CN106902654A - A kind of preparation method and application of lithium ion trace polyethersulfone composite membrane - Google Patents
A kind of preparation method and application of lithium ion trace polyethersulfone composite membrane Download PDFInfo
- Publication number
- CN106902654A CN106902654A CN201710202755.3A CN201710202755A CN106902654A CN 106902654 A CN106902654 A CN 106902654A CN 201710202755 A CN201710202755 A CN 201710202755A CN 106902654 A CN106902654 A CN 106902654A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- composite membrane
- film
- trace
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention is a kind of preparation method of lithium ion trace polyethersulfone composite membrane, function of dominant technical field of material.With poly (ether sulfone) film as basement membrane material, lithium ion is template, 12 4 ethers of hat are binding site, methacrylic acid is function monomer, ethylene glycol dimethacrylate is crosslinking agent, azodiisobutyronitrile is initiator, with reference to dopamine process for modifying surface, silica nanometer complex technique, trace polymerization technology, lithium ion trace polyethersulfone composite membrane is prepared.Staticadsorption experiment is used for adsorption equilibrium, adsorption dynamics adsorption kinetics and the Selective recognition performance of the lithium ion trace polyethersulfone composite membrane for studying prepared；Selectively penetrating experiment is used for studying prepared lithium ion trace polyethersulfone composite membrane to object ion (lithium ion) and the permeance property of non-targeted ion (sodium ion and potassium ion).The lithium ion trace polyethersulfone composite membrane prepared using the present invention has specific adsorption ability higher and identification separating power to lithium ion.
Description
Technical field
The invention belongs to functional material preparing technical field, and in particular to one kind is for Selective recognition and separates mixture
The preparation method and application of the lithium ion trace polyethersulfone composite membrane of lithium ion in system.
Background technology
Membrane separation technique (MST) be in recent years by more concern a kind of isolation technics, refer in particular on a molecular scale, when
The molecule mixture of different-grain diameter when by membrane material, using stopping that a part of material by way of carries out compounding substances
A kind of separate technology.Compared with traditional separate modes such as distillation, extraction, membrane separating process has that loss of effective components is few, institute
Need energy consumption it is low, to separate substance non-secondary pollution, strong adaptability, process is simple, it is easy to operate, be easy to automation etc. it is many excellent
Point.However, for the separation process in ion aspect, traditional microfiltration membranes, NF membrane etc. due to lacking single selective,
Thus membrane separation technique is limited more to be widely applied.
Ionic imprinting technique (IIT) is the technology for receiving much concern for growing up in recent years, and the appearance of IIT is good
Solve the problems, such as membrane material for ion non-selectivity.Under conditions of template ion presence, by function monomer and crosslinking
Polymerization process between agent, the coordination polymer coexisted with template ion is formed on film surface, based on either physically or chemically right
Template ion is eluted, and the imprinted sites matched in bulk and active force with template ion are left on film surface, when
When hybrid ionic passes through blotting membrane, imprinted sites can carry out specific adsorption to object ion, while to non-template ion not
Specific adsorption is carried out, so as to realize the separation of single ionic.MST is combined ion blotting film (IIM) tool of preparation with IIT
Have the advantages that easily operated, separating energy consumption is low, single selective is strong.Additionally, gathering compared to traditional trace microballoon, block trace
Compound etc., the advantages of IIM has stable in properties, preparation process is simple, applied widely, form is regular, be it is a kind of have it is good
The separation material of application prospect.At present, as MST quickly grows, IIM is widely used in the various fields such as chemical industry, food, medicine
In.
Elemental lithium (Lithium) is the larger a kind of element of abundance in nature, and it is mainly used in atomic pile control
The fields such as the preparation of system, light-alloy and battery.Elemental lithium is mainly distributed in mineral and natural salt lake bittern, wherein 60% lithium
Compound comes among salt lake bittern.Although at present carry lithium on salt lake separation have been carried out on solvent extraction,
The methods such as salting out method, ion-exchange, the precipitation method and nano filtering process it is widely studied, but due to lithium ion (Li+) and sodium ion (Na+) and potassium ion (K+) between property is similar, ionic radius is close so that cannot still realize to Lithium from Salt Lake Brine ion at present
Efficiently separate.Research finds, special in the presence of what can spatially be mutually matched with lithium ion in 12-crown-4-ether molecular structure
Structure, it is thus possible to specifically bound with lithium ion, can be realized based on the adsorption and separation material prepared by this principle
To the Selective Separation process of lithium ion.In the present patent application, the film based on polyether sulfone, by nano modification and ion blotting
Technology, is prepared for the lithium ion trace composite film material to lithium ion with efficient selective identification and separating power.
The content of the invention
It is an object of the invention to provide a kind of lithium ion for lithium ion in Selective recognition and separation mixed system
The preparation method of trace polyethersulfone composite membrane, the method with poly (ether sulfone) film as substrate, based on dopamine surface aggregate technology to base
Counterdie carries out surface modification, using nanometer composite technology in dopamine Modified Membrane surface scion grafting silica nanometer composite bed,
Composite film surface builds prepolymerization trace system, is prepared for mixed for Selective recognition and separation by radical polymerization process
The lithium ion trace polyethersulfone composite membrane of lithium ion in zoarium system.
The present invention is multiple with reference to membrane separation technique, dopamine surface aggregate technology, nanometer based on non-covalent imprinting system
Modification technology and ionic imprinting technique are closed, the lithium ion to lithium ion with efficient selective identification and separating power has been prepared
Trace polyethersulfone composite membrane, and prepared membrane material is applied to the separation process of lithium ion in mixed system.
Technical scheme refers to poly (ether sulfone) film (PSMs, 0.22 μm of average pore size, diameter 25mm) as substrate membrane material
Material, carries out surface to PSMs and is modified using dopamine surface aggregate technology, obtains dopamine Modified Membrane dPSMs, multiple based on nanometer
Conjunction technology prepares silica composite films SiO2@dPSMs, using γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-
570) carry out surface to composite membrane to be modified, with lithium ion (Li+) for template, 12-crown-4-ether be binding site, methacrylic acid
(MAA) it is function monomer, ethylene glycol dimethacrylate (EGDMA) is crosslinking agent, and azodiisobutyronitrile (AIBN) is initiation
Agent, based on engram technology, the mode for triggering polymerization using film function of surface monomer prepares Li-IIMs.
The lithium ion trace polyethersulfone composite membrane preparation method that a kind of function of surface monomer prepolymerization system triggers, specific step
It is rapid as follows：
Step one, poly (ether sulfone) film surface dopamine are modified
First, 0.1211g tri- (methylol) aminomethane hydrochloride (Tris) and 0.2g Dopamine hydrochlorides (DA) are placed in
In 100mL deionized waters, it is well mixed under ultrasound condition, regulation mixed solution pH value is 8.5, and 3 poly (ether sulfone) film PSMs are soaked
Enter in mixed solution, reacted 3~9 hours under shaken at room temperature, take out film resulting after reacting, it is each with deionized water soaking and washing
Three times, 10 minutes every time, the film after cleaning is dried at room temperature, obtain dopamine modified poly (ether sulfone) film (dPSMs).
