Article

Fabrication and Performance of PVAc-Incorporated Porous

Self-Standing Zeolite-Based Geopolymer Membranes for Lead
(Pb(II)) Removal in Water Treatment
Samar Amari 1, *, Mariam Darestani 2 , Graeme Millar 1 and Bob Boshrouyeh 3

1 School of Mechanical, Medical & Process Engineering, Faculty of Engineering,

Queensland University of Technology (QUT), Brisbane, QLD 4000, Australia
2 School of Mechanical Engineering, Western Sydney University (WSU), Sydney, NSW 2751, Australia;
[email protected]
3 Sustainable Minerals Institute, The University of Queensland, Brisbane, QLD 4072, Australia
* Correspondence: [email protected]

Abstract: This study explores the fabrication, structural characteristics, and performance
of an innovative porous geopolymer membrane made from waste natural zeolite pow-
der for Pb(II) removal, with potential applications in wastewater treatment. A hybrid
geopolymer membrane incorporating polyvinyl acetate (PVAc) (10, 20, and 30 wt.%) was
synthesized and thermally treated at 300 ◦ C to achieve a controlled porous architecture.
Characterization techniques, including Fourier-transform infrared spectroscopy (FTIR),
revealed the disappearance of characteristic C=O and C-H stretching bands (~1730 cm−1
and ~2900 cm−1 , respectively), confirming the full degradation of PVAc. Thermogravi-
metric analysis (TG) and differential scanning calorimetry (DSC) indicated a total mass
loss of approximately 14.5% for the sample with PVAc 20 wt.%, corresponding to PVAc
decomposition and water loss. Energy-dispersive spectroscopy (EDS) elemental map-
ping showed the absence of carbon residues post-annealing, further validating complete
PVAc removal. X-ray diffraction (XRD) provided insight into the crystalline phases of the
raw zeolite and geopolymer structure. Once PVAc removal was confirmed, the second
phase of characterization assessed the membrane’s mechanical properties and filtration
performance. The thermally treated membrane, with a thickness of 2.27 mm, exhibited
Academic Editor: Simona Căprărescu
enhanced mechanical properties, measured with a nano-indenter, showing a hardness
Received: 24 February 2025
of 1.8 GPa and an elastic modulus of 46.7 GPa, indicating improved structural integrity.
Revised: 11 April 2025
Accepted: 16 April 2025 Scanning electron microscopy (SEM) revealed a well-defined porous network. Filtration
Published: 24 April 2025 performance was evaluated using a laboratory-scale dead-end setup for Pb(II) removal.
Citation: Amari, S.; Darestani, M.; The optimal PVAc concentration was determined to be 20 wt.%, resulting in a permeation
Millar, G.; Boshrouyeh, B. Fabrication rate of 78.5 L/(m2 ·h) and an 87% rejection rate at an initial Pb(II) concentration of 50 ppm.
and Performance of PVAc-Incorporated With increasing Pb(II) concentrations, the flux rates declined across all membranes, while
Porous Self-Standing Zeolite-Based maximum rejection was achieved at 200 ppm. FTIR and EDS analyses confirmed Pb(II)
Geopolymer Membranes for Lead
adsorption onto the zeolite-based geopolymer matrix, with elemental mapping showing
(Pb(II)) Removal in Water Treatment.
a uniform Pb(II) distribution across the membrane surface. The next step is to evaluate
Polymers 2025, 17, 1155. https://
doi.org/10.3390/polym17091155 the membrane’s performance in a multi-cation water treatment environment, assessing
the sorption kinetics and its selectivity and efficiency in removing various heavy metal
Copyright: © 2025 by the authors.
contaminants from complex wastewater systems.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and Keywords: filtration; geopolymer; heavy metal removal; Pb(II) removal; polyvinyl acetate;
conditions of the Creative Commons porous membrane; water treatment; zeolite
Attribution (CC BY) license
(https://creativecommons.org/
licenses/by/4.0/).

Polymers 2025, 17, 1155 https://doi.org/10.3390/polym17091155

Polymers 2025, 17, 1155 2 of 30

1. Introduction
Industrial activities entail a considerable amount of water consumption and, conse-
quently, a substantial amount of wastewater, including a high level of heavy metals. As
an example, lead mining produces large amounts of effluent containing Pb(II), which po-
tentially contaminates the environment and freshwater bodies [1]. The detrimental effects
of heavy metals on human and animal health make the removal of heavy metals from
wastewater and water sources essential. Heavy metals such as Pb(II) are non-biodegradable
and accumulate in living organisms, causing toxic effects, including renal dysfunction and
neurological disorders, even at low concentrations [1,2]. Due to their severe environmental
and health hazards, developing efficient, cost-effective, and sustainable water treatment
technologies is of paramount importance [3].
Various techniques have been employed to remove heavy metals from wastewater,
including membrane filtration, adsorption, chemical coagulation, solvent extraction, and
ion exchange [3]. Membranes, particularly polymeric membranes, dominate wastewater
treatment due to their reliability and widespread use. Membrane separation processes,
such as electrodialysis, ultrafiltration, nanofiltration, and reverse osmosis, have emerged as
effective methods for heavy metal removal from wastewater due to their high efficiency and
selectivity [4]. Compared to the conventional methods mentioned above, the membrane
process offers advantages, including minimal sludge generation, compact system design,
and reduced chemical usage. However, they often face challenges in balancing permeability
and selectivity while addressing membrane fouling, high operational costs, scaling, and
material instability, particularly in demanding industrial applications. Additionally, fossil-
based adsorbents or synthetic membranes can pose environmental or health hazards,
necessitating careful selection and disposal strategies [5].
Recently, inorganic membranes have gained significant attention for heavy metal
separation [6–9]. Porous inorganic membranes are highly tunable, typically resistant to
organic solvents and high temperatures, chemically stable, cost-effective, reusable, and
low-maintenance [9,10]. Additionally, inorganic membranes are less affected by bacte-
rial exposure, which is responsible for the biofouling degradation of most polymeric
membranes [9,10]. Based on their material composition and structural properties, inor-
ganic membranes are typically classified into ceramic membranes, including metal oxides,
zeolites, and MOFs, as well as carbon-based membranes, such as carbon nanotubes and
graphene membranes. [10]. In Table 1, inorganic membranes are compared by their advan-
tages, disadvantages, and applications.

Table 1. Comparison of various inorganic membranes based on performance, applications, and

limitations [10].

Membrane Type Advantages Disadvantages Key Applications

High production costs,
High thermal and chemical Wastewater treatment,
complex multi-step
Metal Oxide stability, suitable for harsh gas separation,
fabrication, high-temperature
Ceramic Membranes environments, tunable pervaporation,
sintering, reproducibility
pore sizes nanofiltration
challenges
Molecular sieving properties,
Fragile support layers, poor
high salt rejection, chemical
compatibility between the Water purification,
stability, eliminates costly
zeolite and substrate, difficult desalination, gas
Zeolite Membranes pretreatment of polymeric RO
large-scale fabrication, separation,
membranes, tunable
presence of intercrystalline pervaporation
hydrophilicity, potential
pores, microdefects
natural source
Polymers 2025, 17, 1155 3 of 30

Table 1. Cont.

Membrane Type Advantages Disadvantages Key Applications

High surface area, tunable High production costs,
porosity, low-temperature Limited industrial
Metal Organic Gas separation, water
synthesis, potential for polymer application, high synthesis
Framework (MOF) purification, solvent
support, mechanically robust, complexity, may suffer from
Membranes recovery, catalysis
lower temperature activation structural instability in
than zeolites aqueous environments
High surface area, antimicrobial
Difficult large-scale Desalination,
activity, ultra-fast water
Carbon Nanotube production, high wastewater treatment,
transport, antimicrobial
(CNT) Membranes cost of synthesis, antimicrobial filtration,
properties, tunable pore size,
reproducibility issues molecular separation
compelling mechanical strength
High water flux, ultra-thin Challenges in creating
Desalination, reverse
Graphene-Based structure, strong chemical uniform nanopores,
osmosis, molecular
Membranes resistance, potential for reproducibility, limited
sieving, gas separation
molecular sieving large-scale availability

Among these techniques, zeolite membranes, known for their molecular sieving proper-
ties, are effective for heavy metal removal from wastewater and gas–liquid separation [10].
Their excellent thermal and chemical stability makes them viable alternatives to organic
membranes [11]. Separation occurs through a combination of size exclusion and ion in-
teractions, leveraging the zeolite’s three-dimensional network to selectively adsorb heavy
metals [12–19]. These membranes are classified as synthetic or natural; synthetic types,
formed on stainless steel or ceramic supports, offer tunable properties but face scala-
bility challenges due to high processing temperatures, intercrystalline voids, and costly
supports [11,17–19]. Natural zeolite membranes provide a cost-effective alternative but
generally exhibit lower water flux [10].
Geopolymer technology, while primarily used in construction [20], has recently gained
attention for membrane fabrication due to its low cost, tunable porosity, and high adsorption
capacity [21]. Several studies have demonstrated the efficiency of geopolymer membranes
in removing toxic heavy metals from aqueous solutions [21]. A ZSM-35 zeolite membrane,
synthesized through the geopolymerization of metakaolin and silica fume, achieved 99.22%
Cd(II) removal at an initial concentration of 500 ppm under vacuum pressure [22]. A
geopolymer–zeolite composite membrane, produced via hydrothermal geopolymeriza-
tion of fluidized bed fly ash waste, showed 85.45% Cr(VI) rejection [23]. These findings
highlight the potential of geopolymer membranes in selective heavy metal adsorption,
benefiting from their ion-exchange capability and high surface area [22]. A bio-inspired
multilayer geopolymer–chitosan membrane demonstrated 97.77% Cu(II) and 99.4% Pb(II)
rejection, alongside the efficient removal of dyes and nanoparticles [23]. The incorporation
of chitosan, a natural biopolymer, enhances metal adsorption via chelation mechanisms,
making it an effective strategy for improving geopolymer membrane performance [23,24].
Zhang et al. [24] developed a geopolymer–chitosan membrane, achieving 95% removal of
triarylmethane dye through a combination of adsorption and molecular sieving. Another
geopolymer–chitosan composite was tailored for broad-spectrum contaminant removal,
achieving 99.38% crystal violet dye rejection, 99.3% oil-in-water separation, and 98.3% PS
nanoparticle removal, suggesting multi-contaminant filtration [25]. Functionalized Cr2 O3 -
geopolymer membranes have also been explored. A self-supporting Cr2 O3 –geopolymer,
synthesized from silica fume and metakaolin, was successfully employed for Cr(III) separa-
tion before being further processed for dye wastewater treatment [26]. A high-strength, self-
supporting NaA zeolite membrane, synthesized through geopolymerization and hydrother-
mal treatment, achieved 99.5% sodium ion rejection during pervaporation desalination [27].
Polymers 2025, 17, 1155 4 of 30

Another NaA zeolite membrane, fabricated via dip-coating a stainless-steel support with
geopolymer paste, was successfully applied for ethanol–water separation under vacuum
pressure [28]. A sodalite–geopolymer membrane, produced using kaolinite-rich laterite
soils, demonstrated efficient ethanol–water separation, indicating the feasibility of utilizing
natural minerals for membrane fabrication [29]. Similarly, analcime–geopolymer composite
membranes, supported on sintered sand core slices, exhibited a 95% rejection rate for
organic pollutants, such as methylene blue [30]. Beyond water treatment, geopolymer
membranes have shown promise in air purification and fuel cell technology. A porous
metakaolin-based geopolymer tube membrane achieved 99.5% particulate matter removal,
demonstrating its potential in air filtration applications [31]. Additionally, a proton ex-
change membrane, developed from chitosan–geopolymer composites, has been proposed
as a cost-effective alternative to Nafion membranes in fuel cells [32]. The separation mecha-
nism of zeolite-based geopolymer filters is not yet fully understood. However, it is widely
recognized as a combination of size exclusion and ion interactions [3]. The geopolymer
structure possesses cation exchange capacity, with exchangeable Na(I), K(I), Ca(II), and
Mg(II) ions embedded within the framework [33]. When heavy metal cations encounter
the filter, they replace these exchangeable cations due to their higher affinity, facilitating
the ion exchange process [34]. In a study on the sorption mechanisms and kinetics of both
natural zeolite and geopolymer sorbents for Pb(II) and other contaminants using sorption
columns, the results revealed that the geopolymer beads exhibited a sorption capacity of
45.32 mg/g, closely matching the 45.93 mg/g recorded for natural zeolite, indicating that
the geopolymer retained its adsorption efficiency [3]. Tables 2 and 3 provide a summary
of geopolymer performance in the removal and separation of heavy metals, highlighting
their adsorption efficiency, structural properties, and experimental conditions. While cation
exchange is the dominant mechanism governing heavy metal sorption, pore architecture
also plays a critical role in the separation efficiency [3]. The highly porous structure en-
hances metal retention by significantly increasing the available surface area and providing
micro- and nanoscale pores that facilitate cation entrapment. Within these pores, metal ions
diffuse and become physically retained through a combination of van der Waals forces and
electrostatic interactions, further enhancing the membrane’s separation performance [35].

