CN108043238B - A kind of composite semipermeable membrane containing Ti3C2, preparation method and purposes for light evaporation water - Google Patents
A kind of composite semipermeable membrane containing Ti3C2, preparation method and purposes for light evaporation water Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 229910009819 Ti3C2 Inorganic materials 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000001704 evaporation Methods 0.000 title claims abstract description 30
- 230000008020 evaporation Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000013535 sea water Substances 0.000 claims abstract description 18
- 238000010612 desalination reaction Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 10
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims abstract description 10
- 229920001220 nitrocellulos Polymers 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 8
- 238000009830 intercalation Methods 0.000 claims abstract description 8
- 230000002687 intercalation Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims 2
- 239000002453 shampoo Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000013505 freshwater Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910009817 Ti3SiC2 Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- -1 steam generation Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/20—Esters of inorganic acids, e.g. cellulose nitrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
- Y02A20/142—Solar thermal; Photovoltaics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Contain Ti for light evaporation water the invention discloses a kind of3C2Composite semipermeable membrane, preparation method and purposes, this method include: step 1, by Ti3AlC2Raw material is added in etching agent, is sufficiently stirred, and obtains suspension, suspension is centrifugated, and is dried in vacuo；Step 2, by Ti3C2Powder and intercalation solution are mixed, and are centrifugated, and vacuum drying, preparation has Ti layered3C2Powder；Step 3, semi-permeable membrane precursor solution is prepared using cellulose nitrate；Step 4, preparation gained had into Ti layered3C2Powder is added in semi-permeable membrane precursor solution, stirs evenly, is uniformly layered in Flat bottom container, spontaneously dries, and obtains containing Ti3C2Composite semipermeable membrane.Preparation method provided by the invention, simple process and low cost can be practical；The photothermal conversion effect of composite semipermeable membrane prepared by the present invention is good, and evaporating the multiple fields such as water, sea water desalination in light has extraordinary application prospect.
Description
Technical field
The invention belongs to the preparation technical fields of film, are related to a kind of composite semipermeable membrane, and in particular to a kind of semiconductor Ti3C2
It is compound with semi-permeable membrane, it is semi-transparent that a kind of NEW TYPE OF COMPOSITE that can be widely applied to the fields such as light evaporation water, sea water desalination is prepared
Film.
Background technique
Freshwater resources problem is a global environmental problem, and Present Global scarcity of fresh water resources is got worse,
Seriously threaten the existence of the mankind, and freshwater resources are as a kind of indispensable necessity of the mankind, therefore solve freshwater resources
The problem of shortage is extremely urgent.Show that nearly the water resource of 97.5 % is seawater in global water resources total amount according to related data
Equal salt water resources, the water of only 2.53 % is the fresh water for human use, since exploitation is difficult and the limitation of Technological Economy, arrives mesh
Before until, seawater, deep phreatic water, ice and snow solid-state fresh water etc. are difficult to be used directly, be easier development and utilization and the mankind
The relations of production of living is the closest for lake, river and shallow underground freshwater resources, only accounts for 0.34 % of fresh water gross reserves,
It is less than a ten thousandth of global water inventory, therefore tellurian freshwater resources do not enrich.According to grinding for World Watch Institute
Report is studied carefully, it is expected that the population in the whole world 2/3 will face water shortage problem when by 2025.As in one of 13 poor-water states in the world
State, freshwater resources are particularly important, and the in short supply of freshwater resources will seriously affect domestic sustainable development, develop new seawater
The technology of desalination is particularly important.
Ocean is the cradle of life, and seawater accounts for about 71 % of earth surface product, has very huge potentiality to be exploited.It is right
In the direct utilization of seawater, i.e., by desalinating sea water into fresh water, it is direct substitution fresh water, solves coastal area freshwater resources weight in short supply
Measure is wanted, is that most viable and most economical fresh water takes mode.Therefore very urgent to the step of ocean Suo Shui.Traditional seawater
Desalination technology is broadly divided into two class of thermal method and embrane method, and to be broadly divided into low temperature more for the production technology for being developed so far sea water desalination
The methods of the way of distillation, multistage flash vaporization, hyperfiltration, pressure steam distillation method, electroosmose process are imitated, wherein first three is to develop ratio at present
More mature manufacturing technique method.