The preparation of step 2, silica nanometer composite membrane
First, 1mL tetraethyl orthosilicates (TEOS) are added to (ethanol in the mixed solution of 35mL second alcohol and waters:Water=
30mL:5mL), it is well mixed under ultrasound condition, the dopamine modified poly (ether sulfone) film dPSMs that 3 steps one are obtained is added to
After in above-mentioned mixed solution, vibrate 5 minutes at room temperature, add 0.5mL ammoniacal liquor (NH3·H2O) follow-up persistent oscillation reaction 3~9 is small
When, film resulting after reacting is taken out, soaking and washing is carried out to it each three times with second alcohol and water respectively, 10 minutes every time, in room
Silica nanometer composite membrane (SiO is obtained after being dried under temperature2@dPSMs)。
Step 3, SiO2The surface of@dPSMs is modified
First, the SiO that will be obtained in 3 step 22@dPSMs are added to (second in the mixed solution of 100mL second alcohol and waters
Alcohol:Water=80mL:20mL), to logical nitrogen (N in solution2) 5 minutes, 3mL γ-(methacryloxypropyls) is added under nitrogen protection
Propyl trimethoxy silicane (KH-570), continues to nitrogen is passed through in solution 10 minutes, with vacuum stopper, degreasing adhesive tape and preservative film
Sealed, reacted 12~20 hours in 80 DEG C of thermostatic control oscillator vibrations, taken out film resulting after reacting, ethanol is used respectively
Soaking and washing is carried out to it each three times with water, 10 minutes every time, obtain improved silica after drying at room temperature nano combined
Film (k-SiO2@dPSMs)。
The preparation of step 4, lithium ion trace polyethersulfone composite membrane
First, by 0.2mmol lithium chlorides (LiCl), 0.2mmol 12-crown-4s-ether (12C4) and 60mL acetonitriles in ultrasonic bar
It is well mixed under part, mixed solution is stirred at ambient temperature makes lithium ion fully be combined with 12-crown-4-ether for 1 hour；To mixed
The k-SiO obtained in 3 step 3 is added in conjunction solution2Lead to nitrogen 20 minutes in solution after@dPSMs, keep logical nitrogen condition
It is lower to press a certain amount of methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA) and azodiisobutyronitrile (AIBN)
According to 1:4:25 (mM:MM:Milligram) ratio be added in above-mentioned mixed solution, continue logical nitrogen 5 minutes, use vacuum
Plug, degreasing adhesive tape and preservative film are sealed, and are reacted 12~36 hours in 60 DEG C of thermostatic control oscillator vibrations, take out institute after reaction
The film for obtaining, soaking and washing is carried out each three times with ethanol and water to it respectively, 10 minutes every time, after being dried at room temperature
To trace polymerization film；1 trace polymerization film is placed in the hydrochloric acid solution that 100mL concentration is 1mol/L, it is right under shaken at room temperature
Trace polymerization film carries out template removal treatment, changes within every 6 hours an eluent, and elution process continues 3 days, and room temperature is obtained after drying
Lithium ion trace polyethersulfone composite membrane (Li-IIMs).
Three (methylol) aminomethane hydrochlorides described in above-mentioned technical proposal, it act as cushioning liquid.
Dopamine hydrochloride described in above-mentioned technical proposal, it act as surface modifying material.
Tetraethyl orthosilicate described in above-mentioned technical proposal, it act as hydrolysis material.
Ammoniacal liquor described in above-mentioned technical proposal, it act as hydrolyst.
γ-(methacryloxypropyl) propyl trimethoxy silicane described in above-mentioned technical proposal, it act as silane idol
Connection agent.
Lithium chloride described in above-mentioned technical proposal, it act as providing template ion.
12-crown-4-ether described in above-mentioned technical proposal, its hole for acting as providing absorption lithium ion.
Methacrylic acid described in above-mentioned technical proposal, it act as function monomer.
Ethylene glycol dimethacrylate described in above-mentioned technical proposal, it act as crosslinking agent.
Azodiisobutyronitrile described in above-mentioned technical proposal, it act as initiator.
Hydrochloric acid described in above-mentioned technical proposal, it act as eluant, eluent.
Poly (ether sulfone) film described in above-mentioned technical proposal, it act as basement membrane material.
Material properties test
In order to lithium ion trace polyethersulfone composite membrane (Li-IIMs) prepared in above-mentioned technical proposal in adsorbing separation
It is contrasted in performance, non-blotting membrane (Li-NIMs), its preparation process and Li-IIMs systems is prepared while Li-IIMs is prepared
Standby process is similar, and in addition to 12C4 is added without in preparation process four, remaining step is identical with Li-IIMs preparation process.
I () Staticadsorption experiment and selective absorption are tested
Take in the corresponding test solution of Li-IIMs or Li-NIMs addition of certain mass, water bath with thermostatic control at ambient temperature is shaken
Swing, investigate influence of the initial concentration of different adsorbent solutions to composite membrane, after absorption after the completion of, unadsorbed lithium concentration is used
Inductive coupling plasma emission spectrograph (ICP) is determined, and calculates adsorption capacity (Q according to resulte, mg/g)：
Qe=(C0-Ce)×V/m (1)
Wherein C0And C (mg/L)e(mg/L) concentration of lithium ion in the front and rear solution of absorption is respectively, m (g) adds Li-
The quality of IIMs or Li-NIMs, V (mL) is the volume of test solution.
(ii) differential permeability experiment
Self-control combined type H-shaped infiltration glass device, centre is broken as two ground branch pipes, Li-IIMs or Li-NIMs is fixed
Between two aquarium grounds, place is tightly connected using degreasing adhesive tape and adhesive waterproof tape, it is ensured that device ne-leakage, side sample cell
The mixed aqueous solution of the lithium chloride, sodium chloride and potassium chloride of middle addition same ion concentration, the body such as addition in opposite side sample cell
Product deionized water, respectively puts one piece of magneton in two sample cells, be stirred at room temperature, is sampled under different time, passes through
ICP determines the ion concentration through trace composite membrane, and calculates infiltration capacity accordingly.
Advantages of the present invention and have the technical effect that：
1st, the present invention 12-crown-4-ether is fixed on by membrane material surface based on surface imprinted polymerization technique, using 12-crown-4-
The ring shaped molecule structure of ether, there is provided for the spatial hole of selective absorption lithium ion, so as to the specificity for realizing lithium ion is known
Not with absorption, and then lithium ion and other ion isolations are caused by process of osmosis；
2nd, trace polymerization occurs on surface in the present invention, it is to avoid recognition site because embed it is too deep reduce adsorption effect
Problem so that the recognition efficiency to object ion (lithium ion) is greatly improved；
3rd, there is the lithium ion trace polyethersulfone composite membrane prepared by the present invention selectivity height, separating effect to show to lithium ion
The advantage of work, while the characteristics of having that stability is high, reproducibility strong, can repeatedly use.
Brief description of the drawings
Fig. 1 is the preparation process and its absorption lithium ion mechanism schematic diagram of Li-IIMs.
