International Journal of Biological Macromolecules 258 (2024) 128890

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Development of environmentally friendly catalyst Ag-ZnO@cellulose

acetate derived from discarded cigarette butts for reduction of organic dyes
and its antibacterial applications
Heba Mousa a, Soad S. Abd El-Hay b, *, Ragaa El Sheikh c, Ayman A. Gouda c,
Samar Abd El-Ghaffar d, Mohamed Abd El-Aal e
a
Department of Special Chemistry, Faculty of Science, Zagazig University, Zagazig 44519, Egypt
b
Department of Analytical Chemistry, Faculty of Pharmacy, Zagazig University, Zagazig 44519, Egypt
c
Department of Chemistry, Faculty of Science, Zagazig University, Zagazig 44519, Egypt
d
Molecular Biology Research and Studies Institute, Assiut University, Egypt
e
Catalysis and Surface Chemistry Lab, Chemistry Department, Faculty of Science, Assiut University, Assiut, 71516, Egypt

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

Keywords: The release of harmful organic dyes from different industries besides its degradation products is a major
Organic dyes contributor to environmental contamination. The catalytic reduction of these organic pollutants using nano­
Eco-friendly catalyst composites based on polymeric material presents potential advantages for the environment. In this study, novel
Cellulose acetate
nanocomposite based on cellulose acetate (CA)-derived from discharged cigarette butts and zinc oxide nano­
Cigarette butts waste
Ag-ZnO@CA nanocomposite
particles (ZnO NPs) was prepared utilizing a very simple and low-cost solution blending method and used as
Antibacterial action support for silver nanoparticles (Ag NPs). A simple reduction method was used to anchor different percentages of
Ag NPs on the ZnO@CA nanocomposite surface via utilizing sodium borohydride as a reducing agent. The Ag-
ZnO@CA nanocomposite was characterized using X-ray diffraction, Fourier transform infrared spectroscopy,
X-ray photoelectron spectroscopy, and transmission electron microscopy. The TEM analysis showed spherical Ag
NPs, with an average diameter of ~17.6 nm, were uniformly anchored on the ZnO@CA nanocomposite surface.
The prepared nanocomposites were evaluated as catalysts for the reduction of organic dyes in water. It was found
that 10 % Ag-ZnO@CA nanocomposite showed a remarkable reduction of Rhodamine B (RhB), Rhodamine 6G
(Rh6G), Methylene Blue (MB), and Sunset Yellow (SY) dyes in short time. In the presence of this nanocomposite,
the rate constant, kapp values for RhB, Rh6G, MB, and SY were 0.3498 min− 1, 1.51 min− 1, 0.2292 min− 1, and
0.733 min− 1, respectively. This nanocomposite was recovered and reused in five successive cycles, with a
negligible loss of its activity. Furthermore, the nanocomposites demonstrated moderate antibacterial activity
toward Staphylococcus aureus and Escherichia coli. Thus, this study directed attention on recycling of waste ma­
terial to a valuable nanocomposite and its applications in environmental protection.

1. Introduction pollutants and eliminate or reduce harmful substances from water and
wastewater. Conventional treatment approaches frequently rely on
Organic dyes find extensive application across several sectors, physical processes such as adsorption, filtration, and flotation to remove
encompassing the cosmetics, textile, paper, pigment, and plastics in­ organic chemicals from water without breaking them down. Despite
dustries. The release of such colored pollutants from these industries is a their effectiveness, physical treatment methods have some drawbacks,
major contributor to environmental contamination [1,2]. The degrada­ including elevated expenses, inadequate remediation, and the potential
tion of these compounds is particularly difficult, and the harmful effects generation of secondary contaminants [7,8]. As a result, there is a need
of these compounds are not limited to humans, and they can also pose a for methods that can completely transform organic pollutants, and this
threat to aquatic life, animals, and plants [3–6]. It is therefore essential can be accomplished with the help of efficient catalysts.
to create effective treatment methods that can degrade organic Metal nanoparticles (MNPs) are effective catalysts for transforming

* Corresponding author.
E-mail address: [email protected] (S.S. Abd El-Hay).

https://doi.org/10.1016/j.ijbiomac.2023.128890
Received 23 November 2023; Received in revised form 14 December 2023; Accepted 17 December 2023
Available online 21 December 2023
0141-8130/© 2023 Elsevier B.V. All rights reserved.
H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

