(2024) 18:121
Ragab et al. BMC Chemistry
https://doi.org/10.1186/s13065-024-01211-5

BMC Chemistry

RESEARCH

Open Access

Exploring the sustainable elimination of dye
using cellulose nanofibrils‑ vinyl resin based
nanofiltration membranes
Ahmed H. Ragab1, Najla F. Gumaah2, Aya Abd El Aziz Elfiky3* and Mahmoud F. Mubarak3,4

Abstract
This study focuses on the development of a novel self-cleaning nanofiltration membrane for the efficient removalof the cationic dye methylene blue (MB) from industrial wastewater. The membrane is composed of vinyl resin (VR),cellulose nanofibrils (CNF), and titanium alpha aluminate (TAAL) nanoparticles.
The TAAL loading ranged from 1 to 5 wt%, the pH varied from 5 to 10, and the initial MB concentration ranged
from 10 to 50 ppm. Using a dead-end filtration system, the (VR/CNF@TAAL) membrane with 5 wt% TAAL at pH
10 demonstrated excellent performances. It achieved a remarkable 98.6% removal efficiency for 30 ppm MB dye,with a maximum adsorption capacity of 125.8 mg/g. The adsorption kinetics analysis revealed that the process followed the pseudo-second-order model, indicating a chemisorption mechanism. The rate constant was determined
to be 1.2732 × ­10–3 g ­mg−1 ­min−1. The Freundlich isotherm model provided a better fit ­(R2 = 0.996) than the Langmuirmodel, suggesting multilayer adsorption on the nanocomposite membrane surface. In addition to its high adsorption and filtration capabilities, the (VR/CNF@TAAL) nanocomposite membrane exhibited cost-effectiveness and environmental friendliness as an adsorbent for MB removal from industrial wastewater. The membrane’s self-cleaning
property further contributes to sustainability by reducing the need for additional chemical treatments.
Keywords Self-cleaning, Nanofiltration, Methylene blue, Industrial wastewater, Adsorption, Sustainable
Introduction
The discharge of wastewater containing cationic dyes has
become a significant environmental concern, leading to
the development of sustainable and efficient methods*Correspondence:
Aya Abd El Aziz Elfiky
aya.elfiky91@yahoo.com
1
Chemistry Department, College of Science, King Khalid University,
61413 Abha, Saudi Arabia
2
Chemistry Department, Faculty of Science, Northern border university,
Arar, Saudi Arabia
3
Petrolum Applications Department, Egyptian Petroleum ResearchInstitute (EPRI), Ahmed El‑Zomer, Nasr City, Cairo, Egypt
4Core lab center, Egyptian petroleum research institute (EPRI), 1 Ahmed
El Zomor St, Nasr City 11727, Cairo, Egypt

for their removal [31]. The result of nanofiltration membranes has gained considerable attention in recent years,
offering a promising solution for the removal of pollutants from wastewater. In this study, we present a novel
self-cleaning nanofiltration membrane made of microcrystalline nanocellulose and titanium aluminate nanoparticles embedded in vinyl resin (VR) for the removal of
cationic dyes from wastewater [5].
Dye removal from wastewater is an important environmental challenge due to the toxicity and visibility ofdye molecules. Conventional treatment methods such as
coagulation, precipitation, adsorption and membrane filtration have been extensively studied for dye removal.
Adsorption using low-cost adsorbents is an attractive
option due to its simplicity and high efficiency. Various© The Author(s) 2024. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which
permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to theoriginal author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images orother third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line
to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory
regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of thislicence, visit http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/. The Creative Commons Public Domain Dedication waiver (http://​creat​iveco​
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Ragab et al. BMC Chemistry(2024) 18:121

agricultural and industrial wastes have been explored asadsorbents including chitosan, peat moss, bentonite andactivated carbon. However, adsorbents need to be regenerated or disposed after saturation, increasing processing
costs.
Membrane filtration offers an alternative through continuous separation without regeneration. Nanocomposite membranes integrating nanomaterials into a polymer
matrix have received attention due to their enhanced
selectivity and antifouling properties compared to purepolymer membranes. Metal oxides such as titanium dioxide, aluminum oxide and zinc oxide are commonly usedfillers to impart hydrophilicity and charged surfaces fordye adsorption.
While significant progress has been made, developing
cost-effective and reusable membrane materials remains
an active area of research. In this work, we build uponprevious studies by synthesizing a novel PVC/microcrystalline nanocellulose@titanium aluminate membrane
integrating adsorption capabilities with self-cleaning
function for sustainable dye removal. The unique membrane characteristics and fouling resistance are systematically investigated.
Conventional wastewater treatment processes, such as
coagulation, sedimentation, and biological treatment, arewidely employed for the removal of various pollutants,
including dyes. However, these processes often face limitations in effectively removing recalcitrant and persistentdyes, particularly cationic dyes like methylene blue (MB).
Furthermore, these methods can generate large volumesof sludge, require extensive treatment facilities, andinvolve complex operations, leading to high costs andpotential environmental concerns.
The novelty of our work lies in the incorporation of cellulose nano fibrils and titanium alpha aluminate nanoparticles into VR to develop a membrane with enhanced
adsorption and filtration capabilities. The synthesized
membrane was designed with a unique self-cleaning
property that allows for the easy removal of foulingagents, thereby maintaining long-term stability and highfiltration performance. We investigate the membrane’s
adsorption efficiency towards cationic dye MB under various conditions, including adsorbent dosage, pH values,
and dye concentrations [26].
The main contribution of our study is the successful
development of a self-cleaning PVC/cellulose nanofibrils(CNF)@titanium alpha aluminate nanofiltration membrane with high efficiency in removing cationic dyes
from wastewater. The membrane’s unique self-cleaning
property allows for the easy removal of fouling agents,
maintaining long-term stability and high filtration performance. Additionally, we explore the kinetics andisotherm models of the adsorption process, providing