Table 2. Geopolymer materials used for the adsorption of heavy metal cations [35].

Source Material Contaminant Removal (mg/g) Adsorbent Dosage/L Adsorption Conditions

Rice husk ash-based geopolymer Cu(II) 126.26 0.1 g pH 8, 25 ◦ C
Metakaolin-based geopolymer Cu(II) 40.9 0.1 g pH 8, 25 ◦ C
Blast furnace slag-based geopolymer As(III) 0.52 25 g pH 6, 20–23 ◦ C
Metakaolin-based geopolymer Mn(II) 72.34 0.08 g pH 6, 30 ◦ C
Rice husk ash-based porous geopolymer Hg(II) 232.60 0.08 g pH 6, 25 ◦ C
Lateritic clay-based geopolymer Co(II) 500 0.5 g pH 7, 60 ◦ C
Metakaolin-based geopolymer Pb(II) 86.2 0.1 g pH 5, 45 ◦ C
Rice husk ash-based porous geopolymer Pb(II) 312.5 0.08 g pH 6, 25 ◦ C
Blast furnace slag-based geopolymer Pb(II) 137.49 2g pH 6.5, 25 ◦ C
Natural zeolite-based geopolymer [3] Pb(II) 45.32 2g pH 7.1, 25 ◦ C

Despite advancements, limited studies have explored the use of natural ultrafine zeo-
lite powders (54 microns) to develop flat-shaped, self-standing membranes with controlled
porosity and high mechanical strength for heavy metal removal. Most existing commercial
applications of zeolites rely on the form and structure of these materials. For example,
water treatment using zeolites is usually achieved by passing water across packed bed
Polymers 2025, 17, 1155 5 of 30

columns filled with larger particles (0.5–2 mm), a common sorption method [4,5], while the
market for ultrafine zeolites remains limited [33]. The geopolymerisation of zeolites can
help to solve these problems and promote the performance of zeolites. Compared to other
inorganic membrane fabrication methods, this approach appears to be more cost-effective,
as it eliminates the need for high-temperature sintering, expensive ceramic supports, and
complex multi-step fabrication processes. Additionally, achieving the porosity of inorganic
membranes, particularly geopolymer membranes, and controlled pore formation remains a
significant challenge. It is vital for membranes to have both high porosity and sufficient
mechanical strength, yet these properties are often counterproductive [3,10,33]. Innovative
fabrication strategies, such as sacrificial phase removal and tailored geopolymerization pro-
cesses, offer potential solutions to optimize pore distribution while preserving membrane
robustness [36].

Table 3. Geopolymer membrane properties and heavy metal removal performances.

Curing
Source Strength Average Pore Removal Water Flux Thickness Adsorption Removal
Contaminant Time and
Material (MPa) Size (nm) (mg/g) (kg/m2 h) (mm) Conditions Rate (%)
Temperature
Metakaolin
Ni (II) 18.67 60 ◦ C–24 h 10–1000 22.69–43.36 99.02 10 pH 6 20–23 ◦ C ~95
geopolymer [37]
NaA zeolite
Na (I) 57 90 ◦ C–6 h 3.77 -- 3.86 <10 -- 99.55%
geopolymer [27]
Metakaolin–Silica
Cd (II) -- 50 ◦ C–48 h -- -- 26.12 10 -- 99.22%
fume [22]
Fly ash–Zeolite [22] Cr (VI) 12.4 80 ◦ C–24 h 15.99 -- 851 6 -- 85.45
Silica fume Cr (III), 80 ◦ C–24 h/
-- -- -- 22 4 -- 100%
Metakaolin [22] Dye 550 ◦ C–4 h

The primary objective of this study is to fabricate a porous zeolite-based geopolymer

membrane and evaluate its Pb(II) removal efficiency using a laboratory-scale dead-end fil-
tration setup. The hypothesis is that the geopolymerization of natural zeolite can effectively
transform ultrafine zeolite powders into a flat-shaped membrane, making them suitable for
Pb(II) removal. Second, to achieve controlled porosity, a polymer was incorporated into
the geopolymer matrix as a sacrificial phase, representing a novel approach in geopolymer
membrane pore formation. This technique involves blending an organic polymer with the
inorganic phase, followed by its removal through dissolution or thermal decomposition to
create a porous structure. However, for the successful integration into zeolite geopolymers,
the polymer must be water-soluble and stable in the highly alkaline geopolymerization
environment. In this study, polyvinyl acetate PVAc emulsion at varying concentrations was
selected to ensure compatibility with the geopolymer matrix, facilitating tailored porosity
while preserving membrane integrity. The major research questions to address include
the following: (1) Is it possible to convert zeolite powders into a permeable membrane
with sufficient mechanical strength? (2) What are the effects of the initial concentration
of Pb(II) ions on water flux and rejection? (3) Would utilizing a water-soluble polymer
(i.e., PVAc) create a desirable porous structure? (4) Can the structure and separation
properties of membranes be manipulated by PVAc?

2. Materials and Methods

2.1. Zeolite Geopolymer Membrane Preparation (ZGM)
To prepare the initial geopolymer slurry, 40 g sodium hydroxide solution (40% w/w,
pH: 12.8), acquired from Chem-Supply Pty Ltd. (Gillman, Australia), and 50 g liquid
sodium silicate (grade D, SiO2 /Na2 O = 1.6–2.6, 55.4–56.4% w/w, pH: 12.3), acquired from
PQ Australia Pty Ltd., Melbourne, Australia, were mixed in a polypropylene beaker. Then,
100 g natural zeolite powder (with an average particle size of 54 µm), supplied from Zeolite
Polymers 2025, 17, 1155 6 of 30

Australia Pty Ltd., Sydney, Australia, was added, and the mixture was blended using a
mechanical mixer for 15 min. Then, 10 mL PVAc emulsion as the structure-directing agent
with different concentrations (10, 20, and 30 wt.%) was added to the slurry (Table 4). The
PVAc used in this study was sourced from Sigma Aldrich, Melbourne, Australia, with an
average molecular weight of 100,000 g/mol and a density of 1.18 g/cm3 , provided in bead
form. The PVAc emulsion was selected due to its water solubility and its non-altering effect
on the pH of materials it contacts. A 30 wt.% PVAc emulsion was prepared by dissolving
30 g of PVAc beads in 40 mL of ethyl acetate under continuous stirring at room temperature
using a magnetic stirrer at 500 rpm, followed by gentle heating to 50 ◦ C until fully dissolved.
During preparation, the relative humidity was 40–60%. The resulting solution was then
slowly added to 70 g of deionized (DI) water while stirring at a high speed of 1000 rpm
to promote emulsification. Finally, the mixture was heated to 50–60 ◦ C under vacuum to
evaporate the solvent, yielding a stable PVAc emulsion with 30% wt. To obtain 20 wt.%
and 10 wt.% emulsions, the 30 wt.% emulsion was diluted with DI water in appropriate
proportions while stirring continuously until homogeneous.

Table 4. Membrane codes and variables examined in preparing geopolymer samples.

Sodium Hydroxide
Membrane Sodium Silicate Natural Zeolite PVAc Emulsion PVAc Emulsion
Solution
Code (55.4–56.4% w/w) Powder Concentration Volume
(40% w/w)
ZGM1 40 g 50 g 100 g 10 wt.% 10 mL
ZGM2 40 g 50 g 100 g 20 wt.% 10 mL
ZGM3 40 g 50 g 100 g 30 wt.% 10 mL

Next, 8 g of the well-mixed slurry were cast into polypropylene Petri dishes with
a diameter of 50 mm. The ZGMs were cured first at 60 ◦ C for 4 h and then at 80 ◦ C for
18 h and demolded after cooling. To create a porous structure, PVAc must be removed
from the geopolymer matrix, following an approach inspired by the phase inversion
technique used in organic polymer membranes [37]. In this process, the hypothesis is
that the thermal decomposition of PVAc at high temperatures facilitates the formation of
interconnected pores, enhancing the porosity and surface area of the geopolymer membrane.
To remove PVAc from the ZGMs and create a porous matrix, the samples were annealed
at a temperature of 300 ◦ C for 1 h. This temperature was chosen because a TGA analysis
confirmed that PVAc decomposed at around 300 ◦ C. The prepared membranes were
immersed in deionized water before being applied for filtration tests. The ZGMs membrane
production process and the filtration setup are shown in Figure 1.

2.2. Water Flux Experiments

To evaluate water flux and contaminant removal performance, the ZGM membranes
were mounted into a custom-designed membrane filtration setup (Figure 2b), which com-
prised two separate compartments. A constant vacuum pressure of 0.1 MPa was applied
throughout the filtration experiment. The filtrate was collected at designated time intervals.
Water flux (J) through the ZGMs was determined using the following equation:

J = m/(A × ∆t) (1)

where J represents the water flux (kg·m−2 ·h−1 ), m is the mass of water permeated through
the membrane, A is the effective surface area of the membrane, and ∆t is the duration
of the filtration process. A schematic representation of the filtration system is shown in
Figure 2a [38].
 a temperature of 300 °C for 1 h. This temperature was chosen because a TGA analysis
confirmed that PVAc decomposed at around 300 °C. The prepared membranes were im-
Polymers 2025, 17, 1155 mersed in deionized water before being applied for filtration tests. The ZGMs membrane
7 of 30
production process and the filtration setup are shown in Figure 1.

Polymers 2025, 17, x FOR PEER REVIEW 7 of 30

2.2. Water Flux Experiments

To evaluate water flux and contaminant removal performance, the ZGM membranes
were mounted into a custom-designed membrane filtration setup (Figure 2b), which com-
prised two separate compartments. A constant vacuum pressure of 0.1 MPa was applied
throughout the filtration experiment. The filtrate was collected at designated time inter-
vals. Water flux (J) through the ZGMs was determined using the following equation:
J = m/(A × ∆t) (1)
where J represents the water flux (kg·m⁻2·h−1), m is the mass of water permeated through
the membrane, A is the effective surface area of the membrane, and Δt is the duration of
the filtration process. A schematic representation of the filtration system is shown in Fig-
Figure 1. 1.
Figure (a)(a)
Schematic ofofZGM
Schematic ZGMmembrane
membraneproduction
production process and the
process and thefiltration
filtrationsetup.
setup.(b)
(b)Surface
Surface
ure 2a [38].
and cross-section
and ofofnon-porous
cross-section non-porousand
andporous
porous cross-section of ZGMs.
cross-section of ZGMs.

Figure 2. (a) Schematic illustration of the filtration process and (b) cross-sectional view of the
two-chamber
Figure membraneillustration
2. (a) Schematic setup operated at room
of the temperature
filtration processand
andpH
(b)6.cross-sectional view of the two-
chamber membrane setup operated at room temperature and pH 6.
Different concentrations of Pb(II) solutions (50, 100, and 200 ppm) were prepared
using lead(II) chloride (PbCl2 ), supplied by Sigma Aldrich (USA). Accurately weighed
Different concentrations of Pb(II) solutions (50, 100, and 200 ppm) were prepared us-
amounts of PbCl2 were dissolved in deionized water under continuous stirring to ensure
ing lead(II)
complete chloride at(PbCl
dissolution room2),temperature.
supplied by Sigma
A stock Aldrich
solution (USA).
of 1000 ppmAccurately weighed
Pb(II) was first
amounts of PbCl 2 were dissolved in deionized water under continuous stirring to ensure
prepared by dissolving a known mass of PbCl2 in deionized water. The final volumes
complete dissolution at room temperature. A stock solution of 1000 ppm Pb(II) was first
prepared by dissolving a known mass of PbCl2 in deionized water. The final volumes were
adjusted to the desired concentrations in volumetric flasks. The pH of each Pb(II) solution
(50 ppm, 100 ppm, and 200 ppm) was monitored using a calibrated pH meter. The initial
Polymers 2025, 17, 1155 8 of 30

were adjusted to the desired concentrations in volumetric flasks. The pH of each Pb(II)
solution (50 ppm, 100 ppm, and 200 ppm) was monitored using a calibrated pH meter.
The initial pH measurements of the Pb(II) solutions were 5.3 for 50 ppm and 4.08 for
200 ppm. Small volumes of 0.1 M NaOH were gradually added dropwise under constant
stirring until the desired pH value of 6.0 ± 0.2 was reached. After pH adjustment, the
solutions were equilibrated for 10 min to ensure pH stability before being used in membrane
filtration experiments. pH was controlled at neutral conditions (pH~6) to avoid additional
complexities, such as metal precipitation or membrane degradation, which may occur under
extreme pH conditions. Temperature was maintained at room temperature (25 ± 2 ◦ C)
to mimic realistic environmental conditions and eliminate the temperature effect on the
diffusion rates. The concentration of Pb(II) in the feed and permeate solutions was analyzed
using an inductively coupled plasma–optical emission spectroscopy (ICP-OES) analyzer,
and the removal efficiency was calculated by the next equation:

C0 − C1
R= × 100% (2)
C0

where C0 and C1 are the heavy metals’ concentrations in the feed and permeate solutions,
respectively [38].

2.3. Characterization Techniques

2.3.1. X-Ray Diffraction
X-ray diffraction analysis was performed to characterize the crystalline phases present
in the zeolite and geopolymer samples. A PANalytical Pro diffractometer (Almelo,
The Netherlands), operating at 40 kV and 40 mA with a cobalt (Co) radiation source,
was used for the measurements for sample preparation. An accurately weighed portion of
the geopolymer sample was mixed with a specific weight percentage of corundum (Al2 O3 ,
Baikowski International), which served as an internal standard. To ensure homogeneity,
10 mL of ethanol were added to the mixture, which was then micronized using a McCrone
mill with zirconia beads for six minutes. The resulting slurry was dried in an oven at 40 ◦ C
for 12 h. Once dried, the uniform powders were backloaded and pressed into sample holder
disks for analysis. During the XRD measurement, the samples were rotated to improve the
counting statistics. The instrument was configured with the following incident optics: a
15 mm mask, 0.04 radian Soller slits, a 0.5◦ fixed divergence slit, and a 2◦ fixed anti-scatter
slit. Data were collected over a 2θ range starting at 5◦ , using a step size of 0.016◦ , with a
total measurement time of 30 min per sample. Phase identification was conducted using
the PANalytical HighScore Plus (Version 4) and MDI Jade (Version 4.1) software packages,
with reference to multiple crystallographic databases, including PDF4+, the American
Mineralogist Crystal Structure Database (2010), the Crystallographic Open Database, and
ICSD FIZ Karlsruhe (2011). Quantitative phase analysis was performed using the Rietveld
refinement method, as implemented in TOPAS (Version 5, Bruker, Billerica, MA, USA) [33].

2.3.2. Fourier Transform Infrared Spectroscopy

Fourier-transform infrared (FTIR) spectra were obtained using a Nicolet iS50 spectrom-
eter (Thermo Scientific, Madison, WI, USA) equipped with a single-bounce diamond ATR
accessory. Each spectrum was collected by averaging 64 scans at a resolution of 4 cm−1 [39].

2.3.3. Thermogravimetric/Differential Scanning Calorimetry

Thermal analysis, including differential scanning calorimetry (DSC) and thermo-
gravimetric analysis (TGA), was carried out using a STA 449F3 TG-DSC system (Netzsch,
Germany). The measurements were performed under a nitrogen atmosphere, applying a
Polymers 2025, 17, 1155 9 of 30

heating rate of 10 ◦ C/min to examine the thermal characteristics of the raw materials and
synthesized geopolymers [33].

2.3.4. Inductively Coupled Plasma–Optical Emission Spectroscopy

Multi-element quantitation was determined using a Perkin Elmer 8300DV (Shelton,
Connecticut, USA), ICP-OES, which was coupled with an ESI SC-4DX autosampler and a Prep-
FAST 2 sample introduction system for automated dilution and online internal standardization.
All standards and blanks were prepared using purified nitric acid. Calibration involved in-
house prepared multi-element standards derived from ICP-MS-grade single-element stock
solutions (High Purity Standards, Charleston, CA, USA). The elements typically calibrated
included aluminum, boron, calcium, cadmium, cobalt, chromium, copper, iron, potassium,
lithium, magnesium, manganese, sodium, sulfur, silicon, strontium, and zinc—commonly
found in environmental water samples. Method accuracy and reproducibility were confirmed
through the regular analysis of certified reference materials (CRMs) from NIST (Gaithersburg,
MD, USA) and the US Geological Survey (Reston, VA, USA). Additionally, certified wastew-
ater samples trace metals A, B, and D (CWW-TM-A, CWW-TM-B, and CWW-TM-D) were
used for non-routine validation, while initial calibration verification standards (ICV-1A and
ICV-1B) were used routinely across a wide concentration range [40].

2.3.5. Surface Area and Pore Size Distribution

The specific surface area and pore distribution of the samples were analyzed using BET
(Brunauer–Emmett–Teller) and BJH (Barrett–Joyner–Halenda) methods via a Micromeritics
3Flex Version 4.05 analyzer. (Micromeritics, Norcoss, GA, USA) Prior to measurement, the
samples were degassed at 250 ◦ C under vacuum for 48 h. Nitrogen adsorption isotherms
were recorded, and the resulting data were processed both manually and using the Mi-
croActive software suite (version 7) [41].

2.3.6. Hardness and Elastic Modulus Analyses

The nano-mechanical properties, including hardness and elastic modulus, were mea-
sured using a Hysitron TI 950 TriboIndenter (Bruker, Billerica, MA, USA). The Oliver–Pharr
method was employed to determine the hardness (H) and reduced elastic modulus (Er)
from the loading curve up to the maximum indentation depth [42].

2.3.7. Scanning Electron Microscopy/Energy-Dispersive Spectroscopy

Sample morphology and surface elemental composition were analyzed using a JEOL
7001F scanning electron microscope (Tokyo, Japan), coupled with energy dispersive spec-
troscopy (EDS). Samples were mounted on conductive carbon adhesive tabs and sputter-
coated with 99.99% pure gold using a Leica EM SCD005 sputter coater under argon gas,
at a chamber pressure of 0.05 mbar and a current of 30 mA. SEM observations were con-
ducted at an accelerating voltage of 10 kV, and secondary electron images were captured at
multiple magnifications [33].

3. Results and Discussion

3.1. Zeolite and ZGMs Characterization
The XRD patterns of both ZGM and natural zeolite are presented in Figure 3. The
quantitative analyses, together with the crystal powder diffraction number (PDF#), can
be found in Table 5. In brief, the natural zeolite with a cation exchange capacity of 134.6
meq/100 g [42] consisted of clinoptilolite–heulandite (~28.1%), with an International Zeolite
Association framework code of HEU, quartz (~20%), stilbite (~19.1%) with framework type
of STI, and minor amounts of feldspar, mordenite, plagioclase and chabazite. About 21.5%
 Table 5. Identified crystalline phases, PDF #, composition, and relative abundance in Zeolite a
Polymers 2025, 17, 1155 geopolymer samples. 10 of 30

Phase PDF # Formula SiO2/Al2O3 Ratio Zeolite (wt.%) Geopolymer (wt.%

Quartz 98-000-0369 SiO2 -- 20 10.3
Plagioclase
of the zeolite was unidentified, including amorphous components such as amorphous
-Albite SiO2 [43] and a trace amount
01-075-1142 NaAlSiof 3O8
smectite. Quantitative 3.4XRD analysis revealed
3.5 a significant5.3
-Andesine reduction in quartz
05-001-0801 content
Na0.51 Ca0.49(Si(up
2.56Alto
1.44~50%)
O8) during geopolymer
2 development, as well as
-Anorthite 00-012-0301 CaAl2Si2O8
a decrease in the clinoptilolite–heulandite 1.13 to ~75%). Approximately 95% of
content (up
K–Feldspar stilbite was removed from the geopolymer matrix. Albite, andesine, feldspar, and mordenite
-Orthoclase 00-019-0931 KAlSi3O8
also diminished (by approximately 60%), while a new 3.4phase, anorthite5.5 (plagioclase), was2.1
-Sanidine 00-010-0353 KAlSi3O8 3.4
formed during the geopolymerization reaction. Overall, the amorphous content increased
Chabazite 01-088-1263 Ca1.76Al3.60Si8.40O24·(H2O)9.87 2.6 0.2 0.3
Clinoptilolite–Heulandite from ~21% to ~73%,
00-039-1383 KNa2Ca which was expected due to the
2(Si29Al7)O72·24H2O 4.1geopolymerization 28.1 process and is7.2
Mordenite consistent with (Ca,Na
00-029-1257 findings2,K2by
)AlUlloa
2Si10O24 et·7H
al.2O[44]. Amari et
5.7al. [33] also observed
2.2 an increase in 1
Stilbite–Na amorphous
00-039-0223 content in zeolite-based
NaCa4(Si27Al9)O72·28(H2O) geopolymers, which
4.6 they attributed
19.1to the disruption 1
Unidentified Amorphous -- original crystalline framework
of the -- --
during alkali activation. 21.4 72.8

Figure3.3.XRD
Figure XRD patterns
patterns of zeolite
of (a) (a) zeolite and
and (b) (b) zeolite-based
zeolite-based geopolymer.
geopolymer. The diffraction
The diffraction peaks are peaks
labeled using color-coded shapes to indicate the identified crystalline phases: clinoptilolite
labeled using color-coded shapes to indicate the identified crystalline phases: clinoptilolite (red (red
diamond), quartz (blue diamond), mordenite (green hexagon), feldspar (purple circle), and Al2 O3
amond), quartz (blue diamond), mordenite (green hexagon), feldspar (purple circle), and Al
(black asterisk).
(black asterisk).
Polymers 2025, 17, 1155 11 of 30

Table 5. Identified crystalline phases, PDF #, composition, and relative abundance in Zeolite and
geopolymer samples.

Phase PDF # Formula SiO2 /Al2 O3 Ratio Zeolite (wt.%) Geopolymer (wt.%)
Quartz 98-000-0369 SiO2 -- 20 10.3
Plagioclase
-Albite 01-075-1142 NaAlSi3 O8 3.4 3.5 5.3
-Andesine 05-001-0801 Na0.51 Ca0.49 (Si2.56 Al1.44 O8 ) 2
-Anorthite 00-012-0301 CaAl2 Si2 O8 1.13
K–Feldspar
-Orthoclase 00-019-0931 KAlSi3 O8 3.4 5.5 2.1
-Sanidine 00-010-0353 KAlSi3 O8 3.4
Chabazite 01-088-1263 Ca1.76 Al3.60 Si8.40 O24 ·(H2 O)9.87 2.6 0.2 0.3
Clinoptilolite–Heulandite 00-039-1383 KNa2 Ca2 (Si29 Al7 )O72 ·24H2 O 4.1 28.1 7.2
Mordenite 00-029-1257 (Ca,Na2 ,K2 )Al2 Si10 O24 ·7H2 O 5.7 2.2 1
Stilbite–Na 00-039-0223 NaCa4 (Si27 Al9 )O72 ·28(H2 O) 4.6 19.1 1
Unidentified Amorphous -- -- -- 21.4 72.8

During the initial slurry preparation, PVAc is introduced in the form of an emulsion
and is evenly dispersed throughout the geopolymer matrix. Its interaction with the geopoly-
mer components occurs at multiple levels. First, physical dispersion in the geopolymer
slurry occurs. Since PVAc is water-soluble in its emulsified form, it is homogeneously
distributed in the geopolymer mixture. PVAc has minimal chemical interaction with the
geopolymer network, and its presence does not alter the pH or disrupt geopolymerization,
allowing the gelation and crosslinking of the aluminosilicate framework to proceed as
normal. As the geopolymer matrix forms, PVAc molecules become physically trapped
within the network, forming polymer-rich domains within the rigid inorganic framework.
ZGMs, before PVAc removal, exhibited low porosity. The SEM image (Figure 4) of the
geopolymer samples before PVAc decomposition shows the membrane being impermeable,
with micro- and macrocracks within the structure, resulting in a weak and fragile membrane.
The cracks originated from the top layer, which had a depth of ~10 µm, and extended
through the intermediate (~58 µm) and non-porous layers, with the most severe cracking
observed in the intermediate zone. The top (dense) layer, which was directly exposed to
air, formed due to rapid phase inversion. During the first drying cycles at 60 ◦ C and 80 ◦ C
for 22 h, since the organic additive (i.e., PVAc) has a significantly higher decomposition
temperature, only water is removed during the drying stage. In this initial phase, interstitial
water occupying the spaces between particles is eliminated, resulting in the first stage of
membrane shrinkage and microcrack formation, as can be seen in Figure 4b. During the
first round of drying, 2.25–2.32 g of water was removed, leading to a linear shrinkage of
28.1–29%, calculated using the mass loss across samples with varying PVAc contents. The
10 wt.% PVAc sample exhibited the highest shrinkage (~29%), while the 30 wt.% PVAc
sample showed the least (~28.13%). The 20 wt.% PVAc exhibited moderate shrinkage
of 28.63%. This trend suggests that higher PVAc concentrations contribute to greater
structural stability, reducing the relative proportion of water available for evaporation-
induced shrinkage and thereby minimizing overall contraction.
Once the geopolymer membranes are cured, the removal of PVAc via thermal de-
composition (annealing at 300 ◦ C) is critical to generating porosity. The phase-inversion
mechanism relies on PVAc acting as a sacrificial phase that, upon decomposition, leaves
behind interconnected voids. At this stage, the interaction is predominantly physical rather
than chemical. Initially dispersed polymer domains become sites of structural evolution
as they shrink, vaporize, and escape the geopolymer matrix. Because PVAc has minimal
chemical interaction and negligible reactivity with the geopolymer network, the inorganic
aluminosilicate structure remains stable and unaffected chemically. However, physically,
as PVAc decomposes and exits, the geopolymer structure experiences localized shrinkage
stress and the formation of internal pores. The process unfolds in several steps, starting
 tion, allowing the gelation and crosslinking of the aluminosilicate framework to proceed
as normal. As the geopolymer matrix forms, PVAc molecules become physically trapped
Polymers 2025, 17, 1155 within the network, forming polymer-rich domains within the rigid inorganic framework. 12 of 30
ZGMs, before PVAc removal, exhibited low porosity. The SEM image (Figure 4) of
the geopolymer samples before PVAc decomposition shows the membrane being imper-
with softening and and
thermogravimetric degradation at around 250–300 ◦
meable, with micro- macrocracks within the structure, resulting in aC, and and
weak breaking
fragile
down into smaller volatile compounds (e.g., acetic acid, acetone, carbon
membrane. The cracks originated from the top layer, which had a depth of ~10 µm, dioxide, and water
and
vapor). The removal of PVAc results in the formation of pores, where
extended through the intermediate (~58 µm) and non-porous layers, with the most severe the polymer-rich
regions observed
cracking previously inexisted with different
the intermediate zone.levels of extensivity
The top (dense) layer,depending
which wason the initial
directly ex-
concentration of PVAc in the formulation. During the second round of heating at 300 ◦ C,
posed to air, formed due to rapid phase inversion. During the first drying cycles at 60 °C
additional mass loss occurred, primarily due to PVAc decomposition and the removal
and 80 °C for 22 h, since the organic additive (i.e., PVAc) has a significantly higher decom-
of residual moisture, as confirmed by the TG-DSC analysis. The 30 wt.% PVAc sample
position temperature, only water is removed during the drying stage. In this initial phase,
exhibited the greatest mass loss (2.80 g) and shrinkage (48.70%), corresponding to its higher
interstitial water occupying the spaces between particles is eliminated, resulting in the
polymer content. This extensive degradation of PVAc facilitated the formation of a more
first stage of membrane shrinkage and microcrack formation, as can be seen in Figure 4b.
interconnected and porous network, resulting in larger pore volumes, as evidenced by the
During the first round
SEM micrographs of drying,
(Figure 4). The 2.25–2.32
20 wt.% PVAc g of sample
water was removed,
showed leading
a moderate to loss
mass a linear
of
shrinkage
1.95 g, with a corresponding shrinkage rate of 34.15%. This indicates the development PVAc
of 28.1–29%, calculated using the mass loss across samples with varying of a
contents. The 10 wt.%
well-distributed pore PVAc sample
structure withexhibited
moderatethe highest
porosity, shrinkage
striking (~29%),
a balance while pore
between the 30
wt.% PVAcand
formation sample showed
structural the least
integrity. (~28.13%).
In contrast, the The 20 wt.%
10 wt.% PVAc PVAc
sampleexhibited moderate
demonstrated the
shrinkage
lowest mass loss (1.10 g) and shrinkage (19.37%), reflecting its lower polymer content. Thisto
of 28.63%. This trend suggests that higher PVAc concentrations contribute
greater structural
resulted in a more stability,
compact reducing
structurethe relative
with fewerproportion
and smallerofpores,
waterpreserving
available for evapo-
a higher
ration-induced shrinkage and thereby minimizing
degree of structural stability following thermal treatment. overall contraction.

Figure
Figure4. 4.
Cross-sectional
Cross-sectional SEM
SEMimages
imagesofofzeolite-based
zeolite-basedgeopolymer
geopolymermembranes
membranes at at different
different magni-
mag-
nifications:
fications: (a–c)(a–c) structure
structure before
before PVAc PVAc decomposition,
decomposition, highlighting
highlighting the the presence
presence of micro-
of micro- andand
mac-
macrocracks; ◦
rocracks; (d–f) (d–f) membranes
membranes afterafter
PVAc PVAc decomposition
decomposition at at
300300
°C,C, demonstratingenhanced
demonstrating enhancedporosity
poros-
ity with
with distinct
distinct micro-,
micro-, meso-,
meso-, andand macroporous
macroporous regions.
regions.

The molecular weight of the organic additive significantly influences the characteristics
of the resulting porous geopolymer. In general, a high molecular weight forms longer
polymer chains, leading to more entangled networks within the geopolymer matrix and
increasing the viscosity, while a lower molecular weight would disperse more uniformly
and may create smaller, less-interconnected pores. The polymer chain structure can also
affect pore morphology, influencing the permeability and surface area of the membrane.
Linear chains tend to form elongated pores when removed, while branched structures
may result in less uniform, more tortuous pore networks. However, the polymer chain
Polymers 2025, 17, 1155 13 of 30

environment significantly influences its structure and performance within the geopolymer
matrix, with pH and temperature being key factors. For example, in a highly alkaline
geopolymer slurry (pH~12.8), polymer chains with acidic functional groups readily ionize,
leading to strong electrostatic repulsion between neighboring carboxylate groups [45]. This
causes the chains to extend and adopt a more linear conformation. In this study, PVAc
was selected because it lacks acidic functional groups and remains neutral under these
conditions. In this study, the polymer molecular weight and chain structure were held
constant. Therefore, the influence of varying these parameters on the pore morphology
and membrane properties was not experimentally explored. Future studies may focus on
systematically varying the polymer molecular weight and branching to fully elucidate their
effects on pore formation and membrane performance.
The Brunauer–Emmett–Teller (BET) isotherm method was employed to calculate the
surface area of the membranes before and after thermal annealing. Based on IUPAC classifi-
cation, the adsorption–desorption isotherm corresponds to Type IV [46]. The hysteresis loop
occurred in the range of ~0.6 to 1.0 P/P0 , indicating the presence of mesopores (Figure 5a,c).
Notably, the hysteresis loop observed was closed, suggesting that the adsorption and
desorption processes were largely reversible and that the pore structure was stable, with
minimal pore blocking or cavitation effects. The closed loop further implies that the pores
have uniform connectivity and that there are no significant ink-bottle-shaped pores, which
can lead to delayed evaporation and typically result in an open loop. This reversibility is
advantageous for consistent performance in applications such as separation membranes, as
it reflects a robust pore architecture [47]. The N2 gas adsorption–desorption isotherm loop
before and after heating is shown in Figure 5b. The specific surface area of the membrane
before heat exposure was 4.26 m2 /g, which increased significantly to 118.3 m2 /g for the
ZGM membrane after PVAc removal. This surface area exceeds the values reported by
He et al. [27], who achieved 97.8 m2 /g in geopolymer–zeolite composite membranes. Our
higher surface area may be attributed to the effective sacrificial role of PVAc, which, upon
decomposition at 300 ◦ C, created a more interconnected mesoporous network. Similar
surface areas (24.59 m2 /g) were reported by Song et al. [25] in biomimetic multilayer
geopolymer membranes. However, their surface area was influenced by multiple factors,
including spin-coating conditions, the composition and concentration of the geopolymer
precursors, and the number of deposited layers. Additionally, the drying process and
post-treatment steps, such as alkali activation and curing temperature, played significant
roles in determining the final porosity and specific surface area of the membranes. In our
study, PVAc initially occupied the pore spaces within the membrane structure, limiting
the accessible surface area. Upon heating, PVAc was thermally degraded and eliminated,
leaving behind additional voids and opening previously blocked pore channels. This
process not only created new pores but also enhanced the interconnectivity of the existing
pores, resulting in a significant increase in both micropore and mesopore volume. Specif-
ically, the percentage of micropores and mesopores in ZGM3 increased slightly (to 10%
and 53%, respectively), while the macropore percentage decreased to 37%. This shift from
macropores to more micropores and mesopores contributed to the substantial increase in
the specific surface area, as smaller pores offer more surface area per unit volume.
According to the Barrett–Joyner–Halenda (BJH) pore size distribution curve of the
sample before heating (Figure 5b), about 6% of the total pore volume belonged to mi-
cropores (<2 nm), represented by a small narrow peak at ~2 nm. Additionally, 50% and
44% of the total volume were attributed to mesopores (2–5 nm) and macropores (>5 nm),
respectively [40,46]. The peaks at 2–3 nm and 5–7 nm can be associated with vacant spaces
between crystals and the geopolymer matrix. The broad peak in the range of 10–21 nm
and the strong peak at 32 nm may be due to void formation during geopolymerization [41].
 and eliminated, leaving behind additional voids and opening previously
channels. This process not only created new pores but also enhanced the inte
Polymers 2025, 17, 1155 14 of 30
of the existing pores, resulting in a significant increase in both micropore a
volume. Specifically, the percentage of micropores and mesopores in ZG
After heating, the redistribution of pore sizes, with enhanced microporosity and meso-
slightly (to 10% and 53%, respectively), while the macropore percentage decr
porosity and reduced microporosity, contributed to a higher total surface area. These
This shift
results from
indicate macropores
that removing PVAc astoa structure-directing
more micropores agentand mesopores
enhanced contribute
the micropore
stantial
and increase
mesopore insignificantly
content, the specific surface
reducing the area,
numberasofsmaller
macroporespores offerand
in ZGM3 more su
leading to
unit volume.a substantial increase in specific surface area. In gas and liquid separations, both
micropores and mesopores play a critical role [40].

