Two-dimensional metal carbide desalination membrane

Abstract

The two-dimensional metal carbide desalination membrane includes a stack of two-dimensional metal carbide layers. A two-dimensional metal carbide included in the two-dimensional metal carbide layers may have the formula Ti.sub.3C.sub.2T.sub.x, where T represents a terminating functional group, and x represents a number of the terminating functional groups. The terminating group may be oxygen, hydroxide (OH), fluorine or combinations thereof. The two-dimensional metal carbide desalination membrane includes nano-channels which are selectively permeable to ions. The two-dimensional metal carbide desalination membrane is selectivity permeable to a number of different cations, including Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, Ni.sup.2+ and Al.sup.3+, with counter Cl.sup. anions. Permeation rates depend on the charges of the cations and the ions' hydrated radius, with a critical point around 4.0 . The two-dimensional metal carbide desalination membranes can be used as desalination and/or water filtration membranes.

Claims

1. A two-dimensional metal carbide desalination membrane, comprising: a polymer substrate, a plurality of stacked, two-dimensional metal carbide layers, each of the two-dimensional metal carbide layers being hydrophilic and including a two-dimensional metal carbide having the formula Ti.sub.3C.sub.2T.sub.x, wherein T represents a terminal functional group, and x represents the number of the terminal functional groups, wherein two-dimensional, carbide layers are configured to define uniform two dimensional nano-channels, orderly stacked and with an overall thickness of between 1 um-2 um, thereby being permeable to ions, molecules, gases and water, further wherein the stacked, two-dimensional metal carbide layers are layered on the polymer substrate.

2. The two-dimensional metal carbide desalination membrane as recited in claim 1, wherein the terminal functional group comprises at least one functional group selected from the group consisting of oxygen, hydroxide (OH), and fluorine.

3. A two-dimensional metal carbide desalination membrane, comprising a comprising a plurality of stacked, two-dimensional, carbide-polymer composite layers, each of the two-dimensional metal carbide layers being hydrophilic and including a two-dimensional metal carbide having the formula Ti.sub.3C.sub.2T.sub.x, wherein T represents a terminal functional group and x represents the number of the terminal functional groups, wherein two-dimensional, carbide-polymer composite layers are configured to define uniform two dimensional nano-channels, orderly stacked and with an overall thickness of between 1 um-2 um.

4. The two-dimensional metal carbide desalination membrane according to claim 1, wherein the polymer substrate comprises polyvinylidene fluoride (PVDF).

5. The two-dimensional metal carbide desalination membrane as recited in claim 3, wherein the polymer comprises polyvinyl alcohol.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A is a scanning electron micrograph of a cross-section of a two-dimensional metal carbide desalination membrane including layers of a two-dimensional metal carbide, according to the present invention.

(2) FIG. 1B is a scanning electron micrograph of a cross-section of a two-dimensional metal carbide desalination membrane including layers of a composite of a two-dimensional metal carbide and a polyvinyl alcohol (PVA).

(3) FIG. 2A diagrammatically illustrates an experimental device for testing permeability of the two-dimensional metal carbide desalination membrane.

(4) FIG. 2B is a graph showing permeability measurements as a function of time for cation permeation across the two-dimensional metal carbide desalination membrane, comparing permeability for Na.sup.+, Li.sup.+, K.sup.+, Ca.sup.2+, Ni.sup.2+, Mg.sup.2+, and Al.sup.3+.

(5) FIG. 3 is a graph showing selective permeation of Na.sup.+, Li.sup.+, K.sup.+, Ca.sup.2+, Ni.sup.2+, Mg.sup.2+ and Al.sup.3+ cations through the two-dimensional metal carbide desalination membrane as a function of cation hydrated radius.

(6) FIG. 4A is a graph showing a selective permeation comparison between the two-dimensional metal carbide desalination membrane of FIG. 1A and a conventional graphene oxide (GO) membrane as a function of cation hydrated radius.

(7) FIG. 4B is a graph showing a selective permeation comparison between the two-dimensional metal carbide desalination membrane of FIG. 1A, the two-dimensional metal carbide desalination membrane of FIG. 1B, and the conventional graphene oxide (GO) membrane as a function of cation hydrated radius.

