CN106731885A - A kind of metal organic framework/metal nano ion composite filtering film and its preparation method and application - Google Patents
A kind of metal organic framework/metal nano ion composite filtering film and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of metal organic framework/metal nano ion composite filtering film and its preparation method and application, metal organic framework/metal nano ion composite filtering film is prepared first, then the metal organic framework/metal nano ion composite filtering film is fitted into biofilter, organic pollutant solution is fitted into needle tubing, the metal organic framework/absorption of the metal nanoparticle composite filtering film to organic pollution is realized by injecting filtration method, surface-enhanced Raman detection is finally directly carried out.Preparation method material requested of the present invention is simple, while the composite filtering film for preparing is stable in properties, can recycle, and cost is relatively low.Organic backbone/metal nano ion composite filtering film energy fast enriching organic pollutant molecule prepared by the present invention, mating surface enhancing Raman spectrum realizes the quick detection to organic pollution.
Description
Technical field
It is compound the invention belongs to technical field of composite materials, more particularly to a kind of metal organic framework/metal nano ion
Filter membrane and its preparation method and application.
Background technology
Unreasonable production and abuse with a large amount of chemicals, environmental monitoring are also on the rise with governing problem.Life is dirty
Water, industrial wastewater are unprocessed just to be discharged in environment, crude oil leakage, and the leakage of nuclear radiation thing is all the important of water environment pollution
Source.The species of water pollutant is a lot, and organic pollution is a wherein major class.Organic dyestuff rhodamine B, food additives Soviet Union
Red I, melamine etc. is all main organic pollution in water body environment, and they have carcinogenic, teratogenesis, and mutagenic murder by poisoning is made
With, it is difficult to degrade, aqueous bio is caused harm, trigger the phenomenons such as red tide, and by food chain enrichment, serious harm people
Class health.
Metal organic framework (MOF) is to compare table with super large by what coordination was formed by metal ion and organic ligand
The porous material of area, because the diversity of metal ion and organic ligand makes it in adsorbing separation, gas storage, pharmaceutical carrier
With release, the field such as catalysis and thin-film device is with a wide range of applications.Metal organic framework is selectively adsorbing and separating master
To include following several：Selective absorption based on size/shape screening；Based on adsorbed material and metal organic framework surface
The different selective absorption of interaction force；The joint effect of the selective absorption effect based on first two.In liquid phase selective
In adsorption process, traditional adsorption method is that metal organic framework powder is soaked in containing carrying out in the solution with binding molecule.
The Chinese patent literature of the A of Publication No. CN 104497055 discloses a kind of preparation of metal-organic framework materials
Method, further discloses the cigarette filter rod and application that with the addition of metal organic framework MOF (Fe) material described above, passes through
Harmful components are such as in cigarette filter rod, in can effectively reducing cigarette mainstream flue gas for addition metal organic framework MOF (Fe) materials
The content of ammonia and benzo [a] pyrene.And it is environmentally friendly, ensure that the security to human body after cigarette added material.Meanwhile,
Metal organic framework MOF (Fe) the materials adsorption capacity superpower to organic dye pollutant, is worthy of popularization.The patent table
Show that adsorption rate depends on molecule diffusion process, it is typically time-consuming more long, and it is not related to Raman detection.
Raman spectrum belongs to molecular vibration spectrum as infrared spectrum, can be with the feature structure of reaction molecular.It is infrared
Spectrum is molecule to the spectrum produced by the absorption of infrared light supply, and Raman spectrum is molecule to produced by the scattering of visible ray
Spectrum.But Raman spectrum effect is very weak, only the 10 of incident intensity-6~10-9, significantly limit its development.Surface
Enhancing Raman spectrum is a kind of related corresponding spectrum of enhancement effect of the Rough Metal Surfaces such as utilization gold, silver, copper, except with drawing
Outside the characteristics of graceful spectrum high resolution, its sensitivity is very high, and test limit can reach single molecules level.Therefore surface increases
Strong Raman technology is suitable for trace and the ultra trace detection of environmental contaminants.
The content of the invention
The technical problem to be solved in the present invention be to provide it is a kind of it is easy to operate, inexpensive, with surface reinforced Raman active
Metal organic framework/metal nanoparticle composite filtering film, and using the combined filtration film combination injection filtration method realize
Organic pollution quick detection.
