

photocatalyst dose resulted in an unfavorable light scattering and a reduction of light

penetration into the solution (Qourzal et al., 2012). From a practical viewpoint, the optimum

dosage of 0.3 g/L was chosen in furthers experiments.

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3.2.3. Effect of initial solution pH

The effect of solution pH on photocatalytic oxidation of caffeine in presence of 1% Mg-

ZnO-Al2O3 was studied at pH of 3.5, 7.5 and 9.5. Fig.7 shows that solution pH affected

significantly the degradation rate of caffeine. The photocatalytic activity was enhanced at pH

of 9.5 and was dramatically decreased at pH of 3.5. Generally, solution pH affects at the same

time the surface charge of the photocatalyst and the ionization of caffeine molecules in solution.

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The pHpzc of 1% Mg-ZnO-Al2O3 catalyst was found to be 8.41. Therefore, at pH>8.41 the

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surface acquire negative charge, favoring the adsorption of cationic molecules. While at

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pH<8.41, the surface of the catalyst acquire negative charge, favoring the adsorption of anionic

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molecules. The pKa of caffeine molecule is 10.4 which means that the molecule is fully

protonated at pH<10.4.
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Since the structure of caffeine was the same in the region of studied pH, the observed
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behavior could be only due to the modification of the proprieties of the photocatalysts. The
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observed trend of the photocatalytic activity observed at pH of 9.5 could be due to the enhanced
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adsorption of caffeine on the photocatalyst favored at pH between 8.41 and 10.4 and more
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efficient formation of hydroxyl radicals. In acidic medium (pH=3.5), the decrease of the

degradation rate could be attributed to many phenomena simultaneously intervening: a) non

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favorable adsorption, b) the dissolution of the photocatalysts and c) the photodecomposition

and dissolution of ZnO according to the following equations:

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Dissolution: ZnO + 2H+ → Zn2+(aq) + H2O (1)

Photodecomposition: ZnO + 2h+VB → Zn2+(aq) + O* (2)

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3.2.4. Effect of initial concentration of caffeine

The effect of initial concentration of caffeine (5–30 mg/L) on its photocatalytic

degradation was studied at the initial solution pH of 7.5 and the optimum catalyst dose of 0.3

g/L. From Fig.8, it is evident that the photocatalytic degradation depends on the initial

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concentration of caffeine. Since the lifetime of hydroxyl radicals is very short (only a few

nanoseconds), they can only react at or near the location where they are formed. A high caffeine

concentration logically enhances the probability of collision with oxidizing species, leading to

an increase in the degradation rate.

According to numerous of works, the influence of the initial concentration of the solute

on the photocatalytic degradation rate of most organic compounds is described by pseudo-first

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order kinetics.

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dC
r  k ap C (3)

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dt

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Integration of that equation will lead to the expected relation:

C0
ln( )  kap t (4)
C
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where kap is the apparent reaction rate constant (min−1), t is the irradiation time, C0 is the initial
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concentration of caffeine and C is the concentration of caffeine at a reaction time t.
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The plot of ln (C0/C) versus t with different initial concentration of caffeine is shown in

Fig.9. The figure shows that the photocatalytic degradation fully follows the pseudo-first order
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kinetic in the case of initial concentrations of 5, 10 and 15 mg/L. However, for concentrations

greater than 15 mg/L, the photocatalytic degradation takes place in two stages, the first stage of
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the process follows pseudo-first order kinetic with respect to caffeine concentrations and a
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second slower stage until the end of the process of the photocatalytic degradation. The length
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time of the first stage decreases with increasing the initial caffeine concentration. This result

can be explained by the competitive adsorption/degradation behavior between caffeine

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molecules and its degradation intermediates, which could be more significant with high

concentration in solution (Barka et al, 2010).

The effect of initial caffeine concentration on the initial rate of degradation is shown in

Fig.10. The figure indicates that the initial rate of degradation increases with increasing initial

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concentration of caffeine until 20 mg/L, and then after star to decrease with the rise in

concentration in solution. This can be explained by the fact with increase in the number of

caffeine molecules, the path length of photons entering the solution decrease and fewer photons

reach the catalyst surface, and the generation of hydroxyl and superoxide radicals gets reduced.

The optimum concentration of caffeine was found to be 20 mg/L.