In recent years, thermal energy is converted the solar into, is obtained by photothermal conversion with the relevant technologies for realizing sea water desalination
Quickly development, especially embrane method is advanced optimized, by with excellent photothermal conversion performance material and film it is compound, prepare
Composite membrane with high efficiency photothermal conversion performance becomes the hot spot of scientific research circle research.Currently, two dimension MXene nanometer sheet is due to it
Surface plasma resonance effect and the strong near infrared absorption shown, to have preferable photothermal conversion effect to have become section
The hot spot of educational circles's research.Recently, Chen Yu seminar (Nano Lett. 2017,17,384-391) is to Ti3C2Correlation is carried out
Research finds Ti3C2With preferable near infrared absorption and higher photothermal conversion efficiency performance.Li Renyuan and its seminar
(ACS Nano 2017,11,3752-3759) is tested and is simulated a sunlight by the photothermal conversion of laser irradiation drop
The researchs such as water evaporation experiment find MXene, especially Ti3C2, there is preferable photothermal conversion efficiency, irradiated in a sunlight
Lower light evaporation water evaporation efficiency is also more considerable.
But Li Renyuan seminar using the method for vacuum filtration by Ti3C2Powder deposits on commercial pvdf membrane,
To preparing the light absorber with double-layer structure, the shortcomings that light absorber is that the light absorber of double-layer structure is by prolonged
Solar irradiation and higher frequency of use, optical-thermal conversion material Ti3C2It is easy to fall off from support construction pvdf membrane, no
Water, the practical application of sea water desalination are evaporated conducive to light.Therefore in order to improve the performance that can be recycled of light absorber, meet wider
General practical application, find it is a kind of low cost, preparation process has simply had the light absorber of preferable photo and thermal stability
Become a very urgent task.
Summary of the invention
The present invention is intended to provide a kind of NEW TYPE OF COMPOSITE semi-permeable membrane, that is, will be provided with the Ti of excellent photothermal conversion performance3C2With it is semi-transparent
Film progress is compound, prepares the NEW TYPE OF COMPOSITE semi-permeable membrane that aqueous energy is evaporated with preferable light, and photothermal conversion effect is preferable, thus
It can be used for the key areas such as light evaporation water, sea water desalination.
In order to achieve the above object, contain Ti for light evaporation water the present invention provides a kind of3C2The preparation of composite semipermeable membrane
Method, the method includes the steps of:
Step 1, by Ti3AlC2Raw material is added in etching agent, is sufficiently stirred, and obtains suspension, suspension is centrifugated,
Vacuum drying；
Step 2, by Ti3C2Powder and intercalation solution are mixed, and are centrifugated, and vacuum drying, preparation has layered structure
Ti3C2Powder has Ti layered3C2, it is smaller to the barrier effect of vapor, be conducive to the evaporation of vapor；
Step 3, semi-permeable membrane precursor solution is prepared using cellulose nitrate；
Step 4, there will be Ti layered3C2Powder is added in semi-permeable membrane precursor solution, stirs evenly, so that
Ti3C2It is compound with the progress of semi-transparent film precursor, it is then uniformly layered in Flat bottom container, spontaneously dries, obtain containing Ti3C2Compound half
Permeable membrane.
Preferably, the raw material selects Ti in step 13AlC2、Ti3SiC2In any one.
Preferably, the etching agent selects hydrofluoric acid, lithium fluoride+hydrochloric acid, sodium hydroxide+sulfuric acid, fluorination in step 1
Any one in hydrogen ammonium；Preferred mass score is the hydrofluoric acid of 40 ~ 50 %.
Preferably, the revolving speed being sufficiently stirred is 800 ~ 1500 r/min in step 1, the time being sufficiently stirred is 12 ~ 18
h。
Preferably, the standard of suspension centrifuge washing is pH > 5 in step 1.