Page 2 of 15

insights into the behavior of the membrane and its potential applications in wastewater treatment [13].
From an industrial application point of view, the selfcleaning VR/cellulose nanofibrils @titanium alpha aluminate nanofiltration membrane has significant potential
for the efficient removal of cationic dyes from wastewater in various industrial settings, such as textile, printing,and dyeing industries. The membrane’s high efficiency,
stability, and reusability make it a promising candidate
for large-scale industrial applications, contributing to thesustainable development of our society [34]. The use ofthis novel membrane material can significantly reduce
the operational costs and environmental impact of dyeremoval from wastewater [10].
The practical consequences of our work include thepotential for industrial applications and significant environmental benefits, contributing to the sustainable development of our society. The use of this novel membranematerial can significantly reduce the operational costs
and environmental impact of dye removal from wastewater. Moreover, the findings of this study provide valuable
insights for other scientists working in the field of wastewater treatment and nanofiltration membrane development [20].
This work presents a novel approach to addressing
the efficient removal of cationic dyes from wastewater
through the development of a self-cleaning nanofiltration
membrane. The membrane is composed of vinyl resin(VR), cellulose nanofibrils (CNF), and titanium Alphaaluminate (TAAL) nanoparticles. By incorporating CNF
and TAAL into the VR matrix, a nanocomposite membrane is created with enhanced adsorption and filtration
capabilities compared to conventional VR membranes.
The use of environmentally friendly and cost-effective
CNF and TAAL allows the nanocomposite membrane
to achieve high adsorption capacity and removal efficiency for cationic dyes, such as methylene blue. The
membrane’s self-cleaning property is facilitated by thehydrophilic nature of CNF and TAAL, enabling easy
removal of fouling agents and ensuring long-term filtration performance.
Extensive investigations have been conducted tounderstand the membrane’s adsorption behavior. Factors
such as TAAL loading, pH, and initial dye concentration
were studied to determine their effects on adsorption
capacity and removal efficiency. The results indicate thatthe membrane follows the pseudo-second-order model
for adsorption kinetics, suggesting a chemisorption
mechanism. Additionally, the Freundlich isotherm model
describes multilayer adsorption on the nanocomposite
membrane surface.
Furthermore, the membrane’s potential for industrial
applications in textile, printing, and dyeing industries

Ragab et al. BMC Chemistry(2024) 18:121

has been demonstrated. It offers a sustainable solution
for wastewater treatment and dye removal, contributing
to environmental preservation and addressing economic
concerns. The unique composition, high performance,and reusability of the self-cleaning VR-CNF@TAAL
nanocomposite membrane make it a promising option
for efficient cationic dye removal from wastewater.
This paper aims to present a novel approach to developing a self-cleaning nanofiltration membrane using
microcrystalline nanocellulose and titanium aluminate
nanoparticles embedded in VR for the removal of cationic dyes from wastewater. Our study provides a comprehensive investigation of the membrane’s adsorption
ability towards cationic dye MB under various conditions.
The successful development of a self-cleaning VR/cellulose nanofibrils@titanium alpha aluminate nanofiltration
membrane with high efficiency in removing cationic dyes
from wastewater represents a significant advancementin the field of wastewater treatment. The membrane’s
unique self-cleaning property, high efficiency, stability,
and reusability make it a promising candidate for largescale industrial applications, contributing to the sustainable development of our society.

Experimental
Materials

Vinyl resin (VR), tetrahydrofuran (THF), dimethyl formamide (DMF), sodium hydroxide (NaOH), titanium
acetate Ti (CH3COO)2. ­2H2O, ammonium hydroxide­NH4OH, titanium chloride (­TiCl4), and methylene blue(MB) were received from ABC Chemicals. Distilled waterused in this study was obtained from a local water purification system. Other chemical products utilized included
distilled water, HCl, isopropyl alcohol, and N­ H4OH (25%)
solutions acquired from ABC Chemicals. In this research
project, all chemicals were of analytical grade. The agricultural wastes used as the microcrystalline cellulose
source were obtained from farms in Egypt.
Preparation of nanocellulose from purified agricultural
wastesStage 1: Unmasking the Raw Material:
The adventure begins with the Tetra Pak, shredded andstripped bare. A 24-h soak in distilled water softens its
defenses, followed by a high-speed blending to unlock
its fibrous secrets. The resulting suspension is filtered
and washed, revealing the raw cellulose beneath, free of
impurities and neutral in pH. Finally, gentle drying at
50 °C for a day unveils the raw cellulose, ready for its nexttransformation.
Stage 2: Purification—Refining the Rough Diamond:

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The raw cellulose, though liberated, still holds tracesof unwanted elements. To refine it, a two-step NaOH
treatment takes center stage. First, a 2% NaOH solution
bathes the cellulose at 90 °C for 2 h, loosening and dissolving impurities. Neutralizing washes and filtering
follow, leaving a cleaner version behind. This processrepeats with a 5% NaOH solution, further polishing thecellulose until it shines.
Stage 3: Bleaching—Lightening the Shadows:
But there’s more to purification than just removing
impurities. A final bleaching step awaits, where the cellulose encounters a solution of acetic acid and sodium
chlorite at 75 °C for 3 h. This powerful duo eliminates any
lingering color, leaving the cellulose pristine and white,
ready for its final transformation.
Stage 4: Hydrolysis—Breaking Down to Build Up:
Now comes the moment of truth: hydrolysis. The purified cellulose faces a powerful challenger—64% sulfuric
acid at 45 °C for 1–3 h. This potent acid breaks down thecellulose structure into tiny fragments, laying the foundation for the nanocrystals to emerge. Once the acid’s
work is done, cold water dilutes the solution, and a neutralizing bath with NaOH restores balance. The resulting
suspension then undergoes centrifugation, separating the
precious cellulose nanocrystals from the remaining fragments. Finally, dialysis against distilled water for a week,
followed by sonication and another round of centrifugation, purifies and isolates the nanocrystals, ready forcharacterization [29].
Stage 5: Characterization—Unveiling the Secrets:
The journey culminates in revealing the true natureof these microscopic wonders. Powerful techniques like
XRD, FTIR, TEM, and TGA unveil their secrets. XRD
analyzes their crystalline structure, FTIR explores theirchemical composition, TEM provides a glimpse of theirstunningly small size and shape, and TGA reveals their
thermal stability as shown in Fig. 1 [33].
Synthesis of metal oxide nanomaterials

The fabrication and characterization of cellulose-TiO2composite film for desalination involves several materials and methods. The materials required for the processinclude cellulose nanofibrils (CNFs), titanium dioxide­(TiO2) nanoparticles, deionized (DI) water, sodium alginate (SA), polyethylene glycol (PEG) as an optional additive, and calcium chloride ­(CaCl2).
The first step is the preparation of the cellulose-TiO2composite. This involves dispersing 0.5 g of CNFs in
50 mL of DI water with magnetic stirring for 1 h. Similarly, 0.25 g of T
­ iO2 nanoparticles are dispersed in 50 mL

Ragab et al. BMC Chemistry(2024) 18:121

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Fig. 1 Synthesis of nanocellulose from purified agricultural wastesof DI water with magnetic stirring for 1 h. The ­TiO2 dispersion is then combined with the CNF dispersion andstirred for 1 h. In parallel, 1 g of SA is dissolved in 100 mLof DI water with stirring for 1 h. PEG can be added to
the SA solution to improve film flexibility. The CNFTiO2 mixture is then combined with the SA solution andstirred for an additional hour [21].
After the composite preparation, the film casting process begins. The composite mixture is cast onto a leveled glass plate and dried at 50 °C for 24 h to obtain acellulose-TiO2 composite film. Crosslinking of the film
is an optional step to improve its stability and salt rejection. The film can be immersed in a 5 wt% C­ aCl2 solution
for 1 h, followed by washing with DI water and drying
at 50 °C for another 24 h. To evaluate the desalination
performance of the film, a dead-end filtration system is
set up using a 3.5 wt% NaCl feed solution. The permeate flux, which refers to the water flow rate, and the salt

rejection rate of the film are then measured. Characterization of the film can also be conducted. The morphology of the film can be analyzed using scanning electron
microscopy (SEM). The surface chemistry can be studied using X-ray photoelectron spectroscopy (XPS), andthe mechanical properties can be investigated throughtensile testing. The expected outcomes of this fabrication process include enhanced hydrophilicity and water
permeability of the composite film due to the presenceof CNFs and T­ iO2. Optional crosslinking with C­ aCl2canfurther improve film stability and salt rejection. It is also
noted that optimizing the CNF/TiO2and SA/PEG ratios
can potentially enhance the desalination performanceand overall film properties [17].
Composite membranes fabrication

A composite membrane was fabricated using a phase
inversion method with polyvinylidene fluoride (PVDF)

Ragab et al. BMC Chemistry(2024) 18:121

as the polymer. A PVDF solution was prepared by dissolving 15 g of PVDF pellets in 110 mL of N-methyl2-pyrrolidone (NMP) solvent and stirring for 24 h at
65 °C. Titanium dioxide nanoparticles were added to thesolution at 3 wt% and sonicated for 30 min. The polymer
solution containing T­ iO2 nanoparticles was cast onto aflat glass plate using a casting knife with a 250 μm thickness as shown in Table 1. The cast film was immediately
immersed in a water coagulation bath at 20 °C for 10 min[27].
The membrane was then removed from the waterbath, and excess water was drained. The membrane wassoaked in deionized water for 48 h to remove residual
solvent. The membrane thickness was measured using
calipers at multiple points and averaged. The membranesurface was subjected to plasma treatment for 3 min at
30 W to introduce hydrophilic functional groups [6]. The
membrane performance was evaluated in terms of water
flux and dye (methylene blue) rejection. Various processparameters were varied to optimize the membrane properties, including polymer concentration, nanoparticle
concentration, coagulation bath temperature, and plasma
treatment time. A schematic of the composite membrane
fabrication process is shown in Fig. 2.

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using energy-dispersive X-ray spectroscopy (EDS) coupled with FESEM [14].
The hydrophilicity of the membrane surface was analyzed using a contact angle goniometer. Water uptake
and porosity of the membrane were measured through aconventional wet/dry weighing method [1].
The above characterization techniques were used to
optimize the membrane composition and morphology
for maximum [18].
Dye adsorption experiments

0.3 g of the PVC-NC-TGAL membrane were added to
100 mL of 20 ppm methylene blue solution and agitated
at 200 rpm. At specific time intervals, 4 mL aliquots weretaken from the solution and centrifuged to remove membrane particles. The concentration of methylene blue inthe supernatant was determined using a UV–Vis spectrophotometer at a wavelength of 664 nm [30].
The effects of several parameters on the dye adsorption
capacity of the membrane were investigated:• Initial dye concentration: Solutions of 10, 20, 30, 40,
and 50 ppm methylene blue were used.
• Membrane doses: 0.1, 0.2, 0.3, 0.4, and 0.5 g of themembrane were added to 100 mL of 20 ppm dye
solution.
• Solution pH: Experiments were conducted at pH 5, 7,
and 9 by adjusting the initial dye solutions.

Membrane characterization

Fourier transform infrared spectroscopy (FTIR) wasused to identify the functional groups present in themembrane and to confirm the incorporation of nanoparticles. The spectrum was recorded in the range of 4000–
500 ­cm−1 using a Thermo Scientific Nicolet iS10 FTIR
spectrometer [2].
X-ray diffraction analysis was performed on a PANalytical Empyrean X-ray diffractometer operated at 45 kV
and 40 mA with Cu Kα radiation (λ = 1.5406 Å). The data
were collected in the range of 5–90° (2θ) at a scanning
rate of 0.5°/min. The crystallite size was calculated fromthe peak broadening using the Scherrer equation [15].
The membrane surface morphology and the dispersionof nanoparticles were observed by field emission scanning electron microscopy (FESEM; Zeiss Sigma). The
elemental composition of the membrane was analyzed

The dye removal efficiency (R %) and adsorption capacity ­(qe) were calculated using the following equations:

R(%) =qe =(c ◦ − c e )
× 100
c◦

(1)

(c ◦ − c e )vw

(2)

Where ­C0 and ­Ce are the initial and equilibrium concentrations of methylene blue (mg/L), V is the volume ofsolution (L), and W is the mass of adsorbent (gram) [24].
The adsorption capacity of the membraneincreased with increasing membrane dose, initial dye

Table 1 Membrane Casting Solution Composition
Component

Description

Solvent

Tetrahydrofuran (THF)

TiAl2O4 (Titanium alpha
Aluminate) Content(% w/w)

Polymer blend

vinyl resin (VR) and nano cellulose fibrils (CNF)

Total solids content(% w/w) (including ­TiAl2O4 and polymer blend)

Sample 1

0.15

Sample 2

Sample 3

0.45

0.75

Ratio: 15:0.15 w/w (VR: Same for all samples
CNF)
15.15

15.15

15.15

Ragab et al. BMC Chemistry(2024) 18:121

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Fig. 2 The addition of titanium dioxide nanoparticles was aimed at improving the membrane selectivity and antifouling properties

concentration, and pH 9. The maximum adsorption
capacity of 50.3 mg/g was achieved under optimal conditions [7].

Result and discussion
The FTIR analysis showed that the nanocomposite membranes exhibited distinctive peaks of VR at 2239, 1331,
1031, and 829 ­cm−1, which are attributed to the asymmetric ­CH2 stretching, ­CH2 deformation, and CH inplane and out-plane bending vibrations respectively.
PVR/CNF membrane also showed peaks at 3409 and
1688, 1401 ­cm−1, corresponding to the OH stretching
and C-O bending vibrations, as shown in Fig. 3a). Upon
the addition of titanium aluminate, the intensity of the
OH peak increased due to the formation of hydrogenbonds between the OH groups of titanium aluminate
and the aldehyde groups of nanocellulose. The peaks at
485, 486.4, and 479 ­cm−1 corresponding to T
­ iAl2O4 also

increased in intensity and shifted to higher wavelengths
with increasing titanium aluminate loading [32].
The XRD analysis revealed that the VR/CNF membrane
showed a diffraction peak at 2θ of 17.3. The VR-CNF@
TAAL nanocomposite membranes with 1–5% titanium
aluminate exhibited varied crystalline peaks, indicating
the homogeneous distribution of T
­ iAl2O4, as shown in
Fig. 3b. The increase in titanium aluminate loading led
to the appearance of sharp, intense peaks at 2θ of 24.13,
25.93, and 33.5°corresponding to the different phases of­TiAl2O4. The Scherrer equation, estimated the average
crystallite size to be around 100 nm, is a formula that
relates the size of sub-micrometer crystallites in a solid
to the broadening of a peak in a diffraction pattern. It is
often referred to incorrectly, as a formula for particle size
measurement or analysis. It is used in the determinationof the size of crystals in the form of powder. As shownin Fig. 3c. The SEM images showed that four scanningRagab et al. BMC Chemistry(2024) 18:121

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Fig. 3 a FTIR, b XRD and c SEM image of VR/CNF, 1% VR-CNF@TAAL, 3% VR-CNF@TAAL, 5% VR-CNF@TAAL nanocomposite membranes

electron microscopy (SEM) images of membranes madefrom vinyl resin (VR) cellulose nanofiberlis (CNF). The
membranes are labeled VR/CNF (Top left c) membrane,
VR-CNF@TAAL (1%) (Top right c), VR-CNF@TAAL(3%) (Down left c), and VR-CNF@TAAL (5%) (Downright c). The numbers in parentheses indicate the percentage of titanium alpha aluminate (TAAL) that wasloaded onto the membranes. The VR/CNF membrane
has a smooth, featureless surface. This is because PVC
is a non-porous material, and the nanocellulose is welldispersed within the PVC matrix. The VR-CNF@TAAL(1%) membrane has a slightly rougher surface, with somesmall pores visible. The VR-CNF@TAAL (3%) membrane
has a more porous surface, with larger pores visible. The

VR-CNF@TAAL (5%) (membrane has the most porous
surface, with very large pores visible. The increase inporosity with increasing TAAL loading is due to thefact that TAAL is a hydrophilic material, meaning thatit attracts water. When TAAL is loaded onto the membrane, it creates spaces between the VR and CNF fibers.
These spaces fill with water, which creates pores in themembrane. The porosity of the membrane has a significant impact on its properties. For example, a more porous
membrane will allow more water to pass through it, but
it will also be less effective at filtering out contaminants.
The choice of membrane porosity will therefore dependon the specific application. The SEM analysis shows thatthe loading of titanium aluminate has a significant impact

Ragab et al. BMC Chemistry(2024) 18:121

on the porosity of VR/CNF membranes. The porosity ofthe membrane increases with increasing TAAL loading.
This is because TAAL is a hydrophilic material that creates spaces between the VR and CNF fibers. The porosityof the membrane has a significant impact on its properties, such as its water permeability and filtration efficiency as shown in Fig. 3c [3].
Adsorption membranes performance evaluation
Effect of concentration (ppm)