Figure 5. N2 gas adsorption–desorption isotherms of ZGM3 membranes (a) before and (c) after
heating ◦ C, and corresponding pore size distribution histograms (b) before and (d) after
Figureat5.300N2 gas adsorption–desorption isotherms of ZGM3 membranes (a) before an
◦
heating at 300 C, highlighting changes in porosity and pore structure due to PVAc removal.
ing at 300 °C, and corresponding pore size distribution histograms (b) before and (
The°C,
at 300 porosity of the membranes
highlighting changeswas significantly
in porosity andenhanced by the thermal
pore structure decomposi-
due to PVAc removal
◦
tion of the organic component, PVAc, at 300 C [48]. In conventional inorganic membrane
fabrication, a porous substrate is generally required, which can be expensive, and a cal-
cination step is necessary to ensure bonding between the support and the selective layer.
In contrast, porous ZGM membranes possess a hierarchical graded structure (Figure 4d),
consisting of layers with varying pore sizes, namely, a macroporous layer with pore sizes
exceeding 5 µm, a microfiltration layer ranging from 0.1 to 5 µm, and an ultrafiltration layer
with pore sizes below 0.1 µm [48]. The topmost layer is the densest, and pore sizes increase
progressively toward the inner layers. This gradation effectively reduces the accumulation
of permeates in the preceding layers, thereby minimizing the risk of pore blockage [48].
An important advantage of the developed membranes was their enhanced mechanical
strength. Although it was expected that ZGMs might exhibit reduced strength due to
increased porosity and the effects of thermal stress [48], the hardness of the material
significantly improved following annealing. Remarkably, thermal treatment also led to
the healing of micro- and macrocracks previously observed in SEM analyses. The fracture
behavior of the membranes, both before and after thermal annealing, was evaluated using
a nano-indentation system. Hardness and elastic modulus values were derived from the
load–displacement curves (Figure 6). Before heating, the hardness and elastic modulus
 Polymers 2025, 17, 1155 15 of 30

were measured at 0.25 and 18.42 GPa, respectively. These values increased significantly after
annealing, reaching 1.81 and 46.75 GPa. The obtained mechanical strength surpassed that
reported in earlier research. For example, Chen et al. [49] synthesized a metakaolin-based
geopolymer and reported maximum hardness and modulus values of 0.14 and 3.16 GPa,
respectively. The comparatively lower mechanical properties in that study were mainly
attributed to a low curing temperature (60–80 ◦ C) and a short curing duration (14 days),
which restricted the extent of geopolymerization, yielding a structure with lower density. It
is well-established that higher curing temperatures and prolonged curing times enhance
mechanical strength by promoting more complete gel formation and reducing overall
porosity. Additional factors, such as elevated water content and variation in the Si/Al ratio,
also influence mechanical performance by contributing to a less compact structure [49].
As evident from the indentation data, the unheated samples exhibited greater penetration
depth, reflecting a softer material. The improved hardness after annealing is likely15due
Polymers 2025, 17, x FOR PEER REVIEW of 30
to continued geopolymerization at elevated temperatures, promoting particle fusion and
bonding within the inorganic phase, which contributes to increased mechanical rigidity [50].

Figure 6. Mechanical properties of membranes before and after heating at 300 ◦ C: (a) Load–displacement
Figure 6. Mechanical properties of membranes before and after heating at 300 °C: (a) Load–displace-
curves, (b) elastic modulus, and (c) hardness, demonstrating the improvement in structural properties
ment curves, (b) elastic modulus, and (c) hardness, demonstrating the improvement in structural
after thermal treatment.
properties after thermal treatment.
Another notable advantage of these membranes was their high mechanical strength.
Another
Although notable
it was advantage
anticipated that of thesewould
ZGMs membranes was their
experience high mechanical
a reduction in strengthstrength.
due to
Although it was anticipated that ZGMs would experience a reduction
increased porosity and thermal stresses [48], the hardness improved considerably. More in strength due to
increased porosity
significantly, and thermal
the micro- stresses [48],
and macrocracks the hardness
detected by SEM were improved
healedconsiderably.
after the thermal More
significantly, the micro- and macrocracks detected by SEM were
annealing. The fractural behaviors of ZGMs before and after annealing were measuredhealed after the thermal
annealing. The fractural
using a nano-indenter behaviors The
instrument. of ZGMs
hardness before
andand after
elastic annealing
modulus of thewere measured
membranes
using a nano-indenter
were determined usinginstrument. The hardness
the load–distance and elastic
curve (Figure 6). Themodulus of the and
initial hardness membranes
elastic
were determined
modulus were 0.25 using
andthe load–distance
18.42 GPa beforecurve (Figure
heating 6). The initial
and increased hardness
drastically to and
1.81elastic
and
modulus
46.75 GPa, were 0.25 and when
respectively, 18.42 the
GPamembranes
before heatingwereand increased
annealed. Thisdrastically
mechanicaltostrength
1.81 and
exceeds
46.75 GPa,therespectively,
values reported in previous
when studies. were
the membranes For instance,
annealed. Chen
Thiset mechanical
al. [49] synthesized
strength
a metakaolin-based
exceeds geopolymer
the values reported and found
in previous the maximum
studies. For instance,hardness
Chen etand al.elastic modulus
[49] synthesized
atometakaolin-based
be 0.14 and 3.16 GPa, respectively.
geopolymer and The
foundlower
the hardness
maximum and Young’sand
hardness modulus
elasticvalues
modulus in
this ◦
to bestudy
0.14 andare 3.16
primarily due to the combined
GPa, respectively. The lower effect of lowand
hardness curing temperature
Young’s modulus (60–80
valuesC)in
and short curing time (14 days), which limited geopolymerization
this study are primarily due to the combined effect of low curing temperature (60–80 and resulted in a less
°C)
dense
and structure.
short curingHigher temperatures
time (14 days), which andlimited
longer geopolymerization
curing are known toand improve mechanical
resulted in a less
strength
dense by enhancing
structure. Highergel formation and
temperatures andreducing porosity.
longer curing areThis is further
known influenced
to improve mechani-by
factors
cal such by
strength as higher watergel
enhancing content and variations
formation in theporosity.
and reducing Si/Al ratio,
Thiswhich also contribute
is further influenced
to reduced mechanical strength [49]. As can be seen, the indentation
by factors such as higher water content and variations in the Si/Al ratio, which also depth was higher
con-
tribute to reduced mechanical strength [49]. As can be seen, the indentation depth was
higher before thermal treatment, indicating a softer structure. Increased hardness after
annealing can be partly attributed to the continuation of geopolymer reaction at higher
temperatures, which can be due to the fusion and bonding of the particles occurring in the
inorganic phase, which improves the mechanical hardness [50].
 Polymers 2025, 17, 1155 16 of 30

before thermal treatment, indicating a softer structure. Increased hardness after annealing
can be partly attributed to the continuation of geopolymer reaction at higher temperatures,
which can be due to the fusion and bonding of the particles occurring in the inorganic
phase, which improves the mechanical hardness [50].
It was hypothesized that residual PVAc particles could contribute to enhanced me-
chanical strength. To verify complete polymer removal following thermal treatment, a
range of analytical techniques was utilized. Initially, thermogravimetric and differential
scanning calorimetry (TG-DSC) analyses were conducted on membranes containing PVAc,
gradually heating the samples from 50 ◦ C to 600 ◦ C at a rate of 10 ◦ C/min in an air atmo-
sphere to observe mass loss and thermal transitions (Figure 7a). After cooling the sample at
room temperature for 24 h to allow for moisture adsorption, a second heating cycle was
applied from ambient temperature to 1200 ◦ C at the same rate (Figure 7b). A slight increase
Polymers 2025, 17, x FOR PEER REVIEWin mass in the TG curves during the early stages of heating—prior to significant weight 16 of 30
loss—was detected in both curves (Figure 7a,b), likely due to oxidation of residual organics
or reduced metal species, or surface adsorption of atmospheric moisture or oxygen. These
behaviors are commonly observed in TG studies under oxidative conditions. The total
conditions. The total mass loss recorded was 14.5% in the first cycle and 12% in the second.
mass loss recorded was 14.5% in the first cycle and 12% in the second. The initial mass loss
The initial mass loss was primarily attributed to the release of absorbed water and thermal
was primarily attributed to the release of absorbed water and thermal decomposition of
decomposition of PVAc within the geopolymer framework, while the latter was mostly
PVAc within the geopolymer framework, while the latter was mostly due to water evapora-
due to water evaporation. A distinct change in the slope of the TG◦curve between ~250 °C
tion. A distinct change in the slope of the TG curve between ~250 C and ~300 ◦ C during
and ~300 °C during the first cycle, accompanied by an endothermic peak in the DSC curve,
the first cycle, accompanied by an endothermic peak in the DSC curve, corresponded
corresponded to PVAc decomposition. This behavior was absent in the second cycle, con-
to PVAc decomposition. This behavior was absent in the second cycle, confirming that
firming
PVAc degradationdegradation
that PVAc had occurredhad occurred
in the in the
first. PVAc first. PVAcindecomposes
decomposes in this
this temperature tem-
range
perature
throughrange throughreleasing
deacetylation, deacetylation,
volatilereleasing
productsvolatile
such as products such
acetic acid, as acetic
followed acid, fol-
by polymer
lowed by polymer
backbone backbone
breakdown. breakdown.
Additional water loss Additional water lossofand
and the degradation the degradation
residual organics alsoof
residual organics also contribute to this mass change. These findings support
contribute to this mass change. These findings support that PVAc was fully eliminated that PVAc
was
fromfully
the eliminated
geopolymerfrom thebelow
matrix geopolymer
300 ◦ C. matrix
A minor below 300 °C.
DSC peak A minor
at ~300 ◦ C inDSC peak at
the second
~300 °C in the second cycle is attributed to the evaporation of mesoporous
cycle is attributed to the evaporation of mesoporous water, which was likely masked water, which
by
was
the likely masked by
decomposition thein
peak decomposition
the first cycle. peak in the first cycle.

TG-DSCanalysis
Figure7.7.TG-DSC
Figure analysis curves
curves for
formembranes
membranescontaining
containingPVAc:
PVAc:(a)(a)
firstfirst
heating cycle
heating 50 ◦ C
fromfrom
cycle 50
◦ ◦
to 600 C at a rate of 10 C/min under air atmosphere, and (b) second heating cycle from room
°C to 600 °C at a rate ◦of 10 °C/min under air atmosphere, and (b) second heating cycle from room
temperature to 1200 C at a rate of 10 ◦ C/min.
temperature to 1200 °C at a rate of 10 °C/min.
To further confirm PVAc removal, EDS elemental mapping of ZGM membranes con-
tainingfurther
To confirm
PVAc was PVAc removal,
performed before andEDS elemental
after mapping of
thermal treatment ZGM8).
(Figure membranes
The mappingcon-
taining PVAc detected
consistently was performed before
Si, Al, Ca, andNa
O, and after thermal
across treatment
the scanned (Figure
areas 8).cases.
in both The mapping
Carbon
consistently detected Si, Al, Ca, O, and Na across the scanned areas in both
mapping, indicated by green signals, showed a dense and widespread distribution cases. Carbon
of
mapping,
carbon inindicated by green
the unheated signals,
sample showed
(Figure a dense
8a), while onlyand widespread
sparse distribution
carbon signals of car-
were present
bon in the unheated sample (Figure 8a), while only sparse carbon signals were present
after heating (Figure 8b), indicating significant polymer elimination. Since PVAc was the
sole carbon-containing component in the matrix, these EDS results confirmed its substan-
tial decomposition. The residual carbon observed could be due to remaining ash or trace
 Polymers 2025, 17, 1155 17 of 30

after heating (Figure 8b), indicating significant polymer elimination. Since PVAc was the
sole carbon-containing component in the matrix, these EDS results confirmed its substantial
Polymers 2025, 17, x FOR PEER REVIEW decomposition. The residual carbon observed could be due to remaining ash or trace 17 of 30
amounts of undecomposed carbon species, rather than intact PVAc. Enhancing the anneal-
ing duration or increasing the thermal treatment temperature could assist in eliminating
these traces completely.

Figure 8. SEM
Figure images
8. SEM and
images andcorresponding
corresponding EDS elementalmapping
EDS elemental mappingof of membrane
membrane cross-sections: (a)
cross-sections:
before heating
(a) before at 300
heating at °C ◦ C and
300and (b) (b)
after heating,
after heating,showing
showing changes inmorphology
changes in morphologyandand elemental dis-
elemental
distribution
tribution due todue to thermal
thermal treatment.
treatment.

FTIR spectroscopy was employed to assess the structural changes in the geopolymer
matrix before and after heating at 300 °C (Figure 9). The IR spectra revealed characteristic
peaks found in natural zeolite and geopolymer materials. The peak at 442 cm−1 corre-
 Polymers 2025, 17, 1155 18 of 30

FTIR spectroscopy was employed to assess the structural changes in the geopolymer
matrix before and after heating at 300 ◦ C (Figure 9). The IR spectra revealed characteristic
peaks found in natural zeolite and geopolymer materials. The peak at 442 cm−1 corresponds
to T–O (T = Al or Si) bending vibrations [33,43], while the signal at 694 cm−1 is associated
with AlO2 functional groups [51]. A band near 797 cm−1 indicates the presence of quartz or
amorphous SiO2 within the zeolite [43], and these fingerprint peaks were also identifiable
Polymers 2025, 17, x FOR PEER REVIEW in the XRD profiles of the samples, supporting the conclusion that the crystal structure 18 of 30
remains largely intact through geopolymerization, despite compositional changes. The
broad band around 3268 cm−1 and the peak at 1694 cm−1 are attributed to the stretching
and bending vibrations of water−1molecules, respectively. Water exhibits O–H stretching in −1
stretching in the 3200–3600 cm range and H–O–H bending around 1600–1650 cm . A
the 3200–3600 cm−1 range and H–O–H bending around 1600–1650 cm−1 . A sharp peak,
sharp peak, originally observed at 1005 cm−1 in natural zeolite, shifted to 973 cm−1 after
originally observed at 1005 cm−1 in natural zeolite, shifted to 973 cm−1 after geopolymer
geopolymer
formation.formation. This band corresponds
This band corresponds to Si–O–Si
to Si–O–Si or Al–O–Si or Al–O–Si
stretching stretching
vibrations [52,53].vibrations
The
[52,53].
observed shift to a lower wavenumber indicates an increase in bond length or abond
The observed shift to a lower wavenumber indicates an increase in length or
reduction
a reduction in bond
in bond angle, angle,
which which isused
is commonly commonly usedmeasure
as an indirect as an indirect measure
of aluminum of aluminum
incorporation
incorporation intonetwork
into the silicate the silicate
[53]. network [53].

◦
Figure 9. FTIR spectra of ZGM membranes before heating (blue line) and after heating at 300 C (red
Figure 9. FTIR spectra of ZGM membranes before heating (blue line) and after heating at 300 °C (red
line). The annotated peaks indicate the functional groups identified at specific wavenumbers and
line). The annotated peaks indicate the functional groups identified at specific wavenumbers and
their corresponding vibrational modes.
their corresponding vibrational modes.
A peak at 1413 cm−1 corresponds to the formation of sodium carbonate, which occurs
A to
due peak
the at 1413 cm
reaction −1 corresponds
between to the formation
sodium hydroxide of sodium
and atmospheric carbonate,
carbon whichthe
dioxide during occurs
duemixing
to theofreaction
the geopolymer
between slurry. In the
sodium FTIR spectra
hydroxide andof atmospheric
the membranes, a prominent
carbon peak
dioxide during
at 1562 cm −1 was evident prior to thermal treatment and is attributed to the carboxylic acid
the mixing of the geopolymer slurry. In the FTIR spectra of the membranes, a prominent
functional groups present in PVAc [54]. This peak completely disappeared after heating,
peak at 1562 cm−1 was evident prior to thermal treatment and is attributed to the carboxylic
indicating the decomposition and elimination of PVAc from the geopolymer structure.
acid functional groups present in PVAc [54]. This peak completely disappeared after heat-
Although the removal of PVAc affected the membrane’s porosity characteristics, it had no
ing, indicating the decomposition and elimination of PVAc from the geopolymer struc-
notable influence on the fundamental chemical composition of the geopolymer membrane.
ture. Although the removal of PVAc affected the membrane’s porosity characteristics, it
had no notable influence on the fundamental chemical composition of the geopolymer
membrane.

3.2. Membrane Performance

 Polymers 2025, 17, 1155 19 of 30

3.2. Membrane Performance

The performance of zeolite-based geopolymer membranes is based on a combination
of size exclusion and ion interactions, both of which are influenced by membrane porosity.
Polymers 2025, 17, x FOR PEER REVIEW 19 of 3
While cation exchange plays a well-established role in heavy metal removal, the relation-
ship between membrane porosity and separation performance remains less understood.
To enhance porosity and surface area, which are crucial for both adsorption and filtration
Additionally,
efficiency, PVActhewaseffect of theasinitial
introduced Pb(II)phase
a sacrificial concentration on membrane
in the geopolymer performance
matrix. To system- wa
atically investigate these effects, ZGMs were synthesized
analyzed to understand its impact on membrane permeability. with varying porosity levels by
adjusting the PVAc concentrations, allowing for controlled pore formation. Their Pb(II)
separation
3.2.1. efficiencies
Influence wereConcentration
of PVAc evaluated under ondifferent
Membraneoperating conditions to determine
Porosity
the influence
and FiltrationofPerformance
porosity on flux rate, rejection efficiency, and adsorption performance.
Additionally, the effect of the initial Pb(II) concentration on membrane performance was
By varying
analyzed the initial
to understand PVAc
its impact concentration
on membrane from 10 wt.% to 30 wt.%, significan
permeability.
changes were observed in the porosity and microstructure of ZGMs, directly impactin
3.2.1. flux
their Influence of PVAc Concentration
and rejection performance. onThe
Membrane
separationPorosity and Filtration
performance Performance
of the membranes with
By varying
out polymer the initial
addition PVAcnot
could concentration
be assessed fromdue10 to
wt.% to 30 wt.%,mechanical
insufficient significant changes
strength, mak
ing them unable to withstand the applied pressure in the permeation test. flux
were observed in the porosity and microstructure of ZGMs, directly impacting their
and rejection performance. The separation performance of the membranes without polymer
As shown in Figure 10, the normalized flux value (i.e., the ratio of permeate flux t
addition could not be assessed due to insufficient mechanical strength, making them unable
initial water flux) was the lowest for the membrane with 10 wt.% PVAc, which corre
to withstand the applied pressure in the permeation test.
sponds As to its lower
shown porosity.
in Figure 10, the Despite
normalized exhibiting
flux value the(i.e.,
lowest flux,ofthis
the ratio membrane
permeate flux toachieve
the highest
initial Pb(II)
water flux) rejection
was the lowestrate
forof
the91% when tested
membrane with 10with
wt.% aPVAc,
50 ppmwhichPb(II) solution. How
corresponds
ever, high rejection
to its lower efficiency
porosity. Despite alone the
exhibiting is not sufficient
lowest flux, thisfor practicalachieved
membrane applications; an industr
the highest
ally viable membrane must also maintain an adequate flux to ensure efficient water per
Pb(II) rejection rate of 91% when tested with a 50 ppm Pb(II) solution. However, high
rejection efficiency
meability. The poor alone is not sufficient
permeability for practical
of this membrane applications;
increased an the
industrially
contact viable
time betwee
membrane must also maintain an adequate flux to ensure efficient
the water and the membrane surface, allowing for more effective contaminant water permeability. The
separatio
poor permeability of this membrane increased the contact time between the water and the
and adsorption.
membrane surface, allowing for more effective contaminant separation and adsorption.

Figure 10. Normalized membrane flux (J/J0, blue circle) and rejection performance (red triangles)
Figure 10. Normalized membrane flux (J/J0, blue circle) and rejection performance (red triangles) o
of ZGM, evaluated at a constant initial Pb(II) ion concentration of 50 ppm, room temperature, and
ZGM, evaluated at a constant initial Pb(II) ion concentration of 50 ppm, room temperature, an
neutral pH.
neutral pH.

ZGM2 (10 wt.% PVAc) exhibited a low degree of pore interconnectivity, with only
few observable pores on the surface. Cross-sectional micrographs confirmed a low voi
content and poor interconnection among the pores. This restricted water permeability
Polymers 2025, 17, 1155 20 of 30

ZGM2 (10 wt.% PVAc) exhibited a low degree of pore interconnectivity, with only a
few observable pores on the surface. Cross-sectional micrographs confirmed a low void
content and poor interconnection among the pores. This restricted water permeability,
resulting in low flux but high Pb(II) rejection efficiency. The reduced flux was attributed to
the limited transport pathways for water molecules, while the dense structure enhanced ion
rejection. Increasing the PVAc concentration to 20 wt.%, (ZGM03), significantly improved
pore formation. SEM images revealed a higher number of interconnected pores on both the
surface and the cross-section. This structural enhancement led to a notable increase in water
flux, as the more open and connected pore network facilitated water transport. However,
the Pb(II) rejection rate was slightly lower than that of ZGM2, likely due to the increased
permeability allowing some lead ions to pass through. Despite expectations, the flux value
of ZGM3 (20 wt.% PVA) was slightly higher than that of ZGM4 (30 wt.% PVA), while its
Pb(II) rejection rate was 87%, which was 2% lower than that of ZGM4 when tested with a
50 ppm Pb(II) solution. To better understand this trend, SEM micrographs (Figure 11) were
analyzed to assess the pore structure and interconnectivity of the membranes. Increasing
the PVAc concentration to 30 wt.% was anticipated to enhance porosity. However, a SEM
analysis revealed a reduction in mesoporous structures and the formation of macrovoids,
likely due to polymer particle agglomeration, which led to the emergence of large voids
after the removal of the organic phase [55]. The presence of these macrovoids negatively im-
pacted pore interconnectivity, reducing surface permeability and leading to a lower water
flux compared to ZGM3. Additionally, while the structural voids facilitated Pb(II) accom-
modation, potentially improving rejection efficiency, the accumulation of Pb(II) ions within
these voids may have partially blocked water pathways, further restricting water flux. This
suggests that excessive Pb(II) adsorption within the macrovoids could have contributed to
the observed permeability reduction, limiting the overall membrane performance.
The balanced performance of ZGM3 (20 wt.% PVAc), in terms of Pb(II) rejection and
water flux, can be directly linked to its optimized pore structure, as observed in the SEM
micrographs and confirmed by BET/BJH analyses. The SEM images (Figure 4) reveal
a well-developed network of uniformly distributed mesopores, with fewer macrovoids
compared to ZGM4 (30 wt.% PVAc), which exhibited irregular, oversized pores due to
polymer agglomeration. This is consistent with the findings by Wang et al. [31], who
demonstrated hierarchical pore formation in geopolymer tube membranes. However, they
have used a surfactant to build stable foams. In our study, the geopolymer membranes
exhibit uniform pore distribution, likely due to the optimized PVAc concentration (20 wt.%).
Unlike the ceramic membranes fabricated by Adam et al. [48], which exhibited significant
macrovoid formation due to uncontrolled viscosity of the ceramic suspension.
This morphology translates into a more controlled pore interconnectivity in ZGM3,
minimizing defects and facilitating uniform flow pathways. BET analysis further supports
this observation, showing a specific surface area of 118.3 m2 /g with 53% mesopores and
10% micropores (Figure 5c,d). The dominance of mesopores in ZGM3 enhances water
permeability by reducing resistance to flow, while the presence of micropores provides
abundant active sites for Pb(II) adsorption, contributing to the 87% rejection rate observed
in filtration tests (Figure 10). Additionally, the well-connected pore network facilitates faster
diffusion of Pb(II) ions, which is consistent with the observed adsorption kinetics, where
ZGM3 achieved equilibrium uptake more rapidly than membranes with lower or higher
PVAc content. This combination of hierarchical pore distribution and interconnectivity
explains why ZGM3 strikes the best balance between flux and rejection performance.
 tion efficiency, the accumulation of Pb(II) ions within these voids may have partially
blocked water pathways, further restricting water flux. This suggests that excessive Pb(II)
Polymers 2025, 17, 1155 adsorption within the macrovoids could have contributed to the observed permeability
21 of 30
reduction, limiting the overall membrane performance.

Figure
Figure SEMSEM
11. 11. micrographs
micrographs of zeolite
of zeolite geopolymer
geopolymer membranes
membranes prepared
prepared with
with differentinitial
different initialPVAc
PVAc concentrations (%), shown at various magnifications: membrane surface morphology, bulk
concentrations (%), shown at various magnifications: membrane surface morphology, bulk cross-
cross-section, and internal cross-section.
section, and internal cross-section.
The exact separation mechanism of zeolite-based geopolymer filters is generally ac-
The balanced
knowledged performance
to involve of ZGM3of(20
a combination wt.%
size PVAc),
exclusion in terms
and of Pb(II) rejection
ion interactions [3]. The and
water flux, canmatrix
geopolymer be directly linked
exhibits to exchange
cation its optimized porecontaining
capacity, structure,exchangeable
as observed in the SEM
cations
within its framework. Upon contact with the membrane, heavy metal cations displace
these exchangeable ions due to their greater binding affinity, thereby driving the ion ex-
change process [3]. A column test study on sorption capacity revealed that geopolymer
beads demonstrated a sorption capacity of 45.32 mg/g, which was comparable to the
45.93 mg/g observed for natural zeolite, indicating that the geopolymer maintained its
adsorption efficiency despite structural alterations [3]. Additionally, the cation exchange
capacity (CEC) of geopolymer beads was measured at 83.96 meq/100 g, closely matching
the 83.65 meq/100 g recorded for natural zeolite, further validating these findings.
To assess the impact of Pb(II) adsorption on the membrane’s pore structure and surface
chemistry, an FTIR analysis was conducted. Figure 12 shows the FTIR spectra of the ZGM
before and after Pb(II) adsorption. Following Pb(II) adsorption, a broad and intense band
around 3358 cm−1 appeared, corresponding to OH-stretching vibrations associated with hy-
drogen bonding to interlayer water molecules [56]. Additionally, a sharp peak at 1637 cm−1
 Polymers 2025, 17, 1155 22 of 30

was attributed to bending vibrations of interlayer water molecules, indicating interactions

between Pb(II) and the membrane matrix. New shoulders appeared in the FTIR spectra
of the geopolymer membrane post-adsorption at around 514 and 692 cm−1 , suggesting
the formation and precipitation of lead hydroxide and the chemisorption mechanism of
Pb(II) uptake by the ZGMs [56]. Similar structural changes have been reported for natural
zeolites, where bands at 673 and 693 cm−1 are associated with ion exchange-induced frame-
work modifications, specifically ring vibrations linked to the SiO4 and AlO4 tetrahedral
structure [52]. Rahmanian et al. [56] also reported comparable spectral changes in layered
double hydroxides upon Pb(II) uptake, indicating chemisorption and ion exchange as
dominant mechanisms. These findings support the proposed ion exchange process in our
ZGM membranes, where Pb(II) displaces other cations within the aluminosilicate frame-
work. These spectral shifts further validate the effective Pb(II) removal mechanism of the
Polymers 2025, 17, x FOR PEER REVIEW 22 of 30
zeolite-based geopolymer membrane, which operates through a synergistic combination of
ion exchange, surface complexation, and precipitation within the membrane pores.

Figure
Figure 12. 12.
FTIRFTIR spectra
spectra of of zeolite-basedgeopolymer
zeolite-based geopolymer membranes
membranesbefore
beforeand
andafter
afterPb(II)
Pb(II)adsorption,
adsorption,
highlighting the chemisorption interactions and associated structural changes. Including a detailed
highlighting the chemisorption interactions and associated structural changes. Including a detailed
table summary of FTIR peak assignments, including wavenumbers, functional groups, vibrational
table summary of FTIR peak assignments, including wavenumbers, functional groups, vibrational
modes, and descriptions of interactions indicating Pb(II) adsorption onto the geopolymer membrane.
modes, and descriptions of interactions indicating Pb(II) adsorption onto the geopolymer membrane.
3.2.2. The Effect of Initial Pb(II) Ions Concentration on the Membrane Performance
3.2.2. The Effect
The ofcontaminant
initial Initial Pb(II)concentration
Ions Concentration on the Membrane
has a significant impact on Performance
membrane perfor-
mance. Figure
The initial 13 presents concentration
contaminant the normalizedhas fluxaand rejectionimpact
significant efficiency at varying initial
on membrane perfor-
Pb(II) concentrations, with the initial PVAc concentration held constant
mance. Figure 13 presents the normalized flux and rejection efficiency at varying initial at 20 wt.%. In
general, the normalized flux decreased as the Pb(II) ion concentration increased for all
Pb(II) concentrations, with the initial PVAc concentration held constant at 20 wt.%. In gen-
membranes, regardless of their porosity. At higher contaminant concentrations, adsorption
eral, the normalized flux decreased as the Pb(II) ion concentration increased for all mem-
saturation of the membrane surface occurred more rapidly, resulting in accelerated pore
branes, regardless of their porosity. At higher contaminant concentrations, adsorption sat-
blockage due to the accumulation of Pb(II) ions and other exchanged ions. This blockage
uration of the
restricted themembrane surface occurred
number of available pathwaysmore rapidly,
for water resulting
permeation, in accelerated
leading pore
to a reduction
blockage due to the accumulation of Pb(II) ions and other exchanged ions.
in flux (Figure 13). Additionally, the increased ionic concentration near the membrane This blockage
restricted
surfacethe
led number of available
to the formation pathways for
of a concentrated water permeation,
boundary layer, whichleading to a develop
may further reduction
in flux (Figure 13). Additionally, the increased ionic concentration near the membrane
surface led to the formation of a concentrated boundary layer, which may further develop
into a gel-like layer on the membrane wall. This phenomenon negatively impacts the per-
meate flux by establishing a positive concentration gradient toward the membrane sur-
Polymers 2025, 17, 1155 23 of 30

into a gel-like layer on the membrane wall. This phenomenon negatively impacts the
permeate flux by establishing a positive concentration gradient toward the membrane
surface, thereby increasing the back diffusion of solutes into the bulk solution and reducing
net transport across the membrane. The rejection performance varied with the Pb(II)
Polymers 2025, 17, x FOR PEER REVIEW 23 ofcon-
30
centration. The highest rejection values for all of the membranes were observed at an initial
Pb(II) concentration of 200 ppm, while the lowest rejection occurred at 100 ppm (Table 6).

Figure
Figure13.
13.Normalized
Normalizedmembrane
membraneflux flux(J/J0,
(J/J0,blue
bluecircles)
circles)and
andrejection
rejectionefficiency
efficiency(%,
(%,red
redtriangles)
triangles)
ofzeolite-based
of zeolite-basedgeopolymer
geopolymermembranes
membraneswith withinitial
initialPVAc
PVAcconcentration
concentrationofof2020wt.%,
wt.%,evaluated
evaluatedatat
varying Pb(II) concentrations (50, 100, and 200 ppm), at room temperature and neutral
varying Pb(II) concentrations (50, 100, and 200 ppm), at room temperature and neutral pH. pH.

Table 6. Flux performance and ion rejection efficiency of zeolite-based geopolymer membranes
Table 6. Flux performance and ion rejection efficiency of zeolite-based geopolymer membranes
(ZGMs) evaluated at varying Pb(II) concentrations (50, 100, and 200 ppm).
(ZGMs) evaluated at varying Pb(II) concentrations (50, 100, and 200 ppm).
Membrane Code ZGM2 ZGM3 ZGM4
Membrane Code ZGM2 ZGM3 ZGM4
Pb(II) concentration (ppm)
Pb(II) concentration (ppm) Flux(L/m 2 .h) 2.h)
Flux(L/m
50 50 61.9 61.9 78.5 78.5 41.2
41.2
100 100 38.6 38.6 42.5 42.5 40.7
40.7
200 200 33.7 33.7 35.8 35.8 35.1
35.1
Pb(II) concentration (ppm) Rejection (%)
Pb(II) concentration (ppm) Rejection (%)
50 91 87 89
50 100 91 88
87 84 8986
100 200 88 97 84 94 8696
200 97 94 96
At an initial Pb(II) concentration of 50 ppm, the ZGM3 membrane exhibited a rejec-
At an initial Pb(II) concentration of 50 ppm, the ZGM3 membrane exhibited a rejection
tion rate of 87%, which is lower than the 99.9% reported by Zhu et al. [57] for Al2O3-NaA
rate of 87%, which is lower than the 99.9% reported by Zhu et al. [57] for Al2 O3 -NaA zeolite
zeolite composite membranes, which is likely due to the hollow fiber structure and inher-
composite membranes, which is likely due to the hollow fiber structure and inherently
ently offers a much larger surface area compared to flat-sheet or self-standing membranes.
offers a much larger surface area compared to flat-sheet or self-standing membranes.
This allows for more contact points between the membrane and the Pb(II)-contaminated
This allows for more contact points between the membrane and the Pb(II)-contaminated
water, enhancing adsorption and separation. Additionally, the presence of the NaA zeo-
water, enhancing adsorption and separation. Additionally, the presence of the NaA zeolite
lite phase, with its smaller pore size (~0.4 nm) and high cation exchange capacity, further
phase, with its smaller pore size (~0.4 nm) and high cation exchange capacity, further
enhances Pb(II) removal efficiency [57]. Compared to polymeric membranes such as the
enhances Pb(II) removal efficiency [57]. Compared to polymeric membranes such as
PES/GO composites reported by Poolachira and Velmurugan [58], which achieved 80.6%
the PES/GO composites reported by Poolachira and Velmurugan [58], which achieved
Pb(II) rejection, the zeolite-based geopolymer membranes demonstrate a higher rejection
80.6% Pb(II) rejection, the zeolite-based geopolymer membranes demonstrate a higher
efficiency and a superior mechanical stability. This enhanced performance is likely at-
rejection efficiency and a superior mechanical stability. This enhanced performance is likely
tributed to the membrane’s combined separation mechanisms of ion exchange and size
exclusion. Pb(II) ions are selectively removed by replacing exchangeable cations (Na⁺, K⁺)
within the geopolymer framework, while the membrane’s well-defined porous structure
restricts ion passage. Furthermore, the negatively charged surface of the geopolymer en-
hances electrostatic attraction, further improving Pb(II) adsorption efficiency [3].
Polymers 2025, 17, 1155 24 of 30

attributed to the membrane’s combined separation mechanisms of ion exchange and size
exclusion. Pb(II) ions are selectively removed by replacing exchangeable cations (Na+ , K+ )
within the geopolymer framework, while the membrane’s well-defined porous structure
restricts ion passage. Furthermore, the negatively charged surface of the geopolymer
Polymers 2025, 17, x FOR PEER REVIEW 24 of 30
enhances electrostatic attraction, further improving Pb(II) adsorption efficiency [3].
The flux decreased when the concentration of Pb(II) ions increased from 50 ppm
to 100 ppm. However, the rejection efficiency did not improve correspondingly. At this
intermediate concentration, partial pore blockage occurred due to the higher number of
intermediate concentration, partial pore blockage occurred due to the higher number of
adsorbed Pb(II) ions, but the reduction in flow rate was not sufficient to prevent the pas-
adsorbed Pb(II) ions, but the reduction in flow rate was not sufficient to prevent the pas-
sage of some contaminant ions. This allowed more Pb(II) ions to permeate through the
sage of some contaminant ions. This allowed more Pb(II) ions to permeate through the
membrane, resulting in lower rejection efficiency despite the slight decrease in flux. In
membrane, resulting in lower rejection efficiency despite the slight decrease in flux. In
contrast, when the Pb(II) concentration increased further from 100 ppm to 200 ppm, there
contrast, when the Pb(II) concentration increased further from 100 ppm to 200 ppm, there
was a more pronounced reduction in flux, indicating major pore blockage and a signifi-
was a more pronounced reduction in flux, indicating major pore blockage and a significant
cant accumulation of Pb(II) ions on the membrane surface. At this higher concentration,
accumulation of Pb(II) ions on the membrane surface. At this higher concentration, the
the concentration gradient between the feed and permeate sides became much steeper,
concentration gradient between the feed and permeate sides became much steeper, provid-
providing a greater driving force that facilitated the rapid mass transfer of Pb(II) ions to-
ing a greater driving force that facilitated the rapid mass transfer of Pb(II) ions toward the
ward the membrane surface. This led to the formation of a dense concentration polariza-
membrane surface. This led to the formation of a dense concentration polarization layer or
tion layer or even a gel-like layer, which acted as an additional selective barrier, effectively
even a gel-like layer, which acted as an additional selective barrier, effectively restricting the
restricting the transport of Pb(II) ions through the membrane. As a result, the rejection effi-
transport of Pb(II) ions through the membrane. As a result, the rejection efficiency increased
ciency increased significantly between 100 ppm and 200 ppm. The element mapping of a
significantly between 100 ppm and 200 ppm. The element mapping of a typical ZGM was
typical ZGM was performed using the SEM/EDS analysis (Figure 14) to locate the Pb(II)-
performed using the SEM/EDS analysis (Figure 14) to locate the Pb(II)-accommodated sites.
accommodated sites. The SEM/EDS images revealed an interconnected porous structure
The SEM/EDS images revealed an interconnected porous structure covered with adsorbed
covered with adsorbed Pb(II) particles, particularly concentrated within the structural
Pb(II) particles, particularly concentrated within the structural pores. This observation
pores. This observation confirms both successful Pb(II) adsorption and the potential for pore
confirms both successful Pb(II) adsorption and the potential for pore blockage, which
blockage, which contributes to the observed changes in flux and rejection performance.
contributes to the observed changes in flux and rejection performance.

Figure 14.
Figure 14. SEM
SEM images
images and
and corresponding
corresponding EDSEDS elemental
elemental mapping
mapping of
of ZGM
ZGM prepared
prepared with
with 20
20 wt.%
wt.%
PVAcafter
PVAc afteradsorption
adsorptionof
ofPb(II)
Pb(II)atataaconcentration
concentrationofof200
200ppm.
ppm.

3.2.3.
3.2.3. Comparison
Comparison of
of Zeolite-Based
Zeolite-Based Geopolymer
Geopolymer Membranes
Membranes with
with Alternative
Alternative
Membrane Materials
Membrane Materials
The
The following
followingtable
tableevaluates
evaluatesvarious
variousmembranes
membranes used for heavy
used metalmetal
for heavy removal, com-
removal,
paring them with this study in terms of flux-rejection trade-offs, mechanical properties,
comparing them with this study in terms of flux-rejection trade-offs, mechanical proper- and
material
ties, andcosts. The costs.
material evaluation of various membranes
The evaluation used for heavy
of various membranes metal
used removal
for heavy reveals
metal re-
key differences in terms of flux-rejection trade-offs, mechanical properties, and material
moval reveals key differences in terms of flux-rejection trade-offs, mechanical properties, costs.
and material costs. While this study focuses on zeolite-based geopolymer membranes, the
comparison with other membrane technologies, such as polymeric and ceramic mem-
branes, highlights distinct strengths and limitations. Direct comparisons between poly-
meric and inorganic membranes are challenging due to the wide variation in polymeric
Polymers 2025, 17, 1155 25 of 30

While this study focuses on zeolite-based geopolymer membranes, the comparison with
other membrane technologies, such as polymeric and ceramic membranes, highlights distinct
strengths and limitations. Direct comparisons between polymeric and inorganic membranes
are challenging due to the wide variation in polymeric membrane compositions, separation
mechanisms, applications, and costs. For meaningful insights, this discussion emphasizes
commonly used polymeric membranes like polyvinylidene fluoride (PVDF) and polyether
sulfone (PES), which are well-established in water treatment applications [59].
As can be seen in Table 7, the zeolite–geopolymer membrane provides a balanced ap-
proach for heavy metal removal, offering a moderate flux and rejection rate combined with
strong mechanical strength and a reasonable lifespan. In comparison, ceramic membranes
generally outperform in terms of flux and rejection efficiency, making them highly effective
for heavy metal removal but with potential trade-offs in cost. Zeolite membranes, known
for their excellent removal efficiency and good mechanical strength, are typically more
expensive, especially synthetic zeolites, which can make them less economically viable for
certain applications. Polymeric membranes, while cost-effective and long-lasting, tend to
have lower performance in rejecting heavy metals compared to inorganic membranes. Poly-
meric membranes, although widely used and cost-effective, tend to underperform in heavy
metal rejection and are generally less durable in complex industrial wastewater environ-
ments compared to their inorganic counterparts. These membranes are more prone to issues
like fouling, scaling, and material degradation, which can undermine their effectiveness
over time. Zeolite-based geopolymer membranes are fabricated using inorganic natural
resources, such as mined zeolites, resulting in environmentally friendly products. Mined
zeolites possess unique properties, like high ion-exchange capacity, porosity, and structural
stability, which make them highly promising for various applications, particularly for heavy
metal removal within water treatment systems. However, the water treatment application
of zeolite heavily depends on the particle size of the natural zeolite. Powdered waste
natural zeolite is typically not used in filtration systems due to the high-water pressure
drop it causes, which limits its practical application.

Table 7. High-level comparison of inorganic membranes characterization.

Mechanical Industrial- Life

Flux Rejection Rate Mean Pore
Membrane Type Contaminant Strength Scale Cost Span
(L/m2 ·h) (%) Size
(MPa) (USD/m2 ) (Years)
Polymeric Membranes
1.8–5
PVDF (/PAN *) [60] 186.14 52.11 - 10–40 0.1–0.5 µm
[61]
Pb(II)
2–5
18.69 38.9 - 50–65 0.1–5 µm
Poly ether sulfone [36,58] [62]
[63]
Ceramic Membranes
Metal oxide Membranes
Kaolin–Dolomite [64] Pb(II) 246.78–1738.56 99.12 1–17 MPa 15–19 nm
Zeolite Membranes
Al2 O3 -NaA zeolite [57] Pb(II) 727.5 99.9 85.8 ± 3.1 40–66 [65] 5–8 0.41 nm
Metal–Organic Framework
Membranes
ZIF-300 MOF membrane [64] Cu(II) 39.2 99.21 - 50–200 - 7.9 Å
Zeolite–Geopolymer 2–5 nm &
Pb(II) 78.5 87% ~180 ~20.6 5–8
Membrane (This Study) >5 nm
Carbon-Based Membranes
Graphene - -
(PSF + GO + DMF) [65] Pb(II) 100 >90 20 30–400 Å
Carbon Nanotubes [2] Pb(II) - 99.99 50 - - 18.8–23.7 µm
Hybrid Membranes
PES/PVP **/GO *** [58] Pb(II) 150.21 80.6 - 50–65 - -
* Polyacrylonitrile. ** Polyvinylpyrrolidone. *** Graphene oxide.
Polymers 2025, 17, 1155 26 of 30

4. Conclusions
This study developed and investigated novel porous zeolite-based geopolymer mem-
branes for Pb(II) ion adsorption and separation. The membranes were fabricated using
waste-grade natural zeolite powder. The membranes initially exhibited limited practical
utility due to insufficient porosity and low mechanical strength. To address these issues, a
polyvinyl acetate (PVAc) emulsion was employed as a structure-directing agent at varying
concentrations and subsequently removed through thermal degradation at 300 ◦ C. This
innovative approach resulted in organic-free membranes characterized by enhanced poros-
ity, improved hardness, and mechanical robustness, with annealing effectively healing
micro- and macrocracks. Optimal performance in terms of balanced flux and rejection
rates was achieved at a 20 wt.% PVAc concentration, while higher concentrations (30 wt.%)
introduced macrovoids, compromising membrane integrity. Performance characterization
demonstrated that higher Pb(II) ion concentrations led to reduced membrane flux. These
geopolymer membranes, leveraging inexpensive raw zeolite without the need for addi-
tional support structures, offer cost-effective and sustainable alternatives to conventional
inorganic membranes. Despite their advantages, challenges such as membrane scaling
and fouling remain, necessitating further optimization of the operational conditions for
effective and practical wastewater treatment applications.
Zeolite-based geopolymer membranes were sustainably produced from waste-grade
materials, offering significant environmental benefits by reducing waste generation. How-
ever, similar to the comparative life cycle assessment (LCA) between zeolite geopolymer
and conventional concrete conducted in this study [20], the geopolymer membrane’s sus-
tainability and environmental performance also require quantitative evaluation through
LCA. Such an assessment will allow for a detailed comparison between geopolymer mem-
branes and polymeric membranes, addressing environmental impacts across their entire life-
cycle, including production, reuse potential, and end-of-life disposal. Evaluating strategies
for reuse, recycling, or responsible disposal of these membranes is particularly important,
as it ensures alignment with zero-waste objectives and promotes long-term sustainability.
Reproducibility and consistency in membrane performance across batches are signifi-
cant challenges in inorganic membrane manufacturing, which is essential for industrial
applications. Future research should prioritize ensuring reproducibility, optimizing flux-
rejection trade-offs, enhancing chemical and mechanical stability, and broadening the
application of these membranes as sustainable filtration materials for complex industrial
wastewater, especially multi-contaminant systems containing heavy metals and organic
pollutants. Additionally, studies focusing on scalability, the optimization of manufacturing
processes, and the economic feasibility of zeolite–geopolymer membranes are crucial to
facilitate their widespread implementation in industrial water treatment.

Author Contributions: Conceptualization, M.D., G.M. and S.A.; Methodology, S.A. and M.D.; Valida-
tion, S.A.; Formal analysis, S.A.; Investigation, S.A.; Writing—original draft, S.A.; Writing—review
& editing, S.A., G.M. and B.B.; Visualization, S.A. and B.B.; Supervision, M.D. and G.M.; Project
administration, S.A.; Funding acquisition, M.D. and G.M. All authors have read and agreed to the
published version of the manuscript.

Funding: This research received no external funding.

Institutional Review Board Statement: Not applicable.

Data Availability Statement: All data are available within the manuscript.

Acknowledgments: The authors extend their gratitude to the personnel at the Central Analytical Research
Facility (CARF) of the Queensland University of Technology (QUT) for their support and the Faculty of
Polymers 2025, 17, 1155 27 of 30

Science and Engineering at QUT and Western Sydney University for facilitating access to the necessary
analytical instruments. Additionally, S. Amari appreciates the research scholarship provided by QUT.

Conflicts of Interest: The authors declare no conflicts of interest.

Abbreviations
The following abbreviations are used in this manuscript:
A Membrane surface area
BET Brunauer–Emmett–Teller
BJH Barrett–Joyner–Halenda
CARF Central Analytical Research Facility
DSC Differential Scanning Calorimetry
EDS Energy-Dispersive Spectroscopy
FTIR Fourier-Transform Infrared Spectroscopy
ICP-OES Inductively Coupled Plasma Optical Emission Spectroscopy
IUPAC International Union of Pure and Applied Chemistry
J Water Flux
MDPI Multidisciplinary Digital Publishing Institute
MPa Megapascal
PVAC Polyvinyl Acetate
QUT Queensland University of Technology
R Removal efficiency
SEM Scanning Electron Microscopy
SiO2 /Al2 O3 Silicon-to-Aluminum Ratio
TGA Thermogravimetric Analysis
t Time
XRD X-ray Diffraction
ZGM Zeolite Geopolymer Membrane

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