Fig. 2 a and Fig. 2 b be respectively in 1~embodiment of embodiment 3 Li-IIMs/Li-NIMs static adsorbances column diagram and
Li-IIMs selective absorption amount column diagrams.
Fig. 3 a~Fig. 3 e are respectively PSMs, dPSMs, SiO in embodiment 22@dPSMs, modified SiO2@dPSMs、Li-IIMs
Scanning electron microscope (SEM) photograph.
Specific embodiment
With reference to specific implementation example, the present invention will be further described.
Embodiment 1
Step one, poly (ether sulfone) film surface dopamine are modified
First, 0.1211g tri- (methylol) aminomethane hydrochloride (Tris) and 0.2g Dopamine hydrochlorides (DA) are placed in
In 100mL deionized waters, it is well mixed under ultrasound condition, regulation mixed solution pH value is 8.5, and 3 poly (ether sulfone) film PSMs are soaked
Enter in mixed solution, reacted 3 hours under shaken at room temperature, film resulting after reacting is taken out, with deionized water soaking and washing each three
It is secondary, 10 minutes every time, the film after cleaning is dried at room temperature, obtain dopamine modified poly (ether sulfone) film (dPSMs).
The preparation of step 2, silica nanometer composite membrane
First, 1mL tetraethyl orthosilicates (TEOS) are added to (ethanol in the mixed solution of 35mL second alcohol and waters:Water=
30mL:5mL), it is well mixed under ultrasound condition, the dopamine modified poly (ether sulfone) film dPSMs that will be obtained in 3 steps one is added
After in above-mentioned mixed solution, vibrate 5 minutes at room temperature, add 0.5mL ammoniacal liquor (NH3·H2O) follow-up persistent oscillation reacts 3 hours,
Film resulting after reacting is taken out, soaking and washing is carried out to it each three times with second alcohol and water respectively, 10 minutes every time, at room temperature
Silica nanometer composite membrane (SiO is obtained after drying2@dPSMs)。
Step 3, SiO2The surface of@dPSMs is modified
First, the SiO that will be obtained in 3 step 22@dPSMs are added to (second in the mixed solution of 100mL second alcohol and waters
Alcohol:Water=80mL:20mL), to logical nitrogen (N in solution2) 5 minutes, 3mL γ-(methacryloxypropyls) is added under nitrogen protection
Propyl trimethoxy silicane (KH-570), continues to nitrogen is passed through in solution 10 minutes, with vacuum stopper, degreasing adhesive tape and preservative film
Sealed, reacted 12 hours in 80 DEG C of thermostatic control oscillator vibrations, taken out film resulting after reacting, second alcohol and water is used respectively
Soaking and washing is carried out to it each three times, 10 minutes every time, improved silica nano composite membrane (k- is obtained after drying at room temperature
SiO2@dPSMs)。
The preparation of step 4, lithium ion trace polyethersulfone composite membrane
First, by 0.2mmol lithium chlorides (LiCl), 0.2mmol 12-crown-4s-ether (12C4) and 60mL acetonitriles in ultrasonic bar
It is well mixed under part, mixed solution is stirred at ambient temperature makes lithium ion fully be combined with 12-crown-4-ether for 1 hour；To mixed
The k-SiO obtained in 3 step 3 is added in conjunction solution2Lead to nitrogen 20 minutes in solution after@dPSMs, keep logical nitrogen condition
It is lower by 0.5mmol methacrylic acids (MAA), 2mmol ethylene glycol dimethacrylates (EGDMA) and the isobutyl of 12.5mg azos two
Nitrile (AIBN) is added in above-mentioned mixed solution, continues logical nitrogen 5 minutes, is sealed with vacuum stopper, degreasing adhesive tape and preservative film,
Reacted 12 hours in 60 DEG C of thermostatic control oscillator vibrations, take out film resulting after reacting, it is carried out respectively with ethanol and water
Each three times of soaking and washing, 10 minutes every time, obtains trace polymerization film after being dried at room temperature；1 trace polymerization film is put
In 100mL concentration is for the hydrochloric acid solution of 1mol/L, template removal treatment, every 6 are carried out to trace polymerization film under shaken at room temperature
Hour changes an eluent, and elution process continues 3 days, and room temperature obtains lithium ion trace polyethersulfone composite membrane Li-IIMs- after drying
1。
Material properties test
I () Staticadsorption experiment and selective absorption are tested
Each 5 parts of Li-IIMs-1 and Li-NIMs-1 is weighed respectively, is respectively put into 10 teat glasses, be separately added into
10mL concentration is 5,10,20,50,100, the water lithium chloride solution of 200mg/L, shake 3 hours at ambient temperature, absorption is completed
Afterwards, by lithium concentration unadsorbed in ICP measure original solutions, and adsorption capacity is calculated according to result.
Shown in Li-IIMs-1 and Li-NIMs-1 adsorbances such as Fig. 2 (a), as a result show that the highest saturation of Li-IIMs-1 is inhaled
Attached capacity is 125.62mg/g, hence it is evident that the 75.48mg/g higher than Li-NIMs-1.
Weigh 5 parts of Li-IIMs-1, be respectively put into 5 teat glasses, be separately added into 10mL concentration for 5,10,20,50,
100th, 200mg/L contains the mixed aqueous solution of same concentrations lithium ion, sodium ion, potassium ion, and 3h is shaken at ambient temperature, inhales
After the completion of attached, by lithium concentration unadsorbed in ICP measure original solutions, and adsorption capacity is calculated according to result.
Li-IIMs-1 and Li-NIMs-1 are to Li+、Na+、K+Adsorbance such as Fig. 2 (b) shown in, as a result show Li-IIMs-1
Highest saturated adsorption capacity to lithium ion in competitive Adsorption is 125.62mg/g, to sodium ion and the highest saturation of potassium ion
Adsorption capacity is respectively 82.97mg/g and 67.41mg/g, and selective factor B is respectively 1.51 and 1.86.
(ii) differential permeability experiment
Self-control combined type H-shaped infiltration glass device, centre is broken as two ground branch pipes, by Li-IIMs-1 or Li-NIMs-1
It is fixed between two aquarium grounds, place is tightly connected using degreasing adhesive tape and adhesive waterproof tape, it is ensured that device ne-leakage, side sample
The mixed aqueous solution of the lithium chloride, sodium chloride and potassium chloride of same ion concentration is added in product pond, is added in opposite side sample cell
Isometric deionized water, respectively puts one piece of magneton in two sample cells, device is placed in water bath with thermostatic control, is stirred at ambient temperature
Mix, the ion concentration through trace composite membrane is determined by ICP, and calculate infiltration capacity accordingly.
