1. Fabrication of MXene-Based Membranes
The ideal filtration membranes should be defect free, ultrathin, a dense film and mechanically robust with a high selectivity for small molecules along with good antifouling and antibacterial properties. Generally, methods such as spin coating, spray coating, vacuum filtration, Langmuir–Blodgett, drop casting, or direction evaporation and dip coating are used for the fabrication of 2D MXene lamellar membranes. Gogotsi et al.
[1][63] used a vacuum filtration method for first time to prepare freestanding and PVDF-supported 2D Ti
3C
2T
x-based membranes. Such membranes demonstrated good hydrophilic properties because of the presence of the useful group in conjunction with excellent elasticity as well as a good mechanical strength, which is an ideal potential in separation membranes. Among these methods, the VF method is widely used for the fabrication of 2D MXene-based membranes due to its simplicity and ease of operation (
Figure 1b). Ding et al.
[2][64] also reported 2D MXene (Ti
3C
2T
x) with enhanced properties using a vacuum filtration method on a porous support whereas Kang et al.
[3][65] fabricated MXene (Ti
3C
2T
x) and GO-based composite membranes by the same method. Sun and coworkers also fabricated GO/MXene lamellar membranes by the filtration method
[4][66]. Wang and co-researchers worked out an improvement of the microstructure and physiochemical properties of an MXene membrane by mixing it with a polymer matrix. Recently, Wang et al.
[5][67] reported Ti
3C
2T
x lamellar membranes produced by employing a multivalent ion as a hydrogel pillar in the interlayer spacing. Researchers for obtaining the uniform composition mixed a solution of sodium alginate (SA) and MXene Ti
3C
2T
x; this composite, SA-Ti
3C
2T
x, was then used for the lamellar SA-Ti
3C
2T
x membranes. Fascinatingly, a molecule of SA attached onto the MXene sheets by hydrogen bonding and Van der Waals forces. Finally, pillared SA-Ti
3C
2T
x laminates were arranged by submerging an SA-Ti
3C
2Tx membrane into a solution of different types of multivalent cations such as Ca
2+, Ba
2+, Mn
2+, and Al
3+. The pillar membrane showed a homogeneous structure similar to a nacre-like composite and it considerably decreased the swelling effect. Liu et al.
[6][68] fabricated Ti
3C
2Tx-CNT hybrid membranes using vacuum filtration (
Figure 1c,d). Liu and coworkers also fabricated pristine Ti
3C
2Tx and CNT membranes for comparative studies using the VF method (
Figure 1g,h). They improved the mechanical stability and permeance of MXene by incorporating CNTs into Ti
3C
2Tx nanosheets. Huang et al.
[7][48] used a phase inversion process to fabricate a PES-Ni@MXene membrane by using an external field and incorporated magnetic Ni@MXene nanoparticles with the upper layer of the PES membrane during a wet phase inversion process. MXene-based lamellar membranes were also prepared by a layer-by-layer (LbL) method
[8][69]. Tian et al. assembled a tris(2-aminoethyl) amine (TAEA) molecule and Ti
3C
2Tx MXene using an LbL assembly and obtained highly ordered multilayer of MXene/TAEA with an interlayer distance ~1 Å. This strategy was a good addition to fabricate MXene-based multilayered membranes for large-scale applications.
Figure 1. (
a) MXene precursors and their common synthesis methods. Reprinted with permission from
[9][70]. Copyright 2020 Springer Nature Group. (
b) Fabrication of MXene/polymer-based composite membrane by the VF method. Reprinted with permission from
[1][63]. Copyright 2015 American Chemical Society. (
c,
d) Fabrication of pristine Ti
3C
2Tx and Ti
3C
2Tx-CNT composite membranes. (
e) The digital photograph of the solutions. (
f) AFM study of Ti
3C
2Tx nanosheets. (
g,
h) Digital photos: surface; cross-sectional SEM images of pristine Ti
3C
2Tx, Ti
3C
2Tx-CNT, and CNT membranes, respectively. Reprinted with permission from
[6][68]. Copyright 2020 American Chemical Society.
From the above studies, it was concluded that the vacuum filtration method was mostly used to fabricate MXene membranes. However, there are several disadvantages associated with the vacuum filtration method. It needs a large volume of solvent, takes long time, and is definitely difficult to scale up. Therefore, alternative methods such as the shear alignment method, printing method, and spin coating method should be utilized to fabricate state-of-the-art MXene-based laminar membranes with advanced physicochemical properties to fully utilize the power of this wonder material.
2. Antibacterial Activity of MXene-Based Membranes
Pathogenic contamination is considered to be the most harmful issue worldwide and is responsible for various kinds of waterborne diseases
[10][90]. It is directly responsible for the biofouling of any water filtration membrane; therefore, it is important that a membrane should be tested against antibacterial properties. Up to date, several bactericidal nanomaterials including graphene, TMDCs, and MXenes have been explored to meet these challenges. The antibacterial activity of graphite, graphite oxide, GO, rGO, MoS
2, and WS
2 against Gram-negative and Gram-positive bacteria have already been tested. Recently, MXenes with unique hydrophilic properties, a good adsorption, an ideal surface functionality, and excellent biocompatibility and photothermal properties have been widely tested for wastewater treatment and desalination, water purification, ion separation and other applications, as shown in
Table 1. MXenes are expected to be resistant to biofouling and offer bactericidal properties
[11][91]. However, very few studies
[11][12][13][14][15][16][17][18][19][91,92,93,94,95,96,97,98,99] have been carried out in this direction. An initial work by Rasool et al.
[17][97] reported that Ti
3C
2Tx membranes could be an ideal platform for antibacterial studies (
Figure 5a–d). Rasool et al.
[17][97] further used Ti
3C
2T
x-based membranes to measure the antibacterial properties against
Escherichia coli (
E. coli) and
Bacillus subtilis (B. subtilis) by using bacterial growth curves based on optical densities (OD) and colony growth on agar nutritive plates (
Figure 5b,c). The membranes showed a high antibacterial efficiency against both Gram-negative
E. coli and Gram-positive
B. subtilis compared with the GO membranes. Concentration-dependent antibacterial activity was observed and more than 98% of bacterial cell viability loss was found at 200 μg/mL in Ti
3C
2T
x for both bacterial cells within 4 h of exposure, as confirmed by a colony-forming unit (CFU) and regrowth curve (
Figure 5d,e). In another study, Ti
3C
2T
x/PVDF composite membranes were tested to measure the antibacterial rate of
E. coli and
B. subtilis [11][91]. The composite membranes showed a ~73% and ~63% antibacterial rate for
B. subtilis and
E. coli, respectively, compared with the control PVDF membranes
[11][91]. Additionally, the Ti
3C
2T
x membrane showed over a 99% growth inhibition of both bacteria under the same conditions. Mayerberger et al.
[12][92] demonstrated Ti
3C
2Tz/chitosan composite nanofiber membranes for a passive antibacterial wound dressing application. The as-prepared composite membrane showed a 95% and 62% reduction in the colony-forming units of Gram-negative
E. coli and Gram-positive
Staphylococcus aureus (
S. aureus), respectively. Jastrzebsa and coworkers also reported the antimicrobial properties of a Ti
3C
2 MXene-based nanocomposite, i.e., Ti
3C
2/SiO
2/Ag, Ti
3C
2/Al
2O
3/Ag, and Ti
3C
2/SiO
2/Pd
[13][93]. They also demonstrated the outstanding bioactive properties of Ti
2C and Ti
3C
2 MXenes against a Gram-negative bacterial strain
[19][99]. Recently, Zhu et al.
[15][95] evaluated the effect of near-infrared (NIR) light on the antibacterial activities of silver (Ag), Ti
3C
2T
x, and an Ag/Ti
3C
2T
x composite. The as-prepared Ag/Ti
3C
2T
x composite showed a high efficacy against Gram-positive
S. aureus and Gram-negative
E. coli bacteria in an in vitro antibacterial test. Upon NIR irradiation, the antimicrobial effect of Ag/Ti
3C
2T
x significantly strengthened compared with the pristine Ag and Ti
3C
2T
x. The growth of
E. coli was completely inhibited during the initial 0–6 h by 200 µg/mL of Ti
3C
2T
x due to the photothermal heat produced killing the bacteria in the surrounding area. The Ag/Ti
3C
2T
x composite exhibited the best antibacterial activities with the same dose of pristine Ag and Ti
3C
2T
x. After NIR irradiation, the Ti
3C
2T
x composite could completely restrain the
E. coli growth when used at 100–200 µg/mL.
Figure 5. Ti
3C
2T
x nanosheet membranes. (
a) Antibacterial activities of Ti
3C
2T
x membranes in an aqueous solution against
E. coli and (
b)
B. subtilis with different concentrations, i.e., 0 µg/mL (
A), 10 µg/mL (
B), 20 µg/mL (
C), 50 µg/mL (
D), 100 µg/mL (
E), and 200 µg/mL (
F), respectively. (
c,
d) Cell viability measurement and comparison studies of Ti
3C
2T
x and GO membranes against
E. coli and
B. subtilis bacterial strains. Bacterial suspensions (107 CFU/mL) were incubated with different concentrations (0–200 µg/mL) of Ti
3C
2T
x and GO membranes at 35 °C for 4 h at a speed of 150 rmp. Reprinted with permission from
[17][97]. Copyright 2016 American Chemical Society.
Table 1. MXene-based membranes for the separation of ions, molecules, and pathogens from water.
Table 1. MXene-based membranes for the separation of ions, molecules, and pathogens from water.
Type of Membrane |
Fabrication Method |
Feed Solution/Concentration |
Rejection (%) |
Permeability (Lm−2 h−1 bar−1) |
Ref. |
Ti3C2Tx |
Vacuum filtration |
RB |
85 |
1084 |
[2][64] |
EB |
90 |
CC (Each 10–20 mg/L) |
97 |
Ti3C2Tx |
Vacuum filtration |
NaCl (10,000 mg/L) |
56–64 |
10 |
[20][100] |
BSA (2000 mg/L) |
Ti3C2Tx |
Vacuum filtration |
CR |
92 |
405 |
[21][74] |
GN |
80 |
MgCl2 |
2.3 |
Na2SO4 |
13.2 |
NaCl (Each 100–1000 mg/L) |
13.8% |
Ti3C2Tx |
Vacuum filtration |
E. coli |
>99 |
37.4 |
[11][91] |
B. subtilis |
>99 |
Ti3C2Tx |
Vacuum filtration |
Na2SO4 |
50–99 |
5–15.25 |
[22][101] |
Mg2SO4 |
MgCl2 |
NaCl |
VOSO4 |
Ti3C2Tx-Ag |
Vacuum-assisted filtration |
RB |
79.9 |
~420 |
[23][84] |
MG |
92.3 |
BSA (50–100 mg/L) |
>99% |
Ti3C2Tx-GO |
Vacuum filtration |
BB |
95.4 |
~25 L |
[3][65] |
Rose Bengal |
94.6 |
MLB |
40 |
MLR |
5 |
MgSO4 |
<1 |
NaCl (Each 10 mg/L) |
Ti3C2Tx-GO |
Vacuum filtration |
RB |
>97 (dyes) |
89.6 |
[24][102] |
MB |
CV |
NR (Each 10 mg/L) |
Na2SO4 |
61 |
NaCl (Each 5 mM) |
23 |
Ti3C2Tx-GO |
Vacuum filtration |
Chrysoidine G |
>99% (dyes) |
71.9 |
[25][80] |
MLB |
NR |
CV |
BB |
HA |
BSA |
Na2SO4 |
61 |
NaCl (Each 10 mg/L) |
23 |
Ti3C2Tx-GO |
Vacuum filtration |
MO |
>95 |
~8.5–11 |
[22][101] |
MLB |
Acid yellow 14 |
IC |
Eosin (Each 10 mg/L) |
Ti3C2Tx-TiO2 |
Spin coating |
Dextran (3000 mg/L) |
>95 |
~90 |
[26][103] |