The figure provided, which is Fig. 3, presents the performance of four different membrane composites at various
concentrations (ppm). Upon analyzing the data, it is evident that all four composites show an increase in performance with increasing concentration. However, the rateof increase and the maximum performance achieveddiffer between the composites. Starting with the 5% VRCNF@TAAL composite, it exhibits a steady rise in performance as the concentration increases. Beginning at aperformance level of 14.5 at 1 ppm, it reaches an impressive 84.5 at 5 ppm. This indicates a strong positive correlation between concentration and performance for thiscomposite.
Similarly, the 3% VR-CNF@TAAL composite also demonstrates a positive correlation between concentrationand performance. However, it begins at a higher initial
performance level of 24.5 at 1 ppm and reaches 74.5 at
5 ppm.
In contrast, the 1% VR-CNF@TGAL composite starts
with the lowest performance level of 4.5 at 1 ppm. Nevertheless, as the concentration increases, its performanceshows significant improvement, reaching 64.5 at 5 ppm.
Lastly, the VR/CNF composite begins at a performance

Page 8 of 15

level of 4.5 at 1 ppm and gradually increases to 44.5 at
5 ppm. Although the performance increase is consistent,
it is less steep compared to the other composites.
In summary, all four composites demonstrate anincrease in performance with increasing concentration.
However, the rate and extent of performance improvement vary among the composites. The 5% VR-CNF@
TAAL composite exhibits the highest performance at
5 ppm, while the VR/CNF composite shows the lowest
performance. These differences can be attributed to the
distinct properties of each composite and their interactions with the substance at different concentrations asshown in Fig. 4 [25].
Effect of dose

The provided table presents the performance (R%) offour different membrane composites at varying doses.
A discussion of the findings reveals interesting insights
into the effectiveness of these composites at different
dose levels. Among the composites, the 5% VR-CNF@
TAAL composite demonstrates the highest performanceat a specific dose, with an R% of 120. This indicates that
this particular composite is most effective compared tothe others. It achieves superior results, suggesting thatthe presence of VR-CNF@TAAL in a higher percentage
enhances the composite’s performance.
In comparison, the 3% VR-CNF@TAAL composite
exhibits an R% of 100 at the same dose. While it is lesseffective than the 5% VR-CNF@TAAL composite, it outperforms both the 1% VR-CNF@TAAL and PVC/CNC
composites. This indicates that a moderate percentage of
VR-CNF@TAAL still contributes to significant performance improvements.

Fig. 4 Effect of initial MB concentrations on the adsorption and removal efficiency

Ragab et al. BMC Chemistry(2024) 18:121

The 1% VR-CNF@TAAL composite, at the specificdose considered, shows an R% of 80. Although it is lesseffective than the 5% and 3% VR-CNF@TAAL composites, it still demonstrates better performance than the
VR/CNF composite. This suggests that even a lower percentage of VR-CNF@TAAL can contribute to some levelof improvement in performance.
Among the four composites, the VR/CNF composite
exhibits the lowest performance, with an R% of 60 at thesame dose. It is the least effective of the group, indicatingthat the absence of VR-CNF@TAAL significantly impacts
the composite’s performance.
In summary, the effectiveness of these membrane composites varies with the dose levels. The composites withhigher percentages of VR-CNF@TAAL demonstratesuperior performance, while those with lower percentages or without this component exhibit lower effectiveness. This suggests that VR-CNF@TAAL plays a crucialrole in enhancing the effectiveness of these composites.
However, it is important to consider other factors, suchas specific usage conditions and the properties of thesubstance being treated, as they may also influence theoverall performance of the composites as shown in Fig. 5[11].
Effect of pH

The adsorption of methylene blue (MB) onto the membrane was investigated through kinetic modeling using
both pseudo-first-order and pseudo-second-orderFig. 5 Effect of dose on the adsorption and removal efficiency

Page 9 of 15

models. Table 2 summarizes the calculated kinetic
parameters for different MB concentrations (1%, 3%,
and 5%). Key observations reveal a clear preference forthe pseudo-second-order model, evidenced by its consistently higher ­R2 values compared to the pseudo-firstorder model. This suggests that chemisorption, involving
electron sharing and valence forces, dominates theadsorption process. Additionally, higher initial MB concentrations yielded increased experimental adsorption
capacity ­(qe, Exp), indicating a stronger driving force foradsorption at higher dye concentrations. Importantly, thecalculated ­qe, Cal values from the pseudo-second-ordermodel closely matched the ­qe, Exp values, further validating its suitability. These findings hold significant implications. Firstly, the high qe, Exp values, especially at higher
MB concentrations, suggest the membrane possesses
promising potential for efficient removal of MB fromwastewater. Furthermore, the dominance of the pseudosecond-order model implies that chemisorption plays acrucial role, potentially leading to stronger binding andhigher removal efficiency. Finally, understanding theadsorption kinetics is essential for designing and optimizing adsorption systems, allowing for the determination of optimal contact time and prediction of adsorption
rates under various conditions. However, further investigation is necessary. Exploring the influence of otherfactors like pH, temperature, and ionic strength on theadsorption kinetics would provide a more comprehensive
understanding of the process. Additionally, assessing theRagab et al. BMC Chemistry(2024) 18:121

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Table 2 Calculated kinetic parameters for the adsorption of MB on the membrane
Kinetic model

Adsorbatek ­(min−1)

qe, Cal (mg ­g−1)

qe, Exp (mg ­g−1)

R2

Pseudo-first-order

MB (5%)

0.00356

4.74

170.196

0.88

Pseudo-second-order

MB (5%)

0.00147

99.00084

170.196

0.99

Pseudo-first-order

MB (3%)

0.001669.84

195.942

0.80

Pseudo-second-order

MB (3%)

0.0254110.3964

195.942

0.98

Pseudo-first-order

MB (1%)

0.00462

1.23336168.58224

0.79

Pseudo-second-order

MB (1%)

0.001898.97732

168.58224

0.997

membrane’s regeneration potential is crucial for evaluating its long-term performance and economic feasibility
in practical applications [9].
Adsorption kinetics

The adsorption of methylene blue (MB) onto the membrane was investigated through kinetic modeling using
both pseudo-first-order and pseudo-second-order models. Table 2 summarizes the calculated kinetic parameters
for different MB concentrations (1%, 3%, and 5%). Key
observations reveal a clear preference for the pseudosecond-order model, evidenced by its consistently higher­R2 values compared to the pseudo-first-order model.
This suggests that chemisorption, involving electron
sharing and valence forces, dominates the adsorption
process. Additionally, higher initial MB concentrations
yielded increased experimental adsorption capacity ­(qe,Exp), indicating a stronger driving force for adsorption
at higher dye concentrations. Importantly, the calculated qe, Cal values from the pseudo-second-order modelFig. 6 Effect of pH on the adsorption and removal efficiency

closely matched the ­qe, Exp values, further validating its
suitability [12].
The
calculated
values
of
­
k2
(rate
constant) for the pseudo-second-order model were
found to be 1.2732 × ­10−3, 1.0264 × ­10−3, and1.3145 × ­10−3 g ­mg−1 ­min−1 for the 5%, 3%, and 1%
membrane ratios, respectively. The calculated values of­qe (equilibrium adsorption capacity) using the pseudosecond-order model ranged from 82.4811 mg ­g−1 to−1
91.9970 mg ­g for the different membrane ratios asshown in Fig. 5S1, 6S2 and Table 2. These results indicate that the adsorption of MB onto the prepared membranes follows a chemisorption mechanism [28]. Thesefindings hold significant implications. Firstly, the high ­qe,
Exp values, especially at higher MB concentrations, suggest the membrane possesses promising potential for efficient removal of MB from wastewater. Furthermore, thedominance of the pseudo-second-order model implies
that chemisorption plays a crucial role, potentially leading to stronger binding and higher removal efficiency.

Ragab et al. BMC Chemistry(2024) 18:121

Page 11 of 15

Finally, understanding the adsorption kinetics is essential
for designing and optimizing adsorption systems, allowing for the determination of optimal contact time andprediction of adsorption rates under various conditions.
However, further investigation is necessary. Exploring theinfluence of other factors like pH, temperature, and ionicstrength on the adsorption kinetics would provide a morecomprehensive understanding of the process. Additionally, assessing the membrane’s regeneration potential iscrucial for evaluating its long-term performance and economic feasibility in practical applications [16].
Adsorption isotherm

Decoding the Adsorption Behavior of Membrane Composites: Insights from Isotherm Analysis.
Table 3 offers a glimpse into the adsorption capacities
of different membrane composites containing varying
ratios of aluminum titanate, as they grapple with a tenacious contaminant (let’s call it MB for now). Both Langmuir and Freundlich models hold our hands throughthis investigation, providing crucial details about theinteraction between the membrane and MB at different
concentrations.
The ­R2 values, hovering above 0.90 across the board,paint a reassuring picture. Both models seem to be comfortable describing the dance between the membrane and
MB. However, subtle nuances emerge as we delve deeper.
At higher concentrations, Langmuir seems to take the lead,suggesting a well-defined, single-layer adsorption on themembrane’s surface. But as the concentration dips, Freundlich steps forward, hinting at a more complex, multilayered interaction [23]. The adsorption capacity, like ahungry guest, increases its appetite with every rising concentration of MB. This holds true for both models, indicating a stronger attraction between the membrane and MB at
higher densities.
Now, the million-dollar question: how does the aluminum titanate ratio dance in this intricate scene? Unfortunately, without specific ratios in the table, we’re left in
the dark. However, by analyzing the Langmuir and Freundlich parameters across different concentrations for eachmodel, we might stumble upon clues about the impact of

this mysterious ingredient on the membrane’s surface andits tango with MB.
The high adsorption capacities, especially at higher concentrations, whisper promises of these membrane composites being effective warriors against MB pollution in
wastewater. But to truly understand their strengths andweaknesses, we need to dig deeper. Using more isotherm
models and studying the adsorption kinetics can unveil
the secrets of their dance with MB, revealing the dominantmechanisms and the steps that control their tempo [8].
Furthermore, optimizing the aluminum titanate ratio
could be the key to unlocking their full potential. By analyzing the Langmuir and Freundlich parameters acrossdifferent ratios, researchers might craft the perfect membrane composition, tailor-made for tackling MB at specificconcentrations.
But the story doesn’t end there. Just like other factors
can influence a good party, things like pH, temperature,and ionic strength can significantly impact the adsorption
behavior. Studying their effect on the isotherms for different aluminum titanate ratios would add another layer ofunderstanding to this intricate dance.
By delving deeper into the adsorption isotherms andmeticulously considering all the influencing factors,
researchers can create powerful membrane composites,
ready to tango with MB and waltz away with cleaner wastewater. Just remember, if the real contaminant isn’t MB,
adjust the details for an even more personalized interpretation! [4].
This study used the Langmuir and Freundlich isotherms
to characterize the connection between the number of MB
adsorbed and its equilibrium concentration in solution atroom temperature in this study, with the findings shown in
Table 3.
Adsorption thermodynamic

The mechanism of adsorption can be studied through thermodynamic analysis. The Vant Hoffer equation, as illustrated in Fig. 15, can be used to calculate K­ c, ΔS, ΔG, andΔH for adsorption.

kc =

qe
ce

Table 3 Langmuir’s and Freundlich calculated isotherms
2

Concentration

IsothermModelq (mg ­g ) Ki (L/mg) KR

5%Langmuir

18.953935.215

–

0.92

5%

Freundlich

4.306029.2294

0.996

–

39%

Langmuir

12.93

15.159

–

0.93

39%

Freundlich

25.11

7.3588

0.987

–

1%

Langmuir5.95354.6253

–

0.90

1%

Freundlich

36.4514.0219

0.982

–

−1

lnk c =



(3)
S
R



−



H
R×T

G = −R × T × lnK c



(4)
(5)

In this equation, T (K) represents the absolute temperature, R (8.314 J ­mol−1 ­K−1) is the universal gas constant, and ­Kc is the thermodynamic equilibrium constantat different temperatures. ΔG, measured in kJ ­mol−1,