organic contaminants because of their large surface area, high catalytic using several characterization techniques. Different kinds of dyes were
efficiency, simplicity of manufacturing, and high selectivity toward reduced catalytically within a few minutes. The ability to reuse the Ag-
specific processes. They have been utilized in a diverse set of chemical ZnO@CA nanocomposite was also demonstrated. Moreover, the anti­
processes, such as coupling, electrochemical, oxidation, and reduction bacterial activity of the prepared nanocomposites was evaluated against
reactions [9]. Nevertheless, a primary drawback of many readily exist­ S. aureus and E. coli bacteria.
ing MNPs is their lack of stability [10], due to the agglomeration process
[11]. The high surface energy of MNPs makes them thermodynamically 2. Materials and method
unstable, despite their large number of active sites. This leads to a
diminution in the quantity of adsorption sites and, subsequently, a 2.1. Materials
decline in the number of active sites on the NPs, which in turn reduces
the interfacial contact area between the MNPs and the materials. To All components were of analytical grade. All the solutions were
address this, MNPs are often placed on appropriate support materials. produced with bi-distilled water. (Zn (CH3COO)2.2H2O; 99.5 %),
However, these support matrices can sometimes hinder the efficiency of (NaOH; 99 %), (NaBH4; 98 %), Starch (99 %) were purchased from
MNPs due to their limited surface area, which might reduce the cata­ Research-Lab Fine Chem Industries (India). AgNO3; 98 %), Rhodamine
lyst’s exposure to reactants [12]. Consequently, there is an ongoing push 2B, Rhodamine 6G, and Sun set yellow dyes were supplied by Sigma
to innovate and design superior support materials for MNPs catalysts. Aldrich (Germany), Research -Lab Fine Chem Industries (India). Ethanol
The aim is to find a balance between stability, top-notch catalytic effi­ (Assay 95 %) and acetone (Assay 95 %) were supplied by Alpha
ciency, simplicity in separation from solutions, and the capability to Chemika. The collection of discarded cigarette filters was conducted by
reuse multiple times [13]. It has been commonly noted that the support us from the streets (Zagazig, Egypt), and sent to our Laboratory in
materials are crucial not just for the stability of the catalyst but also for Zagazig University, Egypt, where the cigarette butts underwent a ster­
its activity. They can act as a metal receptor, dispersing the active metal ilization process, and treated to extract CA.
or participating directly in the reaction [12]. According to research,
polymer composites and hybrids are frequently utilized to fulfill this
need [4]. 2.2. Synthesis of ZnO NPs
Researchers have extensively investigated composites made from
various metallic, semi-conducting, and polymer compounds for waste­ ZnO NPs have been manufactured via a chemical precipitation
water treatment applications [14]. Cellulose acetate (CA), a novel class technique followed as outlined by Ali et al. [10]. During this procedure,
of carbohydrate polymer produced by esterifying natural cellulose fi­ Zn (CH3COO)2.2H2O (13.50 g) was broken down in approximately 500
bers, has been the focus of research because of its small size, practical mL of ethanol, producing solution A. Ethanol used here as a solvent
morphology, simple surface chemistry, increased surface area, enhanced because it acts as a controlling agent for crystal growth and this plays a
sustainability in the environment, and relatively affordable production critical role in reducing the particle size to nano-level [23]. For solution
cost [15]. The profusion of plenty hydroxyl and carboxylate groups on B, NaOH (14.76 g) was dissolved in a 78:1 ratio of ethanol to water by
the CA surface has allowed for a variety of surface changes and reactions volume. Solution B was then slowly introduced into solution A with
to be carried out [16]. Various nanocomposites which contain CA vigorous stirring for 3 h at 60 ◦ C. Afterward, the precipitate that had
polymer are described in the literature for eliminating organic con­ been generated was separated through filtration and washed meticu­
taminants from water. For instance, Bakhsh et al. [7] have prepared Cu, lously using both bi-distilled water and ethanol after it had reached
Ag, and Ni NPs supported on CA/Fe2O3 for reduction of organic pol­ ambient temperature. The precipitate was subjected to drying at 80 ◦ C
lutants from water. They found that Ag@CA/Fe2O3 was able to overnight and subsequently was calcined in a static air atmosphere oven
decompose 4-nitrophenol and methyl orange dye in a short time. Khan at 500 ◦ C for 1 h.
et al. [15] investigated the use of Cu and Ag-NPs@CA nanocomposite for
the reducing of 4-nitrophenol (4-NP). Khan et al. [11] investigated the
use of Cu and Ag-NPs/ZnO/carbon black-CA sheets for the purpose of 2.3. Extraction of cellulose acetate (CA)
reducing nitroarene and azo dyes. They assumed that the incidence of
ZnO NPs prevents the agglomeration of the MNPs and enhances thermal, CA extraction from cigarette butts waste was performed based on the
mechanical, and magnetic characteristics of the composite material. The method that was used by Fenzo et al. [24]. After peeling away the outer
catalytic degradation of organic pollutant over CA-Ce/Zr@Cu0 catalyst paper, the used cigarette butts (CBs) were cleaned in hot water at 50 ◦ C
was investigated by Khan et al. [17]. The properties of the catalysis of for an hour. Subsequently, the CBs were rinsed with frigid water for 3
Ag-NPs anchored on the films of porous CA and wet-spun fibers for times to elongate the CA fiber. To eliminate possible organic contami­
hydrogenation of the 2,6-dinitrophenol were studied [18]. Albukhari nants, the cigarette ends were rinsed twice in 99 % w/w ethanol. Lastly,
et al. [19] have synthesized Ag- NPs@ cellulose acetate filter paper for the extracted CA pieces were subjected to a drying process in an oven at
the catalytic degradation of nitrophenols and dyes. CA-ZA@Ni NPs were 60 ◦ C for an hour.
synthesized for nitrophenols hydrogenation and dye decomposition by
Khan et al. [20]. Ni nanoparticles deposited on CA coated Ce/Zr com­
posite were synthesized by Khan et al. [21] for reducing nitrophenol 2.4. Synthesis of ZnO@CA nanocomposite
isomers and degraded azo dyes. Gul et al. have prepared nanocomposite
of PES-CA-Ag2O supported on Cu-NPs to reduce 4-NP and antibacterial The ZnO@CA nanocomposite was created using the solution
applications [22]. The cellulose acetate that was used for the synthesis of blending method detailed by Khan et al. [21]. In this approach, 10 g of
the previously reported nanocomposites is commercial. Consequently, the extracted CA were initially dissolved in a 43:7 ratio of acetone to
there is a great demand for the development of new nanocomposites water, with persistent stirring. Once a uniform CA solution was ach­
based on the effective transformation of solid wastes into materials that ieved, 10 g of ZnO NPs were incorporated and consistently mixed
are beneficial for water treatment. However, to the greatest extent of our through vigorous stirring. This mixture was then spread onto a pristine
current understanding, this is the first suggested method for using glass substrate and left to set for 24 h at ambient temperature in an open
composites containing Ag NPs, ZnO NPs, and CA derived from cigarette setting. Following this, the resulting film was carefully removed from
butts waste to reduce organic dyes in water with the aid of sodium the glass surface, dried, and subsequently ground using a Fritsch Mini-
borohydride (NaBH4) and study their antibacterial applications. Mill pulverisette 23, GmbH, Duisburg, Germany for a duration of 10
The formation of the Ag-ZnO@CA nanocomposite was established min.

