CN112957923A - Aluminum ion crosslinked MXene-ascorbic acid film and preparation method thereof - Google Patents
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Abstract
The invention discloses an aluminum ion crosslinked MXene-ascorbic acid film and a preparation method thereof, belonging to the field of environment-friendly water treatment. The method utilizes ascorbic acid and aluminum ions to carry out composite crosslinking on MXene nanosheets, and the MXene nanosheets are loaded to the surface of a 100kd polyether sulfone membrane. The MXene-ascorbic acid membrane crosslinked by the aluminum ions prepared by the invention has excellent oxidation resistance, can stably run in water for a long time, intercepts pollutants in the water through size exclusion, and can effectively inhibit the permeation of sodium chloride salt ions in the forward osmosis process. The method is simple and easy to operate, is easy to apply in large scale and is beneficial to popularization.
Description
Technical Field
The invention relates to the field of environment-friendly water treatment, in particular to an MXene-ascorbic acid film crosslinked by aluminum ions and a preparation method thereof.
Background
The quality and quantity of water resources are worsened day by day, and membrane technology is receiving more and more attention. In the aspect of water treatment, the membrane technologies mainly used include Microfiltration (MF), Ultrafiltration (UF), Nanofiltration (NF), Reverse Osmosis (RO) and Forward Osmosis (FO), most of which are prepared by using organic high molecular polymers, but these membranes still face some problems and challenges in the field of water treatment, such as low contaminant rejection rate, poor mechanical properties of membranes, high energy consumption, and some membrane materials are not resistant to chlorine. Transition carbon (nitride) (MXene) is a novel two-dimensional material successfully prepared in 2011. Two-dimensional film that is piled up by MXene nanometer piece has regular controllable transmission path, abundant surface functional group and hydrophilic nature, can realize the transmission of water, can carry out effectual screening to aquatic pollutant simultaneously. However, MXene is easy to swell in water, so that the stable screening of MXene on pollutants is influenced; and is very easy to oxidize, and stability is one of the key factors which plague further application thereof, so that a new method for stabilizing the interlayer spacing of MXene to inhibit swelling and improve the oxidation resistance of MXene needs to be found.
Chinese patent CN 107029562B discloses a composite nanofiltration membrane based on MXene and a preparation method thereof, wherein a dip-coating method is adopted on a support membrane to obtain the composite nanofiltration membrane, and the composite nanofiltration membrane is obtained through high-temperature crosslinking treatment. Chinese patent CN 109701397A discloses application of a two-dimensional MXene membrane prepared by an electrophoretic deposition method in ion interception. Chinese patent CN 106178979A discloses a high-performance two-dimensional layered Ti3C2-MXene membrane and preparation method and application in water treatment thereof, the preparation method is as follows: (1) mixing Ti3AlC2Mixing the powder with HF solution, stirring for reaction, centrifugally washing and drying to obtain Ti3C2Powder; (2) mixing Ti3C2Mixing the powder with a solvent, stirring, washing and drying to obtain treated powder; (3) dissolving the treated powder in a solvent, performing ultrasonic treatment, centrifuging, taking supernatant, and drying to obtain a two-dimensional nanosheet; (4) preparing the nano sheets into a solution, depositing the solution on a porous substrate by a nano self-assembly technology, and drying to obtain the high-performance two-dimensional layered Ti3C2-MXene films. The technical scheme has the technical problem of complicated preparation process or poor membrane stability.
Disclosure of Invention
The invention aims to provide an aluminum ion crosslinked MXene-ascorbic acid film and a preparation method thereof, so as to solve the problems of easy swelling and easy oxidation of the MXene film in the prior art, and enable the prepared MXene film to have high stability and high removal rate.
In order to achieve the purpose, the invention provides the following scheme:
one of the purposes of the invention is to provide a preparation method of an aluminum ion crosslinked MXene-ascorbic acid film, which comprises the following steps:
the method comprises the following steps: mixing Ti3AlC2Adding the solution into a mixed solution of HCl and LiF for reaction, oscillating and centrifuging to obtain a single-layer MXene nanosheet;
step two: adding deionized water into the MXene nanosheets to prepare MXene solution, adding ascorbic acid solution, and stirring in a protective atmosphere to obtain MXene-ascorbic acid mixed solution;
step three: under the pressure condition, the MXene-ascorbic acid in the MXene-ascorbic acid mixed solution is loaded on the surface of a polyether sulfone membrane through filtration to obtain an MXene-ascorbic acid membrane;
step four: and soaking the MXene-ascorbic acid membrane in an aluminum-containing inorganic salt solution to obtain the MXene-ascorbic acid membrane crosslinked by aluminum ions.
Further, the Ti3AlC2Is 300-500 mesh Ti3AlC2And (3) powder.
Further, the Ti3AlC2Mass ratio to HCl and LiF1：(5-8)：1。
Further, the reaction temperature in the step one is 30-40 ℃, and the reaction time is 24-48 h.
Further, the concentration of the MXene solution in the second step is 1 mg/mL; the concentration of the ascorbic acid solution is 0.1-10 mmol/L.
Further, the protective atmosphere in the second step is argon atmosphere; the stirring time is 12-48 h.
Further, the certain pressure in the third step is 0.1MPa of nitrogen pressure; the filtration is a dead-end filtration.
Further, the polyether sulfone membrane is a 100kd polyether sulfone membrane.
Further, the aluminum-containing inorganic salt solution in the fourth step is one or a mixture of aluminum chloride, aluminum nitrate and aluminum sulfate; the concentration of the aluminum-containing inorganic salt solution is 0.1-1mol/L, and the soaking time is 12-48 h.
The invention also aims to provide the MXene-ascorbic acid membrane prepared by the preparation method and crosslinked by aluminum ions.
The invention discloses the following technical effects:
1) the oxidation resistance of the prepared aluminum ion crosslinked MXene-ascorbic acid film is far higher than that of an untreated MXene film, and the oxidation resistance test of 7 days shows that the film has good performance;
2) the apparent retention rate of the prepared aluminum ion crosslinked MXene-ascorbic acid membrane on the dye in water reaches 99.25%, wherein 92.06% is size exclusion, and 7.94% is caused by adsorption;
3) the MXene-ascorbic acid membrane prepared by the method can effectively inhibit transmembrane transmission during sodium chloride forward osmosis, and the permeability in one hour is only 0.065%;
4) the swelling of the aluminum ion crosslinked MXene-ascorbic acid membrane prepared by the invention in water is only
5) The MXene-ascorbic acid membrane crosslinked by the aluminum ions prepared by the method has high stability and high removal rate under the condition that the thickness is only about 1 mu m, and the preparation method is simple and easy to operate, is easy to use in large scale and is beneficial to popularization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a seven day flux change for an aluminum ion crosslinked MXene-ascorbic acid membrane prepared in example 1;
fig. 2 is a seven day flux change for the MXene membrane prepared in comparative example 1;
fig. 3 is a photograph of a real object of the aluminum ion crosslinked MXene-ascorbic acid film (mvca) prepared in example 1, the MXene film (M) prepared in comparative example 1, and the MXene film (MVC) prepared in comparative example 2 after 14 days of operation;
fig. 4 is SEM photographs of the aluminum ion crosslinked MXene-ascorbic acid film (mvca) prepared in example 1, the MXene film (M) prepared in comparative example 1, and the MXene film (MVC) prepared in comparative example 2; wherein (a) M, (b) MVC, (c) MVCAL are SEM photographs as-produced, (e) M, (f) MVC, and (g) MVCAL are SEM photographs after 14 days of operation;
FIG. 5 is an XRD pattern of MXene film in three cases of dry, surface dry and water; wherein (a) is MXene film (M) prepared in comparative example 1, (c) is aluminum ion crosslinked MXene-ascorbic acid film (MVCAAl) prepared in example 1;
FIG. 6 is a graph showing the retention effect of an aluminum ion crosslinked MXene-ascorbic acid membrane prepared in example 1 on Coomassie Brilliant blue (0.1g/L, 50 mL);
fig. 7 shows the effect of inhibiting the permeation of a sodium chloride (0.2mol/L) solution by an aluminum ion-crosslinked MXene-ascorbic acid film (mvca) prepared in example 1 and an MXene film (M) prepared in comparative example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The "parts" in the present invention are all parts by mass unless otherwise specified.
Example 1
The method comprises the following steps: 2g LiF was mixed with 40mL of 9mol/L hydrochloric acid in a Teflon test tube andultrasonic treating for 30min to obtain 2g of 400-mesh Ti3AlC2Adding the solution into a mixed solution of HCl-LiF, reacting for 24h at 40 ℃, oscillating for 1h under the atmosphere of argon gas, centrifuging for 1h at 4000rpm, and obtaining a monolayer MXene nanosheet in the supernatant;
step two: adding deionized water into a monolayer MXene nanosheet to prepare a 1mg/mL MXene solution, adding 1.0mmol/L ascorbic acid, and stirring for 24h in an argon atmosphere to obtain an MXene-ascorbic acid mixed solution;
step three: adding 10mL of 1.0mg/mL MXene-ascorbic acid mixed solution into 40mL of deionized water, carrying out dead-end filtration in an ultrafiltration cup with the nitrogen pressure of 0.1MPa, and loading the MXene-ascorbic acid on the surface of a 100kd polyether sulfone (PES) membrane to obtain an MXene-ascorbic acid Membrane (MVC);
step four: soaking the MXene-ascorbic acid membrane in 0.2mol/L aluminum chloride solution for 24h to obtain the MXene-ascorbic acid membrane (MVCAAl) crosslinked by aluminum ions.
And (3) detection results: the thickness of the prepared MVCAAl is about 1.1 μm, and the MVCAAl is tightly combined with a basal membrane (PES membrane); the seven-day flux change of MVCAAl is shown in FIG. 1, and the calculated deionized water flux is 296.4 + -12.5 L.m-2h-1MPa-1(ii) a A photograph of an MVCAL taken 14 days after operation is shown in FIG. 3; SEM photographs of MVCAL as produced and after 14 days of operation are shown in FIG. 4; the XRD patterns of MVCAL in three cases of drying, surface drying and water are shown in FIG. 5(c), and it can be seen from FIG. 5 that MVCAL swells in water to
The retention effect of MVCAAl on Coomassie brilliant blue (0.1g/L, 50mL) is shown in FIG. 6, and the calculation shows that the apparent retention rate of MVCAAl on small molecular dyes in water is 99.25%, and the actual retention rate is 91.38%; the effect of MVCAAl on the permeation of sodium chloride (0.2mol/L) solution is shown in FIG. 7.
The deionized water flux of the MXene membrane and the apparent retention rate and the actual retention rate of the small-molecule dye in water are calculated as follows:
the deionized water flux of the membrane and the retention rate of the dye were 50mL, and the effective membrane area was 13.4cm-1In an ultrafiltration cup (8050, Millpore, USA). The filtration experiments were all carried out at room temperature and the nitrogen pressure in the ultrafiltration cup was 0.1MPa, and the mass of the filtrate was continuously recorded during the experiments using an electronic balance (AX523ZH, Ohaus, USA).
The deionized water flux is calculated by formula (1):
J＝V/(A·t·P) (1)
wherein V represents the volume (L) of the filtrate, and A represents the effective membrane area (m)2) T represents the filtration time (h), and P represents the pressure (MPa) in the ultrafiltration cup. The density of both the deionized water and the dye solution was taken as 1.0 g/mL.
The apparent retention rate R (%) of the dye was calculated from the formula (2):
R＝(1-Cp/Cf)×100％ (2)
wherein, CpAnd CfThe concentrations of the membrane-passed solution and the stock solution (mg/L) are shown, respectively.
The apparent retention rate R is influenced by factors such as interlayer spacing, surface charge and hydrophobicity of the MXene membrane. The invention divides the dye in the filtering process into three parts, namely the mass (M) of the dye adsorbed by the MXene membraneaMg) mass of MXene film repelling dye (M)rMg) and mass of dye penetrating the Mxene film (M)pMg). Another term relating to the apparent rejection R is the actual rejection Ra(%), representing the retention properties of the membrane on the dye, excluding the adsorption of the dye by the MXene membrane. Ma，Mr，Mp，RaCan be calculated by using the formulas (3) to (6), respectively:
Ma＝Vf·Cf-Vp·Cp-VC·Cc (3)
Mi＝Vp·Cf-Vp·Cp-Ma (4)
Mp＝Vp·Cf-Mi-Ma＝Vp·Cp (5)
Ra＝Mr/(Vp·Cf)×100％ (6)
wherein, Vf，Vp，VcRespectively representing the volumes (L) of the stock solution, the membrane-passing solution and the concentrated solution; cf，Cp，CcThe concentrations (mg/L) of the stock solution, the membrane-passed solution and the concentrated solution are shown, respectively. When the filtration is finished, the volume ratio of the membrane-passing liquid to the concentrated solution is 3: 2.
The concentration polarization layer formed on the surface of the MXene membrane by the dye cannot be completely avoided in the filtering process. Therefore, in the present invention, the influence of concentration polarization is minimized by magnetic stirring, and M is assumeda，Mr，MpCan be approximately determined by equations (3) - (5).
As mentioned above, the calculated value of the apparent rejection R represents all solute rejection and membrane adsorption effects, while the actual rejection RaPhysical or chemical adsorption effects are excluded and represent only true dye retention due to the interlayer spacing, surface charge and hydropathic nature of the MXene membrane.
Example 2
The method comprises the following steps: 2g LiF and 31mL of 9mol/L hydrochloric acid are mixed in a polytetrafluoroethylene test tube and subjected to ultrasonic treatment for 30min, and 2g of 300-mesh Ti3AlC2Adding the solution into a mixed solution of HCl-LiF, reacting for 30h at 30 ℃, oscillating for 1h under the atmosphere of argon gas, centrifuging for 1h at 4000rpm, and obtaining a monolayer MXene nanosheet in the supernatant;
step two: adding deionized water into a monolayer MXene nanosheet to prepare a 1mg/mL MXene solution, adding 0.1mmol/L ascorbic acid, and stirring for 12h in an argon atmosphere to obtain an MXene-ascorbic acid mixed solution;
step three: adding 10mL of 1.0mg/mL MXene-ascorbic acid mixed solution into 40mL of deionized water, carrying out dead-end filtration in an ultrafiltration cup with the nitrogen pressure of 0.1MPa, and loading the MXene-ascorbic acid on the surface of a 100kd polyether sulfone (PES) membrane to obtain an MXene-ascorbic acid Membrane (MVC);
step four: soaking the MXene-ascorbic acid membrane in 0.1mol/L aluminum chloride solution for 12h to obtain the MXene-ascorbic acid membrane (MVCAAl) crosslinked by aluminum ions.
Example 3
The method comprises the following steps: 2g LiF was mixed with 48mL of 9mixing mol/L hydrochloric acid in a polytetrafluoroethylene test tube, performing ultrasonic treatment for 30min, and mixing 2g of 500-mesh Ti3AlC2Adding the solution into a mixed solution of HCl-LiF, reacting for 48 hours at 35 ℃, oscillating for 1 hour under the atmosphere of argon gas, centrifuging for 1 hour at 4000rpm, and obtaining a monolayer MXene nanosheet in the supernatant;
step two: adding deionized water into a monolayer MXene nanosheet to prepare a 1mg/mL MXene solution, adding 10mmol/L ascorbic acid, and stirring for 48 hours in an argon atmosphere to obtain an MXene-ascorbic acid mixed solution;
step three: adding 10mL of 1.0mg/mL MXene-ascorbic acid mixed solution into 40mL of deionized water, carrying out dead-end filtration in an ultrafiltration cup with the nitrogen pressure of 0.1MPa, and loading the MXene-ascorbic acid on the surface of a 100kd polyether sulfone (PES) membrane to obtain an MXene-ascorbic acid Membrane (MVC);
step four: soaking the MXene-ascorbic acid membrane in 1mol/L aluminum chloride solution for 48h to obtain the MXene-ascorbic acid membrane (MVCAAl) crosslinked by aluminum ions.
Comparative example 1
Except for example 1, mixing with ascorbic acid solution and soaking in aluminum chloride solution were omitted, and MXene film (M) was finally obtained.
And (3) detection results: the thickness of the prepared M is about 1.1 μ M, and is tightly combined with a base film (PES film); the seven-day flux change of M is shown in FIG. 2, and the newly prepared M has a deionized water flux of 413.3 + -17.1 L.m-2h-1MPa-1After 7 days of operation, the deionized water flux of M was increased to 858.5. + -. 35.5 L.m-2h-1MPa-1(ii) a The physical photograph of the M after running for 14 days is shown in FIG. 3; SEM photographs of M as prepared and after 14 days of operation are shown in fig. 4; the XRD patterns of M in three cases of drying, surface drying and water are shown in figure 5 (a); the inhibitory effect of M on sodium chloride (0.2mol/L) solution penetration is shown in FIG. 7; the apparent retention rate of M on the small-molecular dye in water is 91.25%, and the actual retention rate is 42.50%.
Comparative example 2
The difference from example 1 is that the step of soaking in an aluminum chloride solution is omitted, and MXene film (MVC) which is not crosslinked with aluminum is finally obtained.
And (3) detection results: the thickness of the prepared M is about 1.1 μ M, and is tightly combined with a base film (PES film); MVC has a deionized water flux of 553.7 + -18.2 L.m-2h-1MPa-1(ii) a The picture of the real object after 14 days of MVC operation is shown in FIG. 3; SEM photographs of MVC as produced and after 14 days of operation are shown in FIG. 4; the apparent retention rate of MVC on the small-molecule dye in water is 98.13%, and the actual retention rate is 64.44%.
Respectively filtering the MXene membrane prepared in the comparative example 1 and the MXene-ascorbic acid membrane prepared in the example 1 and crosslinked by aluminum ions by deionized water, simultaneously connecting an electronic balance with a data display to collect data, and calculating to obtain the flux of the deionized water, wherein the flux of the MXene membrane prepared in the comparative example 1 is gradually increased within 7 days due to oxidation as shown in figures 1 and 2; while the aluminum ion crosslinked MXene-ascorbic acid membrane prepared in example 1 showed excellent oxidation resistance with a flux of 296.4 + -12.5 L.m-2h- 1MPa-1. Fig. 3 is a physical photograph of the film after 14 days of operation, and it can be seen that the MXene film prepared in comparative example 1 has been oxidized, while the aluminum ion crosslinked MXene-ascorbic acid film prepared in example 1 has almost no change, as evidenced by the electron micrograph (fig. 4). As shown in FIG. 5, after MXene membrane is subjected to combined crosslinking, the swelling resistance of the membrane is obviously enhanced, and the swelling of the MXene-ascorbic acid membrane crosslinked by aluminum ions in water is only that
Coomassie brilliant blue solution (0.1g/L, 50mL) was filtered by the aluminum ion crosslinked MXene-ascorbic acid membrane prepared in example 1, 30mL of the solution was filtered, 20mL of the remaining concentrate remained, and the original solution (FS), the filtrate (PS) and the Concentrate (CS) were subjected to ultraviolet-visible spectrophotometer test to calculate the retention rate, as shown in FIG. 6, the apparent retention rate of the aluminum ion crosslinked MXene-ascorbic acid membrane prepared in example 1 for small molecular dyes in water was as high as 99.25%, the retention mode includes size exclusion and adsorption, wherein 92.06% is size exclusion, 7.94% is adsorption result, and the actual retention rate is 91.38%. Testing in U-tubeThe effect of the aluminum ion-crosslinked MXene-ascorbic acid film prepared in example 1 on the inhibition of sodium chloride ion permeation at forward osmosis, as shown in fig. 7, the aluminum ion-crosslinked MXene-ascorbic acid film prepared in example 1 was able to effectively inhibit the permeation of sodium chloride salt ions compared to the MXene film prepared in comparative example 1.