Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Development and characterization of solar active Ag-ZnO/g-C3N4 as a

highly efficient photocatalyst for the detoxification of organic pollutant
Sakthivel Kumaravel , Haekyoung Kim *
School of Materials Science and Engineering, Yeungnam University, Gyeongsan 38541, Republic of Korea

G R A P H I C A L A B S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: In today’s biosphere, a major problem is water pollution caused by the discharge of effluents from dying in­
Dye degradation dustries, such as the printing and textile industries. In our current work, we have successfully fabricated pho­
Methylene blue tocatalytic bare and composite material 1%Ag-ZnO/6% g-C3N4 (Ag-ZnO/gCN), along with pristine ZnO and g-
Ag-ZnO/g-C3N4
C3N4 (gCN), for the efficient degradation of dye wastewater. Structural investigations performed using FT–IR,
Photocatalyst
Solar light
XRD, FE–SEM/EDS, XPS, PL, EIS, and HR-TEM/EDS confirmed the structures of the pristine and composite
photocatalysts. According to XPS studies, Ag exists in the metallic form. The photocatalytic performance of all
the catalysts was evaluated by degrading methylene blue (MB) dye in an aqueous solution under direct sunlight
illumination, and the most active composite catalyst was utilized for conducting dye degradation under visible
light in the optimized experimental conditions. The effects of operating parameters, such as catalyst amount and
initial pH, on MB degradation have been evaluated. Under solar irradiation, the photodegradation of MB dye
over the Ag-ZnO/gCN composite catalyst was measured to be ≈ 100% in 50 min, and its degradation rate
constant Kapp (0.1266 min–1) was higher than that of other pristine and composite catalysts. A Total Organic
Carbon (TOC) study validated MB mineralization. Further experimental results corroborate the conclusion that
2 ) play a pivotal role in this degradation process, with hydroxyl radicals ( OH) and
superoxide radical anions (O•– •

photogenerated holes (h ) following suit insignificant. Moreover, after undergoing 5 consecutive cycles, the
+

* Corresponding author.
E-mail address: [email protected] (H. Kim).

https://doi.org/10.1016/j.colsurfa.2023.132644
Received 15 September 2023; Received in revised form 20 October 2023; Accepted 23 October 2023
Available online 24 October 2023
0927-7757/© 2023 Elsevier B.V. All rights reserved.
S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

catalysts exhibited a remarkable photostability of 88%. A possible photocatalytic mechanism was proposed for
the improved photocatalytic activity.