A kind of preparation method of metal organic framework/metal nano ion composite filtering film, comprises the following steps：
(1) metal nanoparticle is prepared；
(2) metal nanoparticle is assembled on film matrix by chemical bond, obtains metal nanoparticle assembling film；
(3) metal nanoparticle assembling film obtained in step (2) is added sequentially to bridging agent, metal salt solution and organic
Reacted in ligand solution, in surfaces of metal nanoparticles growth in situ metal organic framework, obtain final product metal organic framework/metal and receive
Rice ion composite filtering film.
Preferably, in step (1), using conventional liquid phase reduction reducing metal salt, preparing metal nanoparticle.
Preferably, the metal nanoparticle particle diameter is 20~150nm, and in the particle size range, metal nanoparticle
Surface enhanced best results.
The metal nanoparticle has surface plasma body resonant vibration activity, preferably, the metal nanoparticle is
Golden nanometer particle or Nano silver grain.
Preferably, in step (2), metal nanoparticle is assembled on film matrix using silane coupler.
In step (3), the bridging agent is the ethanol solution of TGA, the concentration of the ethanol solution of the TGA
It is 0.01~0.03mM, the reaction time is 22~36 hours, and reaction temperature is 20~30 DEG C.
In step (3), the metal salt solution is the ethanol solution of six nitric hydrate chromium, the concentration of the metal salt solution
It is 1.5~3mM, the reaction time is 10~20min, and reaction temperature is 60~80 DEG C.
In step (3), the organic ligand solution for terephthalic acid (TPA) ethanol solution, the organic ligand solution it is dense
It is 1.5~3mM to spend, and the reaction time is 20~40min, and reaction temperature is 60~80 DEG C.
Present invention also offers a kind of metal organic framework/metal nano ion composite filtering film, including film matrix, metal
Nanoparticle layers and metal organic framework layer, are prepared by above-mentioned method.
In the metal organic framework/metal nano ion composite filtering film, metal organic framework is rich in metal ion
Unoccupied orbital, is conducive to the Coordination Adsorption of polarity organic pollution；The phenyl ring hole wall that the organic ligand of metal organic framework is provided, has
Beneficial to the π containing phenyl ring or aromatic hydrocarbon-pi-conjugated absorption.
Present invention also offers a kind of application of metal organic framework/metal nano ion composite filtering film, by the gold
Category organic backbone/metal nanoparticle composite filtering film is fitted into biofilter, and organic pollutant solution is fitted into needle tubing,
The metal organic framework/absorption of the metal nanoparticle composite filtering film to organic pollution is realized by injecting filtration method.
Using the extra specific surface area of metal organic framework in composite filtering film and the pore space structure of periodic arrangement to molten
Organic pollution is largely adsorbed in liquid；Using inject filtration method by organic pollutant solution and the metal organic framework/
Metal nanoparticle composite filtering film is quickly fully contacted, and shortens the time that the composite filtering film adsorbs organic pollution.
Preferably, direct to the metal organic framework/metal nanoparticle composite filtering film after absorption organic pollution
Carry out surface-enhanced Raman detection.Composite filtering film and the surface with high-sensitivity detection ability with superpower adsorption capacity
Enhancing Raman spectrum is combined, and greatly reduces the test limit of organic pollution in solution.
Compared with prior art, the invention has the advantages that：
(1) method for preparing metal organic framework/metal nano ion composite filtering film of the invention is convenient, material requested letter
It is single, while the metal organic framework/metal nano ion composite filtering film for preparing can be reclaimed as SERS base properties stabilization
Utilize, cost is relatively low.
(2) present invention compared with absorption method is soaked, effectively shortens adsorption time using filtration method is injected.
(3) metal organic framework/metal nanoparticle composite filtering film has stronger Raman active in the present invention.
(4) present invention by the metal organic framework with superpower adsorption capacity with have high-sensitivity detection ability surface
Enhancing Raman spectrum is combined, and greatly reduces the test limit of organic pollution in solution.
