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Mater. Res. Express 11 (2024) 015006 https://doi.org/10.1088/2053-1591/ad1a82
PAPER
GAD plasma-assisted synthesis of ZnO nanoparticles and their
photocatalytic activity
Ridha Messai1,2 , Mohammed Fouad Ferhat1,2,3,∗, Bilal Belmekki2, Mir Waqas Alam4,∗ ,
Mohd Al Saleh Al-Othoum4 and Shima Sadaf5
1
Faculty of Technology, Department of Process Engineering, University of El Oued, 39000 El Oued, Algeria
2
Laboratory of Sciences and Techniques of the Environment and Valorization, University Abdelhamid Benbbadis of Mostaganem, 27000
Mostaganem, Algeria
3
Renewable Energy Development Unit in Arid Zones (UDERZA), University of El Oued, El Oued 39000, Algeria
4
Department of Physics, College of Science, King Faisal University, Al-Ahsa 31982, Saudi Arabia
5
Department of Electrical Engineering, College of Engineering, King Faisal University, Al-Ahsa 31982, Saudi Arabia
∗
Authors to whom any correspondence should be addressed.
E-mail: toferhat-mohammedfouad@univ-eloued.dz and wmir@kfu.edu.sa
Keywords: synthesis, ZnO nanoparticles, gliding arc discharge-air, photocatalysis, wastewater
Abstract
In this study we present an efficient method for synthesizing highly pure ZnO nanoparticles using a
Gliding Arc Discharge (GAD) plasma system as a non-thermal plasma source. This approach offers
distinct advantages over conventional techniques, including simplicity, a short synthesis time,
utilization of readily available air as the source gas, and potential scalability, rendering it a promising
alternative for sustainable ZnO nanoparticle production. The synthesized nanoparticles physico-
chemical properties were characterized using various techniques, such as scanning electron
microscopy (SEM), energy dispersive x-ray analysis (EDAX), UV-visible spectroscopy (UV–vis),
Fourier-transform infrared spectroscopy (FTIR), x-ray diffraction (XRD), Thermogravimetric
Analysis (TGA), and Differential Scanning Calorimetry (DSC). Furthermore, we evaluated the
effectiveness of the synthesized ZnO nanoparticles for wastewater treatment by assessing their
photocatalytic activity against methylene blue (MB), Brilliant Cresyl Blue (BCB), and Congo Red (CR)
under UV light irradiation for 2 h and 30 min. The results confirmed the successful synthesis of highly
pure ZnO nano-powder with an average size of 27.18 nm and a band gap energy of 3.28 eV in an
exceptionally brief duration and through straightforward steps. Additionally, GAD plasma-assisted
ZnO nanoparticles exhibited a significant dye removal rate, showcasing their potential as highly
effective materials for photocatalytic wastewater treatment. This study contributes new insights into
the application of GAD plasma for nanoparticle synthesis.
1. Introduction
Over the last two decades, nanotechnology has revolutionized our modern life in countless ways, from
improving the efficacy of medical treatments to enhancing the performance of electronics and renewable energy
technologies. These tiny structures, typically less than 100 nanometers, have unique properties due to their small
size and high surface area-to-volume ratio, making them attractive for a wide range of applications. By
manipulating and engineering nanomaterials at the atomic and molecular level, scientists are able to create
materials with specific unique optical, electrical, magnetic, or catalytic properties that were previously
impossible to achieve [1].
Therefore, exploiting nanoparticles has opened up a world of possibilities for researchers and innovators
seeking to develop new materials with desirable properties. Zinc oxide stands out as one of the most remarkable
nanomaterials in terms of its properties and potential applications. These nanoparticles exhibit a unique
combination of attributes, including high transparency and a wide band gap [2], making them excellent
© 2024 The Author(s). Published by IOP Publishing Ltd
Mater. Res. Express 11 (2024) 015006 R Messai et al