3.2.5. Efficiency of regenerated photocatalyst

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Generally, recycling of the photocatalyst is crucially important for industrial

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applications. In order to determine the recyclability of the best catalyst, we carried out a cycle

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of experiment under identical conditions. The suspension were recovered by centrifugation,

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washed with distilled water to remove the residual caffeine, and dried at 100 °C before another

catalytic test. As illustrated in Fig.11, the photocatalytic activity of the prepared photocatalyst
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still maintains a high level even after 3 times cycling. There was no significant catalyst
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deactivation after three cycling runs, confirming that 1% Mg-ZnO-Al2O3 photocatalyst is
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highly efficient and very stable.

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Conclusion
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Mg-ZnO-Al2O3 heterostructured catalysts at various contents of Mg (1, 3 and 5 wt%)

were successfully synthesized from LDH precursors by ceramic process. The synthesized
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photocatalysts were characterized by several physicochemical techniques including XRD,

FTIR and SEM/EDX. It was found that the crystallinity increases with increasing Mg content.
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the 1% Mg-ZnO-Al2O3 catalyst exhibited higher photocatalytic activity than ZnO-Al2O3, pure

ZnO and commercial Degussa P-25 titanium dioxide catalysts for the degradation of caffeine
A

under UV light irradiation. The excellent photocatalytic activity of 1% Mg-ZnO-Al2O3 was

attributed to the adsorption process, crystallinity, particle size and interfacial heterostructure in

the Mg/ZnO-Al2O3 catalysts. The optimum catalyst dosage for the degradation of a 20 mg/L of

caffeine solution was found to be 0.3 g/L. Solution pH significantly affect the photocatalytic

14
degradation and the optimal pH was 9.5. The recycling tests indicated high stability in the

photocatalytic performance. Finally, 1% Mg-ZnO-Al2O3 material may be used as an efficient

photocatalyst for the degradation of pharmaceuticals pollutants in aqueous solution.

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Figure Caption
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Figr-1

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Fig.1. XRD patterns of fresh LDH precursor, pure ZnO, undoped and Mg doped calcined LDH.

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Figr-2

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Fig.10. Plot of ln (C0/C) versus t with different initial concentrations of caffeine.

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Figr-3

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Fig.11. Effect of initial concentration of caffeine on its initial rate of degradation.

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Figr-4

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Fig.12. Photocatalytic degradation of caffeine over three cycles of regeneration of 1% Mg-ZnO-

Al2O3 photocatalyst (Caffeine concentration: 20 mg/L; photocatalyst dosage: 0.3 g/L; solution

pH: ~7.5).
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Figr-5

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Fig.2. FTIR spectra of fresh LDH precursor, pure ZnO, undoped and Mg doped ZnO-Al2O3.

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Figr-6

Fig.3. SEM-EDX images of undoped (a,b) and 1% Mg doped composite (c,d).

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Figr-7

Fig.4. UV–Vis DRS for the ZnO-Al2O3 and 1%Mg-ZnO-Al2O3 nanocomposite.

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Figr-8

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Fig.5. Photocatalytic degradation of caffeine in the presence of undoped and Mg doped calcined

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LDH compared to pure ZnO and standard Degussa P-25 TiO2 (Caffeine concentration: 20
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mg/L; photocatalyst dosage: 0.3 g/L; pH of the natural solution (~7.5)).
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Figr-9

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Fig.6. Correlation between adsorbed quantity and photocatalytic degradation of caffeine

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(Caffeine concentration: 20 mg/L; photocatalyst dosage: 0.3 g/L; pH of the natural solution
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(~7.5)).
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Figr-10

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Fig.7. Effect of catalyst dose on the photocatalytic degradation of caffeine after 70 min of

irradiation (Caffeine concentration: 20 mg/L; initial solution pH: ~7.5).

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Figr-11

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Fig.8. Effect of initial solution pH of the photocatalytic degradation of caffeine (Caffeine

concentration: 20 mg/L; photocatalyst dosage: 0.3 g/L).

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Figr-12

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Fig.9. Photocatalytic degradation of caffeine at different initial concentrations (Photocatalyst

dosage: 0.3 g/L; solution pH :~7.5).

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Table 1. Structural parameters of undoped and Mg-doped ZnO-Al2O3 in comparison with pure

ZnO.

Catalyst Lattice parameter (nm) Cell volume (nm3) Crystallite size (nm)

a c

Pure ZnO 0.3244 0.5196 4.7381 20.9009

ZnO-Al2O3 0.3241 0.5190 4.7224 4.0917

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1%Mg-ZnO-Al2O3 0.3241 0.5190 4.7215 8.2179

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3%Mg-ZnO-Al2O3 0.3240 0.5189 4.7186 35.3175

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5%Mg-ZnO-Al2O3 0.3239 0.5188 4.7144 36.9967

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