Li-IIMs-1 selected area update strategy experimental results show, are in lithium ion, sodium ion, potassium ion initial concentration
In the mixed aqueous solution of 100mg/L, when sample time is respectively 5,10,15,30,45,60,90,120,180,360 minutes, survey
In blank sample cell the concentration of lithium ion be respectively 0.1718,0.2213,0.2570,0.2647,0.2899,0.3113,
0.3270th, 0.3395,0.3957,0.4174mg/L, the concentration for measuring sodium ion is respectively 1.2578,1.5850,1.7910,
1.8431st, 2.0751,2.1759,2.3610,2.5804,2.6842,2.8052mg/L, the concentration for measuring potassium ion is respectively
1.3142、1.7896、2.0843、2.2674、2.4718、2.6081、2.8755、3.0195、3.3537、3.5928mg/L。
Li-NIMs-1 selected area update strategy experimental results show, are in lithium ion, sodium ion, potassium ion initial concentration
In the mixed aqueous solution of 100mg/L, when sample time is respectively 5,10,15,30,45,60,90,120,180,360 minutes, survey
In blank sample cell the concentration of lithium ion be respectively 1.1513,1.5264,2.1225,2.2493,2.3054,2.5854,
2.8252nd, 2.9437,3.6175,3.9142mg/L, the concentration for measuring sodium ion is respectively 1.1419,1.4329,2.1506,
2.2193rd, 2.4172,2.5120,2.9360,3.2382,3.4335,3.9641mg/L, the concentration for measuring potassium ion is respectively
1.1212、0.6066、2.2967、2.2824、2.4795、2.5825、2.8736、3.1042、3.5170、3.8027mg/L。
The scanning electron microscope (SEM) photograph of membrane material is similar to Example 2 in embodiment 1, by scanning electron microscope (SEM) photograph in Fig. 3 can be seen that with
Other steps gained membrane material compares, and one layer of the Li-IIMs surfaces appearance for finally giving is uniformly dispersed, print in irregular shape
Mark polymeric layer, it was demonstrated that success synthesizes ion blotting polymer layer on film surface, with reference to the selective absorption number that Li-IIMs is excellent
According to as a result showing that prepared Li-IIMs has specific adsorption to template ion (lithium ion) and promotes non-template ion (sodium
Ion and potassium ion) infiltration performance.
Embodiment 2
Step one, poly (ether sulfone) film surface dopamine are modified
First, 0.1211g tri- (methylol) aminomethane hydrochloride (Tris) and 0.2g Dopamine hydrochlorides (DA) are placed in
In 100mL deionized waters, it is well mixed under ultrasound condition, regulation mixed solution pH value is 8.5, and 3 poly (ether sulfone) film PSMs are soaked
Enter in mixed solution, reacted 6 hours under shaken at room temperature, film resulting after reacting is taken out, with deionized water soaking and washing each three
It is secondary, 10 minutes every time, the film after cleaning is dried at room temperature, obtain dopamine modified poly (ether sulfone) film (dPSMs).
The preparation of step 2, silica nanometer composite membrane
First, 1mL tetraethyl orthosilicates (TEOS) are added to (ethanol in the mixed solution of 35mL second alcohol and waters:Water=
30mL:5mL), it is well mixed under ultrasound condition, the dopamine modified poly (ether sulfone) film dPSMs that will be obtained in 3 steps one is added
After in above-mentioned mixed solution, vibrate 5 minutes at room temperature, add 0.5mL ammoniacal liquor (NH3·H2O) follow-up persistent oscillation reacts 6 hours,
Film resulting after reacting is taken out, soaking and washing is carried out to it each three times with second alcohol and water respectively, 10 minutes every time, at room temperature
Silica nanometer composite membrane (SiO is obtained after drying2@dPSMs)。
Step 3, SiO2The surface of@dPSMs is modified
First, the SiO that will be obtained in 3 step 22@dPSMs are added to (second in the mixed solution of 100mL second alcohol and waters
Alcohol:Water=80mL:20mL), to logical nitrogen (N in solution2) 5 minutes, 3mL γ-(methacryloxypropyls) is added under nitrogen protection
Propyl trimethoxy silicane (KH-570), continues to nitrogen is passed through in solution 10 minutes, with vacuum stopper, degreasing adhesive tape and preservative film
Sealed, reacted 16 hours in 80 DEG C of thermostatic control oscillator vibrations, taken out film resulting after reacting, second alcohol and water is used respectively
Soaking and washing is carried out to it each three times, 10 minutes every time, improved silica nano composite membrane (k- is obtained after drying at room temperature
SiO2@dPSMs)。
The preparation of step 4, lithium ion trace polyethersulfone composite membrane
First, by 0.2mmol lithium chlorides (LiCl), 0.2mmol 12-crown-4s-ether (12C4) and 60mL acetonitriles in ultrasonic bar
It is well mixed under part, mixed solution is stirred at ambient temperature makes lithium ion fully be combined with 12-crown-4-ether for 1 hour；To mixed
The k-SiO obtained in 3 step 3 is added in conjunction solution2Lead to nitrogen 20 minutes in solution after@dPSMs, keep logical nitrogen condition
It is lower by 1mmol methacrylic acids (MAA), 4mmol ethylene glycol dimethacrylates (EGDMA) and 25mg azodiisobutyronitriles
(AIBN) it is added in above-mentioned mixed solution, continues logical nitrogen 5 minutes, is sealed with vacuum stopper, degreasing adhesive tape and preservative film,
Reacted 24 hours in 60 DEG C of thermostatic control oscillator vibrations, take out film resulting after reacting, it is soaked respectively with ethanol and water
Bubble cleaning is each three times, 10 minutes every time, trace polymerization film is obtained after being dried at room temperature；1 trace polymerization film is placed in
During 100mL concentration is for the hydrochloric acid solution of 1mol/L, template removal treatment is carried out to trace polymerization film under shaken at room temperature, every 6 is small
When change an eluent, elution process continues 3 days, and room temperature obtains lithium ion trace polyethersulfone composite membrane Li-IIMs-2 after drying.
Material properties test
I () Staticadsorption experiment and selective absorption are tested
Each 5 parts of Li-IIMs-2 and Li-NIMs-2 is weighed respectively, is respectively put into 10 teat glasses, be separately added into
10mL concentration is 5,10,20,50,100, the water lithium chloride solution of 200mg/L, shake 3 hours at ambient temperature, absorption is completed
Afterwards, by lithium concentration unadsorbed in ICP measure original solutions, and adsorption capacity is calculated according to result.
Shown in Li-IIMs-2 and Li-NIMs-2 adsorbances such as Fig. 2 (a), as a result show that the highest saturation of Li-IIMs-2 is inhaled
Attached capacity is 172.43mg/g, hence it is evident that the 77.25mg/g higher than Li-NIMs-2.
Weigh 5 parts of Li-IIMs-2, be respectively put into 5 teat glasses, be separately added into 10mL concentration for 5,10,20,50,
100th, 200mg/L contains the mixed aqueous solution of same concentrations lithium ion, sodium ion, potassium ion, and 3h is shaken at ambient temperature, inhales
After the completion of attached, by lithium concentration unadsorbed in ICP measure original solutions, and adsorption capacity is calculated according to result.
Li-IIMs-2 and Li-NIMs-2 are to Li+、Na+、K+Adsorbance such as Fig. 2 (b) shown in, as a result show Li-IIMs-2
Highest saturated adsorption capacity to lithium ion in competitive Adsorption is 172.43mg/g, to sodium ion and the highest saturation of potassium ion
Adsorption capacity is respectively 93.34mg/g and 83.30mg/g, and selective factor B is respectively 1.85 and 2.07.
(ii) differential permeability experiment
Self-control combined type H-shaped infiltration glass device, centre is broken as two ground branch pipes, by Li-IIMs-2 or Li-NIMs-2
It is fixed between two aquarium grounds, place is tightly connected using degreasing adhesive tape and adhesive waterproof tape, it is ensured that device ne-leakage, side sample
The mixed aqueous solution of the lithium chloride, sodium chloride and potassium chloride of same ion concentration is added in product pond, is added in opposite side sample cell
Isometric deionized water, respectively puts one piece of magneton in two sample cells, device is placed in water bath with thermostatic control, is stirred at ambient temperature
Mix, the ion concentration through trace composite membrane is determined by ICP, and calculate infiltration capacity accordingly.
Li-IIMs-2 selected area update strategy experimental results show, are in lithium ion, sodium ion, potassium ion initial concentration
In the mixed aqueous solution of 100mg/L, when sample time is respectively 5,10,15,30,45,60,90,120,180,360 minutes, survey
In blank sample cell the concentration of lithium ion be respectively 0.1151,0.1879,0.2269,0.2396,0.2664,0.2734,
0.2919th, 0.3015,0.3762,0.3967mg/L, the concentration for measuring sodium ion is respectively 0.9780,1.3673,1.7344,
2.0630th, 2.1904,2.2748,2.5237,2.6719,2.7395,2.8948mg/L, the concentration for measuring potassium ion is respectively
1.3023、1.7745、2.0163、2.2169、2.4066、2.5250、2.8525、3.1170、3.5364、3.8421mg/L。
Li-NIMs-2 selected area update strategy experimental results show, are in lithium ion, sodium ion, potassium ion initial concentration
In the mixed aqueous solution of 100mg/L, when sample time is respectively 5,10,15,30,45,60,90,120,180,360 minutes, survey
In blank sample cell the concentration of lithium ion be respectively 1.1845,1.5592,2.1649,2.2705,2.3498,2.5807,
2.8934th, 2.9471,3.6910,3.9948mg/L, the concentration for measuring sodium ion is respectively 1.0972,1.3879,1.8061,
2.1968th, 2.2347,2.2948,2.8661,3.2093,3.7860,3.8795mg/L, the concentration for measuring potassium ion is respectively
1.2419、1.7448、2.2156、2.3491、2.4625、2.5661、2.8614、3.1948、3.5493、3.8834mg/L。
Be can be seen that compared with other steps gained membrane material by scanning electron microscope (SEM) photograph in Fig. 3, the Li- for finally giving
One layer of IIMs surfaces appearance is uniformly dispersed, trace polymerization nitride layer in irregular shape, it was demonstrated that success is in film surface synthesis ion print
Mark polymer layer, with reference to the selective absorption data that Li-IIMs is excellent, as a result shows prepared Li-IIMs to template ion (lithium
Ion) there is specific adsorption and promote the performance of non-template ion (sodium ion and potassium ion) infiltration.
Embodiment 3
Step one, poly (ether sulfone) film surface dopamine are modified
First, 0.1211g tri- (methylol) aminomethane hydrochloride (Tris) and 0.2g Dopamine hydrochlorides (DA) are placed in
In 100mL deionized waters, it is well mixed under ultrasound condition, regulation mixed solution pH value is 8.5, and 3 poly (ether sulfone) film PSMs are soaked
Enter in mixed solution, reacted 9 hours under shaken at room temperature, film resulting after reacting is taken out, with deionized water soaking and washing each three
It is secondary, 10 minutes every time, the film after cleaning is dried at room temperature, obtain dopamine modified poly (ether sulfone) film (dPSMs).
The preparation of step 2, silica nanometer composite membrane
First, 1mL tetraethyl orthosilicates (TEOS) are added to (ethanol in the mixed solution of 35mL second alcohol and waters:Water=
30mL:5mL), it is well mixed under ultrasound condition, the dopamine modified poly (ether sulfone) film dPSMs that will be obtained in 3 steps one is added
After in above-mentioned mixed solution, vibrate 5 minutes at room temperature, add 0.5mL ammoniacal liquor (NH3·H2O) follow-up persistent oscillation reacts 9 hours,
Film resulting after reacting is taken out, soaking and washing is carried out to it each three times with second alcohol and water respectively, 10 minutes every time, at room temperature
Silica nanometer composite membrane (SiO is obtained after drying2@dPSMs)。
Step 3, SiO2The surface of@dPSMs is modified
First, the SiO that will be obtained in 3 step 22@dPSMs are added to (second in the mixed solution of 100mL second alcohol and waters
Alcohol:Water=80mL:20mL), to logical nitrogen (N in solution2) 5 minutes, 3mL γ-(methacryloxypropyls) is added under nitrogen protection
Propyl trimethoxy silicane (KH-570), continues to nitrogen is passed through in solution 10 minutes, with vacuum stopper, degreasing adhesive tape and preservative film
Sealed, reacted 20 hours in 80 DEG C of thermostatic control oscillator vibrations, taken out film resulting after reacting, second alcohol and water is used respectively
Soaking and washing is carried out to it each three times, 10 minutes every time, improved silica nano composite membrane (k- is obtained after drying at room temperature
SiO2@dPSMs)。
The preparation of step 4, lithium ion trace polyethersulfone composite membrane
First, by 0.2mmol lithium chlorides (LiCl), 0.2mmol 12-crown-4s-ether (12C4) and 60mL acetonitriles in ultrasonic bar
It is well mixed under part, mixed solution is stirred at ambient temperature makes lithium ion fully be combined with 12-crown-4-ether for 1 hour；To mixed
The k-SiO obtained in 3 step 3 is added in conjunction solution2Lead to nitrogen 20 minutes in solution after@dPSMs, keep logical nitrogen condition
It is lower by 2mmol methacrylic acids (MAA), 8mmol ethylene glycol dimethacrylates (EGDMA) and 50mg azodiisobutyronitriles
(AIBN) it is added in above-mentioned mixed solution, continues logical nitrogen 5 minutes, is sealed with vacuum stopper, degreasing adhesive tape and preservative film,
Reacted 36 hours in 60 DEG C of thermostatic control oscillator vibrations, take out film resulting after reacting, it is soaked respectively with ethanol and water
Bubble cleaning is each three times, 10 minutes every time, trace polymerization film is obtained after being dried at room temperature；1 trace polymerization film is placed in
During 100mL concentration is for the hydrochloric acid solution of 1mol/L, template removal treatment is carried out to trace polymerization film under shaken at room temperature, every 6 is small
When change an eluent, elution process continues 3 days, and room temperature obtains lithium ion trace polyethersulfone composite membrane Li-IIMs-3 after drying.
