Introduction:

Since all life depends on water in one way or another, environmental preservation is the highest
priority. Human activity is causing rapid industrialization and a daily increase in material
discharge [1]. The textile industry's waste effluents are generating water contamination, which is
gravely harming people's health. [2] More than 7 × 105 metric tons of synthetic dyes are
produced annually, and over 100,000 commercially available dyes have been reported: textile
wastewater discharge accounts for about 15% of global dye production, with the food, chemical,
and textile industries consuming nearly 97% of local dye wastewater. Organic pollutants, such as
dyes and phenolic compounds, are widely used in the textile, paper, cosmetic, pharmaceutical,
paint, leather, food, plastic, and other industries, contributing to severe environmental
contamination, particularly water pollution. However, because the dyes are toxic, mutagenic, and
carcinogenic, the majority of leftover dyes produced during the dyeing and finishing process are
released into the environment, either with or without additional remediation. This could lead to
major problems as the wastewater flows into natural waterbodies. The human body is also
harmed by dyes; for instance, the kidney, liver, reproductive system, brain, and central nervous
system may malfunction. Apart from that, even trace amounts of dyes, less than 1 ppm, are
visible in receiving waterbodies and can prevent sunlight from penetrating and prevent aquatic
plants from performing photosynthesis [3]. Approximately 700,000 tons of dyes of over 10,000
varieties are utilized as coloring agents in various sectors, mostly in the textile sector. Because of
their high toxicity, endurance, and capacity to bioaccumulate in living things, dye releases in
natural media are concerning. [4]. Due to these problems, there is a need to resolve this problem.
There are many methods used for the removal of dyes from water like sedimentation,
coagulation, filtration, chemical method, physical method and adsorption. Among them
adsorption is the best one.

Different adsorbents are used for the removal of pollutants. Among these natural adsorbents like
activated carbon, silica, alumina etc. and MOFs are also available for adsorption of pollutants. A
metal organic framework (MOF) is a novel kind of mixed material composed of organic bridging
ligands and metal ions with a precise coordination geometry. MOFs have garnered a lot of
interest in recent years because of their unique optical characteristics, structure, and framework
structure. In a number academic domains, including non-linear optics, drug delivery systems,
energy storage, gas storage, and chemical reaction, MOFs have offered encouraging prospects.
The use of MOFs has recently been expanded to include new and fascinating areas of adsorption
and sensing for a variety of targeted pollutants like as dyes, insecticides, pharmaceuticals,
explosives, heavy metals and tiny compounds [7]. Vinodhini Subramaniyam and her colleagues
use Zr-MOF for adsorption of Cu from water sample. The maximum adsorption capacity of Zr-
MOF was 79.34mg/g [8]. Kamal [Link] and his co-workers use biomass Zr-MOF for the
removal of Direct red, Methylene blue and Cr(IV). The maximum adsorption capacity of Zr
MOF was 36.07 mg/g for direct red, 79.79mg/g for methylene blue and 19.01 mg/g for Cr(IV)
[9].

Natural adsorbents are also efficient but have less adsorption capacity. In a study conducted by
Meng Zheng and his co-workers, magnetic chitosan was used for the removal of Cu 2+ ions. The
maximum adsorption capacity of chitosan was 55.16 mg/g [5]. In another research conducted by
Hamsina and her colleagues, in which the absorbance power and surface area of chitosan was
checked by using Pb(II) ions. The maximum adsorption capacity was 68.5 mg/g for 100 minutes
[6]. Oktor, K., and coworkers used biopolymer chitosan for the removal of phosphate ions from
water. The maximum adsorption capacity was 87.26 mg/g [10], but when these natural
adsorbents are combined with other materials like metal organic frameworks (MOF’s), there is a
boost in adsorption capacity of these materials.

In current research work Zr-MOF was combined with chitosan using 1,4-benzenedicarboxylic
acid as linker and dimethylformamide as solvent for the removal of organic dye Methylene Red
(MR). Zr-MOF and Zr-MOF@chitosan composite were characterized by advanced spectroscopic
techniques like …… . We have also focused on adsorption studies under different experimental
conditions that are pH, contact time, adsorbent dosage, and initial dye levels. In order to better
understand how the data were achieved, the kinetic and isothermal constants were also used to
evaluate the adsorption results. also dd thermodynamic study.

Material

Chemicals

Zirconium nitrate pentahydrate, 1,3,5-benzenetricarboxylic acid [BTC], N,N-dimethyl forma

amide [DMF], formic acid, chitosan, methanol. All these chemicals were bought from sigma
Aldrich and they were 99.9% pure and were used without any further purification. ………dist
water

Zr-MOF Formation

Zr-MOFs have been prepared through a solvothermal procedure as reported by with minor
modifications. In typical method 0.429 g of zirconium nitrate pentahydrate and 0.630 g of 1,3, 5-
benzene tricarboxylic acid was put in 30 mL DMF and a few drops of formic acid as a modulator
were added. The solution was refluxed at 120 oC in 2 h and allowed 24 h for crystal aging. White
crystals were washed with the help of centrifuge (15 mL batches), using methanol and water at
0000 rpm (5 repeated cycles, 15 min each). Lastly, to obtain pure Zr-MOFs, the product was
dried at 60oC by placing in oven for 12 h period.

Zr-MOF@Chitosan Composite formation

The forming of composite (Zr-MOF@CS) involved the mixing of the material Zr-MOF powder
(0.17 g, 0.25 mmol) with chitosan (1.54 g) according to reported literature with minor
modifications XXXX. Weighed material was put in a clean dish to easily and uniformly mix and
little amount of methanol was added at a time, using a syringe, to disperse the chitosan and
ensure the uniform dispersion of the Zr-MOF particles. This was done due to the careful addition
of the solvent to avoid clumping and facilitate free mixing. The mixture was stirred for 20-30
min such that they turned into a uniform paste-like material. The paste itself was allowed to
prepare at ambient temperature to allow the gradual evaporation of methanol. Then, it was put in
a hot air oven with a temperature of 50 oC for 2 hours to extract any remaining solvents and
moisture. The solid composite was subsequently consolidated, fine ground, and the product
stored in an airtight container to be used for further study.

3. Results and Discussion

3.1 Fourier Transform Infrared Spectroscopy
The effective synthesis and functionalization are confirmed by the FTIR spectra of Zr-BTC MOF
and its chitosan composite. Asymmetric and symmetric stretching vibrations of carboxylate
groups coupled to Zr clusters are represented by the distinctive peaks in Zr-BTC MOF between
1600 and 1400 cm⁻¹, while Zr–O stretching is responsible for the bands below 800 cm ⁻¹,
thereby verifying the existence of the MOF framework. Other peaks show up in Zr-
MOF@chitosan composites, including the broad band at around 3783 cm ⁻¹ associated with –OH
stretching of hydroxyl groups and adsorbed water, and the peak at about 1630 cm ⁻¹ correspond
to C=O stretching of amide groups from chitosan, which overlaps with MOF carboxylate signals.
The band at about 1090 cm⁻¹ is caused by C–O–C stretching from the polysaccharide backbone,
whereas the absorption at about 1375 cm⁻¹ is associated with the C–N stretching vibrations of
chitosan. The incorporation of chitosan into the MOF matrix is validated by these characteristics.
Strong hydrogen bonds and electrostatic interactions between Zr-BTC MOF and chitosan chains,
as opposed to merely physical mixing, are suggested by the minor changes in the C=O and C-N
bands and the enlargement of the -OH area. Other MOF–biopolymer composites have shown
similar FTIR signals, confirming that the hybrid maintains the rigidity of Zr-BTC MOF while
acquiring extra functional groups from chitosan that improve adsorption capabilities.

Figure 1: FTIR spectra of Zr-MOF and Zr-MOF@chitosan composite

3. X-Ray Diffraction
X-Ray Diffraction is an important technique used to find crystallinity of a substance. In Fig 2,

the XRD pattern of Zr-MOF and Zr-MOF@chitosan composite (light and brown) is shown. Zr -

MOF in the pattern XRD has a broad hump in the low-angle range (approximately 2 theta = 10 -

12) that has no sharp crystalized reflections, which means that it is amorphous or (partially)

poorly crystallized. Conversely, the Zr–MOF@chitosan composites have independent peaks in

the spectrum of 2 L = 15-35 as a positive indication of chitosan incorporation, which enhances

organization in the structures. These high peaks near the 2θ value of 20, 25, and 30 degrees are

the semi-crystalline domains of chitosan and potential reorganization of the MOF construction

following the formation of the composite. The fact that these peaks persist in these light brown

and dark brown composites is an indication that the chitosan not only uniformly coats or

interacts with the Zr-MOF, enhancing the crystallinity without collapsing the framework but, at

the same time, this does not obstruct aggregation. Strong interfacial interaction, i.e., hydrogen

bonding of the amino/hydroxyl groups of chitosan with Zr 17O12 clusters of the MOF are

additional evidence of strong interfacial interactions that can be hypothesized based on a

decrease in the peak intensity between pure chitosan and the resin. Accordingly, the XRD

analysis proves that the compound preserves basic structure of Zr -MOF, but adds the semi-

crystalline properties of chitosan, resulting in the increase of structural stability and

heterogeneity that is favorable to adsorption purposes.

 Figure 2: XRD pattern of Zr-MOF and Zr-MOF@chitosan composite

Effect of Time:
Any adsorption process must consider the impact of time. In the comparative studies of
methylene red adsorption on Zr-MOF and Zr-MOF@chitosan composite, UV analysis was
performed. The primary step in adsorption studies is to determine the concentration of methylene
red over a specific time (375 minutes) using Beer Lambert Law, with each reading taken after 15
minutes. In general, it is found that the adsorption capacity increases as the contact time between
the adsorbent and water pollutant increases. As contact duration increases, more metformin
molecules become trapped within MOF and the composite, which explains the rise in adsorption
capacity. With an increase in contact duration, metformin's ability to adsorb onto the surface of
Zr-MOF and Zr-MOF@chitosan composite rises. With increase in time, the adsorption process
slows down because the less active sites remained on adsorbate’s surface for the adsorption of
adsorbent. After 45 minutes, there is no obvious adsorption of methylene occurred in our study.
So, the 45 minutes is equilibrium time, during which the methylene red molecule and active sites
reach saturation level. At equilibrium time, the adsorption capacities for Zr-MOF and Zr-
MOF@chitosan composite were 175.5 mg/g and 200 mg/g, respectively, as indicated in Figure
3a-c. The removal rate was 82% in case of Zr-MOF and 94% in case of Zr-MOF@chitosan
composite. Numerous factors contribute to Zr-MOF and Zr-MOF@chitosan composite's strong
methylene red adsorption capacity and removal effectiveness. With its enormous surface area
and numerous active sites, Zr-MOF's relatively porous structure allows for strong π–π and
electrostatic interactions with dye molecules. In addition to increasing the composite's
hydrophilicity and dispersion in aqueous environments, the inclusion of chitosan improves
adsorption by adding functional groups (-NH₂, -OH) that provide more hydrogen bonding and
electrostatic interactions. Thus, MOF porosity and the functional groups in chitosan work in
concert to provide quick absorption, a high adsorption capacity, and effective removal results.

a b

Figure 3 a) Time vs adsorption capacity for 20 ppm methylene red on MOF and composite b) Time vs ct
for 20 ppm methylene red on MOF and composite c) Time vs %R for 20 ppm methylene red on MOF and
composite

Effect of pH:

The pH effect is another important factor to check how the adsorption of pollutants is affected by
pH. In current study, Zr-MOF@chitosan composite was used for the adsorption of methylene red
using solutions of different pH (2, 4, 6 and 8). It was noticed that from removal efficiency was
increased from pH 2 to pH 4 up to 99% and from pH 4 to pH 8 removal % drops down. This was
because that at low pH, hence (pH =2), the surface of the Zr -MOF/chitosan film is protonated
due to the presence of the H+ amount of H+ ions in the solution. The amino function (–NH 2) of
chitosan easily changes into -NH3+ in acidic conditions to become positively charged on the
surface. Whereas methylene red is an anionic dye monomer, you achieve a sharp repulsion in the
case when the solution is highly acidic which means that the excess Hp+ ions overcomes the dye
molecule in terms of adsorption positions. This is why adsorption is less in PH 2.

Although increasing the pH causes more protonation to cease positely charges of the adsorbent,
the additional free protons are not competing on the same level. It is an indication that the
electrostatic force of attraction between the isomerizing sites (-NH 3+ and Zr0H2+) on the MR dye
and the negatively charged sulfonate dominates on the MR dye is more favorable and thus the
removal efficacy is greater at pH 4.

At even higher pH levels (pH 6 to 8) the number of protons surrounding is less and the surface
groups on both MOF and chitosan are beginning to deprotonate (–NH 2 instead of -NH 3 +, -OH
instead of -OH 2 +). Subsequently, this causes the surface to become less positively charged or
even slightly negative and thus, the electrostatic pull across the anionic MR molecules becomes
weaker and at times even attractive at the alkaline pH. In addition, it becomes harder, because
dye molecules prefer to aggregate at high pH such that they can hardly absorb and that’s why
efficiency decreases beyond pH 4.

Fig 4 pH effect on adsorption of methylene red on Zr-MOF@chitosan composite

Kinetic Study:
Table 1 presents the results of the pseudo-first-order, pseudo-second-order, Elovich, and Weber-
Morris intra-particle diffusion models that were utilized to assess the adsorption kinetic data.

b
a
Fig 5 a) Pseudo second order kinetic model, b) Pseudo first order kinetic model, c) Elovich model, d)
Intraparticle diffusion model

It is discovered that the qt vs. t plots for every MB-adsorbent system are exponential, suggesting
that the adsorption process is 2nd order (Fig. 5(a)).
To determine if the adsorption process adhered to second order kinetics, the generalized second
order kinetic equation that follows as employed

t 1 t
= +
qt K 2 qe qe
2

From fig 5(a), it is cleared that pseudo second order kinetic model is best fitted in case of both
Zr-BTC MOF and Zr-MOF@chitosan composite which directed that chemisorption process had
occurred during the adsorption of methylene red onto the surface of both Zr-BTC MOF and Zr-
MOF@chitosan composite. Both adsorbents' linear t/qt vs time plots demonstrated high
correlation coefficients (R2 = 0.97), suggesting that the adsorption process adheres to PSO
kinetics. According to this hypothesis, chemisorption occurs rather than straightforward
physisorption at the rate-limiting stage through electron sharing or exchange between the
functional groups of adsorbent and dye molecules. Strong connections between methylene red
and active binding sites on the Zr-MOF framework are suggested by the close match, and the
chitosan addition adds more hydroxyl and amino groups to improve adsorption capacity. The
same outcomes have been shown for dye adsorption on biopolymer-MOF composites, where
PSO kinetics outperformed the pseudo-first-order model in terms of fitting. The strong R 2 values,
however, demonstrate the critical role that functional group interactions play in regulating
adsorption by confirming that pseudo-second-order kinetics best describe the adsorption of
methylene red on Zr-BTC MOF and its chitosan composite.

Isothermal Study:
The adsorption equilibrium data of methylene red (MR) onto Zr-MOF and Zr-MOF@chitosan
composite were analyzed using Langmuir, Freundlich and Temkin isotherm models. With
correlation values of 0.98 and 0.99 for Zr-MOF and its composite, respectively, the Freundlich
model was best fitted. This greater degree of association suggests that a heterogeneous surface
adsorption mechanism, as opposed to a strictly monolayer configuration, more properly
describes the adsorption process.

The structural characteristics of MOFs and their composites are compatible with the Freundlich
model's assumption that active sites and adsorption energy are distributed unevenly. By adding
functional groups like -OH and -NH2, chitosan further improves surface heterogeneity and offers
a variety of binding interactions, such as π–π interactions with methylene red, electrostatic
attraction, and hydrogen bonding. Therefore, multilayer adsorption on heterogeneous active sites
of the Zr-MOF framework and the Zr-MOF@chitosan composite is suggested by the superior
fitting of the Freundlich model. This suggests that adsorption happens with different affinities
rather than being limited to homogeneous spots, which is a feature of a complex and porous
network.
The findings demonstrate that the adsorption behavior of MR dye is better described by the
Freundlich model, especially when functional biopolymers such as chitosan are combined with
MOFs to increase surface roughness, heterogeneity, and adsorption capacity.

a
b

c
Fig 6 a) Langmuir model for Zr-MOF and Zr-MOF@chitosan b) Freundlich model for Zr-MOF and Zr-
MOF@chitosan c) Temkin model for Zr-MOF and Zr-MOF@chitosan
Effect of Temperature:

Methylene red adsorption onto Zr-MOF and Zr-MOF@chitosan composite exhibits a non-linear
pattern in response to temperature, with adsorption capacity (Qe) first rising and then falling.
The adsorption capacity is 153.9 mg/g at 288 K and increases to 198.2 mg/g at 298 K, suggesting
that adsorption is improved by a mild temperature increase. Increased methylene red molecule
mobility decreased solution viscosity, and the activation of more active sites on the MOF and
composite surface are all responsible for this improvement. However, adsorption is reduced to
96.9 mg/g when the temperature is raised further to 308 K. According to this characteristic, the
adsorption process is endothermic up to a certain temperature, after which it becomes
unfavorable because the adsorbed molecules become unstable. The combined physisorption–
chemisorption process has been confirmed by similar temperature-dependent patterns for dye
adsorption on MOF-based and polymer-composite materials. Therefore, the ideal adsorption
temperature is close to 298 K, emphasizing how crucial it is to regulate thermal conditions for
effective methylene red elimination.

Fig 7: Effect of temperature on adsorption capacity

The connection between ln(Kc) and 1/T was used to assess the thermodynamic research of
methylene red adsorption onto Zr-MOF and Zr-MOF@chitosan composite. The figure ()
indicates that adsorption is temperature dependent as ln(Kc) decreases linearly with increasing
temperature. The maximum ln(Kc) value of 4.37 was recorded at a lower temperature (288 K,
1/T = 0.00347), indicating a significant affinity between the dye molecules and the adsorbent
surface. With a temperature increase to 298 K (1/T = 0.00336), ln(Kc) dropped to 3.51 and then
to 2.24 at 308 K (1/T = 0.00325), indicating a lower ability for adsorption at higher temperatures.
The negative entropy change (ΔS°) suggests less randomness at the solid–solution interface
during dye absorption, whereas the negative enthalpy change (ΔH°), as determined by the slope
and intercept of the van't Hoff plot, suggests that the adsorption process is exothermic. While the
fewer negative results at higher temperatures indicate that spontaneity declines with heating, the
negative Gibbs free energy (ΔG°) values across the examined temperatures prove that adsorption
is spontaneous. Methylene red adsorption on Zr-MOF and its composite is exothermic,
spontaneous, and more advantageous at lower temperatures, according to these thermodynamic
properties taken together.
 Fig 8: Van’t Hoff plot,

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