Analytical Chemistry Letters

ISSN: (Print) (Online) Journal homepage: www.tandfonline.com/journals/tacl20

Green synthesis of magnetic chitosan composite

hydrogel (Fe3O4@CS photocatalyst) for the solar
light driven catalytic degradation of organic
contaminants

Asif Ullah Khan, Abdus Salam, Humaira Khan, Ayesha Qureshi & Aamer
Saeed

To cite this article: Asif Ullah Khan, Abdus Salam, Humaira Khan, Ayesha Qureshi &
Aamer Saeed (2024) Green synthesis of magnetic chitosan composite hydrogel (Fe3O4@CS
photocatalyst) for the solar light driven catalytic degradation of organic contaminants,
Analytical Chemistry Letters, 14:1, 112-128, DOI: 10.1080/22297928.2024.2304001

To link to this article: https://doi.org/10.1080/22297928.2024.2304001

Published online: 20 Feb 2024.

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 Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 112

HKB Analytical Chemistry Letters

DOI: 10.1080/22297928.2024.2304001 Research Article

Green synthesis of magnetic chitosan composite hydrogel

(Fe3O4@CS photocatalyst) for the solar light driven catalytic
degradation of organic contaminants

Asif Ullah Khan1, Abdus Salam2, Humaira Khan2, Ayesha Qureshi1 and
Aamer Saeed1*

1
Department of Chemistry,
Quaid-I-Azam University,
Islamabad 45320, Pakistan
2
Institute of Chemical Sciences,
University of Peshawar, Khyber
Pakhtunkhwa 25120, Pakistan
*Corresponding Author
Aamer Saeed
asaeed@qau.edu.pk
Received 04 November 2023
Revised 27 December 2023
Accepted 31 December 2023
Abstract
Ecofriendly magnetic chitosan composite hydrogel (Fe3O4@CS photo-
catalyst) was prepared by using an aqueous extract of Boerhevia procombens
leaves for the solar light mediated catalytic degradation of lethal organic Congo
red dye. The prepared composite hydrogel was structurally studied using
Fourier transform infrared spectroscopy (FT-IR) which reveals the formation
of the Fe3O4@CS photocatalyst. The X-ray diffraction (XRD) investigation
of the composite hydrogel signified high crystallinity of photocatalyst and
crystallite structure of 53 nm for magnetite nanoparticles (Fe3O4 NPs).
The surface investigation suggests multilayered porous photocatalyst
owing to the presence of cavities offering more photoactive sites for the
photodecomposition of dye molecules. The energy dispersive X-ray (EDX)
scanning supports the fabrication of Fe3O4@CS photocatalyst due to the
perseverance of carbon, nitrogen, oxygen, and iron. The thermogravimetric
analysis (TGA) together with vibrating sample magnetometry (VSM) certifies
the preparation of thermally stable and magnetic composite hydrogel. The
fabricated Fe3O4@CS photocatalyst possess low bandgap energy of 2.36
eV, supporting the excellent disintegration of dye molecules in the sunlight
irradiations. The photocatalyst exhibited a maximum degradation efficacy
of 99.1% for Congo red dye in the solar light irradiations with refined states
of 70 min radiation time, dye concentration of 20 mg/L, pH 6, and 200 mg
photocatalyst amount obeying the second-order kinetic model (R2 = 0.9959).
The Fe3O4@CS photocatalyst displayed a little decrease in dissociation
efficiency of dye molecules after five repeated cycles owing to the coverage
or rupturing of photoactive sites. Conclusively, the results support Fe3O4@
CS to be an economical and biocompatible magnetic catalyst for the
catalytic decontamination of Congo red dye molecules and other organic
contaminants in domestic and industrial wastewater effluents.

Keywords
Green Synthesis, Chitosan, magnetic composite hydrogel, photocatalytic
degradation, organic pollutants, Boerhevia procumbens.