1. Introduction approach allows us to design cost-effective photocatalysts to address the

energy crisis and wastewater treatment.
In recent years, environmental pollution has gained significant
attention. In particular, there is an urgent need to deal with water 2. Materials and methods
pollution. The major contaminants in water include industrial waste,
cosmetics, pharmaceuticals, fertilizers, pesticides, mixed residential Analytical grade of zinc acetate dihydrate (≥ 98%), sodium hy­
wastewater, and pigments [1–3]. Among them, dyes are often dangerous droxide (≥ 98%), melamine (99%), and ethanol (99.9%) were obtained
compounds used in various fields such as paper, pharmaceuticals, rub­ from Sigma Aldrich. Silver nitrate (99.8%), and methylene blue (97%)
ber, plastics, printing, and textiles [4,5]. Methylene blue (MB), a were procured from Sisco Research Laboratories Pvt. Ltd., India.
representative water-soluble dye that belongs to the phenothiazine
family and is widely used in industry, causes serious environmental 2.1. Fabrication of g–C3N4, ZnO and Ag-ZnO/gCN composite catalysts
pollution [6–8]. Various remediation procedures were tested and eval­
uated to remove contaminants from contaminated water [9]. The Pristine g–C3N4 was prepared by the calcination method reported in
harmful pollutants degradation by photocatalysis process is one of the previous literature [38]. A yellow powder was obtained by calcining 5 g
straightforward, economical, greener, and environmentally sustainable of melamine at 773 K for 2 h and was ground into a fine powder and used
methods used nowadays. In this respect, the use of semiconductor for subsequent studies, this catalyst is denoted as gCN.
photocatalysts has attracted a great deal of attention [10,11]. A sol–gel fabrication process was used to produce pristine and
ZnO is a special semiconductor due to its excellent electrical and composite photocatalysts. In a typical reaction, 12 mmol of zinc acetate
optical characteristics, non-toxicity, strong redox potential, improved dihydrate was dissolved in a 2:1 water/EtOH mixture (150 mL) and
electronic movement, and inexpensive cost compared to other semi­ stirred for 30 min. A calculated amount of 1 wt% Ag (0.0924 mmol of
conductor materials [12,13]. ZnO nanoparticles (NPs) have a narrow AgNO3) and 0.060 g of gCN (6 wt%) photocatalyst were added to the
band gap (3.37 eV), which restricts their ability to absorb visible light above solution and ultrasonication for 30 mins. 4.8 g of NaOH in 100 mL
[14]. It is desirable to modify ZnO to absorb more of the visible region of of H2O was added dropwise into the above reaction mixtures and stirred
the solar spectrum (45%) and reduce its bandgap [4,15]. Doping of at 363 K for 4 h. After the reaction, the resulting solid was rinsed with
metals and non-metals with semiconductors is a strategy described to ethanol and dried at 373 K for 6 h. The subsequent light-yellow solid was
change the optical absorption edge of ZnO to the visible region [16–20]. then calcined at 623 K for 3 h. The primary procedure for producing ZnO
Graphite carbon nitride (gCN) is an ideal material for photocatalytic nanoparticles and ZnO/gCN photocatalysts was the same as described
applications due to its excellent thermal, optical, mechanical, and above, except for adding silver nitrate. The obtained bare ZnO, Ag-ZnO,
electrical properties and its environmentally friendly [21]. Though the ZnO/6%g-C3N4, and 1%Ag-ZnO/6%g-C3N4 materials are denoted as
photocatalytic efficiency of pristine gCN is limited due to its small sur­ ZnO, Ag-ZnO, ZnO/gCN, and Ag-ZnO/gCN, respectively.
face area, poor visible light absorption capacity, and rapid recombina­
tion of photoinduced e–/h+ [22,23], an effective approach to enhance its 2.2. Characterization
separation of e–/h+ during photocatalysts is combining with ZnO to
create a heterojunction at the interface [24]. Noble metals such as Ag, Phase formation of as–synthesized pristine and composites was
Au, and Pt are of great interest in these processes due to their surface analyzed via the XRD technique (BRUKER USA D8 Advance, Davinci and
plasmon resonance (SPR) effect, which absorbs more visible photons, Rigaku, MiniFlex). Fourier transform infrared (FT–IR) spectra were
and metallic properties that accelerate surface catalysis [25–27]. So far, collected using (IRTracer–100–Shimadzu). XPS spectra were measured
there are few reports on the simultaneous formation of heterojunctions using (ULVAC–PHI, PHI5000 Version Probe III). The surface image of
and doping, so this issue needs to be addressed urgently [27,28]. The as–fabricated pristine and composite photocatalysts was characterized
photocatalytic performance of the gCN was improved by the synthesis of by FE–SEM/EDS (TESCAN CLARA S8000) and HR–TEM (JEOL Japan,
gCN/metal oxide heterojunctions. JEM–2100 Plus). The optical band gap of as–fabricated pristine and
According to previous ligature reports, many semiconductors are composite photocatalysts was evaluated by UV–DRS measurements
effective in the degradation of harmful organic pollutants such as g- (JASCO V–650). The degradation of organic pollutants was also
C3N4/Ni–ZnO [4], M–doped ZnO/g–C3N4 [29], ZnO@WO3 [30], analyzed using Total Organic Carbon (TOC, Shimadzu). The PL spectra
g–C3N4/Co/ZnO [31], Ce-doped–ZnO/g–C3N4 [32], ZnO–CuO–Ag [33], were recorded by using a spectrofluorometer (Horiba Lab RAM HR
SnO2/ZnO [34], LaNiO3/g-C3N4/MoS2 [35], Ag/g-C3N4/LaFeO3 [36] micro). Electrochemical impedance spectra (EIS) were measured by
and g-C3N4/MoS2/graphene [37]. We develop a heterojunction of ZIVE LAB electrochemical workstation using a standard three-electrode
Ag/ZnO with gCN as an electron-accepting platform for mitigating system. EIS spectra were obtained in the frequency range of 0.1 Hz to
excessive charge recombination. The SPR effect of Ag nanoparticles al­ 0.1 MHz.
lows for strong absorption of photons in the visible spectrum, thus
driving light-matter interaction. The Ag-ZnO/gCN heterostructure 2.3. Photocatalytic activity tests
catalyst consequently exhibits remarkable photocatalytic activity. In
this work, pristine ZnO and Ag-ZnO/gCN composite catalysts were Photocatalytic activities of the fabricated photocatalysts were
designed and successfully synthesized via the sol–gel method. The ob­ assessed by measuring the degradation of MB dye under sunlight illu­
tained materials were characterized by different analytical techniques. mination. The solar photocatalytic degradation reactions were per­
The photocatalytic performance of pristine and composite catalysts was formed under identical conditions on bright days between 11.30 a.m.
evaluated by the degradation of MB dye solution under solar light illu­ and 12.30 p.m. An open 150 mL capacity borosilicate glass beaker was
mination. The effects of operating parameters such as photocatalyst utilized for the experiment. The intensity of solar light was found to be
weight and initial pH on MB decolorization have been studied in detail. 9.49 × 104 lux using a lux meter. To confirm the adsorption/desorption
The most active Ag-ZnO/gCN photocatalyst preserves good stability and equilibrium between photocatalytic particles and MB dye, the reaction
photocatalytic performance even after degradation for the 5th cycle. This suspension containing 0.020 g of catalyst in 20 ppm of 100 mL dye