candidates for optoelectronic devices such as solar cells, sensors, and LEDs. Additionally, their outstanding
catalytic properties make them useful in chemical synthesis applications, particularly in environmental
remediation, where they have been reported to remove heavy metals, organic compounds, and even
microorganisms through adsorption or photocatalytic degradation [3–5]. Furthermore, zinc oxide
nanoparticles have demonstrated electrochemical sensing and antimicrobial properties, opening up possibilities
for their use in medical applications such as drug delivery and wound healing [5, 6].
Several biological, physical, and chemical methods have been employed for synthesizing zinc oxide
nanoparticle. These methods include vapor deposition [7], where zinc precursor compounds are vaporized and
condensed to form nanoparticles. Laser ablation [8] involves using laser pulses to vaporize zinc and collect the
resulting nanoparticles. Sol gel utilizes hydrolysis and condensation reactions to transform a precursor solution
into a gel, which is then further processed [9]. Spray pyrolysis atomizes a precursor solution into droplets that are
rapidly heated, resulting in the formation of solid nanoparticles [10]. Hydrothermal/solvothermal synthesis
involves the controlled reaction between a precursor solution and a solvent under high temperature and
pressure conditions [6, 11]. Lastly, biosynthesis methods utilize plant extracts or bacteria to reduce and stabilize
zinc ions, facilitating the formation of nanoparticles with desired properties [12–14].
These limitations and concerns can be efficiently overcome by utilizing non-thermal plasma (NTP) sources
to generate reactive species for oxidizing metallic ions, thus producing safe nanoparticles without hazardous
chemicals or solvents. The plasma method enables the production of nanoparticles with a high degree of purity
and can be carried out at relatively low temperatures, making it suitable for temperature-sensitive materials. This
method is distinguished by its short synthesis time compared to the other methods, which makes it highly
flexible and scalable for industrial applications [15].
Previous studies have explored various techniques, such as PLD, sputtering, radio frequency (RF) plasma,
microwave plasma, and atmospheric pressure plasma, for synthesizing ZnO nanoparticles [16, 17]. These
methods require high power and elevated temperatures, making them unsuitable for temperature-sensitive
materials. Additionally, it necessitates a cooling system, involves complex equipment, operates with a mixed gas
at low pressure, and demands effective equipment sealing. Despite the advancements, there is still a research gap
in the realm of plasma-based synthesis of ZnO nanoparticles. To further illustrate the advantages of GAD
plasma, table 1 provides a comprehensive comparison of key parameters between GAD plasma, PLD, sputtering,
and other plasma technologies used for ZnO nanoparticle synthesis [17–22]. This table illustrates the efficiency
of the GAD plasma method, showcasing lower operating temperatures that are conducive to temperature-
sensitive materials and contribute to enhanced sustainability. The GAD plasma method provides a high degree
of controllability and tunability across various parameters, facilitating precise manipulation of ZnO
nanoparticle characteristics tailored for specific applications.
Notably, existing studies lack exploration of the GAD plasma method for ZnO nanoparticle synthesis. We
present the first work utilizing this promising approach, which offers several advantages: (i) utilizing air as the
source gas, promoting environmentally friendly synthesis; (ii) generating a high concentration of reactive species
like OH radicals, potentially enhancing particle growth and crystallinity; (iii) operating at atmospheric pressure,
simplifying process implementation; and (iv) eliminating the need for chemical products, leading to greener
production. Given its unique benefits, this GAD plasma method stands as a powerful tool for producing ZnO
nanoparticles with desirable properties. These nanoparticles hold significant potential for diverse applications,
including photocatalytic degradation of pollutants, next-generation electronics, and targeted drug delivery in
biomedicine.
Therefore, this study aims to investigate the potential of the GAD plasma method for synthesizing ZnO
nanoparticles and to characterize their physicochemical properties using techniques such as SEM, EDAX, UV–
vis, FTIR, TGA/DSC, and XRD. Furthermore, the photocatalytic activity of the synthesized ZnO nanoparticles
was tested against BCB, MB, and CR to evaluate their effectiveness in wastewater treatment.

2. Preparation techniques and materials

2.1. Chemicals
All of the chemicals used, including zinc acetate Zn(CH3COO)2 H2O, Congo Red (CR) (C32H22N6Na2O6S2)
(696,663 g mol−1), Brilliant Cresyl Blue (BCB) (C17H20ClN3O)2 (385.96 g mol−1), and methylene bleu (MB)
(C16H18ClN3S) (319,852 g mol−1) were purchased from Sigma-Aldrich and used exactly as specified.
Demineralized water was used to prepare all of the solutions for the zinc oxide NP formation and the
photodegradation studies.

2
 Mater. Res. Express 11 (2024) 015006
Table 1. Comparison of different physical process used for synthesizing ZnO nanoparticles.

Discharge Parameters Average Particle

Method Zn Salt Precursor Size nm ZnO Morphology Application References
Synth
time Synth
Gas Pressure Power kW min temp K Yield

Cold Plasma GAD Zn(CH3COO)2 H2O Air 0.9 60 Room temp 90% 27.18 pseudo-spheres, and non- Photo-degrada- This work
uniform hexagonal tion of
particles organic dyes
Pr = 1 bar
PLD Method — O2 30–45 — — 150–180 — [17]
Pr = 10–2 mbar
RF plasma torch — Ar/ O2 P = 30 kW f = 3.5 MHz — 300 K with — 100–200 Spherical and hexagonal [18]
water ZnO wurtzite structure
3

cooling
Pr = 0.2 bar
Micro-wave plasma Zn(CH3)2 80% Ar 20% O2 P = 60 W 90 >1800 K — 04–08 spherical [19]
Pr = 30 mbar
RF inductively cou- Zn(CH3)2 Ar as P = 28–31 kW f = 1–3 MHz 15–90 1300 K — 60–70 at Pr1 polygonal at Pr1 round at — [20]
pled thermal 30–50 at Pr2 Pr2 flower-like with hex-
plasma 200–500 at Pr3 agonal nanorods at Pr3
Pr = 0.47, 0.87
and 0.93 Bar
AC (pulse) plasma jet Zn(NO3)2 ZnCl2 Air P = 0.063 kW f = 1–3 MHz 60 310 K Weak 400–1600 (ZN) rods, pillar and, flower-like Anti-bacterial [21]
ZnSO4· 7 H2O for ZN activity
Pr = 1 bar 150–1000 (ZC) flower-like and rods for ZC
500–1000 (ZS) layered and aggregate
structures for ZS
AC sinusoidal DBD Zn(CH3COO)2 H2O H2 U = 15KV f = 38 MHz 05–15 1000 K — 90–150 spherical — [22]
plasma
Pr = 1 bar
RF Sputtering — Ar/ O2 P = 180 W — — — 150–180 — — [17]
Method
Pr = 10–3 mbar

R Messai et al
Mater. Res. Express 11 (2024) 015006 R Messai et al

Figure 1. GAD- reactor.

2.2. Sample preparation

The materials for the experiment were prepared with high precision. To start, 20 grams of Zn(CH3COO)2·2H2O
was dissolved in 1000 milliliters of demineralized water, using a magnetic stirrer, to create a zinc acetate solution.
This solution was stirred for 10 min at room temperature, ensuring the mixture was well combined. The
resulting solution was designed to yield approximately 6.6 grams of pure ZnO nanoparticles, which was required
for the experiment. Once the zinc acetate solution was prepared, individual solutions of CR, MB, and BCB dyes
were methodically formulated. Each solution was created to have a concentration of 7 ppm and was rigorously
agitated for 30 min to ensure the dyes were completely dissolved.

2.3. Gliding arc discharge (GAD) apparatus

In this work, ZnO nanoparticle synthesis utilizes a custom-designed gliding arc discharge (GAD) reactor
(figure 1), drawing inspiration from various configurations reported in the literature for treating polluted liquids
[23–32]. This setup operates on the principle of generating a non-thermal plasma plume at atmospheric
pressure.
The key components and their roles:

• A compressed air saturator: ensures adequate water content in the air stream entering the reactor.
• Inlet nozzle (1 mm diameter): controls the plasma gas flow and its interaction with the electrodes.
• Diverging electrodes with a 3 mm gap: Generate the electric arc and define the plasma plume volume.
• A high-voltage transformer from Aupem Sefli, with a voltage setting of 220 V/9 kV: provides the necessary
voltage (9 kV) to initiate and sustain the arc.
• A plasma plume: sweeps along the electrode gap, generating active species.
• The target solution: uses zinc acetate as a source of Zn2+ ions.
Optimization considerations:
GAD performance depends on several factors, which were optimized in previous studies and maintained
constant in this work [25–32]:
• Nozzle diameter: Affects plasma gas flow and species diffusion towards the target.
• Inter-electrode distance: Determines plasma plume size and stability.

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Mater. Res. Express 11 (2024) 015006 R Messai et al

• Plasma gas: Air saturated with water ensures cost-effectiveness and the generation of desired radicals.
• Gas flow rate: Set at 800 l/h for optimal plasma generation and interaction with the solution.
• Power input: Maintained at 0.9 KW based on established power estimation methods [23, 24].

2.4. Synthesis of ZnO nanoparticle using gliding arc discharge

In our experiment, we started by passing compressed air through a bubbler to ensure that the air became
saturated with water. Then, the airflow passed through an inlet nozzle with a diameter of 1 mm between two
diverging electrodes. These electrodes, with a minimum gap of 3 mm, were connected to a high-voltage. This
setup generated an alternating voltage of 9 kV and a current of 100 mA. The whole setup consumed 0.9 kW of
power, which was impressively efficient. When we turned on the high voltage, an electric arc formed between the
electrodes. This happened because of the voltage difference between the electrodes. The arc did not stay in one
place; instead, it moved away from where it started due to the flowing air. It traveled along the space between the
electrodes, creating a larger area filled with a special kind of glowing air called plasma. This process happened
repeatedly, with each new arc following the same steps as the previous one.
The result of this process is the creation of a non-thermal plasma under atmospheric pressure. This plasma
generates various species, including •OH, O•, H•, NO, and HNOOH. In the subsequent phase of the
experimental system, a flask containing zinc acetate is positioned 5 cm below the upper part of the plasma
column. This arrangement is maintained for a duration of 60 min, resulting in the development of an opaque
solution. This opaqueness serves as an indicator that the chemical constituents have participated in a redox
mechanism, effectively converting Zn2+ into Zn (OH )2.
Following this treatment, the sample undergoes evaporation and drying at 100 °C for a span of 10 min to
eliminate water content. Subsequently, a critical annealing process is undertaken at 600 °C, spanning a duration
of 3 h. This annealing procedure serves multiple purposes, including the removal of organic components, the
initiation of crystallization processes, and the production of zinc oxide nanoparticles.
Research indicates that temperatures at 600 °C play a crucial role in facilitating the complete decomposition
of the precursor, resulting in the formation of well-defined ZnO crystals. Moreover, as the temperature
increases, the crystalline shape transforms into a hexagonal structure [33]. The annealing process at 600 °C is
instrumental in achieving optimal degradation of the organic group attached to the precursor, simultaneously
fostering favorable crystallization, a conclusion corroborated by additional studies [34].
These processes were iterated ten times, with each iteration involving the utilization of 100 ml of solution.
The aim was to achieve a cumulative quantity of approximately 6.6 g of pure ZnO nanoparticles.

2.5. Characterization
Powder XRD data were obtained using a Proto AXRD-2 diffractometer with sample spinner and a Dectris
Mythen 1 K (3.22° active length*) 1D-detector in Bragg–Brentano geometry with a Copper Line Focus x-ray
tube and Ni kβ absorber. The Thermo Scientific TM Quattro SEM combines all-around imaging and analytics
performance with an innovative environmental mode (ESEM) that allows materials to be examined in their
natural condition. The powder samples’ optical characteristics were measured using a Shimadzu 3101PC
double-beam spectrophotometer. The spectrophotometer (Shimadzu model IR Iraffinity-1) measured FTIR
absorption in the spectral region 400–4000 cm−1. To discover the photocatalytic activity of the NPs, the
Shimadzu Spectrophotometer UV-1800 was employed. METTLER TOLEDO’s Simultaneous Thermal Analysis
Device (TGA/DSC): TGA/DSC 3+ 1600 °C has been used to track changes in mass and thermal flow as a
function of temperature. It allows users to evaluate a wide range of samples. The ability to conduct analyses in a
controlled environment at temperatures ranging from 25 to 1600 °C (air, nitrogen or argon). Heater rate: 0.1 to
100 °C min−1. Balance: 5 g measurement range with 1 ug creams available: aluminum and platinum creams
(70 ul) and huge aluminum creams (600 and 900 ul). LUXMETER 400,000 LUX - USB used for measuring
sunlight intensity.

2.6. Photocatalytic activity

Before the photocatalytic process, the dispersion was stirred constantly in the dark room for 30 min to allow the
dye particles and the surface of the catalyst to reach a state of equilibrium between adsorption and desorption.
After the dispersion was stirred for 30 min, it was exposed to UV light for 150 min. Every 15 min, a beaker was
removed, and 4 ml was centrifuged to separate the nanoparticulate suspensions (NPs) of ZnO from the solution.
The irradiation of a 365 nm, 30 W UV lamp was assured by placing it 15 cm above the solution at room
temperature. Ten samples (25 ml) of each aqueous solution dye (CR, MB, and BCB) with initial concentrations
of 7 ppm were mixed with 25 mg of prepared ZnO in an open glass (50 ml) used as a photo-reactor. The
concentration of the dye was determined using a UV-visible spectrophotometer with wavelengths of 498 nm

5
Mater. Res. Express 11 (2024) 015006 R Messai et al

and 625 nm, respectively. The samples were taken at the prescribed time, centrifuged, and the dye concentration
was measured at 498 nm and 625 nm. Using the following formula (equation (1)), the rate of degradation was
determined.
C 0 - Ct
%deg = 100 ´ (1)
C0
Where C0 represents the initial concentration (mg/l) and Ct represents the concentration of the dye at time t.

3. Results and discussion

3.1. Chemical interactions of gliding arc plasma with zinc acetate solution
A gliding arc discharge is a type of ionized gas that is created by the passage of gas through an electric current. The
gas is typically air, and it is often humidified to increase its conductivity. The arc moves along the surface of the
electrodes, and it produces a variety of chemical species, including radicals, ions, and molecules. The chemical
species that are produced in a gliding arc discharge depend on the gas composition, the humidity, and the
operating parameters. In humid air (N2, CO2 , O2, H2O), the primary chemical species are •OH, O•, H•, •NO, O3,
CO32-, and CH3COOH [35–37]. These species are formed as a result of electron impact, dissociation, addition,
transformation, collision events that occur in accordance with the gas vector, and chemical reactions.
The •OH and •NO radicals are of particular interest because they are very reactive. They can disperse in the
treated target, and inducing both acidifying and oxidizing effects in aqueous solutions, react with other
molecules to form new compounds, or they can initiate chemical reactions. This makes gliding arc discharge a
promising technology for a variety of applications, such as water treatment, waste treatment, and material
synthesis.
As a result of electron impact within the arc, the primary formation of •NO and •OH radicals is explained
through (equations (2–4)) [37].
H2 O + e-  H • + • OH + e- (2)
O2 + e-  2O • + e- (3)
N2 + O•  •NO + N • (4)
These species are capable of diffusing in aqueous solutions and interacting with molecules. The hydroxyl
radical is the principal species responsible for the production of metal oxide nanoparticles [38], whose standard
potential is E°(•OH/H2O) = 2.85 V N−1H−1E [39]. The hydroxyl radical •OH is a very reactive species that can
react with other molecules. It can also react with an electron received from ions and molecules dissolved in water
as impurities, as shown in (equation (5)). This reaction produces a hydroxide ion (OH-) [40].
•OH + e -  OH- (5)
The dissolution of zinc acetate in water is expressed by the following, (equation (6)) and (equation (7)) [41].
Zn (CH3 COO)2  Zn2 + + 2 (CH3 COO-) (6)
CH3 COO- + H+  CH3 COOH (7)
The zinc ion reacts with hydroxide ion and then zinc hydroxide is produced as (equation (8))
Zn2 + + 2OH- + 2e -  Zn (OH)2 (8)
Zinc oxide tends to coagulate and deposit in water, so we perform the vaporization process as follows:
(equation (9))
drying Zn (OH)2 at 100C  ZnO (s) + H2 O (9)
The reactions mentioned from (equations (2–9)) demonstrate the fundamental process of ZnO NPs creation
by gliding arc discharge with the air as vector gas.

3.2. Characterization of synthesized ZnO

3.2.1. UV-visible
ZnO is a transition oxide with a hexagonal structure and a direct bandgap of 3.28 eV for n-type semiconductor
materials. For example, the direct band gap of ZnO NPs is between 3.10 and 3.37 eV. Many parameters,
including crystallinity, grain size, particle size, particle shape, and dislocation, affect the band gap of ZnO NPs.
The UV–vis spectrum in figure 2 shows the absorption of ZnO nanoparticles produced using the GAD reactor.
The high absorption peak at 362 nm is due to the surface plasmon resonance of ZnO NPs [42, 43].
The following equation (equation (10)) calculates the nanoparticles’ direct transition optical band gap
energy [44]:

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Mater. Res. Express 11 (2024) 015006 R Messai et al

Figure 2. Absorbance spectra of ZnO NPs.

Figure 3. (a) Plot of (αhν)2 versus photon energy of synthesized ZnO. (b) Inset shows the Urbach energy plot of ln(α) versus(hν).

(ahu)2 = A (hn - E g) (10)

where:
α is the absorption coefficient,
Eg is the optical band gap of the NPs,
hν is the photon energy,
A is a constant independent on hν.
As a result, Tauc’s plot is used in order to compute the optical band gap. This is accomplished by plotting
(hv)2 versus (hv) and then extrapolating the linear section in order to determine the energy axis intercept
figure 3(a). Synthesized ZnO NPs have an optical band gap of 3.28 eV, compared to bulk ZnO. According to the
literature review [45], the band gap varied according to several parameters, such as the ZnO crystal defect,
particle shape, and particle size.
The optical, electrical, and catalytic properties of ZnO nanoparticles are influenced by the anisotropy of their
band gap. The band gap refers to the energy difference between the valence and conduction bands of electrons. The
variation in the ZnO nanoparticle band gap directly affects electrical conductivity, with ZnO having a wide band
gap. By reducing the band gap, electrical conductivity can be improved, which is crucial for applications such as
transparent conductive films, solar cells, and electronics. Furthermore, the band gap difference plays a significant
role in determining ZnO’s redox and catalytic properties, as the surfaces of ZnO nanoparticles catalyze various

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Mater. Res. Express 11 (2024) 015006 R Messai et al

Figure 4. FTIR spectra of ZnO NPs and inset shows the enlarged spectra in the range <600 cm−1.

Table 2. IR peaks and their assignments for the NPs of ZnO system.

Assignments Wavenumber (cm−1) Wave number (cm−1)

Before annealing After annealing

Zn-O Stretching < 600 < 600

N-O Stretching 697 Absent
C-N 954 Absent
C=O 1037 Absent
C-O-C/C-N 1045 Absent
O-H 1386 Absent
O=N 1451 Absent
C=N 1542 Absent
O≡N 2010 2009
C≡N 2158 2156

chemical reactions. The presence of oxygen vacancies enhances catalytic activity. Overall, ZnO nanoparticles
possess the ability to clean, convert energy, and degrade pollutants due to their unique band gap properties.
Band tailing in the band gap commonly results from semiconductor impurity incorporation. Since optical
transitions take place from occupied states in the valence band tail to unoccupied ones at the conduction band
edge, the absorption coefficient α at the band edge is exponentially dependent on the photon energy. The
empirical Urbach (equation (11)) describes local defects’ band tail energy (E00) [46]:
a = a 0 (hn / E 00) (11)

Where αο is a constant and E00 is the gap area tail width of localized states. To calculate αο and Ε00, plot the
logarithmic scale of the absorption coefficient as a function of photon energy hν. The slope of log (α) versus
incident photon energy hν determines the Urbach tail [47]. From the inverse slope of the linear plot of ln(α)
versus hν in figure 3(b), ZnO NPs’ Urbach energy is 0.430 eV. Possible explanations for this result include
structural and thermal disturbances.

3.2.2. FTIR spectroscopy

In order to identify the functional groups for ZnO NPs, FTIR analysis is used. The spectra of the treated zinc acetate
solution by non-thermal plasma (GAD) before and after annealing at 600 °C for 3 h are shown in figure 4. The
wavenumbers of the peaks that appeared in the FTIR and their functional origins are shown in table 2. As a result of
plasma treatment of zinc acetate solution, FTIR spectra before annealing treatment revealed a number of
absorption bands (697, 954, 1037, 1045, 1386, 1451, and 1542 cm−1) corresponding to the functional groups of the
organic molecules [48]. The broad and strong bands at 1451, and 1542 cm−1 attributed to nitrogen-bonded (O=N,
and C=N) respectively. The bands at 1037 and 1045 cm−1 can be attributed to the (C=O) stretching and C-O-C
stretching asymmetric vibrations and the (C-N) stretching vibrations of the aromatic amine.
After annealing, the FITR spectrum of the ZnO NPs shows a sharp peak at 448 cm−1 associated with Zn-O
vibration and a broad peak at 3430 cm−1 related to the O-H bonding due to moisture absorption.

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Mater. Res. Express 11 (2024) 015006 R Messai et al

Figure 5. X-ray diffraction pattern of ZnO NPs.

Table 3. Estimation of structural parameters of ZnO NPs.

Lattice para-
Sample name 2θ (deg) FWHM (deg) D (nm) meter (Â ) ε × 10–4 σ(GPa) ξ × 1014 (line/m2)

ZnO pure 36.318 0.2952 27.18 a=b c 1.921 −0.861 1.35

3.2494 5.2051

In wurtzite hexagonal type ZnO crystals, the Zn-O stretching vibration of the oxygen sublattice (E 2 H ) is
responsible for the 426 and 565 cm−1 absorption bands, while the 1386 cm−1 oxygen vacancies are characterized
as hydrogen-related defects on the surface of ZnO [49].

3.2.3. X-ray diffraction

An x-ray diffractometer was used to study the structure and elements of ZnO nanoparticles, and the results are
displayed in figure 5. As can be observed, there are many peaks that correspond to the planes (100), (002), (101),
(102), (110), and (103) for ZnO that is hexagonal in shape. The treated sample was made up of tiny particles,
according to the XRD data.
Figure 5 displays the XRD pattern of the ZnO NPs sample after preparation. The ZnO single crystal phase is
verified by the diffraction pattern. The crystallographic plane (101) exhibits a hexagonal crystal structure, and all
the diffraction peaks observed in the patterns (100), (002), (101), (102), (110), (103), (200), (112), (201), (004),
and (202) indicate a polycrystalline nature. These values closely correspond to those documented in the standard
card (JCPDS number: 01-089-0551) [50].
Table 3 shows the ZnO NPs’ crystallite size of 27.18 nm, calculated using Scherrer’s formula (equation (12)) [51].
kl
D= (12)
b cos (q )
The wavelength for a hexagonal crystal structure is λ =1.54 Å, the full-width at half-maximum (FWHM) is β,
k = 0.91, and θ is the measured angle at the peak (101).
In addition, the peak location deviation from the reference data of bulk ZnO reveals the presence of stress in
the NPs. These equations (equations (13 and14)) were used to calculate an approximation of the stress level:

C (C + C12 )
s = ⎡- 33 11 + 2C13 ⎤ e (13)
⎢
⎣ C13 ⎥
⎦
c - c0
e= (14)
c0
Where, σ is strain, C33(210 GPa) , C11(210 GPa), C12(120 GPa), and C13 (105 GPa) are the elastic stiffness
constants, ε is the uniform strain, ZnO NPs have a lattice parameter denoted by the letter c, which may be
determined from the plane labeled (101), and the lattice parameter for the bulk material is denoted by c0 [52].
Table 3 provides approximated values for 2θ, lattice parameter, FWHM, crystallite size, stress, strain, and
dislocation. The negative signs of the stress suggest the existence of compressive stress [53]. This compressive
stress is usually caused by distortions and defects in the lattice.

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Mater. Res. Express 11 (2024) 015006 R Messai et al

Figure 6. SEM image of the ZnO NPs plasma synthesized with a magnification of (a) 35.00 KX; (b) 100.00 KX; (c) their corresponding
particle size distribution and (d) Atomic concentration and Typical EDAX spectra.

Figure 7. TGA/DSC thermogram identifies the transformation of the synthesized ZnO.

3.2.4. Scanning electron microscopy (SEM) and EDAX

Scanning electron microscopy (SEM) was employed to investigate the formation, size, shape, and morphology of
the prepared sample’s particles. Figures 6(a), and (b) show low-magnification SEM images revealing the typical
microstructure of ZnO NPs, which is mainly of different sizes and agglomerated grains of nanopowder which
consist of pseudo-spheres and non-uniform hexagonal particles [54], and show particle aggregation related to

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Mater. Res. Express 11 (2024) 015006 R Messai et al

Figure 8. (a) Absorbance spectra of dye solution under UV light irradiation, (b) photocatalytic degradation of dye at different times:
(1) BCB, (2) CR and (3) MB.

the self-assembly of the ZnO nanoparticles [55]. Figure 6(c) depicts the ZnO NPs size distribution histogram; the
averaged grain size is 52 ± 1.26 nm, which is larger than the measurements reported by XRD analyses. While
XRD solely reveals data on the crystalline components and not the amorphous ones, FESEM analysis delivers
insights into the overall shape of the grains [54]. The energy-dispersive analysis x-ray spectra (EDAX) reveal the
chemical composition and atomic percentage of nanoparticles (NPs). Figure 6(d) shows the EDAX spectra
obtained for a sample of ZnO NPs. The elements identified are zinc and oxygen; however, the peak of carbon is
not considered as it is absorbed by the superficial area of the ZnO NPs.

11
Mater. Res. Express 11 (2024) 015006 R Messai et al

Figure 9. The plot of ln(C0/Ct) versus time for (a) BCB, (b) CR (c) and MB dyes.

3.2.5. Thermogravimetric analysis TGA / differential scanning calorimetry (DSC)

The DSC/TGA curve in the (figure 7) shows the product’s behavior when subjected to a 10 °C/min heating rate
from 25 °C to 700 °C. The TGA profile indicates a weight reduction interrupted by three distinct shifts.
Meanwhile, the DSC curve shows three endothermic peaks, which correspond to different stages of
decomposition: the release of physically adsorbed water in the initial stage and the release of chemically adsorbed
water and carbonic matter in the second and third stages, respectively [12, 56, 57]. These findings are consistent
with the peaks observed in the FTIR analysis of these groups. It is showing negligible mass loss of about 0.42% as
a function of temperature, indicating thermal stability between 25 °C and 700 °C. Hence, we can conclude that
the sample is pure.

3.3. ZnO NPs photocatalytic activity

The effectiveness of synthesized ZnO NPs in removing organic pollutants from water was investigated using the
cationic and anionic dyes BCB, MB, and CR (figure 8). The photo-degradation of these dyes was observed under
UV light, and the results were analyzed in terms of contact time and the presence of ZnO NPs.
The findings of the study demonstrate that after 2 h and 30 min of exposure to UV light, the rates of
degradation were 92.9%, 71%, and 88% for BCB, MB and CR dyes, respectively. It was also observed that the
photo-degradation efficiency of BCB was higher than that of MB and CR. The kinetics of the photodegradation
reaction of the dyes were determined using the pseudo-first order equation (equation (15)) [58]:
C
ln ⎛ 0 ⎞ = kt
⎜ ⎟ (15)
⎝ Ct ⎠
Where Ct and C0 are the concentrations of dye at time t = 0 min and t, respectively, and k is the pseudo-first-
order rate constant.
Figure 9 shows the relationship between ln (C0/ Ct ) and the irradiation period for BCB, MB, and CR dyes. As
seen in figure 9, a linear relationship was found between ln (C0/ Ct ) and time, confirming that the photocatalytic

12
 Mater. Res. Express 11 (2024) 015006
Table 4. Comparative study of the degradation of CR, BCB and MB by photocatalysis of different nanoparticles and ZnO synthetizes by plasma.

Gap Catalysis dose

Sample name Synthesis method Size nm Energy eV Dye Experimental conditions g/l Deg efficiency / Time References

ZnO pure hydrothermal method — 3.3 CR V = 50 ml, 20 pmm, 0.4 47%/ 1.16 h 41%/ 1.16 h [59]
NiO pure — 3.0 pH = 3 0.4
400 W- Hg Lamp
— — CR V = 300 ml, 50 ppm, pH = 7 0.16 97% [60]
ZnO Commercial Sun-light 2h
21 2.88 CR V = 20 ml /120 ppm 200 99.9% [61]
ZnO Biosynthesis T° =30 °C, 1.2 h
(λ > 254 nm- 6 W)
TiO2-ZnO hydrothermal method 17.4 −4.18 CR V = 100 ml, 1.0 mM, 0.5 64.5%/ 1.17 h [62]
TiO2-ZnO/Ag 34.8 2.24 under visible light irradiation TiO2-ZnO
(150 W) 87.5% TiO2-ZnO/Ag
V = 100 ml, 1.0 mM, [62]
13

TiO2, ZnO hydrothermal method 44.1 3.16 CR 0.5 80%/1.17 h

TiO2-ZnO 74 3.07 UV light (120 W)
TiO2-ZnO/Ag 17.4 −4.18
34.8 2.24
ZnO Commercial 7–30 — CR V = 5000 ml, 20 ppm, pH = 7 0.3 65%/ 8 h [63]
UV light
(λ= 253.7 nm- 18 W)
Dark Room 30 min
CuO hydrothermal method — CR V = 100 ml, 20 ppm, 0.5 [64]
nano-rods 16 UV light 67%/ 3.5 h
nano-leaves 14 (λ= 256 nm- 18 W) 48%/ 3.5 h
nano-sheets 18 Dark Room 30 min 12%/ 3.5 h
Co@C-60 — 126 — CR V = 50 ml, 100 ppm, pH = 3 1 15.6% / 3 h UV + Co@C-60 [65]
UV light 98.1%/3 h UV + H2O2 + Co@C-60
(λ= 254 nm- 8 W)
ZnO Sol gel 23.6 — CR V = 100 ml, 50 ppm, pH = 4 1 94%/ 1 h [66]
solar light
Dark Room 60 min
ZnO green synthesis 10–15 3.42 CR V = 250 ml, 20 ppm, pH = 9 0.24 90%/ 1 h [13]
UV Light (λ = 254nm-30 W)

R Messai et al
Dark Room 60 min
TiO2 Micro wave method 11.92 3.4 CR V = 50 ml, 100 ppm, 0.1 90%/2 h/ UV light [67]
UV Light (15 W) 99%/2 h/ Vis light
 Mater. Res. Express 11 (2024) 015006
Table 4. (Continued.)
Gap Catalysis dose
Sample name Synthesis method Size nm Energy eV Dye Experimental conditions g/l Deg efficiency / Time References

Visible light (400 W)

Dark Room 30 min
ZnO pure Cold Plasma 27.18 3.28 CR V = 25 ml, 7 ppm, T° = 20 °C, pH = 7 1 88% This work
GAD UV Light / 2.5 h
(λ= 365 nm—30 W)
Dark Room 30 min
TiO2 Commercial — — BCB V = 100 ml, 3 ppm, 2.6 74% [68]
UV Light (200 W) /2 h
Dark Room 20 min
Al2O3 Commercial — — BCB V = 100 ml, 50 ppm, pH = 10 1.7 92.87%/1 h Al2O3+ UV + 10 cm3 /min [69]
air bubble
(8.44 mW cm−2 light intensity)
14

Dark Room 30 min

g-C3N4/ ZnO Co-precipitation 40 — BCB V = 50 ml, 25 ppm, pH = 10 0.5 99.51%/1 h [70]
method Visible Light
(250 w)
Dark Room 30 min
Co3O4/Fe2O3 — 20 2.12 BCB V = 100 ml, 38.6 ppm, pH = 10 1 97% 3 h [71]
Sun-light
ZnO/CuO Precipitation 18 to 40 2.88 BCB V = 100 ml, 15 ppm, 0.15 97.30% 1.66 h [72]
method Visible Light
(250 w)
Dark Room 30 min
Al2O3 doped Mn3O4 low-temperature stirring — 5.30 CBC V = 100 ml, 38.6 ppm, pH = 10 1.2 50%–65% / 5 h [73]
method
Sun-light
Dark Room 30 min
TiO2 Commercial — — CBC V = 100 ml, 19.3 ppm, pH = 11 1.5 96% / 8 h [74]
Visible light (500 W)
Dark Room 10 min
ZnO pure Cold Plasma 27.18 3.28 BCB V = 25 ml, 7 ppm, T° = 20 °C, pH = 7 1 92.92% This work
GAD UV Light / 2.5 h

R Messai et al
(λ= 365 nm—30 W)
Dark Room 30 min
Ag/ZnO sol–gel method — 3.10 MB V = 100 ml, 6.4 ppm, 1 100% [75]
 Mater. Res. Express 11 (2024) 015006
Table 4. (Continued.)
Gap Catalysis dose
Sample name Synthesis method Size nm Energy eV Dye Experimental conditions g/l Deg efficiency / Time References

Visible lamp / 2.5 h

(250 W)
Dark Room 15 min
ZnO Precipitation method 50–200 — MB V = 20 ml, 5 ppm, 5 95% [76]
UV Light (12 W) Dark Room 30 min / 1.5 h
ZnO Sol–Gel 20–100 2.69 MB 10 ppm, 0.86 95% [77]
solar Light / 0.75 h
(300 W)
Dark Room 45 min
ZnO pure Co-precipitation 26.7 3.05 MB V = 20 ml, 20 ppm, 1 93%/4 h [78]
27.92
Ag1.7%/ZnOAg3.4%/ZnO method. 27.40 3.02 UV-C lamp for UV 98%/4 h
15

Ag4.4%/ZnO 25.60
2.98 93%/4 h
2.94 92%/4 h
ZnO pure Co-precipitation 26.7 3.05 MB V = 20 ml, 20 ppm, 1 43%/4 h [78]
27.92
Ag1.7%/ZnOAg3.4%/ZnO method. 27.40 3.02 three Philips TLD 18 W/54–765 lamp for 48%/4 h
Ag4.4%/ZnO 25.60 visible light
2.98 36%/4 h
2.94 35%/4 h
ZnO Sol–Gel 80–100 3.54 MB V = 20 ml, 10 ppm, 0.25 86%/1 h [79]
UV lamp (365 nm −4 W)
Dark Room 60 min
ZnAl2O4: Dy3+ Green 18 3.4 MB V = 100 ml, 10 ppm, pH = 9 1 95%/3 h [80]
combustion UV light
ZnO pure Cold Plasma 27.18 3.28 MB V = 25 ml, 7 ppm, T° = 14 °C, pH = 7 1 71% This work
GAD UV Light / 2.5 h
(λ= 365 nm—30 W)
Dark Room 30 min

R Messai et al
Mater. Res. Express 11 (2024) 015006 R Messai et al

degradation followed the first order mechanism. The value of the degradation rate constant (k) was estimated to
be 0.0190 min−1, 0.0081 min−1, and 0.0086 min−1 for BCB, MB and CR, respectively, based on the slope of the
linear equation utilizing the above equation.
Table 4 presents a comparison of the photocatalytic activities of various nanoparticles in several previous
studies and ZnO synthesized by GAD plasma, for the degradation of BCB, MB, and CR. The results of this
comparison indicate that ZnO nanoparticles produced through Gliding Arc Discharge plasma exhibited higher
photocatalytic activity compared to other synthesis methods [13, 59–80].
The findings of this research could suggest that the method of synthesizing ZnO NPs can significantly affect
their photocatalytic activity, which in turn affects their efficiency in degrading organic pollutants in water.
Therefore, the use of ZnO NPs generated by the plasma GAD of air may be a more effective approach for water
treatment applications.

4. Conclusion

In this paper, we have developed a novel and effective method for synthesizing ZnO NPs using plasma GAD and
air as the vector gas. The zinc acetate aqueous solution was subjected to gliding arc discharge plasma, which
generated hydroxyl radicals. These radicals reacted with the zinc ions in the solution to form zinc hydroxide,
which was then vaporized to form ZnO NPs.
The physical and chemical properties of the synthesized ZnO NPs were characterized using various
analytical techniques, including UV–vis, FTIR, XRD, TGA, DSC, and SEM. The UV–vis analysis confirmed the
band gap energy of ZnO NPs to be 3.3 eV. The FTIR analysis revealed the presence of absorption bands at 426
and 565 cm−1, which are characteristic of the hexagonal structure of ZnO NPs. The XRD analysis confirmed the
wurtzite hexagonal structure of the ZnO NPs, with an estimated diameter of 27.18 nm. The TGA and DSC
exhibited excellent thermal stability of the synthesized ZnO NPs.
The SEM images showed that the ZnO NPs had a porous structure with grains of varying sizes that were
agglomerated and had a regular shape. The synthesized ZnO NPs were found to be highly effective in degrading
organic pollutants in water when exposed to UV light. The photodegradation rates of BCB, MB, and CR dyes
reached 92.9%, 71%, and 88%, respectively, which is a promising result for water treatment applications.
The simplicity and effectiveness of the plasma GAD to synthesize ZnO NPs make it a promising approach for
the development of new and improved photocatalysts for the degradation of organic pollutants in water. Future
work should investigate the synthesis of different nanostructures to further enhance the photocatalytic activity
of ZnO NPs.

Acknowledgments

This work was supported by a grant from the Directorate General for Scientific Research and Technological
Development (DG-SRTD) of the Ministry of Higher Education and Scientific Research of Algeria. This work was
supported by the Deanship of Scientific Research, Vice Presidency for Graduate Studies and Scientific Research,
King Faisal University, Saudi Arabia [Project No: GRANT5242].

Data availability statement

No new data were created or analysed in this study.

Declarations

Ethical approval

This study did not involve the use of human or animal subjects. As such, no ethical approval was required for this
research.

Conflict of interest

The authors declare that they have no conflict of interest.

16
Mater. Res. Express 11 (2024) 015006 R Messai et al

Authors’ contributions

M, W, A: R M writing the manuscript, S S: M F F and M S A revising and editing, B B data collection, N A and D B
result analysis, M R G supervision and editing, all authors reviewed the manuscript.

ORCID iDs

Ridha Messai https://orcid.org/0000-0001-7772-0186

Mir Waqas Alam https://orcid.org/0000-0001-5190-0103
Mohd Al Saleh Al-Othoum https://orcid.org/0000-0002-7843-0938

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