Brief description of the drawings
Fig. 1 is the preparation method flow chart of metal organic framework of the present invention/metal nano ion composite filtering film；
Fig. 2 is the application schematic diagram of metal organic framework of the present invention/metal nano ion composite filtering film；
Fig. 3 is the Nano silver grain transmission electron microscope picture of preparation in embodiment 1；
Fig. 4 is the Nano silver grain uv absorption spectra of preparation in embodiment 1；
Fig. 5 is to adsorb the Raman spectrum curve of the perylenes Shang MIL-101/ Nano silver grain composite filtering films in embodiment 1；
Fig. 6 is the Raman spectrum that the naphthalene on MIL-101/ silver cubic nanometer particle composite filtering films is adsorbed in embodiment 2
Curve；
Fig. 7 is the Raman spectrum that acenaphthene on MIL-101/ gold nano rod-shaped particle composite filtering films is adsorbed in embodiment 3
Curve；
Fig. 8 is the Raman spectrum that the perylenes Shang MIL-101/ silver triangular nano particle composite filtering films are adsorbed in embodiment 4
Curve；
Fig. 9 is the Raman spectrum after recycling MIL-101/ Nano silver grain composite filtering film Xi Fu perylenes in embodiment 5
Curve；
After Figure 10 to the attached MIL-101/ Nano silver grain combined filtration film layers for having perylene of suction in embodiment 5 to elute
Raman spectrum curve.
Specific embodiment
The preparation method flow chart of metal organic framework of the present invention/metal nano ion composite filtering film is as shown in figure 1, gold
The application schematic diagram for belonging to organic backbone/metal nano ion composite filtering film is as shown in Figure 2.
Embodiment 1
Prepare MIL-101/ Nano silver grain composite filtering films
(1) preparation of Nano silver grain
It is 10 by 20ml concentration-2The silver nitrate aqueous solution of M, 20ml mass fractions are that 1% sodium citrate aqueous solution is dissolved in
80ml deionized waters are well mixed；100ml freshly prepared 10 is added with vigorous stirring-2M sodium borohydride aqueous solutions；By gained
Mixed solution be further stirred at room temperature a hour, obtain the silver sol solution of yellow green.Fig. 3 is Nano silver grain
Transmission electron microscope figure (TEM), as can be seen from the figure Nano silver grain is uniform in size, and particle diameter distribution is at 25~35 nanometers
Between；Fig. 4 is the uv absorption spectra of the Nano silver grain, has a maximum absorption band in 385 nanometers, and peak width is very
It is narrow, also prove the uniform in size of the Nano silver grain and be distributed between 25~35 nanometers.
(2) preparation of Nano silver grain assembling film
2ml 3- aminopropyls-trimethoxy silane and 25ml methyl alcohol are sufficiently mixed, 3- aminopropyls-trimethoxy is made
Base silane solution, then by thickness for the glass fiber filter of 30mm is placed in 3- aminopropyls-trimethoxy silane solution
It is modified, then is rinsed well with isopropanol within one day, 110 DEG C is annealed 10 minutes, and storage is in an inert atmosphere.By modified filter
Film is immersed in the silver sol growth from solution Nano silver grain of step (1) preparation, and distilled water flushing is clean after having grown, and obtains silver-colored
Nano-particle assembling film, is placed on preservation in distilled water.
(3) preparation of MIL-101/ Nano silver grains composite filtering film
During Nano silver grain assembling film is immersed into 10mL concentration for the ethanol solution of the TGA of 0.03mM, surpass at room temperature
Sound concussion reaction is taken out after 24 hours, then with respectively washing three times of distilled water and absolute ethyl alcohol, obtains TGA-nano grain of silver
Sub- assembling film, and the assembling film is placed in standby in absolute ethyl alcohol.By TGA prepared above-Nano silver grain assembling film
For in the ethanol solution of six nitric hydrate chromium of 2mM, after reaction 15 minutes, it is 2mM to benzene to be added to 4mL concentration to immersion concentration
In the ethanol solution of dioctyl phthalate, reaction is taken out after 30 minutes and uses absolute ethanol washing, and whole reaction temperature is maintained at 70 DEG C；Follow
Ring above-mentioned steps 5 times, obtain final product MIL-101/ Nano silver grain composite filtering films.
(4) filtration method quick adsorption You machine Wu Ran Wu perylenes are injected
First MIL-101/ Nano silver grain composite filtering films are fitted into biofilter, are then 10 by concentration-6M perylenes
Ethanol solution loads injection needle and is injected through MIL-101/ Nano silver grain combined filtration film layers, carries out quick adsorption.Injection
After the completion of Raman detection is carried out to filter membrane.Fig. 5 is adsorbed on MIL-101/ Nano silver grain composite filtering films in embodiment 1
The Raman spectrum curve of perylenes, 1293,1361 and 1566cm-1Shi perylene Characteristic Ramans peak, 1441,1613cm-1It is MIL-101 special
Peak is levied, illustrates that the MIL-101/ Nano silver grain composite filtering film Dui perylenes have suction-operated and good SERS effects.
Embodiment 2
Prepare MIL-101/ silver cubic nanometer particle composite filtering films
(1) preparation of silver-colored cubic nanometer particle
90mg silver nitrates, 110mg polyvinylpyrrolidones, 20ml ethylene glycol and 1mg sodium chloride are placed in 50ml polytetrafluoros
In ethylene reaction container, dissolving is sufficiently stirred for.The mixed solution is placed in micro-wave oven again carry out heating response 2 under 320 watts
Minute, you can obtain a diameter of 55 nanometers of silver-colored cubic nanometer particle
(2) preparation of silver-colored cubic nanometer particle self-assembled film
2ml 3- mercaptopropyl-trimethoxies silane and 25ml isopropanols are sufficiently mixed, 3- mercaptopropyis-front three is made
TMOS solution, then by thickness for the glass fiber filter of 37mm is placed on 3- mercaptopropyl-trimethoxy solution of silane
In be modified within one day, then rinsed well with isopropanol, 110 DEG C are annealed 10 minutes, and storage is in an inert atmosphere.Will be modified
Filter membrane grows silver-colored cubic nanometer particle in being immersed in the silver-colored cubic nanometer colloidal sol of step (1) preparation, distillation after having grown
Water is rinsed well, obtains silver-colored cubic nanometer particle self-assembled film, is placed on preservation in distilled water.
(3) preparation of MIL-101/ silver cubic nanometer particle composite filtering film
Silver-colored cubic nanometer particle assembling film is immersed in the ethanol solution of the TGA that 10mL concentration is 0.03mM, room temperature
Lower ultrasonic vibration takes out after reacting 24 hours, then with respectively washing three times of distilled water and absolute ethyl alcohol, obtains TGA-Yin Li
Square nano-particle assembling film, and the assembling film is placed in standby in absolute ethyl alcohol.TGA-silver cube prepared above is received
During rice corpuscles assembling film immersion concentration is for the ethanol solution of the six nitric hydrate chromium of 2mM, after reacting 15 minutes, 4mL is added to dense
Spend in the ethanol solution for the terephthalic acid (TPA) of 2mM, reaction is taken out after 30 minutes and uses absolute ethanol washing, whole reaction temperature
It is maintained at 70 DEG C；Circulation above-mentioned steps 5 times, obtain final product MIL-101/ silver cubic nanometer particle composite filtering films.
(4) filtration method quick adsorption organic pollution naphthalene is injected
First MIL-101/ silver cubic nanometer particle composite filtering films are fitted into biofilter, are then 10 by concentration-5M
Naphthalene solution load injection needle and be injected through MIL-101/ silver cubic nanometer particle composite filtering films, carry out quick adsorption.Note
Raman detection is carried out to filter membrane after the completion of penetrating.Fig. 6 is to adsorb in embodiment 2 to be combined in MIL-101/ silver cubic nanometer particles
The Raman spectrum curve of the naphthalene on filter membrane, 1581 and 1068cm-1It is naphthalene Characteristic Raman peak, 1441,1613cm-1It is MIL-101 special
Peak is levied, illustrates that MIL-101/ silver cubic nanometer particle combined filtrations have suction-operated and good SERS effects to naphthalene.
Embodiment 3
Prepare MIL-101/ gold nanorods composite filtering films
(1) preparation of gold nano rod-shaped particle
A) preparation of spherical gold seeds：It is 5x10 by 10ml concentration-4The aqueous solution of chloraurate of M is 0.2M's with 10ml concentration
Cetyltrimethylammonium base ammonia is well mixed to be configured to mixed solution, is the boron of the ice of 0.01M Fresh by 1.2ml concentration
Sodium hydride aqueous solution is added in the mixed solution, is sufficiently stirred for 2 minutes, after waiting solution to be transformed into brown color, stand at room temperature to
It is few 10 minutes.Obtained spherical gold is planted diameter and is about 3 nanometers.
B) preparation of gold nanorods：It is 0.01M aqueous solution of chloraurate and the nitre that 0.3ml concentration is 0.01M by 2.5ml concentration
The sour silver aqueous solution, 47.5ml concentration are 0.1M ascorbic acid for the cetyltrimethylammonium base ammonia and 0.275ml concentration of 0.1M
The aqueous solution is uniformly mixing to obtain mixed solution.Finally, the spherical gold seeds solution of the above-mentioned preparations of 0.06ml is added to allow it to give birth to
It is long, it is gentle to be inverted 10 seconds, 10 hours are stood, then, taking precipitate dispersion. in 7000 rpms of lower centrifuge washings 30 minutes twice
Preserved in ultra-pure water.Long DEG C of obtained gold nanorods are 49 nanometers, and diameter is about 19 nanometers.
(2) preparation of gold nano rod-shaped particle self-assembled film
2ml 3- aminopropyls-trimethoxy silane and 25ml methyl alcohol are sufficiently mixed, 3- aminopropyls-trimethoxy is made
Base silane solution, then by thickness for the glass fiber filter of 30mm is placed in 3- aminopropyls-trimethoxy silane solution
It is modified, then is rinsed well with isopropanol within one day, 110 DEG C is annealed 10 minutes, and storage is in an inert atmosphere.By modified filter
Film grows the bar-shaped particle assembling film of gold nano in being immersed in the bar-shaped colloidal sol of gold nano of step (1) preparation, after having grown
Distilled water flushing is clean, obtains gold nano rod-shaped particle self-assembled film, is placed on preservation in distilled water.
(3) preparation of MIL-101/ gold nanos rod-shaped particle composite filtering film
The bar-shaped particle assembling film of gold nano is immersed in the ethanol solution of the TGA that 10mL concentration is 0.03mM, room temperature
Lower ultrasonic vibration takes out after reacting 24 hours, then with respectively washing three times of distilled water and absolute ethyl alcohol, obtains TGA-Jenner
Rice rod-shaped particle assembling film, and the assembling film is placed in standby in absolute ethyl alcohol.By TGA-gold nanorods prepared above
During shape particle assembling film immersion concentration is for the ethanol solution of the six nitric hydrate chromium of 2mM, after reacting 15 minutes, 4mL is added to dense
Spend in the ethanol solution for the terephthalic acid (TPA) of 2mM, reaction is taken out after 30 minutes and uses absolute ethanol washing, whole reaction temperature
It is maintained at 70 DEG C；Circulation above-mentioned steps 5 times, obtain final product MIL-101/ gold nano rod-shaped particle composite filtering films.
(4) filtration method quick adsorption organic pollution acenaphthene is injected
MIL-101/ gold nano rod-shaped particle composite filtering films are fitted into biofilter first, are then by concentration
10-6The ethanol solution of M acenaphthenes loads injection needle and is injected through combined filtration film layer, carries out quick adsorption.To mistake after the completion of injection
Filter membrane carries out Raman detection.Fig. 7 is the acenaphthene adsorbed on MIL-101/ gold nano rod-shaped particle composite filtering films in embodiment 3
Raman spectrum curve, 1379 and 1241cm-1It is acenaphthene Characteristic Raman peak, 1441,1613cm-1It is MIL-101 characteristic peaks, explanation
MIL-101/ gold nano rod-shaped particle composite filtering films have suction-operated and good SERS effects to acenaphthene.
Embodiment 4
Prepare MIL-101/ silver triangular nano particle composite filtering films
(1) preparation of silver-colored triangular nano particle
A) preparation of silver-colored crystal seed：By 5ml concentration for the sodium citrate aqueous solution of 2.5mM is placed in three-necked bottle, magnetic agitation
Device starts to stir (500 rpms) at room temperature, sequentially adds the polyphenyl sulfonic acid that 0.25ml mass fractions are 500 milligrams per liter
Sodium water solution and 0 DEG C of 0.3ml concentration of preservation are 10mM sodium borohydride aqueous solutions, often add a solution, stir 2 minutes and mix
Uniformly, it is the silver nitrate aqueous solution of 0.5mM then to add 5ml concentration in constant pressure titration funnel, keeps per minute with 2 milliliters
Speed is uniformly instilled in mixed liquor.With the addition of silver nitrate aqueous solution, the mixed solution color in three-necked bottle can gradually occur
Change, slowly turns yellow, and is finally presented faint yellow.Silver nitrate aqueous solution completion of dropping is treated, is kept stirring for 5 minutes, at this moment obtained
It is seed-solution, it is stand-by.
B) growth of Nano Silver triangle：5ml deionized waters are added in clean three-necked bottle, 75 microlitres of concentration of injection are 10mM
Aqueous ascorbic acid, add 100 microlitres of upper obtained seed-solutions of step.Then, continuation constant pressure titrates funnel and adds
3ml concentration is the silver nitrate aqueous solution of 0.5mM, current low speed be maintained at 1 milliliter it is per minute, the color of mixed solution is from most opening
What is begun is faint yellow, is changed into orange, red, and purple is blue, light blue to treat completion of dropping up to green, is rapidly injected 0.5ml dense
Spend the sodium citrate aqueous solution for 25mM.
(2) preparation of silver-colored triangular nano particle self-assembled film
2ml 3- aminopropyls-trimethoxy silane and 25ml methyl alcohol are sufficiently mixed, 3- aminopropyls-trimethoxy is made
Base silane solution, then by thickness for the glass fiber filter of 40mm is placed in 3- aminopropyls-trimethoxy silane solution
It is modified, then is rinsed well with isopropanol within one day, 110 DEG C is annealed 10 minutes, and storage is in an inert atmosphere.By modified filter
Film grows silver-colored triangular nano particle assembling film in being immersed in the silver-colored triangular nano colloidal sol of step (1) preparation, after having grown
Distilled water flushing is clean, obtains silver-colored triangular nano particle self-assembled film, is placed on preservation in distilled water.
(3) preparation of MIL-101/ silver triangular nano particle composite filtering film
Silver-colored triangular nano particle assembling film is immersed in the ethanol solution of the TGA that 10mL concentration is 0.03mM, room temperature
Lower ultrasonic vibration takes out after reacting 24 hours, then with respectively washing three times of distilled water and absolute ethyl alcohol, obtains TGA-silver three
Angle nano-particle assembling film, and the assembling film is placed in standby in absolute ethyl alcohol.TGA prepared above-silver triangle is received
During rice corpuscles assembling film immersion concentration is for the ethanol solution of the six nitric hydrate chromium of 2mM, after reacting 15 minutes, 4mL is added to dense
Spend in the ethanol solution for the terephthalic acid (TPA) of 2mM, reaction is taken out after 30 minutes and uses absolute ethanol washing, whole reaction temperature
It is maintained at 70 DEG C；Circulation above-mentioned steps 5 times, obtain final product MIL-101/ silver triangular nano particle composite filtering films.
(4) filtration method quick adsorption You machine Wu Ran Wu perylenes are injected
MIL-101/ silver triangular nano particle composite filtering films are fitted into biofilter first, are then by concentration
10-6The ethanol solution of M perylenes loads injection needle and is injected through MIL-101/ silver triangular nano particle composite filtering films, carries out quick
Absorption.Raman detection is carried out to filter membrane after the completion of injection.Fig. 8 is adsorbed in embodiment 4 in MIL-101/ silver triangular nano grains
The Raman spectrum curve of perylenes Shang sub- composite filtering film, 1293,1361 and 1566cm-1Shi perylene Characteristic Ramans peak, 1441,
1613cm-1It is MIL-101 characteristic peaks, illustrates that MIL-101/ silver triangular nano particle composite filtering film Dui perylenes have suction-operated
And good SERS effects.
Embodiment 5
The test of MIL-101/ Nano silver grain composite filtering film cycle performances：
(1) the MIL-101/ Nano silver grain composite filtering films prepared in embodiment 1 are fitted into biofilter, then
It is 1.0 × 10 by concentration-4The ethanol solution of M perylenes loads injection needle and is injected through MIL-101/ Nano silver grain composite filtering films
Layer, carries out quick adsorption, and Raman detection is carried out to filter membrane after the completion of injection, and now SERS signal is designated as recycling for the first time
Signal.
(2) and then by the attached MIL-101/ Nano silver grain combined filtrations film layer for having perylene of the suction supersound washing in methyl alcohol is immersed
15 minutes, clean three times altogether.Raman detection is carried out after drying, now SERS signal is designated as the first time signal of elution experiments,
Check whether the MIL-101/ Nano silver grain combined filtration film layers elute totally.