Introduction polyaromatic hydrocarbons (PAHs), fungicides,

Water is the most treasured and significant natural
asset for the survival of living beings that have
been regularly polluted by toxic organic wastes.
The extreme usage of lethal chemicals in textile,
paper, plastic, food, leather, cosmetic and dyeing
industries contribute to water pollution1,2. The
discharge of wastewater from these industries
contains very harmful substances such as dyes,
Anal. Chem. Lett. 2024, 14, 112-128
pesticides and phenols. Among these organic
pollutants, dyes are considered as extremely
dangerous and carcinogenic owing to their
long life span, high stability, accumulation
in the ecological system and high solubility
in water3,4. The preparation and handling of
dyes unleash large amount of various dyes
(12-15%) into water bodies which decrease
© 2024 Har Krishan Bhalla & Sons
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128
sunlight infiltration into the underneath water
thereby damaging the aquatic life and imparting
undesirable water color5. The presence of these
noxious dyes especially Congo red dye has
unpropitious reactions on human health owing to
their carcinogenic and mutagenic nature, leading
to skin problems, allergies, kidney and cardiac
issues6. Therefore the efficient elimination of
these dyes from wastewater has got significant
attention from the researchers in recent time.
Several techniques and methods are employed
for the detoxification of wastewater to high-
quality water. These techniques include sorption7,
precipitation8, flocculation9, filtration10,
ozonation , coagulation and advance oxidation
11 12
processes13. However, some of these methods
have some limitations for the decontamination
of water because industrial effluents largely vary
in composition containing chemically complex
stable dyes. Among these methods, advance
oxidation processes have greatly allured the
interest of researchers owing to their proficient
capability to disintegrate stable organic
contaminants14. Photocatalytic degradation of
dyes in solar light irradiations is considered to be
the most efficient, ecofriendly, sustainable and
preferred method as it involves the deterioration
of the stable and complex organic pollutants into
less injurious or non-injurious compounds in the
presence of an oxidant (atmospheric oxygen) and
sunlight irradiations as an illumination source15.
Various metallic nanomaterials including
ZnO, CuO, and Fe3O4 nanoparticles have been
fabricated for its significant use in water treatment,
sensing applications, catalysis, cancer treatment
and drug delivery16-19. The diverse applications
of nanomaterials is attributed to their facile
synthesis, low cost, high physiochemical stability
and reusability in addition to their nanosized
dimensions in the range of 10-100 nm which
present large surface to volume ratio compared to
their corresponding bulk20. The current high rate
of water quality deterioration make the metallic
nanomaterials highly demanding as they could
decontaminate the water significantly. Therefore,
different attempts have been made to synthesize
metallic nanomaterials including iron and nickel
borne catalysts for the photodegradation of
113
noxious dyes using solar light irradiations but
they exhibit lesser catalytic effectiveness (90%)
in terms of photodecoloration of dyes along with
lower regeneration efficiency of the catalyst21,22.
Recently, the preparation of chitosan based
composite and composite hydrogel has shown
excellent efficacy in the photodegradation
of dyes. These chitosan composites utilize
sunlight irradiations with a bandgap energy of
less than 3 eV. Among these, chitosan based
composite hydrogel photocatalysts with water
swellable properties have high efficiencies in
the photocatalytic reactions because they add all
the physical, chemical and structural properties
of organic and inorganic moieties23. Various
artificial and natural polymers are utilized in the
fabrication of hydrogels but the use of natural
polymers (chitosan, starch, or cellulose) is more
safer and environmentally friendly route owing
to their low toxicity, low cost, biocompatibility,
and biodegradability24. Many chitosan based
composite hydrogels including TiO2 and ZnO
have been fabricated for demineralization
of noxious organic dyes, however no study
has previously been published on the green
preparation of magnetic chitosan composite
hydrogel and its application in the deterioration
of Congo red dye molecules in the presence of
solar light25,26. The green preparation of highly
crystalline and porous Fe3O4@CS photocatalyst
retains its novelty for being fabricated for the
first time.
In this work, well crystalline, economical, highly
porous and biodegradable magnetic chitosan
composite hydrogel photocatalyst (Fe3O4@CS)
has been fabricated via the aqueous extract of
Boerhevia procumbens leaves for the catalytic
decoloration of Congo red dye in the existence
of sunlight27. The fabricated Fe3O4@CS and its
precursors were characterized in the context of
chemical, structural, morphological, elemental,
magnetic, optical and thermal properties using
FT-IR, XRD, SEM, EDX, VSM, UV-visible
and TGA, respectively. Various influential
parameters including radiation time, Congo
red dye primary concentration, photocatalyst
dose and solution pH were regulated to obtain
standard photodeterioration reactions condition.
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128
Experimental work
Chemicals and materials
The analytical grade reagents ferric chloride and
ferrous chloride (purity ≥ 99.5%) were procured
from British Drug Houses (BDH). Chitosan
white powder (78% deacetylated) of analytical
grade was acquired from Oligo Biotech.
Company (China). The acetic acid, isopropanol,
ethanol, methylene-bis-acrylamide, ammonium
persulfate and Congo red dye (each of purity ≥
99) of analytical grade were taken from Sigma
Aldrich Company (USA). Deionized water was
utilized throughout the course of the research
work.
Aqueous extract of Boerhevia procumbens
Fresh leaves of Boerhevia procumbens were
collected from University of Peshawar and
identified with the help of the flora of Pakistan.
The leaves were thoroughly washed with water
and dehydrated in the dark for 30 days. The
dehumidified leaves were crushed into powder
material and sieved employing 1mm sieves.
The aqueous extract of the pulverized leaves
was obtained by heating 0.5 kg of powder plant
material in 3 L distilled water at 70oC for 4 hr
until the solution turned dark greenish in color.
The aqueous extract was further concentrated
in water bath at 65oC for 8 h. The concentrated
extract solution was cooled at room temperature,
labeled as “SKAE” and stored for further
chemical investigation.
Green preparation of magnetite nanoparticles
