Accepted Manuscript

Title: Experimental and theoretical investigations of

photocatalytic activity of Cu doped ZnO nanoparticles

Authors: S. Sriram, K.C. Lalithambika, A. Thayumanavan

PII: S0030-4026(17)30402-3
DOI: http://dx.doi.org/doi:10.1016/j.ijleo.2017.04.013
Reference: IJLEO 59055

To appear in:

Received date: 5-1-2017

Accepted date: 4-4-2017

Please cite this article as: Sriram S., Lalithambika K.C., Thayumanavan A.,
Experimental and theoretical investigations of photocatalytic activity of Cu
doped ZnO nanoparticles, Optik - International Journal for Light and Electron
Opticshttp://dx.doi.org/10.1016/j.ijleo.2017.04.013

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Experimental and theoretical investigations of photocatalytic activity of Cu
doped ZnO nanoparticles

S.Sriram1*,K.C. Lalithambika1 and A.Thayumanavan1

1. Department of Physics, School of Electrical & Electronics Engineering, SASTRA

University,Thanjavur 613401. Tamilnadu, India.

*Corresponding Author:

S.Sriram
Department of Physics,
School of Electrical & Electronics Engineering,
SASTRA University,
Thanjavur 613401
Tamilnadu India
Email : sukansriram@gmail.com
Phone + 91 9629020302

Abstract:

Undoped and Cu doped ZnO nanopowders were synthesized by very simple and cost-
effective soft chemical method by varying copper concentration as 10 at%, 20 at % and 30 at%
for dye degradation test. Dense nanosheets of wurtzite structure with preferential growth of (101)
were formed. The crystallite size decreases from 66.810 nm to 20.360 nm when the Cu content
is increased. The photoluminescence results confirm the shift of near band edge emission (NBE)
towards the lower wavelength with increasing doping concentration. Energy dispersive X-ray
analysis (EDX) studies confirms the presence of Zn, O and Cu elements in the prepared nano
powders. Photocatalytic activity test was conducted for the prepared nanopowders against
Methylyne Blue (MB) dye under visible light. The observed results show that the photocatalytic
efficiency of the prepared nanopowders increase with the increase of Cu content. Theoretical
study based on electrode potentials was performed by employing density functional theory
(DFT) in order to validate the experimental results.

Keywords: ZnO nano powders; Cu doped ZnO; photocatalytic activity; DFT; Structural Studies;

1
1 Introduction

Synthesis and characterization of Zinc oxide (ZnO) nano powders have become an
essential part in material science due to its significant applications and novel properties. Zinc
oxide has the hexagonal wurtzite structure with a wide band gap of 3.4 eV [1]. ZnO is an
interesting material used in various areas, such as optical [2], piezoelectric [3], magnetic [4], gas
sensing [5] and in anti-bacterial activity [6]. It has been used in cathode-ray tubes [7], light-
emitting diodes [8], solar cells [9], ceramics [10], catalysts [11] and selective filters in gas
sensing [12]. Recently, the application of ZnO in ultraviolet (UV) optoelectronic devices has
created more attention for the researchers [13] in optoelectronic industry. Due to its stability at
high temperatures and pressure, it is found to be a suitable material in the food processing
industry [14]. Apart from this the electrical and optical properties of ZnO nanostructures can be
varied by suitable dopants. Metal doping with effective elements such as Li, Al, Mn, Cu, etc.
can modify the grain size, crystalline structure, phase, electrical, optical and magnetic properties
successfully [15-18]. Various methods such as sol-gel [19], co-precipitation method [20],
hydrothermal [21], microwave synthesis [22], thermal evaporation [23] and Chemical bath
deposition [24] have been used for the preparation of ZnO nano powders.
Apart from the experimental studies theoretical design are important since a prior
knowledge will be obtained about the properties of materials. Density functional theory (DFT) is
one of the proven analysis methods using which the properties of materials can be tailored
efficiently. In the present study undoped and Cu doped ZnO nano powders were synthesized
using a soft chemical method [25] at fixed pH value. The prepared samples were characterized
by Photoluminescence, X-ray diffraction (XRD), scanning electron microscopy (SEM), and
EDX. Photocatalytic test was conducted using methylene blue (MB) dye under visible light and
validated by the DFT based theoretical results.
2. Materials and Methods
2.1 Preparation of Undoes and Cu doped ZnO nanopowders
Undoped and Cu-doped ZnO nano powders were synthesized by soft chemical method,
which is easy and prudent. Highly purified zinc sulphate (purity >98%, Sigma Aldrich) with
0.2M was blended in doubly de-ionized water as a base solution to produce ZnO nanopowders.
With constant stirring, liquid ammonia was added drop by drop until the final pH of the mixed

2
solution reaches 9. The prepared solution was heated to a temperature 85 º C, magnetically
stirred for about 90 minutes, cooled to room temperature, and kept undisturbed for 24 hours.
Then it was filtered and washed with a mixture of ethanol and water in the ratio 1:3. The
products were then dried at 100º C and the prepared powders were calcinated at 400º C for 2
hours to get fine structured nano powders. Cu doped ZnO nanopowders were prepared in
different atomic percentage (10, 20 and 30) using copper sulphate (purity >98%, Sigma Aldrich)
as the dopant precursor by repeating the same procedure as said above. For convenience un-
doped, Cu 10 at% -ZnO, Cu 20 at% -ZnO and Cu 30 at% -ZnO nano powders were named as S1,
S2, S3 and S4, respectively.

2.2 Characterization
The structural characteristics and crystalinity of the prepared nano powders were studied
by X-ray powder diffraction (PAN-analytical -PW 340/60 X’ pert Pro) technique. Elemental
analysis and surface morphological studies of the prepared samples were analyzed using Energy
dispersive X-ray analysis (Model: JEOL- JSM 6390 with attachment INCA-Penta FETX3
OXFORD and Field Emission Scanning electron microscope (FESEM). The absorption studies
and photo- luminescence of the powders were studied using FP-8200 Fluorescence Spectrometer.

2.3 Photocatalytic Test

The photocatalytic degradation test for the undoped and Cu doped ZnO nanopowders
were performed against Methylene Blue (MB) dye in aqueous solution. A visible light source
(Xe arc 300W) was used to irradiate the dye solution. 50 mg of the prepared nano powders were
dissolved in 150 mL of MB solution and sonicated 60 mins in order to reach adsorption-
desorption equilibrium. Under the ambient temperature, the solutions were irradiated with the
light source for 60 mins. The reaction solutions were centrifuged and filtered in interval of
20 minutes in order to remove the photocatalyst. The degradation efficiency of MB upon all the
samples was calculated by taking down the absorption spectra of the solutions using a UV-VIS
spectrophotometer (Systronics 2002).

3
2.4 Computational Details
Appropriate super cells for undoped and Cu doped ZnO nanostructures were constructed
along (101) direction and optimized using SIESTA package [26]. SIESTA package implements
full self consistent based DFT implementation with a basisset of linear combination of atomic
orbitals (LCAO) [27]. For the DFT calculation, the exchange correlational effect calculation was
performed by generalized gradient approximation (GGA) with Perdew-Burke-Ernzerhof (PBE)
parameterization [28]. In SIESTA package, the core electron potential was replaced by Troullier-
Martins potential in fully separable form [27]. In the optimization and electronic structure
calculations, a double zeta plus (DZP) polarization orbitals were used for the valance electrons.
In Zn and Cu atoms 3d, 4s and in O 2s and 2p states were considered as valance bands. For the
electronic structure calculations, the Brillouine zone integration is done using a 15  15  9 k-
points sampling grid. The cut of energy of 400 eV was used for the grid integaration. For the
geometry optimization conjugate gradient (CG) algorithm was used. The optimized undoped and
Cu doped nanostructures were shown in the Fig. 1. For simplicity, the structures of undoped
ZnO, Cu @ 10%, Cu @ 20% and Cu @ 30% were named as ZnO, ZnO-Cu@10%, ZnO-
Cu@20% and ZnO-Cu@30%, respectively.

3. Results and Discussion

3.1 Structural study

The X-ray diffractograms recorded with Cu-Kα radiation (1⋅540Å) in Fig.2 shows the
data over 2θ range of 10°-80°. The obtained patterns for S1, S2, S3 and S4 were in match with
the JCPDS card (No 36-1451) and the peaks were identified as (100), (002), (101), (102), (110),
(103), respectively. All the peak positions and relative peak intensities of the samples belong to
wurtzite hexagonal structure. For all the samples, the preferential growth of (101) orientation is
along the c-axis. From the diffractograms, it is seen that the peak along the (101) plane widens
with increase of Cu content, showing degradation in crystalline quality. Change in the
crystallanity may be due to the doping of Cu which shifted the position of the peak (preferential
orientation) and hence the variation in the values of lattice parameters a and c. No other peaks
matching to Cu or other impurities were noticed in the diffraction patterns of all the samples.
Sonal et al [29] reported that the variation in the lattice parameters is due to the replacement of

4
Zn2+ by Cu2+ atom which has a small variation in its ionic radius compared to Zn atom.
However, in this present study, the decrease in the crystalline quality while increasing the Cu
dopant percentage may be due to interstitial placement of Cu atoms in the ZnO lattice. The
metal dopant controls the crystallization and also reduces the porosity of the structure. Due to
this reduction in porosity, the density of the microstructure increases.

The average crystallite size was calculated from the XRD pattern using Debye Scherer’s
formula [30]
0.9 𝜆
𝐷= --------(1)
𝛽 cos 𝜃
where β - Full angular width of a diffraction peak at the half maximum peak intensity, λ -
wavelength of X-ray radiation and θ is the Bragg angle. The calculated crystallite size
decreases due to increase in the Cu doping concentration. Because of this high surface area per
volume proportion, the nano powders may turn out to be more reactive. The wurtzite lattice
constant a, c and the volume of the unit cell (v) were calculated using the following formula [31]
1 4 (ℎ2 +ℎ𝑘+𝑘 2 ) 𝑙2
= + ----(2)
𝑑2 3 𝑎2 𝑐2
The volume of the crystallites V was estimated using the following expression
√3
𝑉= 𝑎2 𝑐 ------(3)
2
The calculated structural parameter values are tabulated in Table 1. From the table values, it is
observed that the increase in the c value was due to the replacement of Cu ion over the Zn sites.
It may be due to the large atomic radius of Cu (1.45 Å) than the atomic radius of Zn (1.42 Å).
The calculated volume of the unit cell of the prepared nano powder samples was almost same
which indicates that all the samples were possessing same ZnO wurtzite unit cell structure.
Variation in the lattice strain shows the prepared nano powders were slightly deviated from the
crystal structure with the standard values which may be due to interstitial Cu atoms in the ZnO
lattice.

3.2 Surface morphology and Elemental analysis

5
 The surface morphology of the samples S1,S2, S3 and S4 were shown in Fig 3. In figure
3, the sample S1 demonstrates anisotropic dimensions of the ZnO platelets due to less
crystallinity. With the addition of Cu, the size of the particles changes quite significantly (Fig 3).
The dimension of the nano-sheets increases with the increase of Cu content. The picture also
confirms the increase in the density and decrease in the porosity of the structure. Fig.4 shows the
EDX spectrum of the samples S1 and S4. Fig. 4 affirms the presence of Zn and O for the sample
S1 indicating the pureness of ZnO nanoparticles. The spectra of sample 4 (Cu-ZnO) reveals the
existence of copper, zinc and oxygen in the sample.

3.3 Photoluminescence study

The densities of defects and oxygen vacancies influenced physical properties of nano
structures significantly. Photoluminescence studies were carried out in the range of 300–600 nm
(excitation wavelength of 325 nm) to correlate between structure and property of the
nanopowders as appeared in Fig 5. PL spectra were additionally used to evaluate the optical
properties and structural defects of ZnO nanopowders. Visible emissions seen in the diagram
were due to some structural defects and it might be due to the oxygen vacancies in ZnO. The
ultraviolet emission intensity of the undoped nanopowder was better than the doped one, which
indicates the decrease in the crystal quality of ZnO. Radiative recombination of a hole and an
electron attributes the near band edge emission (NBE) centered at 388.5 nm. When the doping
concentration increases the NBE peak marginally moves towards the lower wavelength with
broadening. The slow reduction in the intensity of the peak specifies that the intrinsic defect
concentration (responsible for broadband emission) fall with Cu doping in ZnO.

3.4 Photocatalytic activity of ZnO and Cu doped ZnO nanopowders

The photocatalytic activity of the prepared undoped and Cu doped ZnO nanopowders
were evaluated against MB degradation under visible light irradiation. The characteristic
absorption peak at 663 nm was utilized as reference for the degradation process of MB. The
absorption spectra of aqueous solution of MB with the presence of undoped and Cu doped ZnO
nanopowders were shown in Fig. 6. The characteristic peak intensity of MB was found
decreasing with increase in exposure time for all the samples (S1, S2, and S3 & S3). This

6
indicates the degradation of the MB dye with the presence of the nanopowders. An additional
peak with decreasing intensity on increasing the doping concentration was also observed nearly
at 595 nm in Fig 6. This confirms the doping of Cu atom on ZnO structure. The photocatalytic
efficiency of the prepared nano powders can be calculated using the following formula [32]
𝐶0 − 𝐶𝑡 𝐴0 − 𝐴
= × 100 = × 100 − (4)
𝐶0 𝐴0
where C0 is the initial concentration of the dye, Ct is the concentration of the dye at time ‘t’,A0
and A are the corresponding absorbance of the concentration C0 and Ct. The calculated
degradation efficiency of the samples S1,S2,S3 and S3 were 79.61,81.53,83.46 and 85.38 %,
respectively. From theses calculated efficiencies it is evident that Cu doping with ZnO enhances
the photocatalytic process. The increase of efficiency of the catalytic process of ZnO when
doped with Cu was possibly due to the following reasons: (i) the reduction in the band gap which
effectively enables the carrier separation of photogenerated charge carriers (ii) extended carrier
life time (iii) increase in the number of defects or Oxygen vacancy trap centers for the
photogenerated electrons iv) increment in the surface area volume ratio. The oxygen vacancies
were one of the reasons for producing super oxide radicals such as (.O2-) and these super oxide
radicals would enable the production of other radicals such as OH-, H2O2 etc. The mechanism of
the photocatalytic activity is shown in Fig 7.

The kinetics of the photocatalytic activity can be expressed interms of Langmuir and
Hinshelwood model. The photocaltalytic reactions follow pseudo first order reaction and its
kinetics could be expressed using the following formula [33]
𝐶
𝐿𝑛 ( 𝐶0 ) = 𝐾𝑎𝑝𝑝 × 𝑡 - - ---(5)
𝑡

where Kapp is the apparent reaction rate constant. The calculated reaction rate for S1, S2, S3 and
S4 were 0.0151, 0.0159, 0.0167 and 0.0176 min-1, respectively.

3.5 Theoretical investigation of photocatalytic activity

The obtained band structure diagrams for the undoped and Cu doped ZnO nano structures
were shown in Figure 8. The calculated Fermi levels for all the nanostructure were shown in blue
line in the diagram and the band gap observed were direct which was favorable for

7
photocatalytic process [34]. The calculated band gaps were 2.78, 2.56, 2.44, 2.31 eV for ZnO,
ZnO-Cu@10%, ZnO-Cu@20%, ZnO-Cu@30%, respectively. From theoretical calculation, it
was observed that the band gaps of the nanostructures were decreased upon the addition of Cu on
ZnO nanostructure. The energy gap obtained in this study was high compared to the
experimentally observed results [35]. This is because of the well known reason that in DFT
calculations the exact exchange correlation energy was unknown. However, the calculated band
gaps using DFT calculations were in relative variation with the experimental results. The
photocatalytic activity was explained interms of redox potential from the valance and conduction
bands of the nanostructures. The positive value of valance band maximum (VBM) and the
negative value of conduction band minimum (CBM) corresponds to strong oxidation capacity of
the holes and reduction capacity of the electrons, respectively [36]. Electronegativity and the
band gap values of the undoped and Cu doped ZnO nanostructures were used to calculate the
edge potentials of the valance (EVB) and conduction (ECB) bands of the corresponding structures
using the following formula [34]
1
𝐸𝑉𝐵 = 𝜒 − 𝐸𝑒 + 𝐸 − − − − − − − (6)
2 𝑔

𝐸𝐶𝐵 = 𝐸𝑉𝐵 − 𝐸𝑔 − − − − − − − (7)

where χ is the Mulliken electronegativity,Ee is the energy of the free electrons in hydrogen scale
and Eg is the obtained energy gap. The Mullikan electro negativity could be calculated using the
following formula [37]
𝐼𝑃 + 𝐸𝐴
𝜒= − − − − − −(8)
2
where IP and EA are the ionization potential and electron affinity of the corresponding
nanostructures. The calculated edge potentials of VBM and CBM using the equations 6 and 7
were tabulated in table 2 for undoped and Cu doped ZnO nano structures. Usually the
degradation of organic dye pollutants was due to the oxidation of holes or due to oxidization of
the active species such as .O2-, H2O2 and .OH, which can decompose the organic dye pollutants.
The redox potentials of E0 O2/H2O2 with respect to normal hydrogen electrode (NHE) potential
were 1.23 V. From the table 2 values, it is seen that the VEB of all the samples was more positive
than the E0 of O2/H2O2; the holes in the valance band could oxidize the H2O2 and produce O2
there by oxidizing the pollutant organic dye directly. Similarly, the photogenerated electrons

8
from the valance band oxidize the O2 into .O2- because the ECB of all the nanostructures were
more negative than the E0 O2/.O2- which was -0.33 V with respect to NHE. This .O2- reacts
with H+ and produce H2O2 consequently [34]. This will further enhance the photocatalytic
activity of the materials. It is also seen from the table 2 values, that when Cu content was
increased, the band gap reduces considerably and in addition, their redox potential varies and
enhances the photocatalytic activity of the materials.

4 Conclusion
The nanopowders of undoped and Cu doped ZnO were synthesized by a simple soft
chemical method. The XRD affirms that the prepared powders of ZnO with wurtzite structure.
No secondary peaks correspond to CuO phase were observed. The calculated crystallite size
(between 66.8 nm and 20. 36 nm) showed a decreasing trend with an increase in the copper
doping level. SEM micrographs showed that the prepared powders were having platelet
nanosheetshape. The smoothness of the platelets was increased when the copper doping
concentration was increased. EDX studies confirmed the presence of Zn, O and Cu. The
photocatalytic efficiency of the prepared nanopowders was tested against MB dye. The results
reval that Cu doping on ZnO enhances the photocatalytic efficiency. This result was validated
theoretically by performing DFT calculations.

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List of Figures

Figure 1. Optimized geometries of ZnO and Cu doped ZnO nanostructures

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Figure. 2 XRD patterns of undoped and Cu doped ZnO nanopowders

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Figure. 3. SEM Images of the samples S1,S2,S3 and S4

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Figure. 4. EDAX Spectra of Undoped ZnO(S1) and Cu doped ZnO(S4)

Figure. 5. Photoluminescence Spectra of Undoped and Cu doped ZnO nano powders

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Figure. 6 Absorbance spectra of undoped and Cu doped ZnO nano powders against MB.

Figure. 7 Photocatalytic mechanism of ZnO and Cu doped ZnO nanostructures

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Figure. 8. Bandstructure diagrams of undoped and Cu doped ZnO nanostructures

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 Table 1. Structural Parameters of undoped and Cu doped nanopowders.

Lattice Constants (Å) Crystallite Volume of

Sample c/a size D(nm) the unit cell

A C
V (Å3)

S1 3.29323 5.28038 1.6034 66.810 49.595

S2 3.29160 5.27204 1.6016 25.499 49.467

S3 3.30244 5.26174 1.5932 25.859 49.697

S4 3.28919 5.28824 1.6077 20.360 49.547

[standard JCPDS card (36–1451) data a = 3.2498 Å and c = 5.20661 Å]

Table 2 Calculated edge potentials of Valance and Conduction bands of Undoped and Cu
doped ZnO nano structures

Structure EVB (V) ECB (V)

ZnO 1.5 -0.59

ZnO-Cu@10% 1.72 -0.64

ZnO-Cu@20% 1.8 -0.66

ZnO-Cu@30% 1.9 -1.28

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