Material properties test
I () Staticadsorption experiment and selective absorption are tested
Each 5 parts of Li-IIMs-3 and Li-NIMs-3 is weighed respectively, is respectively put into 10 teat glasses, be separately added into
10mL concentration is 5,10,20,50,100, the water lithium chloride solution of 200mg/L, shake 3 hours at ambient temperature, absorption is completed
Afterwards, by lithium concentration unadsorbed in ICP measure original solutions, and adsorption capacity is calculated according to result.
Shown in Li-IIMs-3 and Li-NIMs-3 adsorbances such as Fig. 2 (a), as a result show that the highest saturation of Li-IIMs-3 is inhaled
Attached capacity is 148.59mg/g, hence it is evident that the 72.63mg/g higher than Li-NIMs-3.
Weigh 5 parts of Li-IIMs-3, be respectively put into 5 teat glasses, be separately added into 10mL concentration for 5,10,20,50,
100th, 200mg/L contains the mixed aqueous solution of same concentrations lithium ion, sodium ion, potassium ion, and 3h is shaken at ambient temperature, inhales
After the completion of attached, by lithium concentration unadsorbed in ICP measure original solutions, and adsorption capacity is calculated according to result.
Li-IIMs-3 and Li-NIMs-3 are to Li+、Na+、K+Adsorbance such as Fig. 2 (b) shown in, as a result show Li-IIMs-3
Highest saturated adsorption capacity to lithium ion in competitive Adsorption is 148.59mg/g, to sodium ion and the highest saturation of potassium ion
Adsorption capacity is respectively 87.35mg/g and 74.68mg/g, and selective factor B is respectively 1.70 and 1.98.
(ii) differential permeability experiment
Self-control combined type H-shaped infiltration glass device, centre is broken as two ground branch pipes, by Li-IIMs-3 or Li-NIMs-3
It is fixed between two aquarium grounds, place is tightly connected using degreasing adhesive tape and adhesive waterproof tape, it is ensured that device ne-leakage, side sample
The mixed aqueous solution of the lithium chloride, sodium chloride and potassium chloride of same ion concentration is added in product pond, is added in opposite side sample cell
Isometric deionized water, respectively puts one piece of magneton in two sample cells, device is placed in water bath with thermostatic control, is stirred at ambient temperature
Mix, the ion concentration through trace composite membrane is determined by ICP, and calculate infiltration capacity accordingly.
Li-IIMs-3 selected area update strategy experimental results show, are in lithium ion, sodium ion, potassium ion initial concentration
In the mixed aqueous solution of 100mg/L, when sample time is respectively 5,10,15,30,45,60,90,120,180,360 minutes, survey
In blank sample cell the concentration of lithium ion be respectively 0.1569,0.2126,0.2489,0.2557,0.2777,0.2950,
0.3163rd, 0.3265,0.3891,0.4057mg/L, the concentration for measuring sodium ion is respectively 1.0175,1.2649,1.5498,
1.8310th, 2.0563,2.1544,2.3653,2.5740,2.6931,2.7417mg/L, the concentration for measuring potassium ion is respectively
1.3137、1.7864、2.0273、2.2287、2.4185、2.5360、2.8641、3.1287、3.5474、3.8536mg/L。
Li-NIMs-3 selected area update strategy experimental results show, are in lithium ion, sodium ion, potassium ion initial concentration
In the mixed aqueous solution of 100mg/L, when sample time is respectively 5,10,15,30,45,60,90,120,180,360 minutes, survey
In blank sample cell the concentration of lithium ion be respectively 1.1785,1.5424,2.1782,2.2405,2.3945,2.5449,
2.8412nd, 2.9177,3.6052,3.9159mg/L, the concentration for measuring sodium ion is respectively 1.1924,1.4532,2.1946,
2.2115th, 2.4017,2.5942,2.9057,3.2861,3.4973,3.9527mg/L, the concentration for measuring potassium ion is respectively
1.1017、1.6549、2.2430、2.2681、2.4125、2.5874、2.8708、3.1314、3.5283、3.8913mg/L。
The scanning electron microscope (SEM) photograph of membrane material is similar to Example 2 in embodiment 3, by scanning electron microscope (SEM) photograph in Fig. 3 can be seen that with
Other steps gained membrane material compares, and one layer of the Li-IIMs surfaces appearance for finally giving is uniformly dispersed, print in irregular shape
Mark polymeric layer, it was demonstrated that success synthesizes ion blotting polymer layer on film surface, with reference to the selective absorption number that Li-IIMs is excellent
According to as a result showing that prepared Li-IIMs has specific adsorption to template ion (lithium ion) and promotes non-template ion (sodium
Ion and potassium ion) infiltration performance.
Integrated embodiment 1, embodiment 2 and the experimental data of embodiment 3 and characterization result, as a result show prepared Li-
IIMs has specific adsorption higher to object ion (lithium ion) and promotes non-targeted ion (sodium ion and potassium ion) to ooze
Saturating performance, i.e., prepared Li-IIMs has the performance of efficient identification and point lithium ion.
Claims (4)
1. a kind of lithium ion trace polyethersulfone composite membrane, it is characterised in that：The polyethersulfone composite membrane is with poly (ether sulfone) film as substrate
Membrane material, carries out surface dopamine to poly (ether sulfone) film and is modified based on dopamine auto polymerization process, sets up secondary on poly (ether sulfone) film surface
Order reaction platform, prepares dopamine modified poly (ether sulfone) film；By hydrolytic process in dopamine modified poly (ether sulfone) film area load two
Silica nanometer composite layer, prepares silica nanometer composite membrane；Using γ-(methacryloxypropyl) propyl trimethoxy silicane
Treatment is modified to membrane material, improved silica nano composite membrane is prepared；With lithium ion as template, 12-crown-4-ether for knot
Site is closed, methacrylic acid is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, and azodiisobutyronitrile is initiation
Agent, based on surface imprinted technology, the lithium ion trace polyethersulfone composite membrane of preparation.