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

2.5. Synthesis of Ag-ZnO@CA nanocomposites

Direct reduction method was employed to bind Ag NPs to the

ZnO@CA nanocomposite, forming the Ag-ZnO@CA nanocomposite.
Initially, a predetermined amount of ZnO@CA was mixed in 50 mL of
AgNO3 solution. This solution had a quantity corresponding to pro­
duction of 1–15 % wt% Ag0 on the ZnO@CA nanocomposite. This
mixture was stirred for 30 min at ambient temperature. Separately, a
specific quantity of starch was dissolved with 10 mL of bi-distilled water
with gentle heating and was gradually introduced to the primary
mixture, ensuring consistent stirring. A designated weight of NaBH4 was
dissolved in another 50 mL of water and slowly combined with the
ongoing mixture, which was continually stirred. The entire mixture was
maintained at room temperature, being stirred for an additional 30 min
and the resulting precipitate was separated using filter paper. Then, it
has been washed multiple times with ethanol and bi-distilled water, and
finally dried at 50 ◦ C for 2 h.

2.6. Characterization techniques

Fig. 1. XRD profiles of ZnO NPs and the nanocomposites.
The X-ray diffraction patterns of the synthesized nanocomposites
were investigated using an of the nanocomposites were evaluated by the ZI (zone of inhibition)
X-ray diffractometer (XRD, X’ Pert PRO PANalytical-Netherland around discs as the microbe growth inhibition.
device) at 25 ◦ C with Cu Kα a monochromatic radiation source. The The MIC (minimum inhibitory concentration) and time killing assay
binding state of the samples was characterized by X-ray photoelectron were performed by using microbroth dilution [28]. Different concen­
spectroscopy (XPS, K-ALPHA (Thermo Fisher Scientific, USA)). A Nicolet trations of the nanocomposites (200, 100, 50, 25, 12.5, 6.25, 3.2, and
iS50 FTIR Spectrometer was used to record the FTIR spectra of KBr 1.6 mg/mL) were produced in DMSO. S. Aureus and E. coli with an initial
powder-pressed pellets. The size and the morphology of the synthesized bacterial density of 108 cfu/mL were used in a 200 μL total volume in
nanocomposites were observed using a transmission electron micro­ microliter wells. Bacterial growth was measured every hour for 24 h at
scope (Talos™ F200i, TEM). The reaction conditions were optimized 37 ◦ C by measuring the optical density (OD) with periodic shaking. The
using a UV–vis spectrophotometer (UV/Vis Spectrophotometer, T80; PG OD at 600 nm was determined using Semi-Automated ELISA system
Instruments; UK) with a scanning range of 400–800 nm. Absorbance Reader (TECAN, Switzerland), and MIC50 was then
measured.
2.7. Catalytic reduction of dyes
3. Results and discussion
During the reduction procedure, 1 mL of dye (1 × 10− 2 M) was
introduced to a beaker containing 100 mL of NaBH4 (0.1 M), then the 3.1. Nanocomposites characterization
nanocomposite was added. To monitor the reaction’s progress, a sample
of the reaction mixture was periodically taken and analyzed using UV/ The XRD profiles of pure ZnO, ZnO@CA, 5 and 10 wt% Ag-ZnO@CA
Vis spectroscopy instrument. The subsequent equation was employed to nanocomposites are presented in Fig. 1. Pure ZnO NPs showed re­
ascertain the catalytic conversion efficiency of the dye [4]; flections at 2θ of 31.7◦ , 34.3◦ , 36.2◦ , 47.5◦ , 56.6◦ , 62.8◦ , 66.4◦ , 67.9◦ ,
( ) 69.1◦ , 72.6◦ , and 76.9◦ , which are corresponding to the (100), (002),
A0 − At
Conversion efficiency of dye (%) = × 100 (1) (101), (102), (110), (103), (200), (112), (201), (004), and (202) crystal
A0 planes of ZnO with hexagonal wurtzite structure (JCPSD card no. 00-
036-1451), respectively [29]. Moreover, no extra reflections associ­
where A0 is the dye initial absorbance at λmax, while At is the absorbance
ated with other impurities were observed, suggesting a high purity level
at various time (t) intervals.
in the produced ZnO [10]. The ZnO@CA nanocomposite exhibits
diffraction peaks which are identical to that of ZnO NPs, but with lower
2.8. Antibacterial activity of Ag-ZnO@CA nanocomposites intensities. It was also observed that the feature peaks of the ZnO@CA
nanocomposite show slightly shifts toward lower angle direction
Using the agar diffusion method, the antibacterial activity of the Ag- compared to that of pure ZnO NPs indicating an expansion to a higher
ZnO@CA nanocomposites was assessed toward Staphylococcus aureus lattice parameter [30] (Table 1). This proves the successful loading of
(S. aureus, Gram (+)) and Escherichia Coli (E. coli, Gram (− )) [25]. In this ZnO NPs on the CA polymer surface. The characteristics XRD peaks of
investigation, the E. coli (G-ve MBRU No M-12) and S. aureus (G + ve CA cannot be seen in the XRD pattern of ZnO@CA nanocomposite due to
MBRU C59) bacteria were isolated from the cheese and milk according its amorphous structural nature [31]. The XRD profiles of 5–15 wt% Ag-
to the protocol found in the literature [26], in Molecular Biology ZnO@CA nanocomposites, in addition to the diffraction peaks of ZnO
Research Unit (MBRU), Assiut university, Assiut, Egypt. The nano­ NPs, revealed additional reflections at 2θ values of 37.8o, 44o, 64.2o, and
composite powders were mixed with a dimethyl sulfoxide (DMSO) so­ 77.1o. These peaks may be assigned to (111), (200), (220), and (311)
lution until they were dissolved, at a concentration of 200 mg/mL. The planes of metallic Ag NPs with face-centered cubic (FCC) structure
bacteria strains were pre-cultivated on brain heart infusion broth (BHI) (JCPDS No. 04–0783), respectively [32], which confirms the successful
(Oxford, England) at 37 ◦ C to obtain the inoculum. Petri plates were loading of Ag0 NPs on the ZnO@CA nanocomposite surface. As the Ag
filled with 15 mL of sterilized medium nutrient agar, which was then left loading percentages increase from 5 % to 15 %, the peak intensities of
to set. The inoculum bacterial suspension with a volume of 100 μL was the metallic Ag NPs in the nanocomposite gradually increase, while the
added, spread out over the agar, and given 5 min to dry. The wells in the feature peaks of ZnO NPs are gradually decrease.
gel was made, 100 μL of the nanocomposites was added, and then put The lattice parameters (a, b, c) for hexagonal ZnO and cubic Ag
them in an incubator at 37 ◦ C for 24 h [27]. The antibacterial activities