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S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

solution was stirred for 30 min in the dark. Solar irradiation was con­ groups and look into possible interactions between constituents. The
ducted in the open air with continuous stirring and mixing of the dye characteristic band in the region of 400 cm–1 to 1000 cm–1 is attribut­
solution to create a uniform suspension of the catalyst in the reaction able to the Zn–O stretching and bending vibrations [48]. The broad band
medium. At regular time intervals, a 3 mL of aliquot was withdrawn, and of absorption between 3000 cm–1 and 3500 cm–1 was ascribed to O–H
the catalyst particles were removed through centrifugation before stretching vibrations of H2O molecules which are usually present on the
UV–vis measurements since the dispersed particles will interfere with catalyst surface [42,49–53]. FT–IR spectrum of pristine gCN photo­
the absorbance measurements. Finally, the supernatants were analyzed catalyst exhibits two absorption bands in the range of 3000–3500 cm–1
by UV-Vis spectrometer. The maximum wavelength of absorbance for and 800–1700 cm–1 due to N–H, O–H, s–triazine, C– – N, and C–N bonds
MB dye is λmax = 664 nm was used to calculate the MB dye concentra­ having different vibrational stretching modes. The FT–IR bands at 1203,
tion. The most active Ag-ZnO/gCN composite catalyst (discussed later) 1309, 1386, and 1543 cm–1 correspond to the C–N stretching vibrations
was also tested against MB degradation using visible light (500–watt [54,55]. The observed band at 800 cm–1 was attributed to the s–triazine
tungsten lamp; 420 nm). The intensity of visible light was found to be breathing mode of bending vibration [56]. The absorption peaks of
16.7 × 103 lux using a lux meter. A multi–lamp photoreactor setup, % composite catalysts showed a minor shift toward lower wavenumbers. In
decolorization, and rate constants were determined according to pre­ Ag-ZnO/gCN material, the bands belong to the range of 500–800 cm–1,
vious literature reports [39–43]. which can be ascribed to the stretching vibrations of the Zn–O bond
[57]. The presence of characteristic bands for both gCN and ZnO con­
3. Results and discussion firms the successful synthesis of the ZnO/gCN and Ag-ZnO/gCN com­
posite catalysts.
3.1. Materials characterization: Ag-ZnO/gCN The optical characteristics of the produced pristine and composite
materials were investigated using DRS–UV. Fig. 2 illustrates the UV–DRS
Fig. 1a demonstrates the XRD pattern of the pristine ZnO, gCN, ZnO/ absorption spectra of prepared photocatalysts. The visible absorbance
gCN, and Ag-ZnO/gCN composite materials. Pristine ZnO nanoparticles (400–600 nm) increased after the incorporation of Ag and gCN in Ag-
display characteristic sharp peaks at 2θ = 31.9◦ , 34.55◦ , 36.37◦ , 47.64◦ , ZnO/gCN. The ternary composite modified the optical properties of
56.74◦ , 62.96◦ , 66.48◦ , 68.09◦ , 69.19◦ , 72.62◦ , and 77.03◦ due to the ZnO sample by SPR of Ag particles. The band gaps of pristine and
diffraction from (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 composite materials were determined using the formula Eg = 1240/λ,
1 2), (2 0 1), (004) and (202) planes, respectively. These peaks are where λ is the cutoff wavelength [42]. The absorption edges (cut off)
well–fitted with hexagonal wurtzite crystal phase pristine ZnO (JCPDS
card no. 89–0510) [44]. The clear diffraction peaks show that the
samples are well–crystallized. The pristine gCN observed sharp peaks at
2θ = 13.62◦ and 27.90◦ are indexed to (100) and (002) planes inter­
planar spacing of carbon material [45]. The XRD patterns of ZnO/gCN
and Ag-ZnO/gCN catalysts show the intensity of the peak decreased and
moved towards higher angles. This is due to the lattice expansion of ZnO
and the interaction between Ag, gCN, and ZnO nanoparticles, respec­
tively. The peak corresponding to Ag and gCN in the ZnO material could
not be indexed due to the low concentration of gCN used in the syn­
thesis, close to the usual XRD detection limit of ~ 0.2–5 wt%. This may
be due to the lower concentration and small crystalline size of Ag and
gCN may be responsible for the lack of peaks in the Ag-ZnO/gCN com­
posite [46]. However, the presence of Ag and gCN was confirmed with
SEM/EDS, TEM/EDS, and XPS analyses. The crystal structure of the
ZnO/gCN remains unchanged after Ag modification in the ZnO/gCN
material [46,47].
The results of the FT–IR examination of as fabricated photocatalysts
Fig. 2. UV–Vis–DRS of as-synthesized photocatalysts.
are shown in Fig. 1b, where they were used to determine functional

Fig. 1. (a) XRD patterns and (b) FT–IR spectra for the as-synthesized catalysts.

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S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

were found at 408, 470, 455, and 460 nm for ZnO, gCN, ZnO/gCN, and found to be 3.03 eV, 2.63 eV, 2.72 eV, and 2.69 eV for ZnO, gCN,
Ag-ZnO/gCN photocatalysts, respectively. The remarkable light ab­ ZnO/gCN, and Ag-ZnO/gCN, respectively. A narrower bandgap is ad­
sorption capacity of the ternary composite Ag-ZnO/gCN material is su­ vantageous for enhancing the photocatalytic activity of Ag-ZnO/gCN
perior to the pristine ZnO photocatalyst. The band gap values were due to the SPR effect of Ag particles and the energy band matching

Fig. 3. XPS spectra of as-synthesized Ag-ZnO/gCN composite catalyst: (a) survey spectrum, (b) high–resolution C 1s, (c) N 1s, (d) O 1s, (e) Zn 2p, and (f) Ag 3d.

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S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

between gCN and ZnO. The increased visible light absorption of nanoparticles are demonstrated in the spherical–like morphology
Ag-ZnO/gCN ternary composite material enables more efficient utili­ (Fig. 4a–c). The junction between gCN and ZnO NPs is clearly shown in
zation of light, generating more e–/h+ for photocatalytic reactions under the low and high magnifications SEM images of the composite catalyst
light irradiation [58]. (Fig. 4d–f). The spherical–like ZnO particles are well attached to the
XPS analysis was made to assess the surface components and surface of the gCN sheet to form a heterostructure and the sheet–like
oxidation state of each element in the most active composite catalyst. layered structure of the gCN compound present in the composite [24,45,
Fig. 3(a–f) demonstrates the survey and core–level spectra of the most 46]. After the incorporation of gCN and Ag species into the system,
active Ag-ZnO/gCN composite catalyst. The broad survey spectrum FE–SEM micrographs of the composite catalyst showed small agglom­
confirms the existence of C, N, O, Zn, and Ag in the composite catalyst as erated irregular morphologies. FE–SEM images showed that the particle
demonstrated in Fig. 3a. The deconvoluted into two peaks found at sizes of both materials are in the nanometer range. The particle sizes of
284.7 eV and 288.1 eV in the core level spectrum of C 1 s (Fig. 3b) is both ZnO and Ag-ZnO/gCN composite catalysts are distributed more
attributed to N=C–N and C–C coordination and SP2 hybridized carbon in uniformly, ranging from 50 nm to 100 nm (Fig. 4c and f). The TEM
the lattice of gCN [59]. The peak located at 398.7 eV, 399.1 eV, and image also confirms this observation (discussion comes later). The
400.1 eV in the core level spectrum of N 1 s (Fig. 3c) can be attributed to elemental mapping and composition of the Ag-ZnO/gCN most active
the nitrogen atom with a sp2hybridized (C– – N–C), (N-(C)3), and C–N–H photocatalyst were investigated by EDS analysis using FE–SEM. Fig. 4g
bond of the amino group, respectively [60]. The peak at 530 eV and shows the elemental mapping and EDS of the synthesized Ag-ZnO/gCN
531.5 eV in the high–resolution spectrum of O 1 s (Fig. 3d) is due to the composite catalyst, confirming the existence of C, O, N, Zn, and Ag el­
lattice oxygen (Zn–O) and surface adsorbed water molecule [61]. The Zn ements. Different colors were used to distinguish the positions of C, N, O,
2p core–level spectrum shown in Fig. 3e was split into two binding en­ Zn, and Ag in the photocatalyst. The elemental mapping shows that the
ergies at 1021.1 eV and 1044.2 eV, relating to the Zn 2p3/2 and Zn 2p1/2 brighter area, higher the amount of corresponding element. EDS analysis
states, correspondingly, indicating that the ZnO sample was in the Zn2+ confirms that the synthesized material was effectively formed.
oxidation state [61]. Fig. 3f reveals the core–level XPS spectrum of Ag 3d The images of the Ag-ZnO/gCN composite photocatalyst were ac­
peaks at binding energies of 367.6 eV and 373.8 eV, respectively, quired from TEM, HR–TEM, and corresponding FFT image (Fig. 5a–h).
indexed to the 3d5/2 and 3d3/2 peaks corresponding to metallic Ag. This Spherical shape forms of ZnO nanoparticles can be found in the Ag-ZnO/
results in good agreement with the previous literature report [62]. This gCN composite (Fig. 5a–c). The TEM morphology of the composite
result further confirmed that gCN and the Ag nanoparticles are present catalyst shows that the ZnO nanoparticles are well–embedded on the
in the Ag-ZnO/gCN composite. surface of the gCN sheets [45], as seen in Fig. 5a–c. This advantage, the
FE–SEM was used to investigate the morphology and shape of the heterojunction formed between the two phases accelerates charge
pristine and most active catalysts. Fig. 4(a–f) shows the FE–SEM images transfer and separation, enhancing the photocatalytic performance of
of ZnO and Ag-ZnO/gCN composite catalysts. The pristine ZnO the composite photocatalyst. Fig. 5g and h show the interplanar spacing

Fig. 4. FE–SEM images for (a–c) ZnO, (d–f) Ag-ZnO/gCN composite catalysts, and (g) corresponding EDS spectrum and elemental mapping of the consistent elements
C, N, O, Zn, and Ag.