2. a kind of preparation method of lithium ion trace polyethersulfone composite membrane according to claim 1, it is characterised in that the party
Method is comprised the following steps：
Step one, poly (ether sulfone) film surface dopamine are modified
(methylol) aminomethane hydrochlorides of 0.1211g tri- and 0.2g Dopamine hydrochlorides are placed in 100mL deionized waters, ultrasound
Under the conditions of be well mixed, regulation mixed solution pH value is 8.5, and 3 poly (ether sulfone) films are immersed in mixed solutions, anti-under shaken at room temperature
Answer 3~9 hours, take out film resulting after reacting, each three times with deionized water soaking and washing, 10 minutes every time, after cleaning
Film dry at room temperature, obtain dopamine modified poly (ether sulfone) film；
The preparation of step 2, silica nanometer composite membrane
1mL tetraethyl orthosilicates are added in the mixed solution of 35mL second alcohol and waters, wherein ethanol:Water=30mL:5mL, super
It is well mixed under the conditions of sound, after the dopamine modified poly (ether sulfone) film that 3 steps one are obtained is added in above-mentioned mixed solution, room
Vibration 5 minutes under temperature, add the follow-up persistent oscillation of 0.5mL ammoniacal liquor to react 3~9 hours, take out film resulting after reacting, and use respectively
Second alcohol and water carries out soaking and washing to it each three times, 10 minutes every time, silica nanometer is obtained after drying at room temperature and is combined
Film；
Step 3, the surface of silica nanometer composite membrane are modified
The silica nanometer composite membrane obtained in 3 step 2 is added in the mixed solution of 100mL second alcohol and waters, wherein
Ethanol:Water=80mL:20mL, nitrogen is led to 5 minutes in solution, and 3mL γ-(methacryloxypropyl) third is added under nitrogen protection
Base trimethoxy silane, continues to lead to nitrogen 10 minutes in solution, is sealed with vacuum stopper, degreasing adhesive tape and preservative film,
Reacted 12~20 hours in 80 DEG C of thermostatic control oscillator vibrations, take out film resulting after reacting, it is entered with second alcohol and water respectively
Each three times of row soaking and washing, 10 minutes every time, obtains improved silica nano composite membrane after drying at room temperature；
The preparation of step 4, lithium ion trace polyethersulfone composite membrane
0.2mmol lithium chlorides, 0.2mmol 12-crown-4s-ether and 60mL acetonitriles are well mixed under ultrasound condition, will be mixed molten
Liquid is stirred at ambient temperature makes lithium ion fully be combined with 12-crown-4-ether for 1 hour；To 3 step 3 of addition in mixed solution
In lead to nitrogen 20 minutes in solution after the silica nanometer composite membrane that obtains, will be a certain amount of in the case where logical condition of nitrogen gas is kept
Methacrylic acid, ethylene glycol dimethacrylate and azodiisobutyronitrile are according to 1 mM:4 mMs:25 milligrams of ratio
It is added in above-mentioned mixed solution, continues logical nitrogen 5 minutes, is sealed with vacuum stopper, degreasing adhesive tape and preservative film, at 60 DEG C
Reacted 12~36 hours in thermostatic control oscillator vibration, take out film resulting after reacting, it is soaked respectively with ethanol and water
Bubble cleaning is each three times, 10 minutes every time, trace polymerization film is obtained after being dried at room temperature；1 trace polymerization film is placed in
During 100mL concentration is for the hydrochloric acid solution of 1mol/L, template removal treatment is carried out to trace polymerization film under shaken at room temperature, every 6 is small
When change an eluent, elution process continues 3 days, and room temperature obtains lithium ion trace polyethersulfone composite membrane after drying.
3. the lithium ion trace polyether sulfone that the preparation method of lithium ion trace polyethersulfone composite membrane synthesizes according to claim 2
Composite membrane.
4. lithium ion trace polyethersulfone composite membrane according to claim 3, it is characterised in that：Use it for lithium ion, sodium
The selective absorption and separation process of lithium ion in the mixed aqueous solution of ion and potassium ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710202755.3A CN106902654B (en) | 2017-03-30 | 2017-03-30 | Preparation method and application of lithium ion imprinted polyether sulfone composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710202755.3A CN106902654B (en) | 2017-03-30 | 2017-03-30 | Preparation method and application of lithium ion imprinted polyether sulfone composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106902654A true CN106902654A (en) | 2017-06-30 |
| CN106902654B CN106902654B (en) | 2020-10-02 |
Family
ID=59194980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710202755.3A Active CN106902654B (en) | 2017-03-30 | 2017-03-30 | Preparation method and application of lithium ion imprinted polyether sulfone composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106902654B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107335413A (en) * | 2017-08-29 | 2017-11-10 | 江苏大学 | Bionical multi-layer nano lithium ion Blot PVDF Membrane and preparation method and purposes |
| CN107344095A (en) * | 2017-08-29 | 2017-11-14 | 江苏大学 | A kind of lithium ion Blot PVDF Membrane and preparation method and its usage |
| CN107376655A (en) * | 2017-07-07 | 2017-11-24 | 江苏大学 | A kind of preparation method and use of lithium ion trace nano composite membrane |
| CN108078035A (en) * | 2017-12-13 | 2018-05-29 | 仙桃市鼎业劳保用品有限公司 | Protective garment |
| CN108328804A (en) * | 2018-04-13 | 2018-07-27 | 湖南科技大学 | A kind of processing method of platiniferous waste water |
| CN108339529A (en) * | 2018-01-24 | 2018-07-31 | 江苏大学 | A kind of preparation method and application of ion blotting composite membrane for Selective Separation palladium ion |
| CN109772178A (en) * | 2018-12-17 | 2019-05-21 | 江苏大学 | A kind of preparation method and application of the pyrimethamine molecularly imprinted composite membrane based on the two-sided load of click chemistry |
| CN110078873A (en) * | 2019-04-20 | 2019-08-02 | 太原理工大学 | A kind of preparation method of magnetism carbon-based lithium ion imprinted material |
| CN110227424A (en) * | 2019-06-28 | 2019-09-13 | 江苏大学 | A kind of preparation method and applications of covalent modification high density crown ether functionalization porous adsorbent |
| CN110559868A (en) * | 2019-08-30 | 2019-12-13 | 江苏大学 | Preparation method and application of click chemical imprinting-based o-cloxacillin molecular composite membrane |
| CN111229174A (en) * | 2020-01-13 | 2020-06-05 | 江苏大学 | Preparation method and application of Li-IIMs (lithium-ion organic Compounds) ion imprinting membrane |
| CN113351180A (en) * | 2021-06-08 | 2021-09-07 | 东北电力大学 | Preparation method and application of temperature response type bionic lithium ion imprinting composite membrane |
| CN113368707A (en) * | 2021-06-02 | 2021-09-10 | 江苏大学 | Preparation method and application of three-dimensional porous MOFs/poly dopamine-based polycarbonate track etching imprinted membrane |
| CN113509913A (en) * | 2021-04-21 | 2021-10-19 | 东北电力大学 | Preparation method and application of lithium ion imprinting nano composite membrane with high magnetism, high adsorption amount and high selectivity |
| CN113522061A (en) * | 2021-07-21 | 2021-10-22 | 昆明理工大学 | Preparation method of high-adsorption-capacity lithium ion imprinting nano composite membrane |
| CN115364679A (en) * | 2022-07-27 | 2022-11-22 | 中国地质大学（武汉） | Potassium ion selective film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103105386A (en) * | 2013-01-29 | 2013-05-15 | 福州大学 | Method for detecting malachite green in water body and aquatic products |
| CN103601862A (en) * | 2013-11-18 | 2014-02-26 | 南昌航空大学 | Method for preparing magnetic lithium ionic imprinting microspheres by using surface polymerization method implemented by taking macrocyclic polyethers as functional monomer |
| CN104231166A (en) * | 2014-09-05 | 2014-12-24 | 江苏大学 | Preparation method of bionic artemisinin molecular imprinting composite membrane |
| CN104974317A (en) * | 2015-07-06 | 2015-10-14 | 临沂大学 | Preparation method of strontium ion surface-imprinted polymer coated silica gel microspheres |
-
2017
- 2017-03-30 CN CN201710202755.3A patent/CN106902654B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103105386A (en) * | 2013-01-29 | 2013-05-15 | 福州大学 | Method for detecting malachite green in water body and aquatic products |
| CN103601862A (en) * | 2013-11-18 | 2014-02-26 | 南昌航空大学 | Method for preparing magnetic lithium ionic imprinting microspheres by using surface polymerization method implemented by taking macrocyclic polyethers as functional monomer |
| CN104231166A (en) * | 2014-09-05 | 2014-12-24 | 江苏大学 | Preparation method of bionic artemisinin molecular imprinting composite membrane |
| CN104974317A (en) * | 2015-07-06 | 2015-10-14 | 临沂大学 | Preparation method of strontium ion surface-imprinted polymer coated silica gel microspheres |
Non-Patent Citations (2)
| Title |
|---|
| DONGSHU SUN等: "Fabrication of highly selective ion imprinted macroporous membranes with crown ether for targeted separation of lithium ion", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
| YILIN WU等: "Bioinspired synthesis of pDA/SiO2-based porous ciprofloxacin-imprinted nanocomposite membrane by a polydopamine-assisted organic-inorganic method", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376655A (en) * | 2017-07-07 | 2017-11-24 | 江苏大学 | A kind of preparation method and use of lithium ion trace nano composite membrane |
| CN107335413A (en) * | 2017-08-29 | 2017-11-10 | 江苏大学 | Bionical multi-layer nano lithium ion Blot PVDF Membrane and preparation method and purposes |
| CN107344095A (en) * | 2017-08-29 | 2017-11-14 | 江苏大学 | A kind of lithium ion Blot PVDF Membrane and preparation method and its usage |
| CN108078035A (en) * | 2017-12-13 | 2018-05-29 | 仙桃市鼎业劳保用品有限公司 | Protective garment |
| CN108339529A (en) * | 2018-01-24 | 2018-07-31 | 江苏大学 | A kind of preparation method and application of ion blotting composite membrane for Selective Separation palladium ion |
| CN108328804A (en) * | 2018-04-13 | 2018-07-27 | 湖南科技大学 | A kind of processing method of platiniferous waste water |
| CN109772178A (en) * | 2018-12-17 | 2019-05-21 | 江苏大学 | A kind of preparation method and application of the pyrimethamine molecularly imprinted composite membrane based on the two-sided load of click chemistry |
| CN110078873A (en) * | 2019-04-20 | 2019-08-02 | 太原理工大学 | A kind of preparation method of magnetism carbon-based lithium ion imprinted material |
| CN110227424A (en) * | 2019-06-28 | 2019-09-13 | 江苏大学 | A kind of preparation method and applications of covalent modification high density crown ether functionalization porous adsorbent |
| CN110559868A (en) * | 2019-08-30 | 2019-12-13 | 江苏大学 | Preparation method and application of click chemical imprinting-based o-cloxacillin molecular composite membrane |
| CN110559868B (en) * | 2019-08-30 | 2021-10-12 | 江苏大学 | Preparation method and application of click chemical imprinting-based o-cloxacillin molecular composite membrane |
| CN111229174A (en) * | 2020-01-13 | 2020-06-05 | 江苏大学 | Preparation method and application of Li-IIMs (lithium-ion organic Compounds) ion imprinting membrane |
| CN113509913A (en) * | 2021-04-21 | 2021-10-19 | 东北电力大学 | Preparation method and application of lithium ion imprinting nano composite membrane with high magnetism, high adsorption amount and high selectivity |
| CN113368707A (en) * | 2021-06-02 | 2021-09-10 | 江苏大学 | Preparation method and application of three-dimensional porous MOFs/poly dopamine-based polycarbonate track etching imprinted membrane |
| CN113351180A (en) * | 2021-06-08 | 2021-09-07 | 东北电力大学 | Preparation method and application of temperature response type bionic lithium ion imprinting composite membrane |
| CN113522061A (en) * | 2021-07-21 | 2021-10-22 | 昆明理工大学 | Preparation method of high-adsorption-capacity lithium ion imprinting nano composite membrane |
| CN115364679A (en) * | 2022-07-27 | 2022-11-22 | 中国地质大学（武汉） | Potassium ion selective film and preparation method thereof |
| CN115364679B (en) * | 2022-07-27 | 2023-06-27 | 中国地质大学（武汉） | Potassium ion selective film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106902654B (en) | 2020-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106902654A (en) | A kind of preparation method and application of lithium ion trace polyethersulfone composite membrane | |
| CN108201795B (en) | A kind of preparation method of Selective Separation Enoxacin molecularly imprinted composite membrane material | |
| Sun et al. | Fabrication of highly selective ion imprinted macroporous membranes with crown ether for targeted separation of lithium ion | |
| CN104231166B (en) | A kind of preparation method of bionical artemisinin molecularly imprinted composite membrane | |
| An et al. | Adsorption of heavy metal ions by iminodiacetic acid functionalized D301 resin: Kinetics, isotherms and thermodynamics | |
| Lu et al. | Multilayered ion-imprinted membranes with high selectivity towards Li+ based on the synergistic effect of 12-crown-4 and polyether sulfone | |
| Wei et al. | Design and fabrication of an innovative and environmental friendly adsorbent for boron removal | |
| CN106881069A (en) | A kind of preparation method and application of temperature response type europium ion trace composite membrane | |
| CN107096510B (en) | A kind of preparation method and applications of supermolecule adsorbent | |
| CN108339529B (en) | A kind of preparation method and application of the ion blotting composite membrane for Selective Separation palladium ion | |
| CN105771701B (en) | The preparation method of one metal ion species trace composite membrane | |
| CN105289540B (en) | A kind of method for preparing porous difunctional sorbing material | |
| CN101670274B (en) | Preparation method for novel three-dimensional ordered macroporous chelating resin | |
| CN107511132A (en) | A kind of magnetic ferroferric oxide nano-particles and its Plasma modification method and application | |
| CN107573457A (en) | A kind of poly- N N-isopropylacrylamides of stephanoporate interpenetrating network/alginic acid zirconium gel ball and its preparation method and application | |
| CN109821511A (en) | A kind of preparation and application of polyvinylamine functional magnetic carbon-based nano adsorbent | |
| CN109647232A (en) | A method of cobalt (II) ion blotting composite membrane is prepared with N- methylpyrrole alkyl acrylamide | |
| CN103599757B (en) | The preparation method of a kind of magnetic temp-sensitive type surface strontium ion trace adsorbent | |
| CN105153206B (en) | Two HMeQ[6] microporous supermolecular frame materials as well as preparation and application thereof | |
| CN108160056B (en) | Preparation method of nylon membrane for adsorbing heavy metals | |
| KR101987667B1 (en) | Membrane for metal ion adsorption, method for manufacturing thereof and application thereof | |
| CN113398776A (en) | Preparation method and application of bionic MOFs (metal organic frameworks) -based double-layer molecular imprinting nano composite membrane based on dual continuous imprinting system | |
| CN111440354B (en) | Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure | |
| CN110256726B (en) | Preparation method and application of lead (II) ion imprinting composite membrane | |
| CN101831076B (en) | Silica gel particle surface artemisinin molecularly imprinted polymer and preparation and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |