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Exfoliated MXene/poly-melamine-formaldehyde composite membranes for

removal of heavy metals and organics from aqueous solutions

Article in Journal of Hazardous Materials · October 2023

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 Journal of Hazardous Materials 463 (2024) 132866

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Journal of Hazardous Materials

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

Research Paper

Exfoliated MXene/poly-melamine-formaldehyde composite membranes for

removal of heavy metals and organics from aqueous solutions
Tian-Qi Zhang a, b, 1, Shuang Hao c, 1, Jun-Kai Zhao a, Zhi-Qian Jia a, *, Hong-Wei Tan a, *,
Yu Yang d, *, Li-An Hou d, e
a
College of Chemistry, Beijing Normal University, Beijing 100875, PR China
b
Hangzhou Institute of Technology, Xidian University, Hangzhou 311200, PR China
c
School of Materials Science and Engineering, Tiangong University, Tianjin 300387, PR China
d
School of Environment, Beijing Normal University, Beijing 100875, PR China
e
High Tech. Inst. Beijing, Beijing 100000, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

•A novel MXene/poly-melamine-
formaldehyde (PMF) composite mem­ Mxene/PMF composite membrane has a good ability to remove heavy metal ions and small organic
brane are prepared. molecules while maintaining a high water permeability of 381.2 L m¡2 h¡1 bar¡1.
• The introduction of PMF particles
widens the transmission channel and
increases water permeance.
• PMF and MXene nanosheets have a
synergistic effect on the adsorption of
pollutants.
• Removal rates of Zn2+, Pb2+, phenol
and crystal violet by MXene composite
membranes are above 90%.
• After 4 times of use, the removal rate of
pollutant of composite membrane is
above 90%.

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

Editor: Anett Georgi Heavy metal ions and organic pollutants discharged into various water bodies have caused serious water
pollution, and the efficient removal of these contaminants remains a challenge. Here, we report a novel MXene/
Keywords: poly-melamine-formaldehyde (PMF) composite membrane, in which the PMF particles serve as spacers, and the
MXene composite membranes –NH2 groups of PMF and the hydroxyl groups of MXene nanosheets have a synergistic effect on the adsorption of
Poly-melamine-formaldehyde
pollutants, and the crosslinking of glutaraldehyde inhibits the swelling of the composite membrane. The MXene/
Heavy metal ions
PMF composite membrane with 83.7% PMF particle loading displays a water permeability of 381.2 L m− 2 h− 1
Phenols
Dyes bar− 1 (405% that of MXene membrane) and excellent adsorption ability. In static adsorption, the removal rates of
Dynamic adsorption Zn2+, Pb2+, phenol, and crystal violet reach 96.2%, 91.7%, 99.1%, and 96.4% respectively, 20~100% higher
than those of MXene membranes. In dynamic adsorption, the breakthrough volumes of the membrane for 2 ppm

* Corresponding authors.
E-mail addresses: zhqjia@bnu.edu.cn (Z.-Q. Jia), zhqjia@bnu.edu.cn (H.-W. Tan), yangyu@bnu.edu.cn (Y. Yang).
1
Tian-Qi Zhang and Shuang Hao contributed equally.

https://doi.org/10.1016/j.jhazmat.2023.132866
Received 26 July 2023; Received in revised form 17 October 2023; Accepted 24 October 2023
Available online 30 October 2023
0304-3894/© 2023 Elsevier B.V. All rights reserved.
T.-Q. Zhang et al.
p-nitrophenol solution and methyl blue solution reach 75 mL (about 8500 times membrane volume) and 350 mL
(about 39800 times membrane volume), and the saturation volumes are 1500 mL and 5000 mL, respectively.
After cyclic adsorption/desorption for four times, the removal rate of the membranes still maintains above 90%.
This work provides an efficient composite membrane for removing pollutants from wastewater.
1. Introduction
Water pollution is a major issue for human society today [15,27,47].
Heavy metal ions and organic pollutants are stable and difficult to
degrade in water bodies, leading to the accumulation in organisms, and
posing a threat to human health [3–5]. To control environmental
pollution, various methods, such as chemical precipitation, ion ex­
change, electrochemistry, membrane separation, redox, and adsorption,
are used for removing pollutants from wastewater [21,34,43]. Among
these methods, adsorption is popular due to its ease of operation and
efficiency in removing trace substances. Porous materials, such as
porous organic polymers and metal-organic frameworks, are good ad­
sorbents due to their high porosity and abundant active sites [31,39].
MXenes, as a family of 2D materials, have been paid more attention
recently [13,25,26,30,37]. MXenes are formulated as Mn+1XnTx (n
varying from 1 to 3), where M is a transitional metal, X is C and/or N,
and Tx stands for surface terminations, such as − O, − OH, and − F.
MXenes have proven to be an effective adsorbents for various pollutants
due to the high hydrophilicity and abundant active sites [41,45].
Ti3C2Tx, a type of MXene, has been used in the adsorption of organic
dyes such as methylene blue, acid blue, methylene blue and methyl
orange.
Similar to graphene-based materials, MXenes have unique physical
and chemical properties and nanosized mass transfer channels, making
them suitable for constructing MXene membranes through vacuum
filtration [1]. Nevertheless, the tight stacking of MXene nanosheets may
result in a low water permeability (usually less than 100 L m− 2 h− 1 bar− 1
[32]) and the limited contact between functional groups and pollutants.
Furthermore, MXene-based membranes usually display high rejection
for organic dyes while poor rejection for heavy metal ions [16]. To
address these issue, Wang et al. developed hybrid membranes by
combining MXene nanosheets with carbon nanotubes (CNTs) [35], and
the transportation channel is widened and the water permeability is
improved. In a similar study, Yang et al. combined Fe3O4 particles with
MXene nanosheets to create MXene/Fe3O4 composite membranes [38].
GO, Ag nanoparticles, TiO2 nanoparticles were also used as spacers of
MXene membranes [17,20,29]. The introduction of non-porous particles
widens the transportation channel and significantly increases water
permeability to 330 L m− 2 h− 1 bar− 1, with removal rates of Cu, Cd, and
Cr (10 ppm) about 70%. However, there are few studies on incorpo­
rating porous and hydrophilic nanoparticles into MXene membranes.
Poly-melamine-formaldehyde (PMF), a type of porous organic
polymer with abundant amino groups [39,44], possesses excellent
adsorption capabilities for heavy metal ions and organic pollutants [28,
33]. In this study, to further improve the water permeability and
pollutant removal capacity of MXene membranes, MXene/PMF com­
posite membranes were prepared, in which the PMF particles serve as
spacers and synergistic adsorbents. The effects of PMF size and amount
on the composite membranes, and the adsorption thermodynamics,
adsorption kinetics, dynamic adsorption and recycling were studied.
This work provides a facile method for fabrication of high-flux MXene
membranes with excellent adsorption capacity.
2. Materials and methods
2.1. Materials
Ti3AlC2 (MAX) powder (>98%, 300 mesh) was purchased from
Yuehuan Company (Shanghai, China). Lithium fluoride (LiF, >99.0%),
2
Journal of Hazardous Materials 463 (2024) 132866
hydrochloric acid (HCl, 32%) were purchased from Sigma-Aldrich.
Melamine (99%), and paraformaldehyde (99%) were obtained from
J&K Scientifics Ltd. (Beijing, China). Zinc nitrate (Zn(NO3)2, 99%), lead
nitrate (Pb(NO3)2, 99%), phenol (99%), p-nitrophenol (p-NP, 99%),
methylene blue (MB, 98%), crystal violet (CV, 98%), cresol red (CR,
98%), and methyl blue (MB-1, 98%) were supplied by Sigma-Aldrich.
The solutions used for static adsorption and dynamic adsorption are
obtained by dissolving chemical reagents in deionized water. Nylon
(polyamide) microfiltration membranes with a nominal pore size of
0.22 µm, provided by Sterlitech, were used as the substrates.
2.2. Synthesis of Ti3C2Tx nanosheets and PMF particles
Preparation of 2D MXene nanosheets [7]: 1.98 g of LiF was dissolved in
20 mL of HCl in a 250 mL Teflon beaker. Then, 2 g of Ti3AlC2 was added
to the solution with magnetic stirring at 35 ◦ C for 24 h. Subsequently,
the obtained suspension was diluted and washed by deionized water,
then centrifuged at 5000 rpm for several times until the pH of the su­
pernatant reached 6. The solution containing the single layer MXene
nanosheets was obtained after ultrasonication for 1 h. Then, the sus­
pension was centrifuged at 3500 rpm for 1 h to remove the unexfoliated
precursors, and the supernatant was the 2D MXene nanosheets solution
(~0.54 mg mL− 1).
Preparation of PMF particle: Melamine (0.896 g) and para­
formaldehyde (0.384 g) were dissolved in DMSO (40 mL) at 90 ◦ C for 2
h. Then, the mixture was heated at 170 ◦ C for different time (6 h,12 h,
18 h). After polymerization, the solid sample was obtained by centri­
fugation at 8000 rpm and washed with methanol and acetone for three
times. Finally, the solid powder was dried in vacuum oven at 120 ◦ C for
24 h and dispersed in 40 mL of DMSO. The concentration of the PMF
particle dispersion was ~16.55 mg mL− 1.
2.3. Preparation of MXene/PMF composite membranes
As shown in Fig. 1, the PMF particle dispersion (0.2 mL), MXene
nanosheets dispersion (2.5 mL) and DMSO (2.5 mL) were mixed and
sonicated for 5 min to obtain a uniform dispersion. After a vacuum-
assisted filtration of the mixed dispersion on a nylon membrane
(diameter of 5 cm), the wet membranes were obtained. Then, 10 mL of
glutaraldehyde solution (2 wt%; HCL, 0.5 wt%) was filtrated through
the wet membrane under a negative pressure of 0.6 bar. Finally, the
membranes were obtained after heating in the oven at 50 ◦ C for 5 min
and were named as MXene/PMF-0.2.
2.4. Characterizations
The morphology and thickness of the membranes were observed by
Scanning Electron Microscope (SEM, Zeiss Merlin Gemini 2). The X-ray
diffraction (XRD) analysis was conducted by a Bruker D8 Advance
apparatus. The surface chemical functional groups of samples were
detected by attenuated total reflectance-Fourier Transform Infrared
(ATR-FTIR, PerkinElmer Spectrum 2000). Atomic force microscope
(AFM, Bruker Fast Scan atomic force microscope) was applied to analyze
the roughness of membranes. The contact angle measurement system
(CAM200) was used to detect the static water contact angles of mem­
brane for hydrophilicity evaluation. The surface elemental component
and chemical state of membranes were examined by X-ray photoelectron
spectroscopy (XPS, Thermo, Germany) equipped with a monochromatic
100-eV Al-Kα X-ray source. The concentration of the metal ions solution
T.-Q. Zhang et al.
was measured by Inductively Coupled Plasma mass spectrometry (ICP-
MS) with a Perkin–Elmer plasma 40 emission spectrometer. The phenols
and dyes concentrations were analyzed by UV–vis spectrophotometer
(UV2450, Shimadzu, Japan). The stability of the membranes was
examined by vigorous shaking (250 rpm, 180 min) in aqueous solutions.
2.5. Adsorption
In the static adsorption, MXene/PMF-0.2 composite membranes
were put in 40 mL of single pollutant solution (Zn2+, Pb2+,
0.04 mmol L− 1; phenol, p-NP, MB, CV, CR and MB-1, 0.15 mmol L− 1),
stirred at 25 ℃ for 24 h, and then the membrane was removed from
solution with tweezers. In the dynamic adsorption, 8000 mL of pollutant
solution with an initial concentration of 2 ppm were filtered through
MXene/PMF-0.2 membranes. In the recycling test, 40 mL of 0.1 mol L− 1
NaOH and 0.01 mol L− 1 HCl were used as eluents for dynamic desorp­
tion at a flow rate of 0.2 mL min− 1, followed by the next dynamic
adsorption [19]. The adsorption capacity (Qe) is expressed as [14],
(c0 − ce ) × v0
Qe = (1)
w0
where c0 and ce are the initial and equilibrium concentration (mg L− 1)
respectively, v0 is the solution volume (L), w0 is the adsorbents mass. The
removal rate (R, %) is calculated as,
c0 − ce
R= × 100% (2)
c0
3. Results and discussion
3.1. Fabrication of MXene/PMF composite membranes
The parent Ti3AlC2 powder displays a plate-like morphology
(Fig. 2a) and is transformed into accordion-like Ti3C2Tx powder
(Fig. 2b) through etching with LiF/HCl. Subsequent sonication of the
Ti3C2Tx powder yields Ti3C2Tx MXene nanosheets, which are then
diluted to a concentration of ~0.55 mg mL− 1. This MXene nanosheets
dispersion exhibits the colloidal Tyndall effect (Fig. 2c), and there is no
visible settling of MXene after 90 days of storage at room temperature.
To synthesize PMF particles, melamine and paraformaldehyde react in
DMSO for 12 h, and then the mixture is centrifuged and washed to
obtain PMF particles. The PMF particles are about 100 nm in size
(Fig. S1). The Ti3C2Tx and PMF suspensions are mixed homogeneously
by sonication, filtered onto a nylon membrane using vacuum filtration,
crosslinked by glutaraldehyde, and dried in an oven. The as-obtained
composite membrane is intact, with no apparent fracture or pinhole
(Fig. 2d-f, Fig.S2). The concave valleys of the surface are filled by PMF
particles, resulting in a reduction of the arithmetic average roughness
Fig. 1. Preparation of MXene composite membranes.
3
Journal of Hazardous Materials 463 (2024) 132866
(Ra) from 194 ± 77 nm for MXene membranes (Fig. S3) to 156 ± 41 nm
for the MXene/PMF composite membranes. The PMF particles act as
spacers between the flexible and soft MXene oligolayers, forming a
membrane with thickness of ~7 µm (Fig. 2g).
The XRD patterns show the exfoliation of the bulky MAX, as evi­
denced by the disappearance of an intense diffraction peak of MAX at
39◦ (2θ) and the shift of (002) peak to lower angles. The d-spacing shift
observed in the (002) peak of both the MXene and MXene/PMF com­
posite membranes is similar, suggesting that the PMF particles do not
intercalate between the MXene nanosheets. Instead, the particles are
hybridized with the nanosheets and act as spacers of oligolayers. To
determine the mass ratio and thermal stability of MXene/PMF mem­
branes, thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC) are conducted on MXene/PMF and MXene mem­
branes in a nitrogen atmosphere (Fig. 2i, Fig. S4). The residual mass of
MXene membranes is approximately 84.1% [22,36,46], while our pre­
vious work determined that the residual mass of PMF particles is 23.2%
[39,40,44]. For the MXene/PMF membranes, the residual mass is
33.1%, with two main regions of weight loss: Region I (100–250 ◦ C) and
Region II (380–450 ◦ C). The weight loss in Region I is primarily due to
the removal of -OH and free formaldehyde, while the weight loss in
Region II is associated with the decomposition of -F group and the PMF
polymer. The mass ratio of PMF particle is calculated to be 83.7% by
solving the equations of residual mass ratio of MXene, PMF and MXe­
ne/PMF composite membrane.
In the fourier transform infrared (FTIR) spectra, the characteristic
bands of -OH, -COOH, and Ti-O stretching vibrations are observed at
3480 cm− 1, 1680 cm− 1, and 655 cm− 1 respectively, indicating the
presence of MXene nanosheets (Fig. 3a). For uncrosslinked and cross­
linked MXene/PMF membrane, the bands at 3430 cm− 1 and 1560 cm− 1
are attributed to the stretching vibration and bending vibration of the
amino groups. The bands around 2925 cm− 1 are assigned to the meth­
ylene groups of PMF. The weakening of the bands of crosslinked MXene/
PMF membrane at 3430 cm− 1 and 1560 cm− 1 indicates the occurrence
of chemical crosslinking. The XPS spectra of the uncrosslinked and
crosslinked MXene/PMF membranes are shown in Fig. 3b-d. The O1s of
the uncrosslinked membranes reveals a high fraction of =O/-O- at
531.8 eV (59.5%), which is higher than that of MXene reported in other
literature (~26%) [24] due to the presence of a large number of C– –O
bonds in PMF particles [6]. Additionally, the fraction of C-Ti-OH is about
533.1 eV (35.7%), indicating the presence of active hydroxyl groups.
The introduction of glutaraldehyde during crosslinking results in a sig­
nificant increase in C and O element peaks, and the fraction of =O/-O-
increases to 88.9% and C-Ti-OH reduces to 5.3% because of the chemical
crosslinking of C-Ti-OH by glutaraldehyde. The chemical crosslinking
inhibits the swelling of MXene oligolayers (Fig. S5).
Fig. 4a shows the N2 adsorption and desorption isotherms of MXene
membranes and MXene/PMF composite membranes. The addition of
T.-Q. Zhang et al. Journal of Hazardous Materials 463 (2024) 132866

Fig. 2. SEM images of the compact layered structure of MAX (a) and accordion-like structure of Ti3C2Tx powder (b). Photograph of the dispersion of MXene
nanosheets with the Tyndall effect (c) and the MXene/PMF-0.2 composite membranes (d). SEM images (e) and AFM images (f) of the surface of MXene/PMF-0.2
composite membrane. SEM images of the cross section of MXene/PMF-0.2 composite membranes (g). XRD patterns of MAX, MXene membranes and MXene/
PMF-0.2 composite membranes (h). TGA and DSC of MXene/PMF-0.2 composite membranes in N2 atmosphere from room temperature to 800 ◦ C with a heating
rate of 10 ◦ C min− 1 (i).

PMF particles with a high Brunauer–Emmett–Teller (BET) surface area provide additional transport channels for water, leading to the enhanced
results in a significantly increased BET surface area, from 195.1 m2 g− 1 water permeability. The charge of the MXene membranes and MXene/
for MXene membrane to 434.4 m2 g− 1 (micropore area of 402.1 m2 g− 1, PMF membranes is evaluated using a zeta potential instrument. The
meso/macropore area of 32.3 m2 g− 1) for MXene/PMF composite results show that both membranes display positive charge at pH 1.5–3.5
membrane, and the porosity of the membranes also increased from and become negative as the pH increased (Fig. S8). The incorporation of
47.1% (MXene membrane) to 74.7% (MXene composite membrane). PMF particles into MXene results in a membrane surface with less
This observation is consistent with the SEM images of the composite negative charge (Fig. 4d).
membranes (Fig. 2e), which clearly show the improved surface porosity.
Water contact angles, presented in Fig. 4b, demonstrate the higher hy­
3.2. Effects of PMF particles
drophilicity of MXene/PMF composite membranes (47.5◦ ) than the
MXene membranes (78.3◦ ). For comparison, nanosized SiO2 particles
To investigate the impact of PMF particle size on the structure and
(100 nm, Fig. S6) are also used for fabrication of MXene/SiO2 mem­
performance of MXene/PMF membranes, PMF particles with different
branes by the same procedure. The hydrophilic SiO2 nanoparticles have
sizes (80, 100, 150 nm) are incorporated into the MXene nanosheets.
a similar size as PMF and was used as a control to illustrate the effect of
The surface and cross-section morphology of the resulting membranes
the porous structure of particles on the membrane. It is found that, the
are presented in Fig. S9. The thickness of MXene/PMF composite
MXene/SiO2 composite membranes exhibit a water contact angle of
membranes increases with the size of the PMF particles. The MXene/
66.7◦ . The presence of –NH2 groups of PMF, and high porosity result in
PMF membranes doped with PMF-150 particles show noticeable
low contact angle of MXene/PMF composite membranes. The MXene/
agglomeration of particles on the surface, resulting in non-uniform
PMF membranes exhibit a water permeability of 381.2 L m− 2 h− 1 bar− 1,
mixing of PMF particles and MXene nanosheets. The porosity of the
405% that of MXene membranes. The water permeability decreases with
composite membranes also increases with the size of PMF particles,
the crosslinking time (Fig. S7). In contrast, the water permeability of the
except for PMF-150 (Fig. 5a). The XRD patterns depicted in Fig. 5b
MXene/SiO2 composite membranes is only 210.3 L m− 2 h− 1 bar− 1 due
reveal that the (002) peaks of the MXene/PMF membranes remain un­
to the fewer channels provided by the non-porous SiO2 particles. The
altered, indicating that the interlayer spacing of MXene nanosheets is
PMF particles widen the interlayer channel of MXene oligolayers and
not affected by the size of PMF particles. As the particle size increases

4
T.-Q. Zhang et al.
Fig. 3. FTIR spectra of the MXene membranes, uncrosslinked and crosslinked MXene/PMF-0.2 composite membranes (a). XPS spectra of uncrosslinked and
crosslinked MXene/PMF-0.2 composite membranes (b). O1s peak fitting of uncrosslinked (c) and crosslinked (d) MXene/PMF-0.2 composite membranes.
from 80 nm to 100 nm, the water contact angle of the composite
membranes decreases from 60.9◦ to 47.5◦ (Fig. 5c), and the water and
MB-1 solution (2 ppm) permeability gradually increase from
214.9 L m− 2 h− 1 bar− 1 to 381.2 L m− 2 h− 1 bar− 1 (Fig. 5d), consistent
with the results of Zhang et al. [42]. However, when the particle size is
too large (150 nm), the composite membrane structure becomes
non-uniform, resulting in an increase in contact angle (68.9◦ ) and a
decrease in water permeability (136.8 L m− 2 h− 1 bar− 1). Therefore,
PMF-100 is selected as the optimal particles for subsequent MXene/PMF
membranes.
To explore the effects of PMF amounts on MXene/PMF composite
membranes, different amounts of PMF-100 dispersion are doped in the
MXene nanosheets solution. As the amount of PMF-100 dispersion in­
creases (0.10, 0.15, 0.20, 0.25 mL), the surface of MXene/PMF com­
posite membranes shows no noticeable change, and the thickness of the
membranes increases from 4 µm to 7 µm (Fig. S10), and the porosity of
MXene/PMF membranes also increases, reaching a maximum of 74.7%
(addition of 0.20 mL). When the amount of PMF dispersion is 0.25 mL,
the interaction of MXene oligolayers is weakened, making it difficult to
maintain the structure and to estimate the porosity of MXene/PMF
membranes (Fig. 6a, b). The water contact angle of the membranes
decreases from 64.3◦ to 29.6◦ (Fig. 6c, d) and the solution permeability
of the MXene/PMF composite membranes increases from 169.5 L m− 2
h− 1 bar− 1 to 435.2 L m− 2 h− 1 bar− 1. Therefore, the addition amount of
PMF-100 dispersion is fixed at 0.20 mL in subsequent experiments.
5
Journal of Hazardous Materials 463 (2024) 132866
3.3. Adsorption mechanism
MXene/PMF-0.2 composite membranes (3.5 cm in diameter, 4.7 mg)
are put in 40 mL of Zn2+, Pb2+, phenol, p-nitrophenol, methylene blue,
crystal violet, cresol red, or methyl blue solutions, respectively. The
concentration of contaminants in solution is measured after static
adsorption at 25 ℃ for 24 h. The pH of the solution maintains at 6–7 due
to the low concentration of pollutant. The molecular structure formulas
of the organic pollutants are shown in Fig. S11. The removal rate of
MXene/PMF-0.2 membrane are as follows: Zn2+ (96.2%), Pb2+ (91.7%),
phenol (99.1%), p-nitrophenol (62.4%), methylene blue (37.4%), crys­
tal violet (96.4%), cresol red (47.3%) and methyl blue (59.1%) (Fig. 7).
The repeatability of pollutant removal experiment is good. The removal
rates are 10%− 15% higher than those of MXene membrane due to the
high specific surface area and pore volume, and a large number of ter­
minal amino groups of PMF, indicating that the doping of PMF particles
enhances the adsorption capacity of MXene membranes.
The main factors in the adsorption process includes electrostatic
interaction, hydrogen-bond, steric hindrance, etc. Efome et al., [10,11,8,
9] To further explore the adsorption mechanism of the heavy metals and
organics, density functional theory (DFT) calculations are performed by
using B3LYP functional with Def2-SVP basis set to obtain the optimal
adsorption configurations and adsorption energy. Solvent effects are
considered in the calculations by using SMD solvent model. The opti­
mized structures of different adsorption configurations are shown in
Fig. S12. In order to simulate the PMF microporous structure (the
T.-Q. Zhang et al.
Fig. 4. Adsorption and desorption isotherms of N2 at 77 K (a). Water contact angle (b) and water permeability (c) of MXene, MXene/SiO2 and MXene/PMF-0.2
membranes. Zeta potential of MXene and MXene/PMF-0.2 membranes at pH 7.
aperture measured in our previous work is around 0.78 nm, 1.2 nm), a
cage unit consisting of four PMF is built to model the state of dyes in
micropores. The calculation results clearly show that Zn2+ forms
stronger coordination bonds with PMF compared to Pb2+ (interaction
energy of − 32.38 kcal/mol vs − 11.79 kcal/mol) (Fig. 8), which is
consistent with the experimental observation. As for phenol and p-NP,
the driving force of adsorption is the hydrogen bonds between phenols
and the –NH2 of PMF. It is found that phenol has stronger interaction
energy (− 20.77 kcal/mol) and smaller steric hindrance than those of
p-NP, resulting a higher removal rate. Organic dyes can form hydrogen
bonds with PMF, and there is also electrostatic interaction between the
electronegative composite membrane and cationic dyes. MB has a low
removal rate due to weak interaction energy (− 50.13 kcal/mol) with
PMF, while CV displays a removal rate of 96.4% due to the stronger
interaction energy (− 66.52 kcal/mol) with PMF. The interaction energy
of CR/PMF (− 58.61 kcal/mol) is weaker than that of CV/PMF but
stronger than that of MB/PMF, and the removal rate is only 47.3%.
Compared with MB, CR has a higher removal rate due to greater steric
hindrance. Although MB-1/PMF has the strongest interaction energy
(− 88.85 kcal/mol), the large molecular bring about stronger steric
hindrance in PMF cage, resulting in a low removal rate of MB-1 (59.1%).
The above calculation results can explain the experimental data well.
3.4. Adsorption isotherm
MXene/PMF-0.2 composite membranes are put into p-NP and MB-1
solution (40 mL) of 5, 10, 25, 40, 50, 100, 150 and 200 ppm, respec­
tively. The adsorption isotherm is obtained by static adsorption at 25 ℃
for 24 h. With the increase of pollutant concentration, the adsorption
6
Journal of Hazardous Materials 463 (2024) 132866
capacity of the membranes slowly rises and finally reaches the platform
(Fig. 9a). The maximum adsorption capacity of p-NP and MB-1 are about
152.8 mg g− 1 and 409.2 mg g− 1. To determine the adsorption mecha­
nism, Langmuir model and Freundlich model are used for fitting. The
Langmuir adsorption model assumes monolayer adsorption, and all
adsorption sites on the adsorbent surface are uniform and have equal
affinity for pollutant [14,18]. The fitting formula is as follows:
1 1 1 1
= + × (3)
Qe Qm bQm Ce
where Qm is the maximum adsorption capacity (mg g− 1) and b is
Langmuir constant (L mmol− 1). The linear equation is fitted by taking 1/
Qe as the ordinate and 1/Ce as the abscissa. The calculated coefficient, b,
is 0.0206 L mmol− 1. The Freundlich adsorption model represents
multilayer adsorption, and the fitting formula is as follows:
log Qe = log kF +
1
log Ce (4)
n
where Ce is the equilibrium concentration after adsorption, Qe is the
equilibrium adsorption capacity of the membrane, kF is the adsorption
capacity (mmol1–1/α L1/α g− 1), and n is the Freundlich constant or
adsorption strength. By calculation, kF and n are 8.6297 and 1.0111,
respectively. The results show that Langmuir adsorption model de­
scribes the adsorption better than the Freundlich adsorption model
(Fig. 9b-c), indicating a chemical adsorption mechanism.
3.5. Dynamic adsorption
8000 mL of p-NP and MB-1 solutions with an initial concentration of
T.-Q. Zhang et al.
Fig. 5. Porosity (a), XRD patterns (b), water contact angle (c) and liquid permeability (d) of MXene/PMF composite membranes doped with different PMF parti­
cle sizes.
2 ppm are filtered through MXene/PMF-0.2 composite membranes
(3.5 cm in diameter) at a filtration rate of 40 mL min− 1. The concen­
tration of permeable solution is tested and the breakthrough curve is
obtained (Fig. 9d, e). The same solutions are filtered through the MXene
membranes at the rate of 10 mL min− 1 (limited by its low water
permeability) as control groups. At the initial stage (V<400 mL), the
filtrate concentration is low due to the huge number of active adsorption
sites on MXene/PMF-0.2 membranes. And then the concentration of
filtrate increases because of the decreased active adsorption sites. C/C0
= 0.1 is defined as the breakthrough point, and C/C0 = 0.8 is the satu­
ration point. Under the condition of 400% flux of the control group, the
breakthrough volume (Vb) of p-NP solution on MXene/PMF-0.2 mem­
branes is 75 mL (about 8500 times membrane volume), 150% of that of
the MXene membranes. And the saturation volume (Vs) is 1500 mL,
200% that of the MXene membranes. The Vb of the MB-1 solution is
350 mL (about 39800 times membrane volume), 130% of that of MXene
membrane. And the Vs is 5000 mL, 145% of that of the control group.
Apparently, MXene/PMF-0.2 composite membranes display faster
filtration flux and higher dynamic adsorption performance than those of
MXene membranes.
For the regeneration of MXene/PMF composite membranes, 40 mL
of 0.1 mol L− 1 NaOH and 0.01 mol L− 1 HCl are used as eluents for dy­
namic desorption. Initially, 500 mL p-NP solution (2 ppm) is adsorbed
by dynamic filtration at a flow rate of 40 mL min− 1. Then 50 mL eluent
is eluted for three times at a flow rate of 0.2 mL min− 1, followed by the
next dynamic adsorption. The results are shown in Fig. 9f. After four
times of recycling, the removal rate is still above 90%, thus demon­
strating the remarkable reusability of the membranes.
7
Journal of Hazardous Materials 463 (2024) 132866
3.6. Comparison with literature
The MXene/PMF composite membranes are compared with other
membranes reported in literature and summarized in Table 1. To
improve the water permeability of MXene membranes, researchers have
mixed various materials into the MXene membranes for water purifi­
cation applications. Doping with one-dimensional nanowires (CNTs)
results in high water permeability of 437.6 L m− 2 h− 1 bar− 1 and a 99.8%
removal rate of Au (III) due to the reduction of the hydroxyl group on
MXene nanosheets. However, two-dimensional nanosheets (GO) doping
has resulted in lower water permeability (25 L m− 2 h− 1 bar− 1), indi­
cating that the effect of two-dimensional nanosheets on the channel
expanding of MXene membrane can be ignored. Nanoparticle doping
can significantly improve water permeability, but the particle doping
amount is usually kept below 50% to maintain the membrane structure.
The doping of Al2O3 particle and Fe3O4 particle improves the water
permeability of MXene membranes, which performs well in the rejection
of dyes and poor in the adsorption of heavy metal ions. For comparison,
two-dimensional materials such as GO and reduced graphene oxide
(rGO) have also been listed in Table 1. The solvothermal method used to
combine non-porous or porous particles with rGO greatly influences the
active groups on two-dimensional nanosheets. It is found that porous
particles have a positive effect on the increase of water permeability. In
this work, the high doping amount of PMF particles greatly improves the
porosity, water permeability and removal rate of the composite mem­
brane and chemical crosslinking inhibits the swelling of MXene mem­
branes (Fig. S5). The removal rates of Zn2+, Pb2+, Phenol and CV are
96.2%, 91.7%, 99.1% and 96.4%, respectively. Compared with the
T.-Q. Zhang et al.
Fig. 6. Photographs (a), porosity (b), water contact angle (c) and liquid permeability (d) of MXene/PMF composite membranes doped with 0.10 mL, 0.15 mL,
0.20 mL and 0.25 mL of PMF-100 particles dispersion. The column with * indicates that the measurement error is large.
Fig. 7. Removal rates of MXene membranes and MXene/PMF-0.2 composite
membranes in 40 mL of different pollutants solution. 0.04 mmol L− 1 of zinc
nitrate or lead nitrate solution; 0.15 mmol L− 1 of phenol, p-NP, MB, CV, CR or
MB-1 solution; 4.7 mg of MXene membrane or MXene/PMF membrane.
reported MXene composite membranes, the MXene/PMF membranes
exhibit prominent removal ability of heavy metal ions. In comparison
with the traditional adsorption column, such as activated carbon column
(40 g of activated carbon removed 65% of 0.0283 ppm heavy metal ions
in 15 min) [2], the MXene/PMF membranes also show better perfor­
mance. In the dynamic adsorption of MXene/PMF membranes, the
permeability is 400% that of MXene membranes, the Vb and Vs of p-NP
solution are 75 mL and 1500 mL, and the Vb and Vs of the MB-1 solution
are 350 mL and 5000 mL, respectively, about 130%− 200% those of the
8
Journal of Hazardous Materials 463 (2024) 132866
MXene membranes.
4. Conclusions
MXene/PMF composite membranes were designed and prepared for
the adsorption of various pollutants. The appropriate size (100 nm) and
loading (83.7%) of PMF particles can reduce the water contact angle,
enhance the porosity and water permeability. The water permeability of
MXene/PMF-0.2 membranes is 405% that of MXene membranes,
reaching 381.2 L m− 2 h− 1 bar− 1. In static adsorption, the MXene/PMF-
0.2 membranes show removal rates of 96.2%, 91.7%, 99.1% and 96.4%
for Zn2+, Pb2+, Phenol and CV solution, respectively. The removal rate
of heavy metal ions is much higher than most reported MXene-based
membranes. In dynamic adsorption, the breakthrough volume (Vb)
and saturation volume (Vs) of p-NP solution are 75 mL (about 8500
times membrane volume) and 1500 mL respectively, which are 150%
and 200% that of the MXene membrane. The Vb and Vs of the MB-1
solution are 350 mL (about 39800 times membrane volume) and
5000 mL respectively, which are130% and 145% that of the MXene
membranes. The cyclic adsorption elution experiment of p-NP and MB-1
solution shows that the removal rate of pollutants exceeds 90% even
after four cycles. This work provides a facile and effective way to
fabricate composite membranes for wastewater treatment.
CRediT authorship contribution statement
Tian-Qi Zhang: Methodology, Writing – original draft, Data collect,
Investigation, Validation. Shuang Hao: Data collect, Investigation
Junkai Zhao: Methodology. Zhi-Qian Jia: Supervision,
T.-Q. Zhang et al. Journal of Hazardous Materials 463 (2024) 132866

Fig. 8. Interaction energy calculated at the B3YLP/def2svp level for PMF with Zn2+, Pb2+, phenol, p-NP, MB, CV, CV and MB-1 with specific nomenclature.

9
T.-Q. Zhang et al. Journal of Hazardous Materials 463 (2024) 132866

Fig. 9. Adsorption isotherm of p-NP and MB-1 in MXene/PMF-0.2 composite membranes (a). Langmuir linear fitting (b) and Freundlich linear fitting (c) of p-NP and
MB-1. Breakthrough curves of p-NP solution (d) and MB-1 solution (e) at 2 ppm. Reuse of MXene/PMF-0.2 composite membrane (f). 2 ppm of p-NP or MB-1 solutions,
4.7 mg of MXene membrane or MXene/PMF membrane.

Table 1
Comparison of hybrid two-dimensional materials membranes.
Membranes Method Doping Thickness Permeability (L Applications Ref
amount（wt （μm） m− 2 h− 1 bar− 1)
%）

MXene/ Mixing, ultrasound, vacuum 50.0 >5 437.6 Adsorption removal rate of 99.8% (10 mL, 20 ppm Au Wang et al.
CNT filtration, dopamine bonding (III) solution) [35]
MXene/GO Mixing, ultrasonic, vacuum 11.1 0.09 25 Rejection rate of 68%, 99.5%, 93.5% and 100% Kang et al.
filtration (10 ppm methyl red, methylene blue, bengal red and [20]
coomas bright blue)
MXene/COF Dual-layered structure - 0.012 563 Rejection rate of 99% (100 ppm congo Feng et al.
red) [12]
MXene/ Mixing, ultrasonic, vacuum 50.0 5 88.8 Rejection rate of 99.8% (15 ppm rhodamine B) Long et al.
Al2O3 filtration [23]
MXene/Ag Mixing, ultrasonic, vacuum 35 0.5 420 Rejection rate of 79.93% and 92.32% (50 ppm Pandey
filtration rhodamine B and methyl green) et al. [29]
MXene/ Mixing, ultrasonic, vacuum 33.3 3.4 139.1 Dynamic adsorption removal rate of 63.2%, 64.1% and Yang et al.
Fe3O4 filtration 70.2% (10 ppm Cu2+, Cd2+ and Cr2+ solutions) [38]
rGO/Fe3O4 Nanosheets preparation, 41.6–80.5 6.4 330 Adsorption removal rate of more than 99% (10 mL, Zhang et al.
rGO/UiO- dispersion, vacuum filtration 390 50 ppm rhodamine B, methyl orange and methylene [42]
66 blue)
rGO/TiO2 280
MXene/ Mixing, ultrasonic, vacuum 83.7 7 381.2 Removal rates of 96.2%, 91.7% (Zn2+, Pb2+, 40 mL, This work
PMF filtration, glutaraldehyde 0.04 mmol mL− 1), 99.1% and 96.4% (CV, MB-1,
bonding 40 mL, 0.15 mmol mL− 1)

Conceptualization, Data analysis, Results discussion, Funding acquisi­ Data Availability

tion, Writing – review & editing. Hong-Wei Tan: Gaussian software
teaching. Yu Yang: Supervision. Li-An Hou: Supervision. Data will be made available on request.

Declaration of Competing Interest Acknowledgments

The authors declare no competing financial interest. We gratefully acknowledge the support of National Natural Science
Foundation of China (No. 51920105012, U1607109), and China Post­
doctoral Science Foundation (2021M702451). The authors would like to
thank the Analytical & Testing Center of Tiangong University for XPS

10
T.-Q. Zhang et al.
and AFM characterization.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jhazmat.2023.132866.
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