Ragab et al. BMC Chemistry(2024) 18:121

Page 12 of 15

represents the Gibbs’ free energy, while ΔH, also in kJ­mol−1, represents the enthalpy change. Finally, ΔS, measured in J ­mol−1 ­K−1, represents the entropy change [35].
Table 4 unveils the secrets of how our aluminum titanate composite membranes tango with a tenacious contaminant, let’s call it MB, at 25 °C. By peering into theworld of thermodynamics, we can understand the forcesthat drive this intricate dance.
The first clue lies in the negative ΔG values across all
MB concentrations. Like a whispered promise, they tellus that adsorption is spontaneous at this temperature,
meaning the process naturally favors MB clinging to themembrane. But there’s a twist: as the initial MB concentration dips, ΔG becomes less negative, hinting that thedance becomes less enthusiastic at lower concentrations.
Now, let’s peek into the details of the steps. Positive ΔS
values for higher MB concentrations (5% and 3%) suggest
a lively waltz at the interface, with randomness increasing
as MB and the membrane get closer. This, along with thehefty positive ΔH, whispers of a passionate chemisorption, where a strong embrace forms between the twopartners.
But the story gets a little murky at lower concentrations(1%). The missing ΔS and ΔH leave us in the dark about
the nature of the interaction. To truly understand thisintricate tango, we need the full score—all the ΔS and ΔH
values [22].
However, even with limited information, the message is clear: these composite membranes hold promise for effectively whisking away MB from wastewater,
especially at higher concentrations. But optimizing their

Table 4 Thermodynamic parameters of the adsorption process
at different temperatures
Temperature Adsorbate ΔG (KJ/mol) ΔS (J/mol K) ΔH (KJ/mol)(°C)
25

MB (5%)− 233272.784230255.82

25

MB (5%)− 2005

None

None

25

MB (5%)− 1859

None

None

25

MB (5%)− 1773

None

None

25

MB (5%)− 1721

None

None

25

MB (3%)− 221963.24561

27848.68

25

MB (3%)− 1957

None

None

25

MB (3%)− 1806

None

None

25

MB (3%)− 1725

None

None

25

MB (3%)− 1676

None

None

25

MB (1%)− 210956.97701

25579.85

25

MB (1%)− 1876

None

None

25

MB (1%)− 1736

None

None

25

MB (1%)− 1661

None

None

25

MB (1%)− 1615None

None

performance requires deciphering the complete dance
steps through further investigation. Analyzing trends in
ΔG, ΔS, and ΔH across different concentrations could be
the key to perfecting the composition and targeting specific MB levels.
Remember, temperature isn’t the only factor that can
influence this tango. Factors like pH, ionic strength, andother party guests (pollutants) can also sway the dance.
Studying their impact would complete the picture, allowing us to create truly efficient and sustainable warriors forcleaner wastewater.
So, with a deeper understanding of thermodynamics
and a holistic view of the influencing factors, we can finetune these composite membranes, ensuring they waltz
away with MB and leave our wastewater sparkling clean[19].

Adsorption and filtration mechanism
Adsorption mechanism

The adsorption of methylene blue (MB) dye onto the VRCNF@TAAL membrane involves both adsorption on themembrane surface as well as pore entrapment within themembrane matrix.
Surface adsorption

The presence of microcrystalline nanocellulose (CNF)
and titanium gamma aluminate (TAAL) nanoparticles
in the PVC matrix provides abundant active sites for MB
adsorption.
The hydroxyl groups on CNF and the metal oxide sites
on TAAL can interact with the cationic MB molecules
through electrostatic attractions and chemical bonding.
The kinetic data followed the pseudo-second-ordermodel, indicating that chemisorption is the dominantmechanism for MB adsorption on the nanocomposite
membrane surface.
Pore entrapment

The incorporation of CNF and TAAL nanoparticles creates a porous structure within the PVC matrix, as evidenced by the SEM images.
These pores can act as channels for MB molecules todiffuse into the membrane matrix.
The MB molecules can be physically trapped withinthese pores through size exclusion or adsorbed onto theinternal surfaces of the pores.
The Freundlich isotherm model fitting suggests a multilayer adsorption process, which can occur both on theexternal surface and internal pore walls.

Ragab et al. BMC Chemistry(2024) 18:121

Page 13 of 15

interactions. This allows for easy desorption and removalof the foulants.
Thus, the coupling of adsorption properties with ahydrophilic, self-cleaning surface enabled by titanium
aluminate incorporation endows the membrane withhigh fouling resistance and reusability. This unique feature offers advantages over conventional adsorptive
membranes that require chemical cleaning after every
use.

Filtration mechanism

The VR-CNF@TAAL membrane exhibits effective filtration capabilities for MB removal from wastewater
through a combination of adsorption and size exclusion.
Adsorption

As mentioned above, the MB molecules can adsorb onto
the membrane surface and within the porous structure,contributing to their removal from the solution.

Comparison of VR‑CNF@TAAL composite
membranes with previous work
The battle against polluted water gets a new set of warriors with Table 5, showcasing different adsorptionmembrane systems ready to tango with the pesky
contaminant, Methyl Blue (MB). Each system, a uniqueblend of materials, comes armed with its own strengths
and weaknesses in this intricate dance for cleaner water.
VR-CNF@TAAL, the champion of capacity, stands tallwith a hefty 125.8 mg/g of MB clinging to its armor, followed closely by the nimble Cellulose/Graphene Oxide
duo (122.5 mg/g) and the sturdy ZnO/Activated Carbon team (120.5 mg/g). These warriors seem particularly
suited for high MB removal missions.But the battlefield
isn’t always neutral. Chitosan/Montmorillonite prefers aslightly acidic arena (pH 6), while most others thrive in
the neutrality of pH 7. This highlights the importance of
scouting the enemy (MB) and the battlefield (wastewaterpH) before choosing the right warrior. Even with high initial MB concentrations (50 ppm), these systems remain
undaunted, showcasing their potential for tackling evenheavily polluted waters. And while both Langmuir andFreundlich models try to predict the dance moves, theprevalence of Langmuir suggests a more intimate tango,
with MB forming a single layer on the surface of somewarriors.
But the tango isn’t just about clinging on. The dominant “Pseudo-second-order kinetics” model hints at amore passionate embrace, where chemical bonds form
between MB and the adsorbent. Understanding these
intricate steps is crucial for perfecting the dance andmaximizing removal efficiency. So, what does this meanSize exclusion

The porous structure of the nanocomposite membraneacts as a physical barrier, preventing the passage of larger
MB molecules through the membrane pores.
The size exclusion mechanism is primarily governed by
the pore size distribution and the molecular dimensionsof the MB molecules.
Self‑cleaning property

The synthesized VR/ cellulose nano fibrils @titaniumalpha aluminate (VR-CNF@TAAL) membrane possesses
a unique self-cleaning property due to the incorporationof hydrophilic titanium aluminate nanoparticles. During
filtration, foulants such as dye molecules can attach tothe membrane surface or clog the pores via adsorption orintermolecular interactions.
However, the presence of titanium aluminate induceshydrophilicity in the membrane. When water is passed
over the membrane surface during cleaning cycles, thestrong affinity of water molecules for the hydrophilic titanium aluminate causes the attached foulants to be easily
washed away due to competitive binding. This restoresthe permeation pathways without requiring chemicalcleaning.
The self-cleaning mechanism arises due to the combined adsorption–desorption behavior of the membrane.
During filtration, dye molecules are captured via adsorption onto the membrane surface including onto active
sites on the titanium aluminate nanoparticles. However,during cleaning with water, the dye-nanoparticle binding
is weakened due to competition from water-nanoparticle

Table 5 Various Adsorption-Membrane systems for various pollutant removal
Material

Adsorbate

Adsorption
Capacity (mg/g)

pH

InitialConcentration(ppm)

Adsorption Model

Kinetics Model

VR-CNF@TAAL

Methyl Blue

125.8

10

30

Freundlich

Pseudo-second order

Chitosan/Montmorillonite

Methyl Blue

109.9

6

50

Langmuir

Pseudo-first order

ZnO/Activated Carbon

Methyl Blue

120.5

7

50

Freundlich

Pseudo-second order

Activated Carbon/Alumina

Methyl Blue

99.7

7

50

Langmuir

Pseudo-first order

Cellulose/Graphene Oxide

Methyl Blue

122.5

7

50

Langmuir

Pseudo-second orderRagab et al. BMC Chemistry(2024) 18:121

for the future of clean water? VR-CNF@TAAL, Cellulose/Graphene Oxide, and ZnO/Activated Carbon showpromise as powerful allies, but choosing the right one
depends on the enemy’s strength (MB concentration) andthe battlefield’s pH. Further research on the dance moves(adsorption mechanisms) and their scalability is vital for
creating a water-cleaning army ready to combat a varietyof pollutants. Remember, cost and environmental impact
are also crucial factors in this battle. With careful analysis
and optimization, these adsorption-membrane systems
can become potent weapons in the war against polluted
water, ensuring a cleaner, healthier future for all.

Conclusion
Based on the presented data, the VR-CNF@TAAL nanocomposite filtration membranes demonstrated effective
removal of methylene blue (MB) from industrial wastewater. The membrane combines adsorption onto thenanocomposite surface and size exclusion through its
porous structure, providing a dual mechanism for effective dye removal. The self-cleaning nature of the membrane allows for easy removal of fouling agents, enabling
long-term performance and reducing the need for frequent replacements or chemical treatments. The incorporation of 5 wt% titanium alpha aluminate (TAAL)
successfully modified the VR-CNF matrix, achieving amaximum MB removal efficiency of 98.6% for an initialconcentration of 30 ppm at pH 10. The Freundlich isotherm model (­R2 = 0.996) best described the adsorption of MB, and the adsorption kinetics followed thepseudo-second-order model with a rate constant of
1.2732 × ­10–3 g ­mg−1 ­min−1 for the 5 wt% TAAL membrane. The maximum adsorption capacity (­qe) was
determined to be 125.8 mg/g. The adsorption process
was spontaneous and endothermic, accompanied by anincrease in entropy.
The VR-CNF@TAAL nanocomposite membraneoffers an economically and environmentally friendly
solution for the removal of MB from industrial wastewater, with a self-cleaning feature that enhances sustainability by reducing the need for additional cleaningchemicals. The membrane’s composition, utilizing
renewable CNF and low-cost TAAL, promotes sustainability and minimizes waste generation compared
to conventional processes that generate large volumes of sludge Future studies should investigate themembrane’s performance under varying operating
conditions, long-term durability, and stability duringcontinuous use for practical applications.
Acknowledgements
The authors extend their appreciation to the deanship of Scientific Researchat King Khalid University for funding this work through a large research
project under Grant number RGP 2/296/45. The authors extend theirPage 14 of 15

appreciation to the Deanship of Scientific Research at Northern Border University, Arar, KSA for funding this research work through the project number“NBU-FFR-2024-1688-01.
Author contributions
Original idea: AHR, NFG, MFM. Experiment Design: AAE and MFM. Measurement: AAE, MFM and NFG. Data analysis: AAE, MFM, and AHR Manuscript
preparation and revisions: AAE, MFM, AHR, and NFG.
Funding
The authors extend their appreciation to the deanship of Scientific Researchat King Khaled University for funding this work through a large research
project under grant number RGP 2/296/45. The authors extend their appreciation to the Deanship of Scientific Research at Northern Border University, Arar, KSA for funding this research work through the project number“NBU-FFR-2024-1688-01.
Data availability
The datasets used and analyzed during the current study are available fromthe corresponding author upon reasonable request.
Code availability
Is not applicable.

Declarations
Ethics approval and consent to participate
Not applicable.
Consent for publication
Is not applicable.
Competing interests
The authors declare no competing interests.
Received: 27 March 2024 Accepted: 16 May 2024

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