(Fe3O4 NPs)
Green chemistry approach was employed for
the fabrication of magnetite nanoparticles by
utilizing aqueous extract of leaves of Boerhevia
procumbens28. Each FeCl3 of 1.5 g and 0.75 g of
FeCl2 were dissolved in distilled water (50 mL)
and magnetically stirred for 30 min to attain
homogenous solutions. The above two solutions
were blended and put down in water bath at 80oC
for complete 1 hour. The aqueous extract was
gradually introduced into the blended mixture
while violently stirring for 30 min at 80oC, till the
dark brown solution turns into black magnetite
nanoparticles precipitates. The obtained Fe3O4
114
nanoparticles were isolated using an outward
magnet and rinsed out with distilled water to
nullify its basicity and finally, dehydrated in
vacuum oven at 80oC for 8 hr. The dark black
magnetite nanoparticles were labeled as “Fe3O4
NPs” and stored for characterization studies in
addition to its use in the preparation of Fe3O4@
CS photocatalyst.
Fabrication of magnetite integrated chitosan
composite hydrogel (Fe3O4@CS photocatalyst)
For the preparation of the magnetic chitosan
composite hydrogel (Fe3O4@CS photocatalyst),
the freshly synthesized 1 g of Fe3O4 NPs were
efficiently dispersed in aqueous solution (50 mL)
for 45 min in a sonicator. Then, 0.8 g of chitosan
powder along with 20mL ammonium persulfate
(8% w/v) as an initiator and 20 mL methylene-
bis-acrylamide (4% w/v) as a crosslinker were
introduced to the preceded well dispersed
magnetite solution and the blended solution
was persistently agitated at 60oC for 5 h. The
obtained dark brown colored magnetic chitosan
composite hydrogel was magnetically isolated
and washed with acetone followed by ethanol
and deionized water (three times) for purification
purposes. The as-fabricated magnetic chitosan
composite hydrogel was dried out for 8 h at 60oC
in an oven, labeled as “Fe3O4@CS” and stored
for characterizations as well as its evaluation in
the catalytic deterioration of Congo red dye in
the solar light irradiations.
Characterizations
The fabricated well crystalline Fe3O4@CS photo-
catalyst and its precursors were investigated by
using FTIR, EDX, XRD, SEM, TGA, VSM, UV­‒
Visible and batch photodisintegration reactions to
assess their chemical and elemental composition
along with structural, morphological, thermal,
magnetic, optical, and photocatalytic properties.
The prevalence of major functional moieties and
chemical composition of materials were explored
in 4000-450 cm-1 employing attenuated total
reflectance FT‒IR spectrometer (UATR‒Two
PerkinElmer; USA). The surface morphological
studies and investigation of elemental
composition along with specific ratios of elements
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128
in synthesized Fe3O4@CS photocatalyst and
its precursors were carried out using scanning
electron microscope (SEM JSM‒5910‒JEOL;
Japan) equipped with elemental dispersive
X-ray instrument (EDXINCA-200; UK). The
crystallinity and crystal phases of Fe3O4 NPs
and Fe3O4@CS photocatalyst were examined
in a 2Ө range of 20-70° with kα-Zn (0.154 nm
wavelength)using the X-ray diffractometer
(XRD D8 Advance-Bruker; USA). The thermo-
gravimetric investigation of prepared Fe3O4@
CSphotocatalyst and its precursors were executed
employing thermogravimetric analyzer (TGA
Pyris Diamond Series-PerkinElmer; USA).
The magnetization saturation (Ms), remanent
magnetization value (Mr) and hysteresis loops
(Hc) of Fe3O4NPs and Fe3O4@CS photocatalyst
were probed by vibrating sample magnetometer
(VSM-7304; USA).
Solar light driven catalytic decomposition of
Congo red dye
The proficiency of the Fe3O4@CS photocatalyst
for the photo discoloration of Congo red dye was
explored in an aqueous solution in transparent
glassware with magnetic stirring at 19% humidity,
at an altitude of 34.0031097o N and longitude of
71.4856409o E, under direct sunlight irradiations
in the months of May-June 2022 from 10:00 am
to 03:30 pm with an average sunlight intensity
approximately equal to 930 W/m2 with little
fluctuations in the intensity of ±8 W/m2 during
the batch photodisintegration experiments. The
batch photodisintegration experiments were
performed by regulating radiation time 0-90 min,
20-90 mg/L dye concentration, pH in the range
of 5-10 and photocatalyst dose (25-250 mg) at an
average temperature equal to ~37oC in aqueous
medium. Before illumination, the adsorption/
desorption equilibrium was attained (under
dark conditions) by stirring the blended solution
for 30 min. The solid magnetic photocatalyst
was magnetically segregated from the reaction
mixture via external magnet. The proficiency
of the Fe3O4@CS photocatalyst was figured out
by computing the absorbance values of Congo
red dye solution (λmax= 497 nm) preceding and
succeeding sunlight irradiations, using double
115
beam UV-V is spectrophotometer (BMS UV-
1602). The %degradation of Congo red dye was
determined using Eq. (1).
% Degredation = C - oC × 100
o f
(1)
C
Where Co and Cf are the initial and final
absorbance values of the dye solution35-38.
Recovery and reuse abilities of Fe3O4@CS
photocatalyst
After photocatalytic discoloration reactions,
regeneration and reusability tests were
accomplished to explore the robustness of the
Fe3O4@CS photocatalyst via 5 consecutive
cycles. The performance of CR dye degradation
was studied under optimal conditions i.e.,
radiation time of 70 min, 20 mg/L primary dye
concentration, pH 6 and 200 mg photocatalyst
amount. The photocatalyst was magnetically
separated from the reaction mixture and purified
with ethanol (three times wash) followed by
distilled water to eliminate impurities and finally
desiccated at 60oC in an oven. The recovered
Fe3O4@CS photocatalyst was evaluated up to five
continuous repeated photocatalytic experiments
at refined parameters values to investigate its
reusability.
Results and discussions
FTIR analysis
FTIR analyses were performed using FT-IR
spectrophotometer (4000 to 450 cm-1) to find out
the chemical composition of Fe3O4@CS and its
precursors as displayed in Fig. 1. In the spectrum
of aqueous extract of Boerhevia procumbens, the
intense broad peak around 3100-3600 cm-1 is for
the O-H/N-H vibrations whereas the peak around
1670 cm-1 is attributed to amide functional group.
Moreover, the peak at 1300 cm-1 shows the C-O
whereas the band around 1080 cm-1 is ascribed to
C‒N stretching vibration. In the FTIR spectrum
of Fe3O4 NPs, the characteristic peak appearing
at the 547 cm-1 is associated to Fe-O stretching
vibration that certifies the preparation of Fe3O4
NPs29. The spectrum of chitosan signifies the
prominent characteristic broad band above 3100
cm-1 along with 3356 and 3285 cm-1 are accredited
to the O-H and N-H stretching vibrations30. The
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 116

Fe3O4@CS

Chitosan

Intensity (a.u.)
Fe3O4 NPs

Extract

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)
Figure 1. FTIR spectra of aqueous extract of Boerhevia procumbens
leaves, Fe3O4 NPs, chitosan, and Fe3O4@CS photocatalyst

band appearing at 2910 cm-1 is attributed to sp3
C-H stretch. The band around 1650 cm-1 can
be associated to the amide functionality within
the molecule whereas the band at 1430 cm-1 is
attributed to the -CH3 symmetrical distortion
form31. The intense peak appearing around
1050 and 1130 cm-1 owes to the existence of
C-N and C-O bonds, respectively. Fe3O4@CS
spectrum reveals the peak at 560 cm-1 verifying
the presence of Fe-O bond which indicates the
successful fabrication of composite hydrogel.
Moreover, the spectrum reveals the broad peak
around 3200-3600 cm-1 which is accredited to
O-H stretching in addition to methylene (-CH2)
bending at around (1400 cm-1)32.
XRD analysis
The crystalline properties of Fe3O4 NPs and
Fe3O4@CS photocatalyst were investigated
using X-ray diffractometer at room temperature
between 20 to 70° (2Ө) with kα-Zn of wavelength
equal to 0.154 nm (Fig. 2). The voltage potential
was held up to 20 kV and tube current of about
20mA. The XRD spectrum of Fe3O4 NPs exhibits
the prominent peaks at 2ϴ equal to 30.02°,
35.8°, 42.5°, 54.4°, 56.6o and 62.1° with hkl peak
designations (220), (311), (400), (422), (511) and
(440), respectively, which is in agreement to the
standard pattern (JCPDS 19-0629) which implies
the successful fabrication of cubic single phase
nanosized Fe3O4 NPs33. In the XRD spectrum
of Fe3O4@CS, the shapes and intensities of the
diffraction peaks at 30.02°, 35.8°, 42.5°, 54.4°,
56.6o and 62.1° are significantly altered which
indicates the existence of Fe3O4 nanoparticles and
successful fabrication of composite hydrogel34.
Scherer’s equation was employed to compute the
crystallite structure size of Fe3O4 NPs (Eq. 2).
Dhkl = Kλ (2)
βcos θ
Where Dhkl depicts crystallite structure size
(nm), K represents Scherer’s constant (0.94), λ
denote the wavelength of X-ray source (0.154056
nm), β is the fullwidth at half maximum value
(FWHM) of peak35. The calculated average
crystallite size of Fe3O4 NPs equals 53 nm.
SEM analysis
The surface examination of Fe3O4@CS
photocatalyst was carried out via scanning
electron microscope. The Fig. 3 shows highly
irregular and multi layered porous surface
of magnetic composite hydrogel formed via
polymerization of chitosan powder with Fe3O4
NPs using ammonium persulphate as an initiator
and methylene bisacrylamide as a cross-linker.
The highly porous surface with water swellable
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 117

Fe3O4

(440)
Fe3O4@CS

(511)
(422)
(311)
Intensity (a.u.)

(400)
(220)
20 25 30 35 40 45 50 55 60 65 70
2Θ (degree)
Figure 2. XRD pattern of the green synthesized Fe3O4 NPs and Fe3O4@CS photocatalyst

Figure 3. SEM images of the fabricated Fe3O4@CS photocatalyst

properties of composite hydrogel provides large
surface area in addition to more photoactive
sites for the efficient dissociation of organic dye
molecules via generation of more electrons by
photons36. Conclusively, the SEM micrographs
suggest an excellent photocatalyst porous surface
for the decomposition of complex organic dye
molecules.
EDX analysis
The elemental composition of aqueous extract,
Fe3O4 NPs and Fe3O4@CS was determined using
EDX as displayed in Fig 4. The EDX spectrum
of aqueous extract displays the existence of
various elements owing to the presence of their
characteristics peaks for sodium at 1.0 keV,
magnesium at 1.1 keV, aluminum at 1.5 keV,
silicon at 1.8 keV, phosphorus at 2.0 keV, sulfur
at 2.3 keV, chlorine at 2.2 keV, potassium at 3.3
keV and calcium at 3.7 keV in addition to main
elements i.e. carbon at 0.2 keV, oxygen at 0.5 keV
and nitrogen at 0.3 keV. The carbon is present
in the highest amount (51.60 wt%) followed by
oxygen, nitrogen, calcium and potassium (Fig.
4A). The EDX spectrum of Fe3O4 NPs is depicted
in Fig. 4B that shows the characteristics peaks of
iron at 0.6, 6.5 and 7.0 keV (90.22 wt%), oxygen
at 0.5 keV (6.66 wt%), carbon at 0.2 keV (2.60
wt%), and nitrogen at 1.7 keV (0.52 wt%). The
elemental study of composite hydrogel confers
Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 118

Figure 4. EDX spectra of (A) aqueous extract of Boerhevia procumbens

leaves (B) Fe3O4 NPs and (C) Fe3O4@CS photocatalyst
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 119

the characteristics peaks for the existence of
carbon at 0.2 keV (6.53 wt%), oxygen at 0.5 keV
(11.13 wt%), sulfur at 2.3 keV (2.31 wt%) and
iron at 2.6 keV (79.64 wt%) which implies the
successful interaction of chitosan with magnetite
nanoparticles in Fe3O4@CS photocatalyst (Fig.
4C).
Thermal analysis
The thermal analyses of composite hydrogel and
its precursors were carried out in the range of 30-
700oC in an inert N2 atmosphere (10oC/min) as
shown in Fig. 5A. The analysis of Fe3O4 displays
a weight loss of about 5.4% up to 150oC owing to
the diminution of water molecules and there was
no further loss observed in the whole temperature
range as depicted in Fig. 5A37. The polysaccharide
chitosan shows weight deprivation curves, the
initial deficit of about 8% was observed in the
range of 70-160oC attributed to the water removal
whereas the second loss (67%) was observed
between 230 and 360oC associated to structural
decomposition of polysaccharide chain (Fig.
5B). Further, gradual weight loss of about 4%
appeared in the range of 360-700oC38. Fig. 5C
presents the TG graph of Fe3O4@CS, the primary
weight loss of 7% is ascribed to the desorption
of water molecules followed by 27% weight loss
owing to the decomposition of chitosan materials
in the composite hydrogel. No further weight

100 100

90
99
A 80
B
Weight loss (%)

Weight loss (%)

98 70

60
97
50
96
40

95 30

20
94
100 200 300 400 500 600 700 100 200 300 400 500 600 700
o o
Temperature ( C) Temperature ( C)

100

95

90
C
Weight loss (%)

85

80

75

70

65

60
100 200 300 400 500 600 700
o
Temperature ( C)

Figure 5. Thermogravimetric analysis of (A) Fe3O4 NPs

(B) chitosan and (C) Fe3O4@CS photocatalyst
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128
loss appeared at elevated temperature owing to
the existence of Fe3O4 NPs. The thermal analyses
show the successful fabrication of composite
hydrogel consisting of 24% chitosan by weight.
VSM analysis
The magnetic properties of the prepared
Fe3O4 NPs and Fe3O4@CS photocatalyst were
investigated using VSM at 25oC as displayed in
Fig. 6A. The magnetic saturation (Ms) of bare
Fe3O4 NPs was 55.3 emu/g and 26.1 emu/g for
Fe3O4@CS photocatalyst. The lower Ms value
for Fe3O4@CS photocatalyst compared to
bare Fe3O4 NPs is attributed to the significant
surface effects in composite hydrogel. Both
Fe3O4 NPs and Fe3O4@CS photocatalyst exhibit
no hysteresis loops (Hc and Mr = 0) suggesting
super paramagnetic behavior of the materials39.
This study indicates successful incorporation of
magnetic nanoparticles into the non-magnetic
chitosan layer. Moreover, this implies that
the photocatalyst can be readily magnetically
screened out and recovered from the solution
after completion of catalytic reactions using
outward magnet owing to the considerable
magnetic behavior.
Optical investigation of Fe3O4@CS photocatalyst
Fe3O4@CS photocatalyst of 8 mg was added to
50 mL of isopropanol and sonicated (45 min) for
efficient dispersal of the particles in solvent. The
absorbance values (200-700 nm) of sample were
recorded using BMS UV-1602 Double Beam
Spectrophotometer (Fig. 6B). The band gap of the
Fe3O4@CS photocatalyst was figured out by using
Tauc’s equation and Tauc’s plot (Eqs. 3 and 4)40.
1240
Energy = (3)
Wavelength (eV)
αhυ = (2.303 × Absorption × Energy2) eV2cm−2
(4)
The measured bandgap energy from Tauc's
plot for Fe3O4@CS photocatalyst was 2.36 eV
(Fig. 6C).
Solar light driven catalytic decomposition of
Congo reddye
The photodissociation reaction of Congo red dye
120
in aqueous solution was chosen as an exemplary
reaction to evaluate the degradation proficiency
of the as fabricated Fe3O4@CS photocatalyst in
the presence of sunlight irradiations. The blank
kinetic experiment in the absence of photocatalyst
revealed negligible disintegration of Congo red
dye molecules which emphasize the primary
function of the Fe3O4@CS photocatalyst during
the photocatalytic decomposition reactions. Then
the photocatalytic dissociation reactions were
performed by using Fe3O4 NPs and Fe3O4@CS as
photocatalysts. The photocatalytic decomposition
reactions in the presence of sunlight radiations
suggested the improved % degradation efficiency
for Fe3O4@CS photocatalyst (95.7%) compared
to bare magnetite nanoparticles (73.4%) at
25oC, 200 mg photocatalyst dosage, 20 mg/L
dye concentration, and 70 min irradiation time
in neutral aqueous solution (data not provided).
This study indicated that the integration of
chitosan with magnetite nanoparticles modified
and improved the surface as well as structural
properties of the Fe3O4@CS photocatalyst. The
higher %degradation efficiency for Fe3O4@
CS photocatalyst is accredited to the growing
proportion of photoactive sites over the Fe3O4@
CS photocatalyst surface and low bandgap energy.
The Fe3O4@CS was chosen as an optimum
photocatalyst for the photodecomposition of
Congo red dye molecules owing to its high
degradation efficiency. When a photocatalyst
in aqueous solution is exposed to UV or solar
light, the excitement of electrons from valence
to conduction band occurs which leads to the
production of electron-hole pair that in turn leads
to the creation of impetuous O2̄ and OH ̄ radicals.
These generated radicals in aqueous solution
are distinctive species for the deterioration of
Congo red dye via photocatalytic degradation
chain reactions. Various reaction parameters
including radiation time, dye concentration, pH
and photocatalyst dosage were regulated for
achieving high degradation efficiency.
Influence of radiation time
The effect of solar light irradiations time on
photodecoloration of Congo red dye was
explored by executing the reactions in the range
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 121

60 n−π∗
0.8

A
50
40 π−π∗ B
Magnetization (emu/g)

30

Absorbance (a.u)
20 0.6
10
0
Fe3O4 0.4
−10
−20
Fe3O4@CS
−30
0.2
−40
−50
−60
0.0
−20000 −10000 0 10000 20000 200 300 400 500 600 700
Applied magnetic field (Oe) Wavelength (nm)

Figure 6. (A) VSM curves of green prepared Fe3O4 NPs and Fe3O4@CS photocatalyst (B) UV-
Visible spectrum of fabricated Fe3O4@CS photocatalyst and (C) Bandgap energy plot of Fe3O4@CS
photocatalyst

of 0-90 radiation time (Fig. 7A). The intensity
of the colored solution significantly decreased
with time that demonstrated an increase in
decomposition of dye with increasing radiation
time. Initially, the rate of disintegration of
Congo red dye was higher and nearly 79% of
dye molecules were decomposed in first 20
min of radiation time owing to the openness of
more photoactive sites for degradation process.
However, increasing interaction time above 20
min, a gradual increase in the %degradation
was observed owing to the less accessibility to
photoactive sites on photocatalyst’s surface as
they were occupied by high concentration Congo
red dye (60 ppm). The highest degradation of
dye (95.8%) was obtained after 70 min. Further
Increase in radiation time above 70 min leads to
no considerable change in disintegration of dye,
therefore 70 min was considered as an optimal
reaction time for this reaction. A previous study
on catalytic decomposition of Congo red dye
by NiO/SiO2 nanocomposite displayed that the
decontamination efficiency of the photocatalyst
increases concerning time41. In another report
85% disintegration of Congo red dye was
obtained in 160 min by using NiO photocatalyst42.
Since Fe3O4@CS photocatalyst displayed higher
catalytic properties in comparison to the reported
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 122

catalysts; therefore, it can be considered as best
catalyst for the photolysis of Congo red dye.
Influence of primary dye concentration
The consequence of Congo red dye initial
concentration in the batch photodegradation
reactions were studied in the concentration range
of 20-90 mg/L (Fig. 7B). The %decontamination
of Congo red dye is highest (99.1%) at low
concentration of 20 mg/L, however, with
increasing primary dye concentration, the percent
decomposition of dye continuously dwindled
from 99.1 to 78.5% owing to the coverage of
photoactive sites due to increased sorption of
organic Congo red dye molecules. Moreover,
concentrated dye solution decreases the solar
light infiltration to the photocatalyst’s surface
through the assemblage of dye molecules,
thereby reducing the development of electron-
hole pairs4. A study reported that the photolysis
of Congo red dye by TiO2 nanoparticles is
higher at a lower concentration and dwindled at
higher concentration43. Since the highest percent
decomposition of Congo red dye occurs at 20
mg/L, therefore it was chosen as an optimal
concentration.
Influence of solution pH
The reaction medium pH can affect the photolysis
reactions therefore the pH of the Congo red
dye solution was varied between 5 to 10 (Fig.
7C). The photodisintegration of Congo red dye
was maximum in the acidic solution due to its
anionic nature and the prominent (98.9%) was

100
A 100 B
80 80
% Degradation
% Degradation

60 60

40 40

20 20

0 0
20 30 40 50 60 70 80 90 20 30 40 50 60 70 80 90
Radiation time (min) Concentration of dye (mg/L)
100
C
100

D
80 80
% Degradation

% Degradation

60 60

40 40

20 20

0 0
5 6 7 8 9 10 25 50 75 100 125 150 175 200 225 250
pH Photocatalyst dosage (mg)

Figure 7. Influential parameters (A) radiation time (B) dye

concentration (C) pH of dye solution and (D) photocatalyst dose
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128
obtained at pH 6. The decomposition efficiency
was lesser in basic media which is ascribed to the
columbic repulsion between negatively charged
photocatalyst’s surface and Congo red dye
molecules, therefore optimal pH 6 was selected
for further analysis44. A similar trend is reported
that the degradation processes were efficient in
acidic solution because of the action of sulphonic
moiety in the dye molecule make soluble Congo
red anion45.
Influence of photocatalyst dosage
The optimum photocatalyst dosage is crucial
in batch degradation reactions for the high
%dissociation of Congo red dye by using
low quantity of photocatalyst in commercial-
scale applications. The significance of catalyst
dose on the decomposition of Congo red dye
in aqueous solution employing Fe3O4@CS
photocatalyst was assessed in the range of
25 to 250 mg (Fig. 7D). The results displayed
that the photodeterioration of Congo red dye is
higher in the reaction solution containing more
catalyst amount and the elevated% degradation
(98.6%) was attained at 200 mg. There was no
considerable increase in the %dissociation of
Congo red dye after 200 mg, therefore, it was
Figure 8. The mechanism of photodisintegration of Congo red dye over Fe3O4@CS photocatalyst
123
considered as an optimum photocatalyst dosage.
The increasing trend in the dissociation efficacy of
Congo red dye with increasing catalyst amount is
ascribed to the availability of additional exposed
surface presenting more number of photoactive
sites for the photodisintegration reactions46. In
addition, the more catalyst amounts present large
surface area for generating a greater number of
electron-hole pairs which are impetuous for the
photocatalytic dissociation of Congo red dye
molecules.
Mechanism of the degradation reaction of
Congo red dye
Fig. 8 displays the mechanistic pathway of the
photocatalytic dissociation reaction of the Congo
red dye has been reported in the literature47.
When Fe3O4@CS photocatalyst is exposed to
light energy higher than its associated bandgap
energy, the electronic excitation from valence
band to conduction band occurs which results in
the formation of hole in the valence band, and this
way the electron-hole pair (e- + h+) is generated
(Eq. 5). The excited electrons in the conduction
band interact with more oxygen molecules on
Fe3O4@CS surface to produce highly reactive
superoxide radical species (Eq. 6). These radicals
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 124

are responsible for the deterioration of Congo red Reuse and recycling abilities of Fe3O4@CS
dye into CO2 and H2O (Eq. 7). Simultaneously, photocatalyst
the generated positive holes in the valence The significance of photocatalysts employed in
band oxidize water molecules of the solution the water treatment for sustainable environment
to produce hydroxyl radical ion and hydrogen is assessed by their regeneration and reuse
ions (Eq. 8). The hydroxyl radical ions further abilities. The eminent chemical stability as
dissociate Congo red dye molecules into CO2 and well as durability of the photocatalysts are
H2O (Eq. 9).The photodisintegration reaction important parameters in determining their
of Congo red dye molecules is highly affected photocatalytic performance. The fabricated
by the recoalescence of electron hole pairs. Fe3O4@CS photocatalyst was regenerated by
The high discoloration of dye molecules with magnetic segregation from its reaction mixture
the Fe3O4@CS photocatalyst suggests that the and subsequent steps of washing with ethanol
recombination of electron hole pair is prevented and distilled water for removal of impurities.
in an aqueous medium of reaction solution. The The retrieved photocatalyst was dehydrated in
scheme of the mechanism of degradation process an oven at 60 oC and reutilized for five cycles to
is summarized. appraise its cycle economy (Fig. 10). The results
Fe3O4@CS photocatalyst + hv g Fe3O4@ revealed that the Fe3O4@CS photocatalyst
CS photocatalyst + (ē + h⁺) (5) retains almost the same degradation efficiency
ē + O2 g O2̄ ˙ (6) up to three cycles and an incidental decline in
O2̄ ˙+ Congo red dye g CO2 + H2O (7) degradation efficacy was witnessed after third
h + H2O g OH̄ ˙ + H
+ ⁺
(8) cycle. The decrease in deterioration efficacy is
OH̄ ˙ + Congo red dye g CO2 + H2O (9) associated to the rupturing and covering of the
photoactive sites of Fe3O4@CS photocatalyst.
Kinetics of the degradation reaction of Congo The degradation efficiency of Congo red dye was
red dye 99.1, 98.3, 97.34, 92.5, and 84.6% during 1st, 2nd,
Both first and second order kinetic fits were 3rd, 4th and 5th cycles, respectively as displayed
executed to appraise the rate of Congo red dye in Fig. 9. The Fe3O4@CS photocatalyst with
decomposition reaction (Eqs. 10 and 11)48. excellent recycling properties and reusability
ln [A]t = - kt + ln[A]o (10) lead to decrease in the cost and production of
secondary pollutants. Therefore, the fabricated
(11)
Fe3O4@CS is considered as an excellent,
Where [A]o and [A]t are the initial and final economical, eco-friendly, reusable and highly
absorbance values before and after sunlight proficient photocatalyst for the photocatalytic
irradiations respectively, t is the solar irradiations decomposition of Congo red dye and other
time and k shows rate constant of the degradation organic pollutants in water.
reactions. The absorbance values were plotted
against time as shown in Fig. 9C. The graph Conclusion
of ln[A] against time and inverse of [A] as a Ecofriendly and cost-effective Fe3O4@CS
function of time was plotted to suggest the best photocatalyst was green synthesized for the
fitted kinetic model for the photodissociation photodeterioration of Congo red dye. The
of dye molecules in the presence of Fe3O4@CS formation of high crystalline, porous, and
photocatalyst. Fig. 9A presents first order kinetic thermally stable magnetic composite hydrogel
plot for the degradation processes, the correlation photocatalyst was confirmed through FTIR,
coefficient (R2) was 0.95187, whereas 0.9959 for XRD, SEM, EDX, TGA, and VSM analysis.
second order kinetic model as depicted in Fig. The low bandgap value (2.36 eV) signifies solar
9B. The R2 value is close to unity in second order light driven photocatalyst. The photocatalyst
kinetic fit suggests that the dissociation processes was employed suggesting the 99.1% efficacy
obey second order kinetics. The rate constant of in photodecomposition of Congo red dye under
this reaction was calculated to be 0.09506 min-1. refined reaction conditions of reaction irradiation
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128 125

10
0.0

−0.5 A 8
B
6
−1.0

1/ [A]t
ln[A]

Equation y = a + b*x
y = a + b*x Plot 1/[A]
Equation
Plot ln[A] 4 Weight No Weightin
−1.5 Weight No Weightin Intercept
0.14527 ± 0.
10856
Intercept -0.20309 ± 0.
0.09506 ± 0.
Slope -0.02423 ± 0. Slope 00203
Residual Sum of 0.21651 2
−2.0 Squares
Residual Sum of
Squares
0.27293

Pearson's r -0.97837 Pearson's r 0.99817

R-Square (COD) 0.95722 R-Square (COD) 0.99635
Adj. R-Square 0.95187 0 Adj. R-Square 0.9959
−2.5
0 20 40 60 80 0 10 20 30 40 50 60 70 80 90
Time (min) Time (min)

1.6 00 min

1.4 C 10 min
20 min
30 min
1.2
Absorbance (a.u)

40 min
1.0 50 min
60 min
0.8
70 min
0.6 80 min
90 min
0.4

0.2

0.0
300 400 500 600 700
Wavelength (nm)

Figure 9. (A) First order kinetic plot (B) second order kinetic plot
and (C) UV-Visible absorbance values at different interval of time

120

100

80
% Degradation

60

40

20

0
1st 2nd 3rd 4th 5th
Cycles

Figure 10. Recycling of Fe3O4@CS photocatalyst for the photodeterioration of Congo red
 Asif Ullah Khan et al. / Anal. Chem. Lett. 14 (1) 2024 pp 112 - 128
time (70 min), 20 mg/L dye concentration, pH 6
and 200 mg photocatalyst dose and concentration
at 25oC. The solar light driven disintegration
reactions of Congo red dye were best fitted with
the second-order kinetic model (R2 = 0.9959).
The synthesized Fe3O4@CS photocatalyst was
easily separable and regenerated using external
magnet and simple washing suggesting the
potential use of this catalyst for the solar light
driven deterioration of detrimental organic dyes.
Conflicts of interest
The authors declare that they have no known
competing financial interests or personal
relationships that could have appeared to
influence the work reported in this paper.
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