(8) FIG. 5 shows X-ray diffraction patterns of the two-dimensional metal carbide desalination membrane of FIG. 1A in both a wet state and a dry state, both before and after permeation of MgCl.sub.2.

(9) Similar reference characters denote corresponding features consistently throughout the attached drawings.

BEST MODES FOR CARRYING OUT THE INVENTION

(10) The two-dimensional metal carbide desalination membrane can include a plurality of two-dimensional metal carbide layers. The plurality of two-dimensional metal carbide layers can include a two-dimensional metal carbide, such as MXene. Preferably, the MXene included in the plurality of two-dimensional metal carbide layers has the formula Ti.sub.3C.sub.2T.sub.x, where T represents a terminating functional group (O, OH and/or F) and x represents the number of terminating groups. The two-dimensional metal carbide desalination membrane can include nano-channels with specific selectivity to a number of different cations, including Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, Ni.sup.2+ and Al.sup.3+, with counter Cl.sup. anions.

(11) The two-dimensional metal carbide desalination membrane can be formed from layers of a composite of the two-dimensional metal carbide and a polymer, such as polyvinyl alcohol. A stack of two-dimensional metal carbide layers or two-dimensional metal carbide-polymer composite layers may be supported on a polymeric filtering substrate, such as a polyvinylidene fluoride (PVDF) supporting substrate.

(12) The two-dimensional metal carbide desalination membrane can have relatively high selectivity to ions and robust mechanical stability. As such, the two-dimensional metal carbide desalination membrane can be used for water desalination and/or water filtration applications. The two-dimensional metal carbide desalination membrane can have a thickness of from about 1 m to about 2 m, e.g., 1.3 m to about 1.8 m. Preferably, the two-dimensional metal carbide desalination membrane has a thickness of about 1.5 m. The two-dimensional metal carbide desalination membranes can be flexible, have relatively high mechanical strength, have hydrophilic surfaces, and have relatively high conductivity. The two-dimensional metal carbide desalination membrane or layered structure can form nano-channels which are permeable to ions, molecules, gases and water, but with specific selectivity to a number of different cations, including Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, Ni.sup.2+ and Al.sup.3+, with counter Cl.sup. anions. Permeation rates can rely on the ions' hydrated radius, with a critical point around 4.0 , and on the charges of the cations. The interlayer spacing parameter of the MXene layers and the negative charges on the MXene surfaces can affect the permeation of ions. For example, the interlayer spacings for dry and wet Ti.sub.3C.sub.2T.sub.x membranes can be about 7.98 and 11.98 , respectively.

(13) MXene can have the general formula M.sub.n+1X.sub.n where M represents a transition metal (such as titanium, vanadium, chromium, niobium), X is carbon and/or nitrogen, and n ranges between 1 and 3. MXene is produced by etching the element A layer from MAX phases with a composition of M.sub.n+1AX.sub.n, where A represents a group A element (aluminum, silicon, tin, indium, etc.). MAX phases are a large family of hexagonal-layered ternary transition metal carbides and/or nitrides. The etching process is carried out by immersing the MAX phase in hydrofluoric acid at room temperature. Using a vacuum-assisted filtration process, the two-dimensional metal carbides may be layered to produce membranes having thicknesses on the order of hundreds of nanometers to several micrometers.

(14) The present inventors have examined the permeation of metal cations (Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, Ni.sup.2+ and Al.sup.3+) with counter Cl.sup. anions and of acid blue dye molecules through Ti.sub.3C.sub.2T.sub.x membranes. In order to increase mechanical stabilities of the Ti.sub.3C.sub.2T.sub.x membranes in an aqueous environment, Ti.sub.3C.sub.2T.sub.x/polymer membranes were also prepared. When compared to the Ti.sub.3C.sub.2T.sub.x membranes, Ti.sub.3C.sub.2T.sub.x/polymer membranes showed equal or even better selectivity. As will be discussed in detail below, both the Ti.sub.3C.sub.2T.sub.x membranes and the Ti.sub.3C.sub.2T.sub.x/polymer membranes performed better than graphene oxide (GO) membranes, which were prepared and tested under the same conditions. As will be further discussed in detail below, based on the interlayer spacing parameter from several density functional theory (DFT) calculation reports, and charge intercalation theory, a mechanism of ion transport through the Ti.sub.3C.sub.2T.sub.x membranes was determined.

(15) The thickness of the Ti.sub.3C.sub.2T.sub.x membranes being tested was controlled between 1.3 and 1.8 m, with most of the test membranes having a thickness of about 1.5 m. FIG. 1A is a scanning electron micrograph of a cross-section of a Ti.sub.3C.sub.2T.sub.x membrane, formed from stacked Ti.sub.3C.sub.2T.sub.x layers having an overall thickness of approximately 1.47 m and a mass of approximately 5 mg. FIG. 1B is a scanning electron micrograph of a cross-section of a Ti.sub.3C.sub.2T.sub.x/polyvinyl alcohol (PVA) composite membrane, having an overall thickness of approximately 1.66 m and a mass of approximately 5.6 mg. Both membranes showed high solvent permeability. No permeation of acid blue dye molecules through the membranes was detected by conductivity probe after a 24 hour test, showing that no pinholes existed in the membranes.

(16) In order to obtain smooth and orderly stacked Ti.sub.3C.sub.2T.sub.x laminates, dilute colloidal Ti.sub.3C.sub.2T.sub.x suspensions for filtration were provided. In particular, dilute concentrations as low as 0.01 mg/ml were used, resulting in a long filtration time of approximately four hours. The smoothness and ordered stacking of nano-sheet layers is important since it ensures formation of uniform two-dimensional nano-channels which are selective to water molecules and ions, and also exhibit robust integrity in water. Additionally, the membranes may be mounted on a supporting substrate, such as a polyvinylidene fluoride (PVDF) supporting substrate. Due to the relatively high pressure exerted on Ti.sub.3C.sub.2T.sub.x membranes in use as desalination and filtration membranes, commercial polyvinylidene fluoride membranes with a pore size of 450 nm were used as supporting substrates. Pure PVDF membranes typically show no hindering effect on molecules, even molecules as big as acid blue, which are larger than any ions or molecules used in the experiment. Thus, the PVDF supporting membrane does not affect the Ti.sub.3C.sub.2T.sub.x membrane's selectivity to ions and molecules. Table 1 below shows permeation of a pure PVDF membrane compared with permeation of a Ti.sub.3C.sub.2T.sub.x/PVDF membrane as a function of time.

(17) TABLE-US-00001 TABLE 1 Comparison of Permeation of PVDF Membrane and Ti.sub.3C.sub.2T.sub.x/PVDF Membrane Permeation Conductivity (S/cm) PVDF Ti.sub.3C.sub.2T.sub.x/PVDF Time (hours) Acid Blue (137.6 S/cm) Acid Blue (137.6 S/cm) 1 18.5 1.9 2 33.8 3.8 3 56.1 5.3 4 70.2 7.1 24 29

(18) The Ti.sub.3C.sub.2T.sub.x membrane with the PVDF substrate was assembled into a U-shaped testing device 10, as shown in FIG. 2A, for studying the ionic conductivity of permeate solution. The Ti.sub.3C.sub.2T.sub.x/PVDF membrane 12 was placed centrally within the U-shaped housing 14, dividing the U-shaped housing 14 into a feed compartment 16 and a permeate compartment 18. Ionic conductivity of the permeate solution P was measured and converted to salt concentrations based on molar conductivity. The cation concentrations were obtained assuming that cations and anions move through membranes in stoichiometric amounts, and were plotted as a function of time, reflecting the permeability of the cations under investigation. For all salt solutions studied, the cation concentrations' permeation increased linearly with time, with increasing rates following the progression of Na.sup.+.fwdarw.Li.sup.+.fwdarw.K.sup.+.fwdarw.Ca.sup.2+.fwdarw.Ni.sup.2+.fwdarw.Mg.sup.2+.fwdarw.Al.sup.3+. FIG. 2B shows permeated ion concentration across membrane 12 as a function of time for each of the salt solutions under investigation, with 0.2 M feed solutions, all with counter Cl.sup. anions. In the experiment, a 50 mL sample of each aqueous solution (0.2 mol/L in deionized water) was injected with the same speed into the feed compartment 16. Magnetic stirring was used in the permeation compartment 18 to ensure no concentration gradients. The conductivity in the permeation compartment 18 was recorded with increasing permeation time.

(19) In order to examine cation selectivity of the two-dimensional metal carbide desalination membranes, the cations' permeation rates were compared against their sizes and charges, as shown in FIG. 3 and in Table 2 below. FIG. 3 shows the selective permeation rate through a 1.5 m thick Ti.sub.3C.sub.2T.sub.x membrane with counter Cl.sup. anions, shown as a function of cation hydrated radius.

(20) TABLE-US-00002 TABLE 2 Permeation Rates for Differing Cations Solutions K.sup.+ Na.sup.+ Li.sup.+ Ni.sup.2+ Ca.sup.2+ Mg.sup.2+ Al.sup.3+ Permeation Rates 0.94 1.53 1.40 0.22 0.23 0.16 0.06 (mol/h/m.sup.2)

(21) The effective volume occupied by a cation in water is characterized by its hydrated radius. The smaller species permeate with similar speeds, whereas larger ions exhibit much smaller permeation speeds. The permeation curves can be classified with similar permeation rates. Three separate groups, including Na.sup.+, Li.sup.+ and K.sup.+; Ca.sup.2+, Ni.sup.2+ and Mg.sup.2+; and Al.sup.3+. Na.sup.+ ions, have the largest permeation rate of 1.53 mol/h/m.sup.2, which is about 25 times faster than that of Al.sup.3+ ions. It was noted that, with regard to the selectivity, there is a cut-off trend of permeation around 4.0 , indicating cations larger than this size were sieved out. Thus, Ti.sub.3C.sub.2T.sub.x membranes are shown as being selective towards ions of different size and/or charge, such as Li.sup.+, Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, Ni.sup.2+ and Al.sup.3+.

(22) FIG. 4A shows the results of a selective permeation comparison between an MXene-based membrane (Ti.sub.3C.sub.2T.sub.x) and a conventional graphene oxide (GO) membrane as a function of cation hydrated radius. FIG. 4B shows the results of a selective permeation comparison between the MXene-based membrane, an MXene/PVA-based membrane (Ti.sub.3C.sub.2T.sub.x/PVA) and the conventional graphene oxide (GO) membrane as a function of cation hydrated radius. With respect to the conventional GO membrane, the two-dimensional metal carbide desalination membrane is highly hydrophilic with a contact angle of 35 against water and has sufficient mechanical strength for handling.

(23) The tensile strength of a MXene film having a thickness on the order of 3.3 m is about 22 MPa, with a Young's modulus of 3.5 GPa, both of which can be further improved with polymer additives. A comparison between a 2.5 m thick GO membrane and a 3.3 m MXene-based membrane is summarized below in Table 3.

(24) TABLE-US-00003 TABLE 3 Comparison of Mechanical Properties Properties GO MXene Contact Angle () 33.7 35 Conductivity (S/m) Insulator (~6.8 10.sup.8) 240,238 3,500 Young's Modulus (GPa) 30 3.5 Tensile Strength (MPa) 55 22

(25) FIG. 5 shows X-ray diffraction patterns of Ti.sub.3C.sub.2T.sub.x membranes in both a wet state and a dry state, both before and after permeation of MgCl.sub.2. The transport mechanisms through Ti.sub.3C.sub.2T.sub.x membrane films can be size and charge selective due to the presence of interlayer slit pores and negative charges on hydrophilic Ti.sub.3C.sub.2T.sub.x-based film surfaces. Ti.sub.3C.sub.2T.sub.x flakes are negatively charged, which leads to absorption of cations and repulsion of anions. This results in Ti.sub.3C.sub.2T.sub.x's selectivity to ions with different charges, in addition to sizes. Further, the Ti.sub.3C.sub.2T.sub.x nano-layer sheets have been separated into two types of regions: functionalized and origin, similar to the regions of conventional GO nano-sheets. The functional groups (OH, O, F) on the Ti.sub.3C.sub.2T.sub.x surface may act as spacers to support nano-sheet interlayer spacing, as well as acting as hurdles to impede the transportation of ions. The origin regions form the network of capillaries that allow or hinder the flow of water or ions. First principle calculations models predict that the interlayer spacing separated from Ti.sub.3C.sub.2T.sub.x layers is about 10-11.5 . The XRD patterns of Ti.sub.3C.sub.2T.sub.x show a c-Lp of 25.4 at the dry state in air and 33.4 at the wet state, which includes two sets of a rigid Ti.sub.3C.sub.2 layers plus an interlayer spacing. From molecular dynamics (MD) simulations, one rigid layer of Ti.sub.3C.sub.2 has a thickness of 4.72 . Thus, from calculations and a combination of XRD and simulations, the interlayer spacings for dry and wet Ti.sub.3C.sub.2T.sub.x membranes are about 7.98 and 11.98 , respectively.

(26) In order to make the Ti.sub.3C.sub.2T.sub.x membrane, a Ti.sub.3C.sub.2T.sub.x colloidal solution is first prepared. So as to obtain few- and/or single-layer flakes, Ml-Ti.sub.3C.sub.2T.sub.x powders are first delaminated by ultrasonication. In experiment, the Ml-Ti.sub.3C.sub.2T.sub.x powders were obtained from etching Ti.sub.3AlC.sub.2 powder with LiF/HCl solution. Then, the produced Ml-Ti.sub.3C.sub.2T.sub.x powder is dispersed in deaerated water with a weight ratio of Ml-Ti.sub.3C.sub.2T.sub.x:water of 250:1. The suspension is sonicated under flowing Ar for 1 hour, and then centrifuged at 3500 rpm for 1 hour to obtain the supernatant containing Ti.sub.3C.sub.2T.sub.x flakes, thus producing the Ti.sub.3C.sub.2T.sub.x colloidal solution.

(27) In order to prepare the Ti.sub.3C.sub.2T.sub.x/PVA composite, the Ti.sub.3C.sub.2T.sub.x colloidal solution was mixed with a PVA having a molecular weight of 115,000 in aqueous solution. Specifically, aqueous solutions of Ti.sub.3C.sub.2T.sub.x (0.3 mg mL.sup.1) and PVA (0.1 wt %) were mixed and the mixture was sonicated in a water bath for 15 min. The Ti.sub.3C.sub.2T.sub.x to PVA weight ratios chosen were 90:10. In all cases, the mass of the starting Ti.sub.3C.sub.2T.sub.x was 50.1 mg.

(28) In order to prepare the Ti.sub.3C.sub.2T.sub.x-based membrane supported on PVDF, the Ti.sub.3C.sub.2T.sub.x and its polymer composite solutions were diluted to 0.01 mg mL.sup.1 (i.e., the concentration of Ti.sub.3C.sub.2T.sub.x in solution). The films were fabricated via vacuum-assisted filtration (VAF) of the diluted solutions through a PVDF substrate, which was hydrophilic and had a pore size of approximately 0.45 m, with a diameter of 47 mm. A glass microfiltration apparatus, with a fritted alumina supported base, was used for the vacuum filtration. The filtered films were air dried on the PVDF filter substrate.

(29) In the above, the measured ionic conductivity variation of each permeate solution was converted to ion concentrations based on molar conductivity calculations. Molar conductivity is defined as the conductivity of an electrolyte solution divided by the molar concentration of the electrolyte, which is given by: .sub.m=/c, where K is the measured conductivity, and c is the electrolyte concentration. Thus, the electrolyte concentration can be obtained as c=K/.sub.m, in which the ionic conductivity of all of the salt solutions can be found in standard references. Then, the ion permeation rate (J) was calculated by the classical diffusion equation:

(30) $J=\frac{V_{\mathrm{eff}}.Math.C}{A_{\mathrm{eff}}.Math.t},$
where V.sub.eff is the effective volume of the solution on permeate side; AC is the concentration gradient across the membrane; A.sub.eff is the effective area of the MXene-based membrane, and t is the diffusion time.

(31) With regard to the characterizations described above, a scanning electron microscope (SEM) was used to study the morphology of the produced flakes and films. Elemental analysis was conducted using an energy dispersive X-ray (EDX) spectrometer. A transmission electron microscope (TEM) operating at 200 kV was used to obtain images of the Ti.sub.3C.sub.2T.sub.x flakes and the Ti.sub.3C.sub.2T.sub.x/PVA films. The Ti.sub.3C.sub.2T.sub.x flakes for TEM were prepared by dropping the colloidal solution on a lacey carbon-coated copper grid. The Ti.sub.3C.sub.2T.sub.x/PVA cross-sections were produced by first embedding the films in epoxy resin and then cutting them using a glass microtome. The produced chips were placed on a lacey carbon-coated copper grid.

(32) It is to be understood that the present invention is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims.