Accepted Manuscript

Title: Adsorption kinetic and photocatalytic degradation of

malachite green (MG) via Cu/ZnO nanocomposites

Authors: A. Modwi, M.A. Abbo, E.A. Hassan, O.K. Al-Duaij,

Ammar Houas

PII: S2213-3437(17)30582-1
DOI: https://doi.org/10.1016/j.jece.2017.11.024
Reference: JECE 1991

To appear in:

Received date: 9-8-2017

Revised date: 12-9-2017
Accepted date: 6-11-2017

Please cite this article as: A.Modwi, M.A.Abbo, E.A.Hassan, O.K.Al-Duaij,

Ammar Houas, Adsorption kinetic and photocatalytic degradation of malachite
green (MG) via Cu/ZnO nanocomposites, Journal of Environmental Chemical
Engineering https://doi.org/10.1016/j.jece.2017.11.024

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Adsorption kinetic and photocatalytic degradation of malachite
green (MG) via Cu/ZnO nanocomposites

A. Modwi a*, M. A. Abbob,d, E. A. Hassand, O. K. Al-Duaij a, Ammar. Houas a,c

a
Al Imam Mohammad Ibn Saud Islamic University (IMSIU), College of Sciences, Department of

Chemistry, Riyadh 11623, Saudi Arabia.

b
Taif University, College of Education and Science, Chemistry Department, Saudi Arabia.
c
Unité de Recherche Catalyse et Matériaux pour l'Environnement et les Procédés (URCMEP);

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Université de Gabès; Campus Universitaire -Cité Erriadh-6072 Gabès, Tunisie.

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d
Sudan University of Science and Technology, College of Science, Chemistry Department,

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Khartoum, Sudan.

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Graphical abstract

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1.5
1.4
1.3
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1.2
1.1
1.0
0.9
MG (C/C0)

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0.8 Dark Adsorption

0.7
0.6
0.5
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Photolysis
0.4 ZnO pure T550 °C
Cu/ZnO T250 °C
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0.3 T350 °C
0.2 T450 °C
T550 °C
0.1
First order
0.0
-60 -40 -20 0 20 40 60 80 100 120 140
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Time(min)

Abstract

Cu/ZnO composites were synthesized via a simple sol-gel method catalyzed by

2.3.dihydroxysuccinic acid and annealed at different temperatures (TC). The obtained

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nanomaterials were characterized by means of several analytical techniques.

Photocatalytic performances of nanomaterials were evaluated by adsorption and

degradation of malachite green (MG) solutions (300 ppm high concentration) under

UV light irradiation. The results show a wurtzite phase for Cu/ZnO nanoparticles with

a crystallite size of 15.86 to 24.25 nm, depending on the annealing temperature. A

mesoporous structure of type IV with hysteresis type H3 was obtained for all

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synthesized nanomaterials, with mean pore diameter from 24.63 to 52.88 nm and

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surface area in the range of 35.1 to 8.66 m2/g. Adsorption and degradation results

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showed the effect of copper doping on the ZnO. At the same TA (550 °C), 14.49 and

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23.55 % MG were adsorbed on pure ZnO and Cu/ZnO, respectively. The adsorption

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isotherm of Cu/ZnO composite was fast, and it agreed well with the Langmuir model
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with a capacity of 1539 mg/g. The MG degradation rate constant of Cu/ZnO reaches

10 x 10-3 min-1 when the initial concentration of MG was 300 ppm, about 8 times
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higher than that of pure ZnO (1.28 x 10-3 min-1). The optimal annealing temperature
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was at 550 °C for Cu/ZnO nanoparticles with 92.62 x 10-3 and 10 x 10-3 min-1 as
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adsorption and degradation rate constant, respectively. This makes the

nanocomposite Cu/ZnO a promising and good candidate for wastewater treatment at

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high dye concentrations.

Keywords: Characterization; Cu/ZnO composites; Adsorption kinetics; Degradation.

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1- Introduction

The rapid proliferation of industries and the release of huge amount of wastewater has
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brought about increasing environmental pollution. Wastewater is contains hazardous

substances such heavy metals, organic dyes, bacterial pathogens, pharmaceuticals,

complex chemicals compounds, etc. [1,2]. Moreover, some dyes are skin sensitizers

and mutagens that can cause various kinds of human cancer [3,4]. Most organic dyes

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are non-biodegradable and, stable and feature high resistance to biodegradation [5].

Among these are organic dyes such as methyl red, methylene blue, methyl orange,

malachite green, etc. Many methods of dye removal from industrial effluents can be

used. Most of them are physical/chemical methods as for example: adsorption,

coagulation/flocculation, electrocoagulation [6-8] and photodegradation [9-11].

Lately, doping zinc oxide with transition metals has been shown to be a more

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effective way for the photocatalytic degradation process. This is because doping ZnO

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leads to a reduction in optical band-gap energy and significant changes in the

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electrical and magnetic properties [12,13]. Much research on doping ZnO with

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transitions metals such as Co, Mn, Fe, Ni, Ag and Cu has been carried out to improves

its heterogeneous photocatalytic activity [14-19]. In particular, doping ZnO with Cu is

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of interest due to the similar size of Zn and Cu in doped ZnO, which works to reduce
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band-gap energy of ZnO, creates defects in the lattice and increase optical absorption

in the visible region [20-24]. On top of that, enhances photocatalytic degradation of

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organic dye pollutants in aqueous solution.

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In this work, we report the influence of annealing temperature on the rate of

adsorption and photocatalytic activity of Cu/ZnO composites. The nanomaterials

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prepared were characterized by X-ray powder diffraction (XRD), Brunauer-Emmett-

Teller (BET) surface area analysis, scanning electron microscopy (SEM), energy
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dispersive X-rays (EDS) and transition electron microscopy (TEM). Adsorption

kinetics and photocatalytic degradation were carried out to investigate the observed
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UV photodegradation. We used malachite green (MG) as a model organic dye.

Generally most researches mention low concentrations of dyes in wastewater

effluents. However real effluents can be much more charged in dyes. Their

concentrations in wastewater effluents depend on countries and the norms used. Also

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the type of dyes and their effluents sources are very different (dye house effluents,

dyebath residues, industries, etc ). Vandevivere et al [25] cite a range of 600 - 800 ppm.

It can be seen that most dye concentrations cited for both real and simulated wastes

are below 500 ppm. Koprivanac et al [26,27] stated that 7000 ppm dye was

representative of concentrations found in waste streams in the reactive dye industry

when discussing the choice of simulated textile wastewater. In the case of MG, Ling

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et al [28] measured a concentration of 800 ppm in industrial wastewater. In this

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present study 300 ppm of MG can be considered as an average and reasonable

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concentration to approach real dyes effluents. Additionally, we showed the influence

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of a rise in annealing temperature on Cu/ZnO catalytic activity and the formation of

polar surfaces in the ZnO microstructure.

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2. Experimental
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2.1. Materials:
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Zinc acetate dihydrate (Zn (CH3COO)2.2H2O) and absolute methanol (99.99%) were

purchased from Panreac, and tartaric acid (CHOH-COOH)2 was obtained from
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Techno Pharm Chem. Cupper nitrate trihydrate (Cu(NO3)2.3H2O) and the model

organic pollutant malachite green (MG) were purchased from Panreac. The structure
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of the latter is shown in Table.1. All chemicals were utilized without further
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purification.
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2.2. Synthesis of pure ZnO and Cu/ZnO composites

For a typical fabrication of ZnO nanoparticles, Cu/ZnO catalyst was first synthesized

through a procedure used in our previous work [29]. 8 g of zinc acetate dihydrate was

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dissolved in 75 ml of methanol. After stirring for 30 minutes, the appropriate amount

of copper nitrate trihydrate to have a molar ratio Cu/Zn of 5.26% was added, and the

mixture was stirred for a further 30 minutes. Then, double distilled water solution of

tartaric acid (45 ml) was added drop-wise to the previous mixture. A gel formed

rapidly at room temperature under vigorous magnetic stirring and was dried at 85 oC

for 16 hours. Subsequently, the dry gel was annealed at 250, 350, 450 and 550 oC for

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one hour. A flow chart of the synthetic procedure for Cu/ZnO photocatalysts by the

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fast sol-gel method is briefly shown in Fig.1.

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2.3. Characterization techniques

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The composition and average crystallite size of nanoparticles were determined by the

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powder X-ray diffraction patterns. The samples were recorded on a diffractometer

(D8 Advance Bruker) using Cu-Kα radiation, λ = 0.15406 nm, accelerating voltage of
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40kV and scanning angle of 20o-75o. The surface area and pore sizes of nanoparticles
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were determined by The BET method collected on a Micrometrics ASAP 2020

apparatus, (degas temperature: ambient to 200 °C for 20 minutes with a pressure

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range from 0 to 950 mmHg). The morphology of samples was observed by a field

emission scanning electron microscope (FE-SEM, JEOL-6700F). The composition of

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the Cu/ZnO composite was evaluated through a energy dispersive X-ray spectrometer

(EDS). Transmission electron microscopy (TEM) for the composite was performed on
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a JEOL JEM-2100.

2.4. Photocatalytic performance

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2.4.1. Kinetics adsorption of MG procedure:

Kinetics adsorption was studied using 250 ml of MG solution with a fixed

concentration of 300 ppm (very large relative to those used in the literature). 750 mg

of the composite was added to MG and stirred in darkness. A sample was withdrawn

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every 15 min, diluted and centrifuged, and residual concentration was measured by

spectrophotometer (Labomed – UVS-2800) at a maximum wavelength of 618 nm.

The quantity of MG adsorbed per gram of catalysts at time (min) can be calculated by

the following equation [30].

(𝐶0 −𝐶𝑡 )V
qt = (1)
𝑚

where qt represents the quantity of adsorbed MG per gram of adsorbent (catalysts) at

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time t, 𝐶0 is the initial MG concentration, 𝐶𝑡 the concentration of MG at time t, V the

volume of the MG solution (mL) and 𝑚 the mass of the solid used (mg).

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All data were fitted using a pseudo-first order nonlinear Lagergren model [31]:

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q t = q e × (1 − 𝑒 −𝑘×𝑡 ) (2)

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where qt and qe are the amount of MG adsorbed at equilibrium and time t,
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respectively, and kads is the apparent adsorption kinetic constant. The experimental
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results are the average of at least three adsorption/ photodegradation experiments and

the nanocomposites used are the mixture of amounts prepared in tow preparations.
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3.4.2. Dye photocatalytic degradation

The photoactivity performance of ZnO and Cu/ZnO specimens were evaluated using
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(MG) dye as a pollutant under U.V irradiation. All photocatalysis experiments were
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carried out in a photoreactor equipped with a Pyrex cell addition to a circulating water
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jacket, and the irradiation source was a Philips HPK 125W lamp (365). The

photoreactor used for UV degradation was an immersed and external lamp

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photoreactor. The concentration of MG was 300 ppm, while that of the different

photocatalysts was 150 mg/L. After achieving adsorption equilibrium in the dark, the

solution was illuminated for the photocatalytic kinetic study. A sample of the MG

solution was withdrawn every 15 min, diluted, centrifuged and residual concentration

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measured by UV-visible spectroscopy at a wavelengthmax = 618 nm. Absorption

measurements were converted to concentration using the Beer-Lambert law. The

photocatalytic degradation efficiency was calculated using the following equation [32]:

(𝐶0 −𝐶𝑡 )
𝑀𝐺 𝑑𝑒𝑔𝑟𝑎𝑑𝑎𝑡𝑖𝑜𝑛 % = × 100 (3)
𝐶0

Where Co and Ct are MG initial concentration (fixed at 300 ppm) and time t

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concentration, respectively.

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3. Results and discussion

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3.1. Characterization of the prepared catalysts by X-ray diffraction

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The effect of annealing and loading 5% Cu on the structure of ZnO nanoparticles was

investigated using XRD as depicted in Fig. 2 (a). The obtained results showed broad

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peaks at positions 31.61°, 34.39°, 36.11°, 47.40°, 56.52°, 62.72°, 66.29°, 67.91° and
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69.08°, which were assigned to the 100, 002, 101, 102, 110, 103, 200, 112 and 201
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planes of the wurtzite phase of ZnO, as was clear from the spectra. These values are
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in good agreement with standards (JCPDS 36-1451) for ZnO and could be indexed as

the hexagonal wurtzite structure. Besides that, the samples of Cu/ZnO annealed at
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higher temperature exhibited extra peaks with low-intensity diffraction peak at

positions 38.65° (111) and 35.2o (110) belonging to the CuO monoclinic (base-
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centered) phase (JCPDS#18-1916) Fig .2 (b). The peaks are probably due to the
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quantity of Cu being high enough to be located at interstitial sites of Zn or to un-

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reacted Cu ions in solution. Moreover, the findings obtained suggest that the Cu5%

doped ZnO had two phases, Cu-doped ZnO, and CuO, that worked to form polar
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surfaces in photocatalysts of Cu-doped ZnO [33]. The average diameters of crystallite

(D) of the prepared nanomaterials are presented in Table 2. and were calculated using

the Scherrer ,s equation [34]:

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 0.9 𝜆
D= (4)
𝛽𝑐𝑜𝑠𝜃

where 𝜆 is the wavelength of Cu Kα radiation, 𝛽 is the full width half maxima

(FWHM) of the diffraction peak and 𝜃 is the Bragg peak angle.

The lattice parameters a and c can be calculated by using the following equations [35]:

λ
𝑎= (5)
√3𝑠𝑖𝑛𝜃

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λ

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𝑐= (6)
𝑠𝑖𝑛𝜃

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The crystal sizes calculated from Scherrer s equation were 22.26 nm for pure ZnO at

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550 oC and 15.86-24.25 for Cu/ZnO annealed at different temperature. In the

literature, the crystallite sizes of pure ZnO decrease when it is doped with low

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concentration of Cu ion; this is mainly attributed to the formation of Cu – O – Zn on
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the surface, which hinders the growth of crystal grains [36]. Meanwhile, in our case,
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the crystallite size of ZnO increase from 22.26 to 24.25 nm when it was doped by 5%
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Cu at the same annealing temperature. This finding may be due to the presence of
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CuO on the surface and the formation of a Cu-doped ZnO-CuO composite. The

crystallite sizes of the Cu/ZnO that annealed at different temperature were 15.86 -
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24.25 nm, and this increase in crystallite size was due to the enhanced crystallinity

and reduced surface area as annealing temperature rise (Table 2).

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3.2. Morphological and composition analysis

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The results of the SEM images of pure ZnO and Cu/ZnO photocatalysts at 550 oC, the

TEM image and EDS of Cu/ZnO at 550 oC are showed in Fig. 3 (a)-(d). From the
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SEM images, it is clear that the shape was spherical and slightly tangled for Cu/ZnO.

The TEM image of the Cu/ZnO composite is presented in Fig. 3 (c) and also suggests

the formation of almost spherical nanoparticles with particle size in the range of 12 -

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15 nm. The EDS results revealed that the Cu/ZnO weight ratio was equal to 4.8%,

with a molar ratio of 4.6% deduced from the Fig. 3 (d).

3.3. Surface area analysis

The nitrogen adsorption-desorption isotherms and Barett-Joyner-Halenda (BJH) pore

size distribution for pure ZnO and Cu/ZnO composites at the temperature can be seen

in the Fig. 4(a) and (b). All the isotherms obtained were Type IV, related to a capillary

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condensation, according to the International Union for Pure and Applied Chemistry

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(IUPAC) classification. The hysteresis was Type H3, characteristics of mesoporous

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material with slit-shaped pores. Based on the results seen in Fig. 4(a), all the

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desorption branches were different from adsorption ones, representing differences in

their pore’s texture [37]. Amongst all the catalysts, the Cu/ZnO composite that
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annealed at TC of 250 °C demonstrated the highest volume adsorption and widest
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desorption branch, as shown in Fig. 4(a). The pore size distributions for each
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photocatalysts are displayed in Fig. 4(b). The plots were located in the mesoporous

range, which is in good agreement with an adsorption isotherm of Type IV. By

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comparison, the pore size distribution of ZnO and Cu/ZnO at TC of 550 °C (Fig. 4(b))

indicated that the different features of Cu/ZnO annealed at TC of 250, 350 and 450 °C,
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in particular the average pore diameter that was centered at around 70 nm. This was

due to the modification in pore texture. Because of these observations, we can suggest
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that the annealing temperature had a clear effect on the specific surface area and the

pore size distribution of the composites (Table 2) as SBET decreases from 35.1 to 8.66
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m2/g when TC increased from 250 to 550°C. With an increase of annealing

temperature, a marked decrease in the surface area was noticed both for the pure

material and Cu/ZnO. This phenomenon could be explained by clogging pores caused

by possible aggregation occurs when the annealing temperature increases. Certainly,

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as both volume and average pore size decreased, the observed clogging effect would

happen.

3.4. Photocatalytic activity

3.4.1. Adsorption kinetics

To understand the degradation process, it is very important to study the darkness

adsorption phenomena of the substrate to be degraded. However, this sort of study is

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generally ignored by many researchers of the heterogeneous photocatalytic

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degradation of organic compounds in aqueous solution. Indeed, studying the

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adsorption phenomenon in the dark, in terms of the MG adsorbed amounts (mg/g) in

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the solid and not of residual concentration in solution, is essential both to determine

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the adsorption equilibrium time and its kinetics. This kinetics is shown in Fig. 5 for
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the catalysts annealed at different temperatures (TC). It can be seen that, all kinetics
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were first order according to the nonlinear Lagergren model (equation (2);
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experimental data are represented by scattered points and Lagergren simulation by a

continuous line).
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As one can deduce from Fig. 5, stirring the MG + catalyst suspensions had to be

maintained in the dark for at least 60 minutes, which represents the solid saturation
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time (tsat) before the degradation reaction.

The effects of annealing temperature on the apparent adsorption kinetic constants

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(kads) and equilibrium-adsorbed amounts (qe) deduced from the Fig. 5 by the

Lagergren simulation are displayed in the Fig. 6(a) and (b). For the same annealing
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temperature (TC= 550 °C), doping ZnO with Cu decreased the rate of adsorption

reaction (Fig. 6 (a)). In contrast, the equilibrium adsorbed amount qe was

approximately doubled (1.7 times higher; Fig. 6 (b)) which both can be explained by

an increase of the specific surface area (1.15 times higher) and the site number created

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by the presence of copper (1.4 times higher). On the other hand, the adsorption rate

seemed to be dependent on both annealing temperature and specific surface area.

Indeed, the normalized adsorption rate constant increases gradually with the increase

of TC. Nevertheless, despite the decrease of adsorbed amount (qe) with the increase of

TC, the normalized adsorbed amount increased from 2.35 to 8.49 mg/m2. Table 3

shows the increase in the number of adsorption sites.

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3.4.2. Adsorption isotherms

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The adsorption results are described by isotherm models such as those of Langmuir

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and Freundlich, which are the models most commonly used in studying aqueous

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system adsorption. Langmuir's isotherm model is represented by the following

expression [38]:
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𝐾𝐿 𝐶𝑒
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q e = q max (7)
1 + 𝐾𝐿 𝐶𝑒
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where qe and qmax are the adsorbed amounts in solid phase in mg/g at equilibrium and
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at saturation, respectively, Ce (mg/L) is the residual concentration in liquid phase and

KL (L/mg) is the adsorption thermodynamic equilibrium constant of Langmuir.

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The empirical Freundlich expression is represented by the following expression [38]:

q e = 𝐾𝐹 𝐶𝑒 1/𝑛 (8)
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where qe is the adsorbed amount in solid phase in mg/g at equilibrium, Ce (mg/L) is

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the residual concentration in liquid phase, KF is the binding energy constant reflecting

the affinity of the adsorbents to photocatalyst (mmol1-(1/n) L1/n g-1) and n is the
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Freundlich exponent related to adsorption intensity. The simulation of the MG

adsorption isotherms on pure ZnO and Cu/ZnO composites annealed at TC = 550°C

by both models are showed in the Fig.7 (a) and (b).

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3.4.3. MG photocatalytic degradation studies for annealed Cu/ZnO nanoparticles

The photocatalytic activity of the ZnO annealed at (550 oC) and Cu/ZnO annealed at

TC from 250 to 550 oC catalysts after 60 minutes of dark MG adsorption are displayed

in Fig. 8 (a). It can be seen that no photoactivity was observed in the absence of the

photocatalyst and a very low photocatalytic activity was obtained with pure ZnO

(only 15% of MG was degraded after one hour of irradiation). Meanwhile, for

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Cu/ZnO composites, the photocatalytic efficiency of MG degradation was increased

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significantly with annealed temperature rise. Fig. 8 (b) shows that all kinetics are well

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fitted by the software Origin.8 to pseudo first order, and the obtained values of the

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rate constant are given in Table 3.

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On the other hand, at first sight, the MG photocatalytic degradation depends on the
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development of the surface area resulting from the Cu/ZnO composites, as long as it is
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usually thought that photocatalytic efficiency is greatly tied to the catalyst surface
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area. Nevertheless, despite adsorption is being a very important step in the

photocatalytic process; we will declare here that it is not simply a question of specific
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surface area and adsorption. Indeed, Fig. 8 (a) shows that the highest adsorption was

obtained for the Cu-doped catalyst annealed at TC = 250 °C which is in good

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agreement with the determined specific surface area value (35.10 m2/g), but this

catalyst is found to be less photoactive towards (MG) degradation than other Cu-
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doped catalysts.

We note also the important effect of annealing temperature on the photocatalytic

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efficiency towards degradation of MG with Cu/ZnO. This clearly demonstrates that

the photocatalytic activity depended on the annealing temperature rather than particles

size and surface area. Generally, photocatalytic activity is related to the

microstructure, such as the crystal plane, crystallinity, surface properties, BET

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specific surface area, etc., of the catalyst [39,40]. Recent studies show that the

difference in photocatalytic activity among all catalysts, not only relates to the surface

adsorption ability but also to the type and concentration of oxygen defects on the

surface and/or surface layers. Certainly, two major parameters can be affected by the

annealing temperature: the increase of the crystalline and the decrease of surface OH

groups. Normally, as the photocatalysis process is a surface phenomenon, the

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decrease of surface OH groups may causes a loss of the catalyst photoactivity.

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However, we found that the highest photoactivity either in terms of MG degradation

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rate or of the kinetic constant was obtained from the catalyst annealed at the highest

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temperature (TC = 550 °C) with the lowest specific surface area (8.66 m2/g).

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Therefore, it is clear that an optimal quantity of hydroxyl groups on the catalyst
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surface combined with a certain degree of crystallinity and specific kinds of oxygen
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defects on the surface and/or surface layers, are required to achieve the optimal

photoactivity [41]. In our case, the increase of the Cu/ZnO TC = 550 °C catalyst
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photoactivity may be attributed to the increase of grain size, crystallinity and oxygen
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defects, as has been reported for pure ZnO [42,43].

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3.4.4. Photocatalytic mechanism of MG degradation

The photocatalytic mechanism of MG decomposition is depicted in Fig. 9. In the

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photocatalysis process, when a Cu/ZnO composite is irradiated with UV light having

energy greater than the band gap of ZnO and CuO on the surface, an electron from
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valence band moves to the conduction band leaving a hole at the back. The

conduction band can be reacted with dissolved oxygen to give a superoxide radical,

which results in the formation of hydroxide radicals [44]. While the valence band

reacts with H2O molecules to also from hydroxide radicals. The .OH radical formed in

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the solution is a strong oxidizing agent and is responsible for MG degradation.

Furthermore, copper ion substituted in ZnO lattice work as electrons traps. Hence, it

leads to a delayed recombination process.

4. Conclusion

In summary, Cu/ZnO composites, which consisted of Cu doped ZnO surrounded by

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CuO on the surface, were synthesized by acid catalyzed sol-gel method. The phase

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structure and surface area of prepared photocatalysts were investigated using XRD

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and BET. The shape and composition of Cu/ZnO composites were analyzed via SEM,

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EDS and TEM techniques. The adsorption rate and adsorption isotherms of MG dye

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by composites were determined. Our results showed that the equilibrium contact time
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of MG adsorption in dark by Cu/ZnO and ZnO is equal to 35min with an ultimate
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adsorption capacity of 1539 and 899 mg/g, respectively. The photocatalytic activity
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results showed that the degradation of MG under UV light was enhanced 8 times than

pure ZnO at the same annealing Tc. Moreover, the photocatalysis performance of
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Cu/ZnO nanocomposite was improved with annealing temperature rise.

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18
 Zn (CH3COO)2.2H2O Sintering for 30 min Methanol
o
at 27 C

Cu(NO3)2.3H2O SOL 2.3 dihydroxysuccinic

Acid aqueous solution

GEL Sintering for 5 min

o
at 27 C

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Drying for 16 hours XEROGEL Calcination for 1hour
o o
at 110 C at 250, 350, 450, 550 C

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Photocatalysts

Fig.1. A flow chart of the procedure for synthesis of the Cu/ZnO Photocatalysts
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3600

(101)
550/ZnO pure
(b)
(a) 800 550/Cu/ZnO
A
3200 CuO
550/Cu/ZnO

2800
M

600
Intensity (a.u)

2400 450/Cu/ZnO
Intensity (a.u)

CuO (monoclinc)
(002)

2000
ED

400
350/Cu/ZnO
1600

1200 250/Cu/ZnO
(110)
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(111)

200

800

400 550/ZnO pure 0

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0.064
0
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33 34 35 36 37 38 39 40
30 40 50 60 70
2Theta (deg.) 2Theta (deg.)
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Fig.2. (a) XRD patterns of ZnO and Cu/ZnO composites (b) Enlargement of the

principal peaks (101) for ZnO and Cu/ZnO specimens at 550oC

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 (a) (b)

(c) (d)

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Fig.3. SEM images of (a) pure ZnO and (b) Cu/ZnO, (c) TEM image of

Cu/ZnO and (d) EDS of Cu/ZnO photocatalysts.

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A
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E PT
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A

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 160 0.0035
550/ZnO
250/Cu/ZnO
Quantity Adsorbed (cm³/g STP)

140 250/Cu/ZnO (a)

350/Cu/ZnO
0.0030
350/Cu/ZnO (b)
120 450/Cu/ZnO 450/Cu/ZnO
550/Cu/ZnO

Pore Volume (cm³/g·nm)

550/Cu/ZnO 0.0025
100 550/ZnO pure
0.0020
80

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60 0.0015

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40 0.0010

20
0.0005

R
0
0.0000

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0.0 0.2 0.4 0.6 0.8 1.0 0 20 40 60 80 100 120 140 160
Relative Pressure (P/Po) Pore Diameter (nm)

Fig.4. (a) N2 adsorption-desorption isotherms and Pore size distribution of pure ZnO
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annealed at 550 °C and Cu/ZnO annealed at different temperatures.
A
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90

80
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70

60
qt (mg/g)

50
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40

30 550/ZnO pure
250/Cu/ZnO
20 350/Cu/ZnO
450/Cu/ZnO
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550/Cu/ZnO
10
Lagergren

0
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0 20 40 60 80 100 120
Time (min)

Fig.5. MG Adsorption kinetics on catalysts annealed at different temperatures and

A

Lagergren simulation
130 18
120 (a)
16
110
Cu/ZnO
100 14
Normalized kads (min .m .g)

90
-2

12
80
-1

10
kads (min )

70
-1

60 8
50
550/ZnO pure

6
40
30 214
20
2
10
0 0
A TC= 250 TC= 350 TC= 450 TC= 550
Catalyst
 90
Cu/ZnO
80 8
(b)
70

Normalized qe (mg/m )
60 6

2
50
qe (mg/g)

40 4
550 ZnO pure

30

20 2

10

0 0
A TC= 250 TC= 350 TC= 450 TC= 550

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Catalyst

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Fig.6. Effect of annealing temperature (a) on the MG adsorption kinetic constant and

R
(b) on the equilibrium MG adsorbed amount.

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300 300
(a) (b)
250 250

200 200

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qe (mg/g)
qe (mg/g)

150 150
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Freundlich Model : qe= KF*Ce^(1/n)
100 Langmuir Model : qe = qmax*KL*Ce/(1+KL*Ce) 100 R^2 = 99.85%
R^2 = 99.90 %
550/ZnO pure
A
550/ZnO pure 0.2 -1 0.8
qmax = 899.33 mg/g KL
-3
= 2.32 10 L/mg KF = 3.97 mg .g .L n = 1.24
50 50
550/Cu/ ZnO 550/Cu/ZnO
-3 0.1 -1 0.9
qmax = 1539.71 mg/g KL = 1.11 10 L/mg KF = 2.43 mg .g .L n = 1.12
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0 0
0 50 100 150 200 250 0 50 100 150 200 250
Ce (mg/L) Ce (mg/L)
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Fig.7. Adsorption isotherms simulation of MG on ZnO pure and Cu/ZnO TC = 550°C

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(a) with Langmuir Model and (b) with Freundlich mode

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A

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 1.5
1.4
1.3 (a)
1.2
1.1
1.0
0.9
MG (C/C0)

0.8 Dark Adsorption

0.7
0.6
0.5 Photolysis

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0.4 ZnO pure T550 °C
Zn0.95Cu0.05O T250 °C

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0.3
T350 °C
0.2 T450 °C
0.1 T550 °C

R
First order
0.0
-60 -40 -20 0 20 40 60 80 100 120 140

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Time(min)

0.0
(b)
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-0.2
A
Ln(Ct/Co)

Photolysis
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-0.4
550/ZnO pure
250/Cu/ZnO
350/Cu/ZnO
-0.6 450/Cu/ZnO
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550/Cu/ZnO

-0.8
0 20 40 60
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Time (min)

Fig.8. (a) Influence of Cu/ZnO composites at different temperature on MG

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degradation and (b) Pseudo – first order for rate degradation constant.
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A

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Fig.9. Scheme of possible photocatalytic mechanism of MG degradation.

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A

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 Table. 1. Chemical structure and physical properties of MG

Chemical structure

Mw (g/mol) 364.911

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Melting point 112 oC

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𝛌max (nm) 618

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Table.2. Average crystallite sizes and lattice parameters of the undoped and

Cu/ZnO nanoparticles prepared at different annealing temperatures.

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Lattice parameter (Ǻ)
Samples Crystallite size (nm) BET Surface area (m2/g)
(a) (c)
A
550/ZnO 22.26 3.2628 5.2256 7.48
M

250/Cu/ZnO 15.86 3.2732 5.2442 35.10

350/Cu/ZnO 16.95 3.2608 5.2608 19.39
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450/Cu/ZnO 20.95 3.2491 5.2088 12.55

550/Cu/ZnO 24.25 3.2588 5.2178 8.66
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Table.3. Kinetic parameters obtained of MG adsorption and photocatalytic

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degradation reactions for catalysts annealed at different temperatures.

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Adsorption Degradation
SBET
Catalyst kads qe R (m2/g) kdeg t1/2 R
A

(10 min-1)
-3
(mg/g) % (10-3 min-1) min %

250/Cu/ZnO 73.04 82.57 99.25 35.08 6.97 98.7 98.95

350/Cu/ZnO 62.58 78.22 95.60 19.39 7.39 92.85 99.51

450/Cu/ZnO 68.92 77.59 97.96 12.54 8.91 77.02 99.53

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550/Cu/ZnO 92.62 70.65 97.85 8.65 10.12 68.42 97.65

550/ZnO pure 124.03 43.48 96.77 7.48 1.28 541.52 92.87

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A
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