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S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

Fig. 5. (a–c) TEM and (d–h) HR–TEM images of Ag-ZnO/gCN and the corresponding FFT images (inset), (d, g) HR–TEM and FFT images for the ZnO phase, (e, f)
HR–TEM and FFT image for the isolated and embedded Ag nanoparticles and (i) EDS spectrum of Ag-ZnO/gCN composite photocatalyst.

of 0.273 nm, which can be indexed to (100) crystallographic plane of

ZnO [63,64]. Moreover, a well–developed ZnO single crystal can be seen
in the inset of Fig. 5g, showing a comparable FFT pattern with well­
–defined diffraction spots. Fig. 5f and f (inset) show the HR–TEM and
FFT patterns and are visible as lattice fringes with a d–spacing of
0.229 nm, corresponding to the (111) crystallographic plane of Ag NPs.
However, the Ag NPs that developed on the composite are tiny and
cannot be seen clearly in this view (Fig. 5e). Fig. 5i displays the EDS
study of the Ag-ZnO/gCN photocatalyst. EDS analysis proves the exis­
tence of elements such as C, N, O, Zn, and Ag species. This result in­
dicates the purity and successful formation of the Ag-ZnO/gCN
composite photocatalyst.
Recombination of electron-hole pairs is one of the fundamental
limitations of semiconductor photocatalysis. Fig. 6 shows the photo­
luminescence (PL) spectra of as prepared photocatalysts. A strong PL
signal corresponds to a decrease in photocatalytic performance and an
increase in the recombination rate, while a weak signal indicates the
opposite [65]. In particular, the Ag-ZnO/gCN catalyst exhibits lower PL
intensity compared to pristine ZnO. This suggests that the Ag-ZnO/gCN
catalyst is likely to exhibit superior photocatalytic activity due to less Fig. 6. PL spectra of as-prepared photocatalysts.
recombination compared to ZnO.
Electrochemical impedance spectroscopy (EIS) measurements were
enhanced photoinduced electron-hole transfer and transfer, supporting
performed to investigate the efficiency of interfacial charge separation.
the enhanced photocatalytic activity of Ag-ZnO/gCN composites. The
Fig. 7 shows typical EIS plots for as-prepared catalysts. The charge
presence of Ag and gCN in the composite plays a crucial role in pro­
transfer resistance is directly represented by the size of the arc in the
moting electron transport and contributes to the overall improvement of
Nyquist plot. In particular, the impedance plot of Ag-ZnO/gCN exhibits a
photocatalytic performance.
smaller arc radius compared to pure ZnO and ZnO/gCN composite cat­
alysts, indicating lower charge transfer resistance. This result suggests

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S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

organic dye molecules, with pH = 7.4 for the test dye molecules.
Hereafter, the pH has been optimized at 7.4 for further studies.

3.2.2. Effect of catalyst amount

The effect of catalyst amount on MB dye degradation rate was
studied under optimized experimental conditions with weights ranging
from 10 to 40 mg and the subsequent results are demonstrated in Fig. 9
(a and b). When the photocatalyst dose was increased by 10, 20, 30, and
40 mg, the corresponding degradation rates were 92.8%, 99.8%, 89.4%,
and 79.0% at 50 min exposure. The degradation percentage increased
from 92.8% to 99.8% when the catalyst amount was increased from 10
to 20 mg, however, further increasing the catalyst amount resulted in a
decrease in the degradation percentage. The kinetic (Kaap) and t1/2
values of different catalyst loading are in the following order:
0.1266 min–1; 5.47 min (20 mg) > 0.0555 min–1; 12.48 min (10 mg)
> 0.0431 min–1; 16.07 min (30 mg) > 0.0297 min–1; 23.33 min
(40 mg). The more active sites on the catalyst surface and the penetra­
tion of light into the solution are responsible for the increased degra­
Fig. 7. Electrochemical impedance spectroscopy (EIS) Nyquist plots of as pre­ dation that occurs with increasing catalyst weight [67]. However, as the
pared catalysts. catalyst weight increased, the light penetration decreased and the
catalyst surface enhanced the light scattering effect [68]. Hence, it was
3.2. Photocatalytic activity determined that the optimum catalyst weight for the following reactions
was 20 mg.
3.2.1. Effect of solution pH
The photocatalytic degradation of MB dye is highly influenced by the 3.2.3. Photodegradability of MB dye by pristine and composite
initial pH of the solution, as it affects the surface charge of the catalyst. photocatalysts
Three different pH assays were used to examine the impact of pH on the Methylene blue dye was successfully degraded using the as-prepared
photocatalytic degradation of MB dye (3.4, 7.4, and 10.1) under solar photocatalyst materials under solar light irradiation. Studies were first
light irradiation and obtained results are presented in Fig. 8(a and b). performed in the dark for 30 min to determine whether photo­
The degradation percentage increased from 32.4% to 99.8% when pH degradation occurs without irradiation or whether the methylene blue
increased from 3.4 to 7.4, further increasing pH (pH = 10.1), the dye is adsorbed by the photocatalyst materials. Adsorption experiments
decrease in the percentage of degradation (63.6%) observed, and the in the dark were conducted and the initial adsorption of the dye was
relevant kinetics and rate constant values are shown in Fig. 8b. The ki­ found to be 5–8%. The photodegradation experiments for evaluating the
netic (Kaap) and t1/2 values of various pH are in the following order: photocatalytic activity of pristine and composite photocatalysts are
0.1266 min–1; 5.47 min (pH = 7.4) > 0.0204 min–1; 33.97 min (pH = depicted in Fig. 10 (a and b). As found in Fig. 10a, the photodegradation
10.1) > 0.0075 min–1; 92.4 min (pH = 3.4). This finding suggests that studies of the Ag-ZnO/gCN composite catalyst were compared to those
pH = 7.4 has higher kinetic values than acidic and basic environments. ZnO, Ag-ZnO, gCN, and ZnO/gCN composite photocatalyst materials.
MB is also as a cationic dye and has a strong repulsion behavior in the The degradation results demonstrated that Ag-ZnO/gCN degraded
acidic medium due to a positive surface charge of the catalyst at low pH. methylene blue dye completely (99.8%) in 50 min, which is quicker
Moreover, strong acidity at pH < 3.5 causes the dissolution of AgZ­ than other ZnO, gCN, Ag-ZnO, and ZnO/gCN photocatalysts when
nOgCN and reduces the degradation efficiency [66] The pH of the so­ exposed to solar light irradiation. After 50 min of solar light irradiation,
lution is a key factor in the photocatalytic degradation of the selected the dye degradation efficiency of ZnO, Ag-ZnO, gCN, ZnO/gCN, and Ag-

Fig. 8. (a) Effect of different pH = 3.4, 7.4, and 10.1 and (b) pseudo–first–order kinetics and rate constant values of most active Ag-ZnO/gCN composite catalyst at
different pH {Reaction conditions = 20 ppm of MB dye, 20 mg catalyst, irradiation–direct solar light}.

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S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

Fig. 9. (a) Effect of catalysts amount and (b) pseudo–first–order kinetics and rate constant values of most active Ag-ZnO/gCN composite catalyst at different loading
{Reaction conditions = 20 ppm of MB dye, pH = 7.4; irradiation– direct solar light}.

Fig. 10. (a) Photodegradability of MB dye and (b) pseudo–first–order kinetics values of as–synthesized bare and composite catalysts {Reaction conditions = 20 ppm
of MB dye, pH = 7.4, 20 mg of catalyst weight, irradiation–direct solar light}.

ZnO/gCN was 74.5%, 86.9%, 60.3%, 97.0%, and 99.8%, respectively. materials. Fig. 10b shows the degradation rate constant (k) values for
The dye degradation ability of synthesized photocatalysts follows the Ag-ZnO/gCN, ZnO/gCN, gCN, Ag-ZnO, and ZnO were to be 0.1266,
order of Ag-ZnO/gCN > ZnO/gCN > Ag-ZnO > ZnO > gCN. After Ag 0.0761. 0.0193, 0.039, and 0.0278 min–1, respectively, under similar
modification significantly affects carrier charge transfer and enhances conditions. The photocatalytic degradation rate constants of the Ag-
the photocatalytic efficiency. In the presence of sunlight irradiation, the ZnO/gCN composite catalyst were determined to be 1.6, 6.5, 3.2, and
Ag-ZnO/gCN composite catalyst demonstrates higher photocatalytic 4.5 times those of ZnO/gCN, gCN, Ag-ZnO, and ZnO, respectively. The
performance. This result clearly indicates that the photocatalytic dye t1/2 values in the degradation of MB dye using ZnO, Ag-ZnO, gCN, ZnO/
degradation efficiency of the Ag-ZnO/gCN composite catalyst is greatly gCN, and Ag-ZnO/gCN catalysts were found to be 24.92, 17.76, 35.90,
improved by Ag impregnation. 9.10, and 5.47 min, respectively. Due to the efficient separation of
Using the Langmuir–Hinshelwood model, the degradation efficiency photocarriers, the Ag-ZnO/gCN ternary composite catalyst has signifi­
of MB dye was investigated in terms of the kinetics model of the pho­ cantly higher photocatalytic efficiency than other ZnO/gCN, Ag-ZnO,
todegradation performance of pristine and composite photocatalysts. To ZnO, and gCN photocatalysts. The Ag-ZnO/gCN composite catalyst
study the order of the reaction and its kinetics, the following equations was determined to be the most active photocatalyst synthesized in this
were used (–ln (C0/Ct) = t, where C0 is the initial concentration and Ct is study.
the concentration at time t). Pseudo–first–order kinetics influenced the Fig. 11a and b shows the UV–vis spectra of methylene blue dye at
overall photocatalytic degradation rate. Fig. 10b provides the deter­ various times after exposure to the most active photocatalysts under
mined apparent rate constant and relationship correlation (R2) value for solar and visible light illumination at optimized experimental condi­
the decolorization of MB dye using as–prepared pristine and composite tions. According to the spectral data, the Ag-ZnO/gCN composite

8
S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

Fig. 11. (a) Solar light and (b) visible light absorption evolution spectra of MB dye over Ag-ZnO/gCN composite catalyst {Reaction conditions = 20 ppm of MB dye,
pH = 7.4, 20 mg of catalyst weight}.

photocatalyst is extremely efficient at degrading the methylene blue analysis and the obtained results are shown in Fig. 12a and b. A low
dye, as depicted in Fig. 11a and b, as indicated by the peak intensity of percentage of degradation means that not all organic dye molecules are
the methylene blue dye diminishing with extending time. Furthermore, mineralized. The resulting photocatalytic findings indicate that the
we show that the methylene blue dye is almost completely degraded, organic molecules were partially decomposed into CO2 and H2O, rather
and no additional compounds were formed that absorb at the analytical than being completely converted into non–toxic chemicals such as ac­
wavelength of 664 nm. The photocatalytic most active Ag-ZnO/gCN etate and formate [69].
composites showed activity under visible light illumination for com­ One of the most effective Ag-ZnO/gCN ternary composite catalysts is
parison purposes. recyclability for five consecutive runs of MB dye degradation under solar
The Ag-ZnO/gCN photocatalytic composite catalyst showed ≈ 100% illumination and optimal experimental reaction conditions. The ob­
decolorization and 85% mineralization of MB for 50 mins under solar tained result is depicted in Fig. 13. Photocatalysts used in previous
light irradiations (Fig. 12a). The reaction was performed for up to cycling experiments must be centrifuged, filtered, and dried before
75 min to achieve ≈ 100% degradation and 87% mineralization of MB utilization in the next cycling experiment. The photocatalytic activity of
under visible light illumination (Fig. 12b). The rate constant values in the Ag-ZnO/gCN composite catalyst showed a slight decrease in MB dye
the degradation of MB dye using Ag-ZnO/gCN catalyst were found to be decomposition from 99.8% to 88% after the fifth catalytic cycle. The
R2 = 0.9684, Kaap = 0.0621 min− 1 and t1/2 = 11.59 min, respectively, spent catalyst was further characterized by SEM analysis. Fig. 14(a,b)
under visible light illumination, which is 2.0 times lower than that of shows the FE-SEM images of the used Ag-ZnO/gCN composite photo­
solar light irradiation. The findings reveal that the photocatalytic catalyst. It is clearly understood from the figures that even after the fifth
degradation rate under sunlight is higher than the degradation rate run of the used photocatalyst, negligible changes were maintained in the
under visible light illumination. This can be ascribed to the incredible catalyst surface morphology. The FE-SEM image clearly proved the high
energy and heat caused by solar lighting. The degradation of organic dye stability and durability of the spent catalyst during the photocatalytic
compounds was also investigated using total organic carbon (TOC) degradation reaction.

Fig. 12. (a) Solar light and (b) visible light degradation and mineralization of MB dye over Ag-ZnO/gCN composite catalyst {Reaction conditions = 20 ppm of MB
dye, pH = 7.4, 20 mg of catalyst weight}.

9
S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

Fig. 13. The reusability of Ag-ZnO/gCN composite catalyst for degradation of

MB dye under solar light illumination {Reaction conditions = 20 ppm of MB
dye, pH = 7.4, 20 mg of catalyst weight}.

Radical trapping experiments using ammonium oxalate (AO) [holes Fig. 15. Radical trapping experiments of Ag-ZnO/gCN composite catalyst for
(h+) scavenger], tert–Butyl alcohol (t–BuOH) [hydroxyl radical (•OH) degradation of MB dye under solar light illumination {Reaction conditions
scavenger], and p–benzoquinone (BQ) [superoxide radical anion (O•– 2 ) = 20 ppm of MB dye, pH = 7.4, 20 mg of catalyst weight}.
scavenger] [70] were conducted to analyze the mechanism behind the
photocatalytic degradation performance of MB dye with Ag-ZnO/gCN
ternary composite photocatalyst under optimized reaction conditions.
In the presence of various scavengers, the performance of MB dye
degradation is shown in Fig. 15. The results demonstrate that every
species strongly influences the photocatalytic decolorization procedure.
At 50 min, 99.8% degradation was observed without scavenger. The
degradation percentages with the addition of p–benzoquinone, tert–Bu­
tyl alcohol, and ammonium oxalate were 24%, 29%, and 52%, respec­
tively. The addition of p–benzoquinone significantly decreased the
photocatalytic activity among the different scavengers, demonstrating
that superoxide radical anion (O•–2 ) was the main active species in this
degradation process, followed by hydroxyl radicals (•OH), and photo­
generated holes (h+).
Fig. 16 shows the band energies of ZnO and gCN to illustrate the
possible mechanism of photocatalytic decomposition of MB by Ag-ZnO/
gCN. The conduction band (CB) and valence band (VB) potentials of ZnO
are − 0.095 eV and +2.935 eV, while for gCN were − 1.085 eV and
+1.545 eV, respectively. The more negative CB potential of gCN
compared to ZnO facilitates the transfer of photogenerated electrons
from the CB of gCN to the CB of ZnO when subjected to solar irradiation, Fig. 16. A possible mechanism for photocatalytic degradation of MB by Ag-
the holes transferred oppositely. However, this arrangement is not ZnO/gCN under solar irradiation.