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A preparation method of an aluminum ion crosslinked MXene-ascorbic acid membrane is characterized by comprising the following steps:
the method comprises the following steps: mixing Ti3AlC2Adding the solution into a mixed solution of HCl and LiF for reaction, oscillating and centrifuging to obtain a single-layer MXene nanosheet;
step two: adding deionized water into the MXene nanosheets to prepare MXene solution, adding ascorbic acid solution, and stirring in a protective atmosphere to obtain MXene-ascorbic acid mixed solution;
step three: under the pressure condition, the MXene-ascorbic acid in the MXene-ascorbic acid mixed solution is loaded on the surface of a polyether sulfone membrane through filtration to obtain an MXene-ascorbic acid membrane;
step four: and soaking the MXene-ascorbic acid membrane in an aluminum-containing inorganic salt solution to obtain the MXene-ascorbic acid membrane crosslinked by aluminum ions.
2. The method according to claim 1, wherein the Ti is3AlC2Is 300-500 mesh Ti3AlC2And (3) powder.
3. The method according to claim 1, wherein the Ti is3AlC2The mass ratio of HCl to LiF is 1: (5-8): 1.
4. the method according to claim 1, wherein the reaction in the first step is carried out at 30-40 ℃ for 24-48 hours.
5. The preparation method according to claim 1, wherein the concentration of MXene solution in step two is 1 mg/mL; the concentration of the ascorbic acid solution is 0.1-10 mmol/L.
6. The method according to claim 1, wherein the protective atmosphere in the second step is an argon atmosphere; the stirring time is 12-48 h.
7. The production method according to claim 1, wherein the pressure condition in step three is a nitrogen pressure of 0.1 MPa; the filtration is a dead-end filtration.
8. The method of claim 1, wherein the polyethersulfone membrane is a 100kd polyethersulfone membrane.
9. The preparation method of claim 1, wherein the aluminum-containing inorganic salt solution in the fourth step is one or more of aluminum chloride, aluminum nitrate and aluminum sulfate; the concentration of the aluminum-containing inorganic salt solution is 0.1-1mol/L, and the soaking time is 12-48 h.
10. The MXene-ascorbic acid film crosslinked with aluminum ions prepared by the method according to any one of claims 1 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114247306A (en) * | 2021-12-22 | 2022-03-29 | 大连理工大学 | Self-supporting MXene rigid separation membrane and preparation method and application thereof |
| CN114314591A (en) * | 2021-12-28 | 2022-04-12 | 华南理工大学 | MXene nanosheet with free radical capturing function and preparation method and application thereof |
| WO2023092809A1 (en) * | 2021-11-26 | 2023-06-01 | 中南大学 | Modified nb2ctx nanosheet membrane and preparation method therefor |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59143573A (en) * | 1983-02-07 | 1984-08-17 | Mitsubishi Gas Chem Co Inc | Preservation of laver |
| JP2011251208A (en) * | 2010-05-31 | 2011-12-15 | Taisei Corp | Method for recovering performance of permeable ground water purifying body |
| EP2437906A2 (en) * | 2009-06-05 | 2012-04-11 | Honeywell International Inc. | Methods of forming solid lubricant coatings on substrates |
| CN106178979A (en) * | 2016-08-31 | 2016-12-07 | 华南理工大学 | High-performance two-dimensional stratiform Ti3c2mXene film and preparation method thereof and the application in water process |
| WO2018178706A2 (en) * | 2017-03-29 | 2018-10-04 | The University Of Manchester | Membranes for filtering organic solutions |
| CN110252159A (en) * | 2019-06-25 | 2019-09-20 | 杭州电子科技大学 | A kind of composite hybridization film and its preparation method and application |
| CN110280147A (en) * | 2019-05-23 | 2019-09-27 | 西安建筑科技大学 | A kind of swelling resistance two-dimensional layer film, preparation and application that inter-layer passages size is controllable |
| CN110354697A (en) * | 2019-06-24 | 2019-10-22 | 大连理工大学盘锦产业技术研究院 | A kind of mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof based on MXene material |
| CN111151304A (en) * | 2020-02-26 | 2020-05-15 | 吴晓峰 | Preparation of three-dimensional MXene/MOF hydrogel and application thereof in water treatment |
-
2021
- 2021-02-04 CN CN202110154451.0A patent/CN112957923B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59143573A (en) * | 1983-02-07 | 1984-08-17 | Mitsubishi Gas Chem Co Inc | Preservation of laver |
| EP2437906A2 (en) * | 2009-06-05 | 2012-04-11 | Honeywell International Inc. | Methods of forming solid lubricant coatings on substrates |
| JP2011251208A (en) * | 2010-05-31 | 2011-12-15 | Taisei Corp | Method for recovering performance of permeable ground water purifying body |
| CN106178979A (en) * | 2016-08-31 | 2016-12-07 | 华南理工大学 | High-performance two-dimensional stratiform Ti3c2mXene film and preparation method thereof and the application in water process |
| WO2018178706A2 (en) * | 2017-03-29 | 2018-10-04 | The University Of Manchester | Membranes for filtering organic solutions |
| CN110280147A (en) * | 2019-05-23 | 2019-09-27 | 西安建筑科技大学 | A kind of swelling resistance two-dimensional layer film, preparation and application that inter-layer passages size is controllable |
| CN110354697A (en) * | 2019-06-24 | 2019-10-22 | 大连理工大学盘锦产业技术研究院 | A kind of mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof based on MXene material |
| CN110252159A (en) * | 2019-06-25 | 2019-09-20 | 杭州电子科技大学 | A kind of composite hybridization film and its preparation method and application |
| CN111151304A (en) * | 2020-02-26 | 2020-05-15 | 吴晓峰 | Preparation of three-dimensional MXene/MOF hydrogel and application thereof in water treatment |
Non-Patent Citations (3)
| Title |
|---|
| LI DING，ET AL: "Effective ion sieving with Ti3C2T x MXene membranes for production of drinking water from seawater", 《NATURE SUSTAINABILITY》 * |
| XINGYU LI等: "In situ decoration of nanosized metal oxide on highly conductive MXene nanosheets as efficient catalyst for Li-O_2 battery", 《JOURNAL OF ENERGY CHEMISTRY》 * |
| ZHAO, XIAOFEI，ET AL: "Antioxidants Unlock Shelf-Stable Ti3C2Tx", 《MATTER 》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023092809A1 (en) * | 2021-11-26 | 2023-06-01 | 中南大学 | Modified nb2ctx nanosheet membrane and preparation method therefor |
| CN114247306A (en) * | 2021-12-22 | 2022-03-29 | 大连理工大学 | Self-supporting MXene rigid separation membrane and preparation method and application thereof |
| CN114247306B (en) * | 2021-12-22 | 2022-09-09 | 大连理工大学 | Self-supporting MXene rigid separation membrane and preparation method and application thereof |
| CN114314591A (en) * | 2021-12-28 | 2022-04-12 | 华南理工大学 | MXene nanosheet with free radical capturing function and preparation method and application thereof |
| CN114314591B (en) * | 2021-12-28 | 2023-08-22 | 华南理工大学 | MXene nano-sheet with free radical capturing function and preparation method and application thereof |
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