Arabian Journal of Chemistry

Photocatalytic kinetics of Acid Blue 40 degradation using rod-shaped CuO

nanoparticles and conditions optimization
--Manuscript Draft--

Manuscript Number: ARABJC-D-21-01593

Article Type: Original Article

Section/Category: Materials for Environment and Wastewater Purification

Keywords: Copper oxide; Precipitation; Characterized; Photocatalysis; acid blue 40; Process
variables

Abstract: Wastewater treatment using metal nanoparticles has gained much attention due to
higher efficiency and in the present investigation, copper oxide (CuO) nanoparticles
were synthesized using chemical precipitation method and same was employed for the
removal of dye acid blue 40 (AB-40). Copper oxides (CuO) NPs were characterized by
XRD (X-ray diffraction), SEM (Scanning electron microscopy), Energy dispersive X ray
spectroscopy (EDX) and FT-IR (Fourier transform infrared spectroscopy). Photo
catalytic degradation potential of synthesized CuO was evaluated for the degradation
of AB-40 dye. Different experimental parameters such as pH, concentration of dye,
catalyst doses and contact time were optimized. The synthesized copper oxide
nanoparticles showed excellent photo catalytic activity (84.87%) for the degradation
AB-40 in the presence of sunlight at optimized conditions. Among different kinetics
models, the AB-40 followed BMG kinetic model. Results revealed CuO nanoparticles
showed promising efficiency for dye degradation of dye and can possibly be used for
remediation of dyes in textile effluents under solar light irradiation.

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4 Photocatalytic kinetics of Acid Blue 40 degradation using rod-shaped CuO nanoparticles and
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6 conditions optimization
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10 Arfa Aslam1, Haq Nawaz Bhatti1, Shumaila Fatima1, Sobhy M. Ibrahim2 and Munawar Iqbal3*
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13 Department of Chemistry, University of Agriculture, Faisalabad, Pakistan
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15 Department of Biochemistry, College of Science, King Saud University, P.O. Box: 2455, Riyadh
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11451, Saudi Arabia
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Department of Chemistry, The University of Lahore, Lahore, Pakistan
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20 Shumaila Fatima: Munawar.iqbal@chem.uol.edu.pk
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24 Abstract
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26 Wastewater treatment using metal nanoparticles has gained much attention due to higher efficiency
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29 and in the present investigation, copper oxide (CuO) nanoparticles were synthesized using
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31 chemical precipitation method and same was employed for the removal of dye acid blue 40 (AB-
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34 40). Copper oxides (CuO) NPs were characterized by XRD (X-ray diffraction), SEM (Scanning
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36 electron microscopy), Energy dispersive X ray spectroscopy (EDX) and FT-IR (Fourier transform
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39 infrared spectroscopy). Photo catalytic degradation potential of synthesized CuO was evaluated
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41 for the degradation of AB-40 dye. Different experimental parameters such as pH, concentration of
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43 dye, catalyst doses and contact time were optimized. The synthesized copper oxide nanoparticles
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46 showed excellent photo catalytic activity (84.87%) for the degradation AB-40 in the presence of
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48 sunlight at optimized conditions. Among different kinetics models, the AB-40 followed BMG
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51 kinetic model. Results revealed CuO nanoparticles showed promising efficiency for dye
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53 degradation of dye and can possibly be used for remediation of dyes in textile effluents under solar
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56 light irradiation.
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4 Keywords: Copper oxide; Precipitation; Characterized; Photocatalysis; acid blue 40; Process
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7 variables
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10 1. Introduction
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In the field of science, day by day nanotechnology play a very important role. Nanoparticles
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16 represents different application due to high surface to volume ratio. Nanotechnology showed
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18 different applications due to its wide range in the fields like medical, biotechnology,
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21 pharmaceuticals, information technology, catalysis, environment and energy etc [1-7]. Copper
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23 oxide has been widely considered due to different applications like as wastewater treatments [8],
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26 solar sensors [9], battery electrodes for lithium ion cells [10], photo catalytic degradation of
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28 organic pollutants, solar energy conversion [11-13] and photo conductive compounds [14-16].
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31 This metal oxide shows different characteristics like as, antimicrobial activity [17], electrical,
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33 optical [18,19], thermal stability and thermal superconductivity [20] etc. The different metals
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35 (platinum, gold and silver) considering costly as compared to copper metal because it has been
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38 used in catalytic and antifungal applications [4].
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41 Copper oxide have been prepared by different methodologies like as hydrothermal method,
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[21,22,23] electrochemical method [24], thermal decomposition method [25], chemical
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46 precipitation method [26], solvothermal method [27], wet chemical reduction method [28,29,30],
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48 microwave irradiation method, [31] sol-gel method, [32] sonochemical method, [33] thermal
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51 oxidation method [34], electro deposition method [35-38] and hydrothermal microwave method
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53 [39]. Nanometer copper oxide obtained different dimensions and shape, like as nanosheets [40],
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56 nanotubes [41], and nanoneedles [42] etc. Nanostructure have great attention due to novel
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58 applications with well-defined structure and shape [43–45]. It has many unique morphologies that
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4 have been acquired like as, dendrites [46], spherical like [47], flower like [48], tadpole shaped
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7 [49], octahedral [50] and urchin like [51].
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10 Hence, copper oxide NPs were prepared by precipitation method. Co-precipitation synthesis has
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13 many advantages over other methods as it involves, large surface area, well-defined size, catalyst
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15 free growth, uniform production, costly effective and use of simple equipment’s etc. The uniform
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18 reaction temperature also makes it more suitable than others [52, 53, 54, 55]. The synthesized CuO
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20 nanoparticles characterized by using advanced techniques. In the presence of sunlight, photo
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catalytic activity was examined (textile dye) by degradation of acid blue 40 (AB 40). The
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25 degradation of organic pollutants has been necessary because of the harmful effect on human
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27 health, atmosphere and water pollutants etc [56,57,58]. Water pollution is one of the most
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30 thoughtful issue producing various health problems, which need to be tackled to avoid the
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32 hazardous dye discharged in to water bodies.
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38 2. Material and methods
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41 2.1 Chemical
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Analytical grade of Copper nitrate tri hydrate, Sodium Hydroxide and sodium dodecyl
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46 benzenesulfonate (SDBS) were purchased from Sigma-Aldrich. Distilled water was used for
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48 preparation of solution throughout the study.
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51 2.2 Synthesis of CuO NPs
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53 A 0.2 M of Cu (NO3)2. 3H2O solution was prepared in 100ml distilled water. 0.4 M NaOH solution
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56 was added drop wise in the aqueous solution of Cu (NO3)2. 3H2O. Aqueous solution of Cu (NO3)2.
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58 3H2O was continuously stirred while addition of NaOH. Sodium dodecyl benzenesulfonate
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4 (SDBS) is added in above solution. After addition of surfactant precipitation will be formed and
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7 color change will be observed. Reaction mixture was placed overnight for further precipitation and
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9 centrifuged at 5000 rpm for 20 min. The resultant precipitates were rinsed with deionized water
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12 followed by absolute methanol or ethanol (4 to 5 times) to remove impurities. Then dried the
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14 precipitant in oven at about 60℃ for overnight. Calcination of the obtained product was done at
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17 500℃ for 4 hours in the furnace.
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19 2.3 Dye degradation
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21 Photo catalytic activity of synthesized product (CuO) was evaluated using AB-40 as test dye under
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24 sunlight irradiation. For evaluating optimized conditions for degradation, the effect of different
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26 parameters (pH, concentration, catalyst dose and contact time) on rate of degradation were gone
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29 through using copper oxide as catalyst. 0.05g of CuO was added in 20 ml of 40 ppm AB-40
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31 solution and stirred using magnetic stirrer in the dark for 5 minutes before placing them under
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34 sunlight. Solution having catalyst was then kept under sunlight for degradation of dye. After 30
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36 minutes 2 ml solution was withdrawn, centrifuged to remove catalyst and analyze using UV-vis
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spectrophotometer at 553nm. Percentage degradation of AB 40 was calculated by following
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41 relation
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47 Where, co is the initial concentration when time is equal to zero and ct is the final concentration of
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49 dye with the passage of time, after degradation.
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52 3. Results and discussion
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55 3.1 XRD analysis
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57 The XRD gives information about the crystallinity of the synthesized substance. The X ray
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59 diffraction pattern of copper oxide nanoparticles is shown in Fig. 1. The XRD of the synthesized
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4 copper oxide NPs show the peaks at 2 theta corresponding to 32.590, 35.590, 38.880, 48.760, 53.500
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7 and 58.490 corresponding to the miller indices values of (1 1 0), (0 0 2), (2 0 0), (2 0 2), (0 2 0)
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9 and (2 0 2) respectively. This crystallographic distribution pattern verifies that the synthesized
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12 CuO nano particles are crystalline in nature. So, through X-rays diffraction the synthesized copper
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14 oxide NPs give face centered cubic crystalline form. The sharpness of the peaks shows that the
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17 synthesized CuO nano particles material is impurities free [59].
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19 Fig. 2 shows the proposed structure of as synthesized CuO nano particles. Figure (a) shows the
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21 basic structure of synthesized CuO nano particles in one unit cell arrangement. Figure (b) shows
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24 the simple attachment of Cu and oxygen atoms while figure (c) shows the bonds between Cu and
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26 oxygen atoms in synthesized CuO nano material. Figure (d) is the polyhedral arrangement of CuO
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29 nano particles and Figure (e) is the space fill arrangement of CuO nano particles in one unit cell
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31 arrangement. Figure (f) shows the wireframe arrangement of the synthesized material of CuO nano
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34 particles.
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36 3.2 SEM analysis
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Scanning electron microscopy analysis images of the synthesized copper oxide NPs are shown in
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41 Fig. 3. Synthesized product is present in the form of regular rod shaped particles. Random size
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43 distribution of the synthesized CuO nanoparticles can be seen in obtained SEM images. Particles
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46 size is not homogenous as some particles are attached with each other. Some of the particles are
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48 agglomerated in the form of bunch giving long oval like morphology. Some irregular shaped
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51 particles are also present along with these rods, which may be broken parts of other rods.
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56 3.3 EDX analysis
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4 Energy Dispersive X-ray analysis examined the elemental analysis of copper oxide nanoparticles.
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7 The energy dispersive also confirmed the formation of copper oxide nanoparticles. It is also
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9 observed from EDX spectrum that carbon and oxygen are also present in copper (Fig. 4).
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12 According to the mass %age of the sample 51. 85 percent of samples consisted of copper. Carbon
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14 was present up to 24.70 percent and oxygen 23.44 percent.
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19 3.4 FTIR analysis
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21 The major peaks indicated by the metal nanoparticles are under the range of 897 cm-1 to 700 cm-1
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24 gives information about copper oxide synthesized through chemical methods. The peaks at 997
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26 cm-1 to 1036 cm-1 is credited to C-O vibration of epoxy and alkoxy group. The strong peak appears
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29 at 1220 cm-1 to 1254 cm-1 that indicates the O-C-O band (Fig. 5). There is a spectrum up to the
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31 fingerprint region. The major peaks indicated by the metal nanoparticles are under the range of
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34 897 cm-1 to 700 cm-1 gives information about copper oxide synthesized through chemical methods.
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36 The peaks at 997 cm-1 to 1036 cm-1 is credited to C-O vibration of epoxy and alkoxy group. The
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strong peak appears at 1220 cm-1 to 1254 cm-1 that indicates the O-C-O band [60].
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41 4. Photocatalytic activity performance
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44 4.1 Effect of pH
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48 Effect of pH (2-10) on degradation rate of AB-40 was evaluated using CuO nano catalyst. The
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results obtained are shown in Fig. 6. Degradation efficiency upto 67 % was achieved at pH 8. The
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53 result showed that CuO NPs are effective for degradation of AB-40 at basic range. So it is
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55 concluded that the production of OH• radicals become greater at basic pH value while lesser at
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58 acidic pH value The photo catalytic degradation of (AB-40) dye is mainly dependent on the pH
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4 value due to its effect on the aggregates size, catalyst charge, conductance and valance bonds
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7 position [61].
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10 4.2 Effect of dye concentration
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14 The effect of dye concentration on the degradation of dye AB-40 was determined by using copper
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16 oxide Np’s as catalyst at various concentrations (10, 20, 30, 40 and 50 ppm) using 0.005 g catalyst.
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19 The results are shown in a given Fig. 7. The synthesized CuO NPs showed excellent degradation
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21 results upto 70% at 50 ppm dye solution. Results revealed that catalytic degradation of dye usually
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24 depends upon initial concentration of pollutant. Degradation of dye was found to be increased by
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26 increasing the initial dye concentration. By increasing the concentration of dye, then higher will
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29 be the organic matter available for catalyst. [62].
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32 4.3 Effect of catalytic dose
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36 In the degradation of dye, catalyst dose is another parameter effecting the rate of dye degradation.
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38 Photocatalytic degradation of AB-40 was evaluated at various catalyst dosage from 0.005 to 0.03
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41 g per 20 ml of dye solution. The results are shown in this Fig. 8. The synthesized CuO NPs showed
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43 excellent degradation results up to 76.58% at 0.02 g catalytic dose. At starting point the rate of
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degradation is increasing by increasing the amount of catalyst (NPs) but with the flow of time it
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48 seems to be decrease [63]. This is because higher the number of active site on the surface of the
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50 catalyst by increasing the catalyst amount. So, number of radicals are also increases. At the
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53 optimized catalyst dose all the active sites are available for degradation [64].
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56 4.4 Effect of irradiation time
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4 The degradation of AB-40 was also dependent on contact time. Results obtained are shown in Fig.
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7 9. The graph represents that at starting point the percentage of degradation increasing with
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9 increasing time but with the flow of time it decreases [65]. Degradation rate of dye increases upto
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12 84.87% in 1 hour, then it seems to be no prominent effect on degradation with increasing time. In
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14 photolytic degradation a lot of binding surfaces (empty spaces) are available at the initial stage of
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17 reaction. With the flow of time binding surface (empty spaces) are enclosed and more connection
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19 points are not existing for dye molecules. That’s why at the starting of reaction more rate of
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21 degradation of dye was accomplished.
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25 5. Kinetic studies
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Pseudo first order, pseudo second order and Behnajady-Modirshahla-Ghanbery (BMG) kinetic
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31 models were used to study degradation kinetics of AB-40 (dye) by copper oxide nanoparticles.
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33 These models evaluated rate of kinetics, determination coefficient, reaction order and rate constant
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36 [66,67]. In the case of pseudo first order kinetic model graph is plotted between ln (C◦/Ct) and t.
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38 The graphical representation of data is given in Fig. 10. The results represent that coefficient of
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41 determination (R2) is very low, evaluating that results do not follow pseudo first order model. The
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43 graphical representation (t vs 1/Ct) of pseudo second order kinetic model data is given in Fig. 11.
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R2 values in that case is also low, depicting given model is not appropriate for result obtained. Data
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48 evaluated through Behnajady-Modirshahla-Ghanbery kinetic model is graphically represented in
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50 Fig 12. The graph is plotted between t vs t/1-C /C . Regression analysis calculated the coefficient
t ◦
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53 of determination. The data fit with a linear curve when R =1 [68]. Result indicates that BMG
2

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55 kinetic model best fits with the experimental data. Because of the coefficient of determination
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58 values for BMG model are larger than co-efficients of determination for pseudo first and pseudo
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60 second order kinetics models.
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5 6. Conclusion
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8 The copper oxide nanoparticles were synthesized using chemical approach (precipitation method).
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Synthesized material characterized by XRD, SEM, EDX and FT-IR was used for degradation of
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13 dye (AB-40). The size of CuO nanoparticles was found to be in the range of 40 to 60 nm. The
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15 photo catalytic degradation process of copper oxide NPs of AB-40 was examined in the presence
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18 of sunlight assessing effect of different parameters on degradation efficiency. At optimized
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20 conditions of pH (8), dye concentration (50ppm), catalyst dose (0.02g) and time (60 min)
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23 degradation efficiency upto (84.87%) was attained. Results were also assessed through kinetic
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25 modeling. BMG kinetic model was best fitted with achieved results.
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Figure Click here to access/download;Figure;Figs.docx

(002)
Intensity (200) [96-152-6991] CuO

(202)

(110) (202)
(020)

20 25 30 35 40 45 50 55 60
2-theta

Fig. 1. X-ray diffraction pattern of CuO NPs.

Fig. 2 Proposed structures of synthesized CuO nanoparticles in different arrangements of single
unit cell.
Fig. 3. SEM analysis of CuO NPs.
Fig. 4. Energy Dispersive X-ray analysis of CuO NPs.
Fig. 5. FTIR analysis of CuO nanoparticles
 80
70
60
% Degradation

50
40
30
20
10
0
0 2 4 6 8 10 12
pH

Fig. 6 Effect of pH on photocatalytic degradation of AB-40

 80
70
% Degradation 60
50
40
30
20
10
0
0 10 20 30 40 50 60
Concentration (ppm)

Fig. 7 Effect of dye concentration on photocatalytic degradation of AB-40

 78

77
% Degradation
76

75

74
0 0.01 0.02 0.03 0.04
Catalyst Dose (g)

Fig. 8. Effect of catalysts dose on photocatalytic degradation of AB-40

 85.5
85
84.5
% Degradation 84
83.5
83
82.5
82
81.5
81
80.5
80
0 20 40 60 80 100
Time (min)

Fig. 9 Effect of time on photocatalytic degradation of AB-40

 2

1.9
R² = 0.6494
1.8

1.7

1.6
0 20 40 60 80 100

Fig. 10 Graphical representation of pseudo first order kinetic model

 14

13.5

13 R² = 0.8947

12.5

12

11.5

11
0 20 40 60 80 100

Fig. 11 Graphical representation of pseudo second order kinetic model

100

80
R² = 0.9999

60

40

20

0
0 20 40 60 80 100

Fig. 12 Graphical representation of BMG kinetic model