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

Table 1
The crystal structure and lattice parameters, average crystallite size (D), the active surface area (SA), micro-strain (ε), and the dislocation density (δ) of the prepared
nanocomposites.
3 3
Sample Phases Crystal structure a b c ρ D Dav SA ε × 10− δ × 10−
(Å) (Å) (Å) (g/cm3) (nm) (nm) (m2/g) (nm− 4)

ZnO ZnO Hexagonal 3.2585 3.2585 5.2200 5.61 23.7 23.7 45.10 3.62 1.78
ZnO@CA ZnO Hexagonal 3.2689 3.2689 5.2340 3.45 16.5 16.5 105.4 5.28 3.67
5 % Ag-ZnO@CA ZnO Hexagonal 3.2862 3.2862 5.2600 3.80 18.6 18.9 83.54 4.72 2.89
Ag Cubic 4.1240 4.1240 4.1240 19.2 4.71 2.71
10 % Ag-ZnO@CA ZnO Hexagonal 3.2966 3.2966 5.2800 4.15 23.1 21.2 68.19 3.78 1.87
Ag Cubic 4.1378 4.1378 4.1378 19.3 4.39 2.68
15 % Ag-ZnO@CA ZnO Hexagonal 3.2943 3.2943 5.2700 4.51 23.2 21.7 61.31 3.73 1.86
Ag Cubic 4.1344 4.1344 4.1344 20.3 4.04 2.43

structures were calculated by Eqs. (2) and (3), respectively [33].

( ) 2
1 4 h2 + hk + k2 l
2
= 2
+ 2 (2)
d(hkl) 3 a c

1 h2 + k2 + l2
2
= (3)
d(hkl) a2

where d(hkl) is the interplanar distance, while h, k, l are Miller indices.

The average crystallite size (D) of the nanocomposites was deter­
mined using the acclaimed Scherrer’s equation [10,34] (Eq. (4)).
0.9λ
D= (4)
βcosθ
In the above equation, λ represents the radiation wavelength used,
specific to Cu Kα (1.5406 Å). The term β stands for the full width at half-
maximum, while θ signifies the angle at the position of the maximum
peak (expressed in radians).
The effective surface area (SA) of the nanocomposites was deter­
mined utilizing the Sauter Eq. [34] (Eq. (5)):
6000
SA = (5) Fig. 2. FTIR spectra of ZnO NPs and the nanocomposites.
ρD

where, ρ is the density of the samples and D is the average crystallite nanocomposites [36]. While the active surface area follows this trend:
size. ZnO@CA > 5 % Ag-ZnO@CA > 10 % Ag-ZnO@CA > 15 % Ag-ZnO@CA
The microstrain (ε) was estimated using the Williamson–Hall > pure ZnO. The variations of the dislocation density and the micros­
approach [35] (Eq. (6)): trian for the ZnO phase follow this order: ZnO@CA > 5 % Ag-ZnO@CA
> 10 % Ag-ZnO@CA > 15 % Ag-ZnO@CA > pure ZnO. While the var­
βcosθ =
0.9λ
+ 4εsinθ (6) iations in the dislocation density and the microstrain values for the Ag
D phase are followed this trend: 5 % Ag-ZnO@CA > 10 % Ag-ZnO@CA >
By plotting βcosθ against 4sinθ, straight lines are produced. The 15 % Ag-ZnO@CA.
microstrain of the samples was then deduced from the slope of these Fig. 2 displays the FTIR spectra of ZnO NPs, ZnO@CA, and 1–15 wt%
lines. Additionally, the influence of dislocation density on crystallo­ Ag-ZnO@CA nanocomposites. The FTIR spectrum of pure ZnO displayed
graphic properties is noteworthy. The dislocation density (δ) was band at 3378 cm− 1 may be attributed to the O–H stretching vibration of
determined using Eq. (7). adsorbed water molecules [37]. In addition, the band at 1552 cm− 1 is
ascribed to the C––O symmetric stretching vibration, potentially related
to the zinc acetate precursor. While the band at 1429 cm− 1 may be
1
δ= (7)
D2 belonged to the methyl group (CH3) in-plane bending vibrations [38].
Table 1 summarized the results of the crystal structure, lattice pa­ The detected bands at 841 cm− 1, 754 cm− 1, and 694 cm− 1 are related to
rameters, average crystallite size, active surface area, micro-strain, and the metal‑oxygen bond (Zn–O) stretching vibrational mode [10,39].
dislocation density of the nanocomposites. It was found that the lattice The FTIR spectrum of ZnO@CA observed besides the characteristic’s
parameters for ZnO phase in the ZnO@CA and Ag-ZnO@CA nano­ bands of ZnO, new bands at 1738 cm− 1, 1224 cm− 1, and 1030 cm− 1, and
composites are slightly higher compared to pure ZnO. In addition, the 899 cm− 1. The observed bands at 1738 cm− 1, 1224 cm− 1, 1030 cm− 1,
lattice parameters for Ag phase in the 5 % Ag-ZnO@CA nanocomposite 899 cm− 1 are ascribed to C– –O stretching, C–O carboxylate group
are slightly lower compared to 10 % and 15 % Ag-ZnO@CA nano­ asymmetric stretching, C-O-C ether group in the pyranose ring asym­
composite. The average crystallite size of the samples takes the metric stretching, and C–H out of plane deformation, respectively [40].
following order: pure ZnO > 15 % Ag-ZnO@CA > 15 % Ag-ZnO@CA > This result confirmed the successfully loaded ZnO on the surface of CA
5 % Ag-ZnO@CA > ZnO@CA. The average crystallite size of ZnO NPs is polymer. The FTIR spectra of 1–15 wt% Ag-ZnO@CA nanocomposites
23.7 nm which is higher than that of all the nanocomposites. The showed FTIR bands are typically of that observed in the spectrum of
observed decrease in the crystal sizes of the nanocomposites was due to ZnO@CA nanocomposite. In addition, the intensities of the character­
that the interaction of functional groups (CA) on ZnO has reduced the istic bands of ZnO and CA gradually decrease by increasing the per­
crystallinity and increased the broadening patterns of the centages of Ag NPs loading. Our findings align with those of Bakhsh