(3) after wash-out is clean, it is 1.0 × 10 to continue by " injection filtration method " adsorption concentration in step (1)-4M perylenes
Ethanol solution, Raman detection is carried out after the completion of injection to filter membrane, and now SERS signal is designated as recycling second signal, with
MIL-101/ Nano silver grain combined filtration film layers are eluted using the method in step (2) afterwards, after cleaning is dried every time
Raman detection is carried out, so circulation four times.
Fig. 9 and Figure 10 are the experimental results of embodiment 5.Wherein, Fig. 9 is combined to recycle MIL-101/ Nano silver grains
Raman spectrum curve after filter membrane Xi Fu perylenes, wherein, the Raman signal that curve (a) is obtained when being and using for the first time, curve (b)
It is the Raman signal obtained when recycling second, curve (c) is to recycle the Raman signal obtained during third time, curve
D Raman signal that () obtains when being and recycling the 4th time.It can be seen from Fig. 9, the SERS signal for obtaining almost phase is detected every time
Together, signal is not decayed, and illustrates that MIL-101/ Nano silver grains composite filtering film can repeat Xi Fu perylenes, and reuse timeliness
It is really constant.Figure 10 is to be set a song to music to inhaling the Raman light after the attached MIL-101/ Nano silver grain combined filtration film layers for having perylene are eluted
Line, wherein, curve (a) is the Raman signal that obtains after wash-out for the first time, and curve (b) is the Raman letter obtained after second wash-out
Number, curve (c) is the Raman signal that obtains after third time wash-out, and curve (d) is the Raman signal obtained after the 4th wash-out.Root
Understood according to Figure 10, the MIL-101/ Nano silver grain combined filtration film layers after wash-out do not detect the SERS letters of the perylene mutually answered
Number, illustrate that inhaling the attached MIL-101/ Nano silver grain combined filtration film layers for having perylene has cleaned up.Illustrate that the MIL-101/ silver is received
Rice corpuscles combined filtration film layer can be reused as SERS substrates, and cleaning is simple.
Claims (9)
1. the preparation method of a kind of metal organic framework/metal nano ion composite filtering film, it is characterised in that including following step
Suddenly：
(1) metal nanoparticle is prepared；
(2) metal nanoparticle is assembled on film matrix by chemical bond, obtains metal nanoparticle assembling film；
(3) metal nanoparticle assembling film obtained in step (2) is added sequentially to bridging agent, metal salt solution and organic ligand
In solution react, in surfaces of metal nanoparticles growth in situ metal organic framework, obtain final product metal organic framework/metal nano from
Sub- composite filtering film.
2. the preparation method of metal organic framework according to claim 1/metal nano ion composite filtering film, its feature
It is that the metal nanoparticle particle diameter is 20~150nm.
3. the preparation method of metal organic framework according to claim 1/metal nano ion composite filtering film, its feature
It is that the metal nanoparticle is golden nanometer particle or Nano silver grain.
4. the preparation method of metal organic framework according to claim 1/metal nano ion composite filtering film, its feature
It is in step (2), metal nanoparticle to be assembled on film matrix using silane coupler.
5. the preparation method of metal organic framework according to claim 1/metal nano ion composite filtering film, its feature
It is that in step (3), the metal salt solution is the ethanol solution of six nitric hydrate chromium, and the concentration of the metal salt solution is
1.5~3mM.
6. the preparation method of metal organic framework according to claim 1/metal nano ion composite filtering film, its feature
It is that in step (3), the organic ligand solution is the ethanol solution of terephthalic acid (TPA), the concentration of the organic ligand solution
It is 1.5~3mM.
7. a kind of metal organic framework/metal nano ion composite filtering film, it is characterised in that the metal organic framework/gold
Category nanoparticle composite filtering film includes film matrix, metal nanoparticle layer and metal organic framework layer, by claim 1~6
Method described in any one is prepared.
8. a kind of application of metal organic framework according to claim 7/metal nano ion composite filtering film, its feature
It is that the metal organic framework/metal nanoparticle composite filtering film is fitted into biofilter, organic pollution is molten
Liquid is fitted into needle tubing, realizes the metal organic framework/metal nanoparticle composite filtering film to organic by injecting filtration method
The absorption of pollutant.
9. the application of metal organic framework according to claim 8/metal nano ion composite filtering film, its feature exists
In, to absorption organic pollution after metal organic framework/metal nanoparticle composite filtering film directly carry out surface enhanced drawing
Graceful detection.
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