Fig. 14. (a-b) FE-SEM images of Ag-ZnO/gCN composite after reusability test.

10
S. Kumaravel and H. Kim Colloids and Surfaces A: Physicochemical and Engineering Aspects 679 (2023) 132644

feasible for the production of highly reactive oxygen species such as Table 1
superoxide radical (O•¡ 2 ) anions and hydroxyl ( OH) radicals, because
• Compared with the recent state of the art literature reports.
the accumulated electrons in the conduction band of ZnO have less Catalysts Pollutant Irradiation Light % Ref.
negative than the standard redox potential of E0 = (O2/O•¡ 2 ; ¡ 0.33 eV Concentration Time (min) source Degradation
vs NHE) [71] also the holes present in the VB of gCN is not produced ZnO/ 10 ppm MB 75 solar 80 [75]
hydroxyl (•OH) radicals, since it has less positive potential than standard N–CQD
redox potential E0 = (OH¡/•OH; +1.99 eV vs NHE). However, Ni–doped 3 ppm RhB 60 visible 98 [76]
Ag-ZnO/gCN efficiently degrade the MB dye under solar light, therefore ZnO
5% 10 ppm RhB 150 solar 92 [77]
the possibility of a Z-scheme mechanism has been proposed (Fig. 16). S–doped simulator
Under solar light irradiation, both semiconductors can be excited, the ZnO
excited electrons (e-) in the CB of g-CN generates reactive superoxide F–doped 10 ppm RhB 75 40 W 97 [78]
radical (O•¡
2 ) anions, which are highly active toward MB degradation, at
g–C3N4/ LED
ZnO
the same time, the electrons in the CB of ZnO recombine with the holes
g–C3N4/ 10 ppm MB 70 300 W, 98 [79]
present in the VB of g-CN. Meanwhile, the holes in the VB of ZnO can ZnO visible
react with water and produce highly reactive hydroxyl (•OH) radicals. Ag-ZnO/ 20 ppm MB 50 solar ≈ 100 This
As a result, the separation of energy levels prevents the recombination of gCN work
electron-hole pairs and reduces the recombination of electron-hole Ag-ZnO/ 20 ppm MB 75 500 W, ≈ 100 This
gCN visible work
pairs. Moreover, the incorporation of Ag nanoparticles enhances the
photocatalytic activity, which is mainly attributed to the surface plas­
mon resonance (SPR) effect of Ag. Previous studies have shown that Ag cycles of study, revealing the excellent stability of the catalyst. A low­
in ZnO/gCN composites enhances visible light absorption and acts as an –cost, easy–to–synthesize, sunlight–responsive photocatalyst could be
electron mediator [72] the presence of Ag on the surface of ZnO and gCN very useful in removing toxic dyes from wastewater.
would enhance the production of active species by effectively capturing
electrons from the conduction bands and promoting the efficient sepa­ CRediT authorship contribution statement
ration of photogenerated charge carriers, leading to increased photo
mineralization of dyes. Both O•¡ 2 and OH species are effective for the
•
Sakthivel Kumaravel: Conceptualization, Investigation, Resources,
degradation of dye and produce CO2 and H2O [73]. The reaction Formal analysis, Writing – original draft. Haekyoung Kim: Conceptu­
equations proposed for the photocatalysis of MB dye and the generation alization, Supervision, Investigation, Writing – review & editing.
of electron-hole pairs in Ag-ZnO/gCN are as follows [74]:

Ag-ZnO/gCN + hν → (Ag-ZnO/gCN)e- h+
CB + (Ag-ZnO/gCN)VB (1)
Declaration of Competing Interest
O2 +(Ag-ZnO/gCN)e- •–
CB → O2 (2)
The authors declare that they have no known competing financial
h+ + H2O → •OH + H+ (3) interests or personal relationships that could have appeared to influence
(O•– •
(4) the work reported in this paper.
2 + OH) + MB dye → CO2↑ + H2O

The obtained results revealed the photocatalytic durability of the Data availability
prepared Ag-ZnO/gCN composite catalyst. The photocatalytic efficiency
of modified ZnO–based materials used for the degradation of various Data will be made available on request.
organic pollutants under different experimental conditions was
compared with the produced Ag-ZnO/gCN composites photocatalyst Acknowledgments
and the results are shown in Table 1. By varying the degradation time,
pollutants concentration, and light source, the current investigation This work was supported by the Korea Innovation Foundation
allowed us to compare the photocatalytic activity of the as–prepared (INNOPOLIS) grant funded by the Korea government (MSIT) (2020-DD-
material with other reported ZnO–based materials. UP-0278).

4. Conclusion
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