Preferably, the intercalation solution selects dimethyl sulfoxide, methylformamide, hydrazine hydrate, the tetrabutyl in step 2
Any one in ammonium hydroxide；The time of stirring is 15 ~ 18 h.Ti3C2Itself there is layer structure, but layer structure is easy
It stacks.By the way that the insertion of intercalation solution molecule to be had to the basis material Ti of layer structure3C2In, Ti can be significantly increased3C2Interlayer
Away from later using the bonding force of the method destruction interlayer of sonic oscillation, the available significantly pure Ti of layered effect3C2。
Preferably, cellulose nitrate can be dissolved in concentrated nitric acid by absorbent cotton and is made with concentrated sulfuric acid mixed solution in step 3,
Semi-permeable membrane precursor solution can dissolve in cellulose nitrate with ethyl alcohol by ether and be made.
Preferably, the time of stirring is 1 ~ 2 h in step 4, what is be prepared contains Ti3C2The thickness of composite semipermeable membrane is about
20-500 μm (preferably 150 μm).
The present invention also provides a kind of composite semipermeable membrane prepared according to above-mentioned method, in the composite semipermeable membrane containing with
The Ti of 5.0 ~ 80 % of mass ratio meter3C2。
The present invention also provides a kind of purposes of composite semipermeable membrane prepared according to above-mentioned method, which contains
Ti3C2, can be applied to the fields such as light evaporation water, sea water desalination, there is important use value.
Due to Ti3C2With LSPR(local surface plasma resonance) effect, it shows strong near infrared absorption and photo-thermal and turns
Change efficiency.The present invention is by Ti3C2It is compound with semi-permeable membrane, using plasma resonance effect, it is compound semi-transparent that a kind of high-performance is prepared
Film converts the solar into thermal energy, realizes photothermal conversion, to achieve the effect that light evaporates water, realize by absorbing sunlight
The purpose of sea water desalination.
The preparation process of composite semipermeable membrane provided by the present invention is simple, at low cost, practical；The photo-thermal of semi-permeable membrane turns
It is good to change effect, evaporating the fields such as water, sea water desalination in light has extraordinary application prospect.
Detailed description of the invention
(A)-(B) of Fig. 1 is two dimension Ti in present invention specific implementation3C2(the Ti with layer structure3C2) different amplifications
Scanning electron microscope (Scanning Electron Microscope, abbreviation SEM) photo of ratio.
(A) of Fig. 2 is the photo in kind for the semi-transparent pure film of collodion being prepared in comparative example of the present invention；(B) of Fig. 2
To be prepared in the specific embodiment of the invention containing Ti3C2The photo in kind of composite semipermeable membrane.
Fig. 3 a contains Ti for what present invention specific implementation was prepared3C2The ultraviolet-visible absorption spectroscopy figure of composite semipermeable membrane is composed,
Fig. 3 b is the UV, visible light transmitance map that present invention specific implementation and comparison are implemented.
Fig. 4 a, 4b are the empirical curve map and column map that light of the invention evaporates aqueous energy；Fig. 4 c is of the invention
Light evaporates water efficiency map；Fig. 4 d is that light of the invention evaporates water speed rate map.
Specific embodiment
Contain Ti for light evaporation water the present invention provides a kind of3C2The preparation method of composite semipermeable membrane, it includes following steps
It is rapid:
Step 1, by Ti3AlC2Raw material is added in etching agent, is sufficiently stirred 12 ~ 18 h, revolving speed be 800 ~ 1500 r/
Min obtains suspension, suspension is centrifugated (standard of suspension centrifuge washing is pH > 5), vacuum drying；Described
Etching agent selects hydrofluoric acid, lithium fluoride+hydrochloric acid (i.e. the mixed liquor of lithium fluoride and hydrochloric acid), sodium hydroxide+sulfuric acid (i.e. sodium hydroxide
With the mixed liquor of sulfuric acid), any one in ammonium acid fluoride；Preferred mass score is the hydrofluoric acid of 50 %；
Step 2, by Ti3C215 ~ 18 h are mixed in powder and intercalation solution, are centrifugated, and vacuum drying, preparation has
Ti layered3C2Powder；The intercalation solution selects dimethyl sulfoxide, methylformamide, hydrazine hydrate, tetrabutyl hydrogen-oxygen
Change any one in ammonium；
Step 3, semi-permeable membrane precursor solution is prepared using cellulose nitrate；Cellulose nitrate can be dissolved in by absorbent cotton
Concentrated nitric acid is made with concentrated sulfuric acid mixed solution or buys through commercially available, and semi-permeable membrane precursor solution can dissolve in fiber by ether and ethyl alcohol
Plain nitrate is made；
Step 4, preparation gained had into Ti layered3C2Powder is added in semi-permeable membrane precursor solution, stirs evenly
1 ~ 2 h, is uniformly layered in Flat bottom container, spontaneously dries, and obtains containing Ti3C2Composite semipermeable membrane, thickness are about 20-500 μm (excellent
Select 150 μm).
Below in conjunction with attached drawing and specific implementation, the following further describes the technical solution of the present invention.
Prepare Ti3C2Dry powder: by 5.00 g Ti3AlC2It immerses in the 50 mL hydrofluoric acid that mass fraction is 50 %, magnetic force
15 h are sufficiently stirred, obtain stable suspension.With deionized water by suspension centrifuge washing to pH > 5, gained sample is 60
Dry 12 h obtain Ti in DEG C vacuum oven3C2Dry powder.
Preparation layering Ti3C2Dry powder: by 1.00 g Ti3C2Dry powder is mixed with 20 mL dimethyl sulfoxides at room temperature,
15 h are sufficiently stirred in magnetic force, 30 min of deionized water centrifuge washing are used under the conditions of 3500 rpm, gained sample is in 60 DEG C of vacuum
Dry 12 h obtain layering Ti in drying box3C2(A) and (B) of dry powder, SEM figure such as Fig. 1 of different magnification ratios is shown,
It can be clearly seen that the Ti prepared3C2After powder removes Al layers, open gap is showed, and can obviously observe
To layer structure.
Prepare semi-permeable membrane precursor solution: the concentrated nitric acid and concentrated sulfuric acid mixed solution that preparation volume ratio is 1:2.It takes above-mentioned molten
15 mL of liquid immerses 1.00 g absorbent cotton, takes out absorbent cotton after 1 h, is rinsed 10 times with deionized water, in 30 DEG C of electric heating air blast
24 h are dried in drying box, obtain cellulose nitrate.The above-mentioned dry fiber element nitrate of 1.00 g is taken, 25 mL are dissolved in
It in the mixed solution of ether and 25 mL ethyl alcohol, fullys shake, obtains transparent semi-permeable membrane precursor solution.
Embodiment
73.5 mg are layered Ti3C2Dry powder is added in the above-mentioned semi-permeable membrane precursor solution of 4 mL, is sufficiently stirred 90
Min gets a uniform mixture.2 mL are taken out from above-mentioned mixed solution, are added it to 500 mL that diameter is 75 mm and are burnt
In cup, film forming is spontaneously dried.Composite membrane after drying is taken out, the circular membrane that diameter is 35 mm is cut to, is prepared into
Thickness to black is about 150 μm, content is 8 mg containing Ti3C2Composite semipermeable membrane, shown in (A) of photo in kind such as Fig. 2.
Comparative example
In order to compare, we are also prepared for being not added with Ti3C2The semi-transparent pure film of collodion.Take the above-mentioned semi-transparent film precursor of 2 mL
Solution adds it in the 500 mL beakers that diameter is 75 mm, spontaneously dries film forming.Film after drying is taken out, is cut out
It is cut to the circular membrane that diameter is 35 mm, the semi-transparent pure film of transparent collodion, (B) institute of photo in kind such as Fig. 2 is prepared
Show.