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

Fig. 3. XPS spectra of the 10 % Ag-ZnO@CA nanocomposite: (a) full survey spectrum, (b) Zn 2p spectrum, (c) Ag 3d spectrum, (d) O 1 s spectrum, and (e) C 1
s spectrum.

et al. [7], they observed no significant differences in the spectra of CA/ [41,42]. The high-resolution XPS spectrum of the silver (Ag) 3d doublet
Fe2O3 and metal nanoparticle-loaded CA/Fe2O3. This suggests that the (Fig. 3c) showed two peaks at binding energies of 367.3 eV (Ag 3d5/2)
loading of metal nanoparticles did not alter the chemical composition of and 373.3 eV (Ag 3d3/2), which were spaced apart by 6 eV [43]. These
the CA/Fe2O3 composite. two peaks demonstrated the presence of Ag0 on the surface of the
XPS technique was utilized to investigate the electronic structure and ZnO@CA nanocomposite [44]. Furthermore, the spectrum showed also
chemical composition of a 10 % Ag/ZnO@CA nanocomposite as seen in another two peaks at 367.7 eV (Ag 3d5/2) and 374.4 eV (Ag 3d3/2),
Fig. 3(a-c). Fig. 3a displays survey of the whole spectrum, indicating the indicating the presence of Ag+ ions [45]. This suggests that both Ag2O
presence of zinc (Zn), silver (Ag), oxygen (O), and carbon (C) in the and Ag0 coexist in the nanocomposite, probably due to the oxidation of
nanocomposite. The high-resolution Zn 2p area spectra (Fig. 3b) display Ag0 by ambient oxygen [46]. Fig. 3d shows the O 1 s spectrum, which
two peaks at binding energies of 1044.3 eV and 1021.3 eV, corre­ has two peaks, peak at 529.9 eV (from the oxygen atoms in ZnO), and
sponding to the Zn 2p1/2 and Zn 2p3/2 states, respectively. The spin- peak at 531.9 eV (from the oxygen atoms in the hydroxyl groups (C-OH)
orbital splitting of ~23.0 eV indicates that Zn with +2 oxidation state in CA) [47]. One can see three apparent peaks in the C 1 s curve (Fig. 3e),

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

Fig. 4. TEM images of (a, b) ZnO NPs, (c-d) ZnO@CA, and (e) 10 % Ag-ZnO@CA nanocomposites.

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

Scheme 1. The chemical structures of (a) RhB, (b) Rh6G, (c) MB, and (d) SY.

which represent three different chemical environments. The cellulose- reasons that rhodamine is chosen as a sensor are its extended absorption
derived polymer contains three types of carbon atoms, each with a and emission wavelengths, in addition to its high fluorescence quantum
different binding energy: aliphatic carbons (284.7 eV), carbons from CA: yield and high extinction coefficient. Additionally, RhB serves as a
C–O (286.3 eV), and carbon in the cellulose ring linked to two oxygen pathological marker in laboratory tests. Though widely used in textile
atoms (287.9 eV) [48]. manufacturing, RhB is known to be a carcinogenic substance potentially
Fig. 4 displays TEM images of ZnO NPs, ZnO@CA, and 10 % Ag- leading to tissue sarcoma and can affect neurological and reproductive
ZnO@CA nanocomposites. ZnO NPs are showed in Fig. 4(a, b), as functions. Ingesting RhB can be harmful, and it can irritate and burn the
spherical particles with an average diameter of ~62.6 nm. Meanwhile, eyes, skin, and respiratory system. Its harmful effects, including carci­
the TEM image of the ZnO@CA nanocomposite (Fig. 4c, d) shows some nogenicity, chronic toxicity, and neurotoxicity, have been confirmed
agglomeration and spherical particles with an average diameter of through experiments [52]. Some nations have banned RhB in food items
~40.9 nm. This result is aligning with the XRD data, which indicates due to its risks, yet its unauthorized inclusion in food and other sectors
that the ZnO@CA nanocomposite has a smaller crystallite size than pure remains a challenge due to its durability, vibrant color, and affordable
ZnO NPs. This result is in agreement with that obtained by Gurunathan production [53].
et al. [36], they found that the particles size of ZnO NP are larger than The catalytic reduction of RhB in the context of NaBH4 was chosen as
that of ZnO/CA nanocomposite. This behavior may be attributed to that the first model reaction to test the efficacy of Ag-ZnO@CA nano­
the CA covered on ZnO further prevents the agglomeration of ZnO and it composites as catalysts. RhB dye is a type of water-soluble basic red
decreases the particle size. The TEM image of the 10 % Ag-ZnO@CA xanthene that is commonly employed as a coloring agent in the indus­
nanocomposite (Fig. 4e) reveals a mixture of larger particles (grey in trial sector [54]. The presence of RhB dye in industrial effluents is
color) with an average diameter of ~60.3 nm, representing the ZnO@CA harmful to the environment and humans. At 555 nm, an aqueous RhB
nanocomposite [49], and smaller spherical particles (darker in color) dye produced in the visible area a single high absorption peak. Even
corresponding to Ag NPs with ~17.6 nm particle size. This result further following the introduction of NaBH4, the peak intensity at 555 nm
confirms an efficient loading of Ag NPs onto the surface of the ZnO@CA remained constant over 1 h (Fig. 5a). Nevertheless, upon the introduc­
nanocomposite. tion of the catalyst in the reaction mixture, the intensity of the peak
decreased. The UV–vis spectrophotometer was employed to follow up
3.2. Catalytic reduction studies the decrease in peak intensity over time. According to the literature, in
the existence of an active catalyst NaBH4 de-ethylates the RhB molecule
3.2.1. Assessment of various Ag-ZnO@CA for the reduction of RhB at the -N(C2H5)2 site by creating aromatic amines. The UV–Vis absorp­
RhB (Scheme 1), a commonly used synthetic dye, belongs to the tion behavior of RhB dye over ZnO NPs, ZnO@CA, and 5–15 % Ag-
methylxanthene family, and can dissolve in water up to 50 g L− 1 [50]. It ZnO@CA nanocomposites catalysts in the presence of NaBH4 is pre­
has multiple applications, including as a tracer, a cell fluorescence re­ sented in Fig. 5(b-g). In the context of ZnO NPs as a catalyst, only ~6.3 %
agent, and a coloring agent for materials like glass, wool, silk, leather, activity for RhB reduction was observed after 1 h. This result confirmed
herbicides, jute, sprays and cotton. Industries such as paper, textiles, that ZnO NPs has a little catalytic performance for the reduction of the
pulp, paint, rubber and tannery often release effluents tainted with the RhB, aligning well with the existing literature [10,55]. An improvement
dye directly into water sources without adequate treatment [51]. The in the reduction of RhB about 29.2 % was observed using ZnO@CA

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

Fig. 5. UV–Vis absorption spectra for the reduction of RhB (a) without the nanocomposite, (b) utilizing ZnO NPs, (c) utilizing ZnO@CA, (d) using 5 % Ag-ZnO@CA
as a catalyst, (e) using 7 % Ag-ZnO@CA as a catalyst, (f) using 10 % Ag-ZnO@CA as a catalyst, (g) using 15 % Ag-ZnO@CA as a catalyst (h) plots of (At/A0) vs.
reaction time in the presence of different catalysts.

8
H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

nanocomposite as a catalyst after 1 h. In case of using 5 % Ag-ZnO@CA

nanocomposite as a catalyst, a fast decline in the peak intensity at ʎmax
= 555 nm was noted, and the peak was completely disappeared after 40
min. Further increase the percentages of Ag NPs in the nanocomposites;
the catalytic reduction time of RhB was decreased, and the 10 % Ag-
ZnO@CA nanocomposite exhibited the shortest reaction time (~ 6
min). This is because there is a rise in the number of effective sites that
transmit electrons from NaBH4 as a reducing agent to the RhB dye as
acceptor. Kebir-Medjhouda et al. [56] stated that using catalyst with
higher Ag NPs concentration results in an augmentation of the rate
constant and decreases the reaction time during the catalytic reduction
process of Congo red dye. Although, the 15 % Ag-ZnO@CA nano­
composite has the highest Ag NPs percentage in comparison to the other
composites, the complete reduction of RhB dye occurred at ~18 min.
This may attribute to the agglomeration of Ag NPs on the surface of
ZnO@CA nanocomposite, which leads to decrease the efficiency of the
catalyst.
Bakhsh et al. [7] found that the time required for RhB decomposition
was 8.5 min over Ag@CA/Fe2O3 nanocomposite. Khan et al. [11,17]
observed that the CuAg/ZCA-5 and the CA-Ce/Zr@Cu0 nanocomposites
reduced 88 % and 100 % of RhB in 14 min and 12 min, respectively. Fig. 6. Recyclability of 10 % Ag-ZnO@CA nanocomposite toward catalytic
Albukhari et al. [19] demonstrated the outstanding performance of RhB reduction.
Ag@CAF nanocomposite, achieving 99 % reduction of RhB in just 12
min. The CA-ZA10@Ni NPs nanocomposite that was synthesized by
Table 2
khan et al. [20] completed the reduction of RhB in 9 min. Compared to Comparison data with the literature for RhB reduction.
the above mentioned nanocomposites, the 10 % Ag-ZnO@CA demon­
Catalyst Time (min) kapp (min− 1) Conversion (%) Reference
strated complete reduction of RhB in a short period (6 min). This result
proves that this nanocomposite has excellent catalytic performance PdNPs/PCNF 30 0.181 97.1 [60]
compared to similar nanocomposites that published in the literature. Ag@CAF 12 2.5 × 10− 5 99.0 [19]
AuNPs /CNC 3.6 4.5 × 10− 4 100 [61]
NaBH4 alone could not reduce the RhB molecule, even in excess. CA-ZA@Ni 9 7.5 × 10− 3 100 [20]
Consequently, the reduction of RhB using NaBH4 followed pseudo-first- BR-AgNPs 12 1.01 × 10− 4 100 [62]
order kinetics [19]. The rate constant (kapp) was determined from the Ag-NPs 32 – 96.0 [63]
time of reduction vs. ln(At/Ao) using Eq. (8) [4,6]. Ag decorated ZnO 60 0.0432 94.0 [64]
AgNPs@Lac/Alg 6 3.6 × 10− 4 100 [65]
At DENAgNPs-NFC 30 – – [66]
ln = − Kapp t (8) CuAg/ZCA 14 – 88.0 [11]
A0
Pd@PPM2 1 2.95 95.3 [67]
The absorption peak intensities of RhB at times t and 0 are denoted Ag@CA/Fe2O3 8.5 – 100 [7]
by At and A0, respectively. The linear relationship between (ln(At/A0)) CA-Ce/Zr@Cu0 12 0.0038 100 [17]
10 % Ag-ZnO@CA 6 0.3498 100 This work
and reaction time (t) for the reduction of RhB is presented in Fig. 5h. The
calculated kapp for RhB were 0.0011 min− 1, 0.0039 min− 1, 0.0678
min− 1, 0.2475 min− 1, 0.3498 min− 1, and 0.1121 min− 1 for pure ZnO for complete reduction of RhB remained consistent for the 5th cycle. The
NPs, ZnO@CA, 5 % Ag-ZnO@CA, 7 % Ag-ZnO@CA, 10 % Ag-ZnO@CA, obtained findings confirm the stability and robustness of our nano­
and 15 % Ag-ZnO@CA nanocomposite, respectively. The rate constant composite. In order to further confirm the stability of the nanocomposite
of nanocomposites is largely affected by factors like the size and amount after the reduction process, the XRD analysis of the 10 % Ag-ZnO@CA
of the nanoparticles, as well as their aggregation state. These factors are nanocomposite before and after catalysis was performed and the result
directly influenced by synthesis parameters, like reaction time, reducing is shown in Fig. S1. It revealed that the XRD patterns of the nano­
agent concentration, medium pH, and the molar ratio used as precursors composite before and after the catalytic reduction are identical, which
for the nanoparticles [57]. In our study, the difference between all the proves that the material can be regenerated.
tested nanocomposites is the Ag NPs percentage, that exhibited a key The reduction and degradation of dyes on the surface of a 10 % Ag-
function in determining the agglomeration of Ag NPs on the nano­ ZnO@CA nanocomposite is thought to occur through the Langmuir-
composites surface. A lesser quantity of Ag NPs may be distributed Hinshelwood mechanism, that involves the capturing and adsorption
uniformly over the nanocomposites surface, while increasing this of NaBH4 and RhB dye on the catalyst surface [20]. The proposed
quantity leads to particle agglomeration, resulting in a reduction in the mechanism for the RhB degradation using NaBH4 and 10 % Ag-ZnO@CA
rate constant. Hence, selecting the right concentration of Ag for making nanocomposite can be summarized as follows: (i) NaBH4 decomposes in
Ag-based composites is essential [58]. Given that 10 % Ag-ZnO@CA water to produce BO2− and a significant quantity of activated hydrogen
nanocomposite demonstrated effective catalytic performance in the (H• radical), (ii) the H• radical then reacts with Ag NPs to form Ag–H
reduction of the RhB, it was selected as the catalyst for subsequent tests. intermediate, (iii) the dye molecules are adsorbed on the surface of the
The recycling and reuse of catalysts is a major challenge in their nanocomposite, primarily on the ZnO@CA, (iv) the Ag–H intermediate
practical application. To address this challenge, we investigated the transfer the H• radical to the dye molecules, and (v) the H• radical then
possibility of reusing the 10 % Ag-ZnO@CA nanocomposite in the attacks the N––C bonds in the dye molecules, resulting in the formation
reduction of the RhB. Following the initial cycle, the nanocomposite was of N–C bonds as (leucorhodamine B (LRhB) [59]. The superior catalytic
successfully isolated through filtration from the reaction mixture, activity of the 10 % Ag-ZnO@CA nanocomposite could be attributed to
following that rinsing with water and ethanol, and subsequently dried in the synergistic effect of the Ag NPs, ZnO NPs, and CA. The present study
air. Following five cycles of reuse, the nanocomposite demonstrated a compared to the previously reported catalysts in the literature, suggests
nearly identical level of catalytic activity in the reduction of RhB that 10 % Ag-ZnO@CA nanocomposite has a higher catalytic activity for
(Fig. 6). The experimental results indicate that the duration necessary

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

Fig. 7. UV–vis spectra of reduction of (a) Rh6G, (b) MB, (c) SY dyes and (d) plots of ln (At/A0) vs. reaction time in the presence of 10 % Ag-ZnO@CA nanocomposite
as a catalyst.

RhB reduction. Hence, the current study is deemed more favorable disappeared after 2, 5, and 6 min, respectively. In our experiment, dyes
owing to its enhanced catalytic efficacy activity and high reusability, as were used at lower concentrations (0.05 mM) because their large mo­
shown in Table 2. lecular structures and strong absorption of UV–visible light make them
less sensitive to detection by these spectrometers at high concentrations.
3.2.2. Efficiency of 10%Ag-ZnO@CA nanocomposite for various This can lead to increased noise in the measurements [7]. Fig. 7d il­
compounds lustrates the plot of lnAt/Ao versus time for Rh6G, MB, and SY. The rate
The degradation of different dyes Rhodamine 6G (Rh6G), Sunset of the reaction (kapp) was determined from the linear fitting of lnAt/Ao
Yellow (SY), and Methylene Blue (MB) (Scheme 1)) was investigated and versus time, as described by Eq. (6). The kapp values for Rh6G, MB, and
compared to RhB. The UV–visible spectra of the dyes as a function of SY reduction were found to be 1.51 min− 1, 0.2292 min− 1, and 0.733
time with and without the 10%Ag-ZnO@CA nanocomposite and NaBH4 min− 1, respectively. The reaction rate difference of Rh6G, MB, and SY
are shown in Figs. 7(a-c). The absorbance peaks of the Rh6G, MB, and SY dyes may be ascribed to their different chemical structures, charges,
dyes, which are located at 527 nm, 668 nm, and 490 nm, respectively, donor atoms, hydrophobicity, reduction potentials, and other factors.
were observed to gradually decrease over time, and completely These factors affect the activation energy of the catalytic reduction re­
action, which is the minimum amount of energy needed to start the
reaction [59].
Table 3
The antibacterial activity of pure ZnO, pure CA, and Ag-ZnO@CA nano­
composites against S. aureus and E. coli bacteria. 3.3. Antimicrobial activity of Ag-ZnO@CA nanocomposites
Samples Antibacterial activity inhibition zone diameter (mm)
S. aureus is a Gram-positive bacterium with a high peptidoglycan
S. aureus E. coli
concentration in its cell wall. It may live under a variety of environ­
ZnO 18 25
mental circumstances, such as low pH or hunger. It is regarded as a
ZnO@CA 20 20
5 % Ag-ZnO@CA 14 18 significant human pathogen, which capable of causing serious skin in­
7 % Ag-ZnO@CA 12 17 fections or interior infections when it penetrates the defense barriers
10 % Ag-ZnO@CA 21 20 [68]. E. coli is a Gram-negative bacterium with a cell wall that is
15 % Ag-ZnO@CA 20 18 completely different from Gram-positive bacteria in that it is bordered
CA 0.0 0.0
on the exterior by a lipid membrane. It is a type of bacteria that can

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

Table 4 ZnO@CA nanocomposites against S. aureus and E. coli are listed in

The MIC values of pure ZnO, pure CA, and Ag-ZnO@CA nanocomposites against Table 4. The ZnO@CA nanocomposite has the highest MIC value, while
S. aureus and E. coli bacteria. pure ZnO NPs showed the lowest value. The 15 % Ag-ZnO@CA nano­
Samples Inhibition zone diameter (mg/ml) composite showed the highest MIC value compared to the other Ag-
S. aureus E. coli
ZnO@CA nanocomposites. The MIC values of the tested samples have
ranged from 3.15 to 25 and 1.6–12.5 mg/mL for S. aureus and E. coli,
ZnO 3.2 1.6
respectively, which lower than that found by Meikle et al. [72]. Fig. 8
ZnO@CA 25 12.5
5 % Ag-ZnO@CA 3.15 1.6 shows how the different treatments affected the growth of S. aureus and
7 % Ag-ZnO@CA 6.25 1.6 E. coli, including no treatment (control), treatment with pure ZnO,
10 % Ag-ZnO@CA 6.25 3.15 treatment with ZnO@CA, and treatment with Ag-ZnO@CA nano­
15 % Ag-ZnO@CA 12.5 6.25 composites. After 6 h of inoculation, the bacterial growth was reduced in
CA 0.0 0.0
both bacteria and all treatments, compared to the control. The growth
inhibition of S. aureus was similar for ZnO and the nanocomposites,
indicate fecal contamination, as it is normally found in the intestines of whether or not they contained Ag NPs [28]. While the growth inhibition
people and animals. Most E. coli are harmless and play an important role of E. coli was higher in ZnO NPs compared to the nanocomposites with or
in a healthy human gut. However, some E. coli strains are pathogenic, without Ag NPs at all sampling times, although the nanocomposites still
meaning they can cause diarrhea or other illnesses outside of the gut. have a bacterial growth lower compared to the control.
These pathogenic E. coli strains can be transmitted through contami­
nated water, food, animals, or people. They can also develop resistance 4. Conclusion
to antibiotics, making them even more dangerous. Therefore, control­
ling the growth of these bacteria is essential to protect human health Novel Ag-ZnO@CA-derived cigarette butts nanocomposites were
[28]. successfully synthesized using two-step method. First, the ZnO@CA
The antibacterial activity of pure ZnO, pure CA, ZnO@CA, and (5–15 nanocomposite was prepared using the solution blending method, and
%) Ag-ZnO@CA nanocomposites were determined in vitro against then the Ag NPs was anchored on the nanocomposite surface with
S. aureus and E. coli bacteria, and the calculated ZIs were cited in Table 3. different percentages by using simple adsorption of metal ions on the
The ZIs of ZnO NPs against S. aureus and E. coli were 18 and 25 mm, nanocomposite followed by the reduction with NaBH4. The FTIR result
respectively. This result is consistent with that obtained in the literature confirmed the successfully loaded ZnO NPs on the surface of CA poly­
[69,70]. While, pure CA has not antibacterial action against the tested mer. The XRD and XPS results confirmed the successful formation of
bacteria. Gonçalves et al. [71] found that the CA films incorporated with zero-valent Ag NPs on the surface of the ZnO@CA nanocomposite. The
sweet fennel essential oil have not antimicrobial efficiency. On the other synthesized Ag-ZnO@CA nanocomposites exhibited excellent reduction
hands, ZnO@CA nanocomposite showed ZIs of 20 mm against both properties of organic dyes including RhB, Rh6G, MB, and SY. The 10 %
bacterial models. Unfortunately, the Ag-ZnO@CA nanocomposites have Ag-ZnO@CA nanocomposite had the best catalytic performance,
lower ZIs values toward the tested bacteria than that of pure ZnO NPs reducing RhB in 6 min with good recyclability. In the presence of 10 %
and ZnO@CA nanocomposites. However, 10 % Ag-ZnO@CA nano­ Ag-ZnO@CA nanocomposite as a catalyst, the greatest rate constant kapp
composite shows the largest ZIs values in comparison to the other Ag- was obtained for Rh6G reduction, which is 1.5 min− 1 compared to SY
ZnO@CA nanocomposites. Cuadra et al. [28] found that increasing the (0.733 min− 1), RhB (0.3498 min− 1) and MB (0.2292 min− 1). The anti­
antibacterial activity of the ZnO/Ag nanocomposites against the microbial screening against two different bacteria validated the nano­
S. aureus and E.Coli bacteria are not correlated with the rise in the Ag composite particles’ antibacterial activity. The 10–15 % Ag-ZnO@CA
NPs concentrations. As the proportion of Ag NPs increases, they tend to nanocomposites exhibit almost the same antibacterial activity of ZnO
clump together, reducing their overall surface area and the amount of NPs against S. aureus and E. coli bacteria. The Ag-ZnO@CA nano­
surface area that can be exposed to bacteria. [28]. Therefore, the composite is a less toxic antimicrobial agent than pristine Ag NPs,
nanocomposites with lower Ag NPs concentration may have greater making it suitable for use in wound dressings, health products, hygienic
efficacy against bacteria. materials, coatings for medical equipment, antimicrobial filters, and
The MIC values of pure ZnO NPs, ZnO@CA, and (5–15 %) Ag- textile products. It can also be utilized as a catalyst with for the

Fig. 8. The growth inhibition S. aureus and E. coli in the absence of treatment (control), with ZnO, ZnO@CA and (5–15 %) Ag-ZnO@CA nanocomposites.

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H. Mousa et al. International Journal of Biological Macromolecules 258 (2024) 128890

reduction of organic pollutants such as dyes. This study demonstrates [14] A. Gupta, L.K. Brar, O.P. Pandey, Influence of laboratory and waste grade cellulose
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A. Begum, S.B. Khan, Reduction of nitrophenol isomers and degradation of azo
The authors declare that they have no known competing financial dyes through zero-valent Ni nanoparticles anchored on cellulose acetate coated Ce/
interests or personal relationships that could have appeared to influence Zr composite, J. Water Process Eng. 44 (2021), 102383, https://doi.org/10.1016/j.
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