What the embodiment of the present invention was prepared contains Ti3C2The ultraviolet-visible absorption spectroscopy figure of composite semipermeable membrane is composed as shown in 3a,
That prepares contains Ti3C2Composite semipermeable membrane have within the scope of 400-1100 nm one it is preferable absorb, especially near infrared region,
Since there are local surface plasma resonance effects, there is more potent fruit to the absorption of near-infrared.The embodiment of the present invention and comparative example
UV, visible light transmitance map it is as shown in Figure 3b, Fig. 3 b also demonstrates this effect, as can be seen from the figure in entire wave
In long range, compared to the transparent semi-transparent pure film of collodion, contain Ti3C2The transmitance of composite semipermeable membrane is obvious universal lower, illustrates pair
Stronger in the absorption of sunlight, the energy of absorption is more, and the energy of the thermal energy of conversion is higher.As it can be seen that of the invention contains Ti3C2It is multiple
Closing semi-permeable membrane has very good assimilation effect for sunlight.
The prepared semi-permeable membrane of specific implementation is deployed in (opening diameter 35 on the weighing bottle water surface equipped with 20 mL water
The mm of 40 mm × 25 weighing bottle of mm), under the irradiation for simulating a sunlight (1 sun) with xenon lamp, pass through precise electronic
Balance accurately observes the mass change of water, and is recorded with pertinent instruments.Its test result is shown in Fig. 4 a-4d(wherein, water-
Dark. env. indicates evaporation effect of the water under the irradiation of no simulated solar irradiation, and water-1 sun indicates that water is simulated at one
Evaporation effect under sunlight irradiation, Ti3C2- Nanofluids is indicated Ti3C2In a simulated solar after powder is soluble in water
Water evaporation effect under light irradiation).Fig. 4 a-4b shows since light evaporation leads to the direct variation diagram and column of water reduction amount
Figure, it can be clearly seen that compared to other three kinds, contain Ti3C2Composite semipermeable membrane evaporates the effect of water in the case where a sunlight irradiates
More preferably.Fig. 4 c shows light evaporation efficiency, as can be seen from the figure contains Ti3C2The light evaporation efficiency of composite semipermeable membrane is up to
48.1 %, hence it is evident that be higher than pure water (17.3 %) and Ti3C2The light evaporation efficiency of solution (38.3 %).It can be seen from fig. 4d that most
Good light evaporation rate is containing Ti3C2Composite semipermeable membrane, up to 0.77 kg m-2 h-1.Therefore, we can see that preparation contains
Ti3C2Composite semipermeable membrane is compared to pure water and Ti3C2Solution shows the superior aqueous energy of light evaporation, has better photo-thermal
Conversion performance.
In conclusion containing Ti prepared by the present invention3C2Composite semipermeable membrane, by will be provided with excellent photothermal conversion performance
Ti3C2It is compound with semi-permeable membrane, the solar energy of absorption is converted into thermal energy, reaches efficient photothermal conversion effect, realizes light evaporation
Water.And preparation process of the present invention is simple, at low cost, practical, and it is multiple to evaporate water, steam generation, sea water desalination etc. in light
Field has extraordinary application prospect.
It is discussed in detail although the contents of the present invention have passed through examples detailed above, but it should be appreciated that the description above is not
It should be considered as limitation of the present invention.After those skilled in the art have read above content, a variety of repaired for of the invention
Changing and substituting all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (9)
1. a kind of contain Ti for light evaporation water3C2The preparation method of composite semipermeable membrane, which is characterized in that this method includes following
Step:
Step 1, by Ti3AlC2Raw material is added in etching agent, is sufficiently stirred, and obtains suspension, suspension is centrifugated, vacuum
It is dry；
Step 2, by Ti3C2Powder and intercalation solution are mixed, and are centrifugated, and vacuum drying, preparation has layered
Ti3C2Powder；The described intercalation solution selection dimethyl sulfoxide, methylformamide, hydrazine hydrate, appointing in tetrabutylammonium hydroxide
It anticipates one kind；
Step 3, semi-permeable membrane precursor solution is prepared using cellulose nitrate；
Step 4, there will be Ti layered3C2Powder is added in semi-permeable membrane precursor solution, stirs evenly, so that Ti3C2With
Semi-transparent film precursor progress is compound, is then uniformly layered in Flat bottom container, spontaneously dries, obtains containing Ti3C2Composite semipermeable membrane.
2. containing Ti for light evaporation water as described in claim 13C2The preparation method of composite semipermeable membrane, which is characterized in that institute
The etching agent selection hydrofluoric acid stated, lithium fluoride+hydrochloric acid, sodium hydroxide+sulfuric acid, any one in ammonium acid fluoride.
3. containing Ti for light evaporation water as claimed in claim 23C2The preparation method of composite semipermeable membrane, which is characterized in that institute
The etching agent selection hydrofluoric acid stated, the mass fraction of the hydrofluoric acid is 40 ~ 50 %.
4. containing Ti for light evaporation water as described in claim 13C2The preparation method of composite semipermeable membrane, which is characterized in that step
In rapid 1, the revolving speed being sufficiently stirred is 800 ~ 1500 r/min, and the time is 12 ~ 36 h.
5. containing Ti for light evaporation water as described in claim 13C2The preparation method of composite semipermeable membrane, which is characterized in that step
In rapid 3, cellulose nitrate is dissolved in concentrated nitric acid by absorbent cotton and is made with concentrated sulfuric acid mixed solution, semi-permeable membrane precursor solution be by
Ether and ethyl alcohol dissolve in cellulose nitrate and are made.
6. containing Ti for light evaporation water as described in claim 13C2The preparation method of composite semipermeable membrane, which is characterized in that step
In rapid 4, what is be prepared contains Ti3C2Composite semipermeable membrane with a thickness of 20-500 μm.
7. a kind of composite semipermeable membrane of the preparation of method described in any one of -6 according to claim 1, which is characterized in that this is multiple
Close the Ti in semi-permeable membrane containing by quality ratio 5.0 ~ 80%3C2。
8. composite semipermeable membrane as claimed in claim 7, which is characterized in that the composite semipermeable membrane passes through Ti3C2With semi-transparent membrane precursor
Body carries out compound preparation.
9. a kind of purposes of composite semipermeable membrane according to claim 7, which is characterized in that the composite semipermeable membrane is steamed for light
Shampoo, sea water desalination.
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| CN109261181A (en) * | 2018-09-10 | 2019-01-25 | 浙江大学 | Utilize the Ti of isopropylamine intercalation and layering3C2Fabricated in situ TiO2@Ti3C2Method and product |
| CN109225290B (en) * | 2018-09-10 | 2021-02-02 | 浙江大学 | Intercalation and delamination of Ti with hydrazine hydrate3C2In-situ synthesis of TiO2@Ti3C2Method and product of |
| CN109261180A (en) * | 2018-09-10 | 2019-01-25 | 浙江大学 | Utilize the Ti of dimethyl sulfoxide intercalation and layering3C2Fabricated in situ TiO2@Ti3C2Method and product |
| CN109701397B (en) * | 2019-01-16 | 2021-12-21 | 华南理工大学 | Application of two-dimensional MXene membrane prepared by electrophoretic deposition method in ion interception |
| CN111111720A (en) * | 2020-01-06 | 2020-05-08 | 大连理工大学 | Alkali-assisted intercalation in two-dimensional semiconductor Ti3C2O2Application in synthesis |
| CN111715250B (en) * | 2020-03-16 | 2021-09-03 | 同济大学 | Preparation method and application of supported transition metal carbide Fenton-like nano catalyst |
| CN114164646A (en) * | 2021-12-02 | 2022-03-11 | 聚纳达(青岛)科技有限公司 | Preparation method and application of electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity |
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| CN107029563B (en) * | 2017-06-16 | 2019-11-08 | 上海海事大学 | A kind of composite semipermeable membrane containing Ag, preparation method and the usage for light evaporation water |
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