CN107158964A - A kind of composite film material based on metal organic framework nanometer sheet and graphene oxide, preparation method and the application in gas separation - Google Patents
A kind of composite film material based on metal organic framework nanometer sheet and graphene oxide, preparation method and the application in gas separation Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- 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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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Abstract
A kind of composite film material based on metal organic framework nanometer sheet and graphene oxide and the application in gas separation, belong to membrane material and its separation technology field.Prepare metal oxide nano-sheet at room temperature first, it is paved into composite film material with graphene oxide dispersion by layer-by-layer methods, graphene oxide is as the main body of film, and metal oxide nano-sheet doping is wherein.Obtained composite film material and organic ligand reaction are converted into the graphene oxide composite film material of metal organic framework nanometer sheet doping.It is successful while ultrathin is kept by this strategy, metal-organic framework materials with homogeneous duct are incorporated into membrane material, so as to improve 6 times of separation selectivity relative to simple graphene oxide membrane, obtain membrane material relative to direct method and also lifted substantially.Compare the membrane material of the different numbers of plies, it can be found that as period increases, the selectivity lifting of film is obvious, is optimum value to 4 circulations, declines on the contrary to 5 circulations.
Description
Technical field
The invention belongs to membrane material and its separation technology field, and in particular to one kind based on metal organic framework nanometer sheet and
The composite film material of graphene oxide and its application in gas separation.
Background technology
The separation of compounding substances and purification process are an important steps in industrial production, consume the substantial amounts of energy,
And pollution is generated therewith.Mixed gas typically has close physical property and molecular size, therefore its separation process has one
Fixed challenge.Membrane separating process is relative to traditional separation method, with efficient energy-saving, easy operation, continuous work and sky
Between the advantage such as small.Membrane material is one of core of membrane separating process, and preferable separation membrane material should have high gas to ooze simultaneously
Saturating rate and selectivity.The more membrane materials of research mainly include polymeric membrane and inorganic material film at present.Polymeric membrane because
The advantages such as it is easily worked, low cost have been widely used in separation field.The pore-size distribution heterogeneity and appearance of polymeric membrane
Easily occur plasticizing phenomenon, influence the stability of gas separating property, it is impossible to while reaching high selectivity and permeability.Inorganic point
It is used for more mainly molecular sieve and the metal organic framework film materials of gas Separation Research from film, with homogeneous aperture point
Cloth, can overcome the shortcoming of polymeric membrane, while reaching high selectivity and permeability.This kind of inorganic microporous membrane material typically passes through
Hydro-thermal or solvent-thermal process, easy processing and cost be not high.Researcher is by by macromolecule and inorganic microporous Material cladding
Method prepares mixed substrate membrane containing nano-grade molecular sieve, is used as the solution in the short time.
In recent years, researcher is by by two-dimensional material (graphene oxide, molybdenum disulfide, molecular sieve and the organic bone of metal
Frame nanometer sheet) film forming is prepared, the thickness of film is reduced to lift the performance of film.The composition of single material still suffers from some and asked
Topic, such as graphene oxide (GO) film is that, using lamellar spacing and defect infiltration gas molecule, influence is selective, and with homogeneous hole
The inorganic microporous material nano piece in road is mainly prepared by stripping process from top to down, and scale and yield all receive influence.
The content of the invention
It is an object of the invention to provide a kind of compound film material based on metal organic framework nanometer sheet and graphene oxide
Material, preparation method and its application in gas separation.Metal oxide nano-sheet is prepared at room temperature first, by itself and oxygen
Graphite alkene dispersion liquid is paved into composite film material by layer-by-layer methods, and graphene oxide is used as the main body of film, metal oxide nano
Piece adulterates wherein.Obtained composite film material and organic ligand reaction are converted into the oxygen of metal organic framework nanometer sheet doping
Graphite alkene composite film material.It is successful while ultrathin is kept by this strategy, by the gold with homogeneous duct
Category organic framework material is incorporated into membrane material, so as to improve 6 times of separation selectivity relative to simple graphene oxide membrane.
Involved metal-organic framework materials HKUST-1 (Stephen S.-Y.Chui, Samuel M.-F.Lo,
Jonathan P.H.Charmant,A.Guy Orpen,Ian D.Williams,“A Chemically
Functionalizable Nanoporous Material[Cu3(TMA)2(H2O)3]n”,Science,1999,283,5405,
1148-1150) it is three dimensional skeletal structure that propeller type is formed by metal copper ion and organic ligand trimesic acid (BTC), hole
Road size is that the hydrone for having a weak coordination on 9 Ethylmercurichlorendimides, each copper ion can remove to form unsatuated metal site, for
Carbon dioxide molecule has suction-operated, and the gas separation selectivity of membrane material is lifted by selective absorption.
A kind of preparation of composite film material based on metal organic framework nanometer sheet and graphene oxide of the present invention
Method, its step is as follows：
(1) graphene oxide solution is prepared
Graphene oxide (analysis is pure) and deionized water are hybridly prepared into concentration for 0.05~0.2gL-1Oxidation stone
Black alkene solution, the solution ultrasonic disperse is uniform, labeled as solution A, sealing and standing；
(2) cupric oxide nano piece solution is prepared
Copper nitrate is added into deionized water, concentration is made into for 1~3mmolL-1Copper nitrate solution；Monoethanolamine is added
Deionized water, is made into concentration for 1~2mmolL-1Ethanolamine solutions；Above two solution is mixed in equal volume, it is closed,
Reacted under magnetic agitation 0.5~3 hour, it is then closed at room temperature to stand 20~30 hours, so as to obtain cupric oxide nano piece
Solution, labeled as solution B；
(3) ligand solution is prepared
Trimesic acid is dissolved in the mixed solvent of second alcohol and water, concentration is made into for 0.5~2mmolL-1Trimesic acid it is molten
Liquid, labeled as solution C；Wherein the volume ratio of second alcohol and water is 1：1, sealing and standing；
(4) layer-by-layer methods prepare two-dimentional composite membrane
The solution A and solution B that 5mL is sequentially added into Suction filtration device carry out suction filtration, complete 2~5 circulations；When complete most
One cycle and after draining completely, then add one layer of 1~10mL solution A to bind afterwards, completes preliminary film after draining completely；Then again
10~50mL solution Cs are added into Suction filtration device, cupric oxide nano piece HKUST-1 are converted into, so as to obtain having based on metal
The composite film material of machine skeleton nanometer sheet and graphene oxide.
Composite film material of the present invention can be widely used for mixed gas (H2/CO2,CH4/CO2,N2/CO2) separation, especially
It is for hydrogen and carbon dioxide separation.
Relevant testing conditions of the present invention and method：
SEM (SEM) photo：SEM uses the S4800 SEM of FDAC.
X-ray electronic diffraction (XRD) spectrogram：XRD tests the LabX XRD-6000X light for using Japanese Shimadzu SHIMAZU
Diffractometer.Using Cu launching sites, scanning 2theta scopes are 4-40 °.
AFM (AFM) photo：MultiMode Scanning Probe Microscope.
Transmission electron microscope (TEM) photo：JEOL JEOL JEM-2100.
Gas separation test, uses Wicke-Kallenbach Technique devices
(Angew.Chem.Int.Ed.2006,45,7053-7056), two kinds of gas, vapor and carrier gas Ar are in mass flow controller
Control under enter membrane module from gas cylinder, gas outlet end is controlled the pressure difference at film two ends by counterbalance valve.The gas of transmission is by carrier gas
Purging enters gas-chromatography and checks various gas contents to determine separating effect.
Gas-chromatography (GC) is analyzed：Shimadzu GC2014；Column temperature：50℃；Detector：TCD, the composition of mixed gas is volume
Than 1：1 carbon dioxide and hydrogen.
Brief description of the drawings
Fig. 1：The XRD spectra of HKUST-1@GO composite membranes in embodiment 1-4；
Fig. 2：The front SEM photograph of HKUST-1@GO composite membranes in embodiment 1-4；
Fig. 3：The section SEM photograph of HKUST-1@GO composite membranes in embodiment 1-4；
The standard spectrogram of comparative simulation in Fig. 1, it can be found that the spectrogram peak position of synthesis and the standard spectrogram phase one simulated
Cause, illustrate that membrane material prepared by embodiment 1-4 is doped with HKUST-1.
Fig. 2 is that (right part of flg is left hand view for the front SEM photographs of the HKUST-1@GO composite membranes prepared in embodiment 1-4
Enlarged drawing), a and b are 2 circulations, and c and d are 3 circulations, and e and f are 4 circulations, and g and h are 5 circulations.We are it can be found that remove from figure
The HKUST-1@GO-2 of two circulations are found that defect, the membrane material for being obtained for continuous formation of other circulations.
Fig. 3 is the section SEM photograph of the HKUST-1@GO composite membranes prepared in embodiment 1-4.A is 2 circulations, and b follows for 3
Ring, c is 4 circulations, and d is 5 circulations.The thickness that we obtain film from figure illustrates that we are drawing in 100~300 nanometer ranges
Ultra-thin film thickness is maintained while the HKUST-1 for entering homogeneous duct.
Embodiment
Embodiment 1
(1) graphene oxide solution (solution A) is prepared
Graphene oxide (analysis is pure) product of pioneer's nanometer company is bought, takes graphene oxide and deionized water to be configured to
0.1g·L-1Graphene oxide original content solution.The graphene oxide original solution being configured to is positioned in ultrasonic dispersers and surpassed
Sound disperses, and seals stand for standby use.
(2) cupric oxide nano piece solution (solution B) is prepared
Copper nitrate is accurately weighed with electronic balance in beaker first, plus deionized water and stir acceleration dissolving be made into 2mmol
L-1；Beaker second separately is taken, 1.6mmolL is prepared with deionized water-1Ethanolamine solutions, the solution in beaker first, second is isometric
Mixing.The magneton of clean dry is put into mixed solution beaker along wall of cup, and covers last layer sealed membrane, a large amount of steamings of water are prevented
Hair.The mixed solution beaker of good seal is placed on electronic stirrer, after stirring 1 hour, 25 degrees Celsius are positioned over
Constant temperature 24 hours in vacuum drying chamber.After the completion of cupric oxide nano piece solution is prepared, sealing and standing is standby.
(3) ligand solution (solution C) is prepared
BTC solids are weighed with electronic balance and prepare 1mmolL-1BTC ethanol/water solutions, the volume ratio of second alcohol and water is
1：1, sealing and standing is standby.
(4) layer-by-layer methods prepare two-dimentional composite membrane
Suction filtration device is cleaned and rinsed with deionized water, after drying, the upper Suction filtration device of rationally assembling, with nylon leaching film
(diameter 47mm, aperture 200nm) is used as substrate, it is ensured that after clamp, opens water pump, and appropriate running water is taken with large beaker and is gone
Ionized water is flushed three times respectively, removes suction filtration head, and the water in filtrate bottle is clean, and assembles Suction filtration device again.Prepare
After the completion of work, thin layer deionized water is added on the core of suction filtration head, in order to which next step places nylon support
What can be placed during layer is steady without depositing bubble.Rubber washer is and then put after nylon supporting layer, it is therefore an objective to anti-in placement
Remainder in leak-stopping liquid, assembling, opens Suction filtration device water pump, pours into appropriate amount of deionized water leak test, and flashback is removed if leak
Device simultaneously spreads slight vacuum fat in interface；If water-tight, continue next step.
5mL solution A and B is sequentially added into Suction filtration device, 2 circulations are completed.When completion last time is circulated and is waited
After draining completely, continue again plus one layer of 5mL solution A binds, wait is drained completely.Complete after preliminary film, add 25mL
Solution C is converted, and cupric oxide nano piece is converted into HKUST-1, obtains composite membrane HKUST-1@GO-2.
(5) sign of film
The test of powder X-ray diffraction collection of illustrative plates, SEM, transmission electron microscope, atomic force microscopy are carried out to it
Mirror characterizes and test is separated with mixed gas, and gas test result is as shown in table 1.
Embodiment 2
Step (1) is same as Example 1 to (3).
(4) layer-by-layer methods prepare two-dimentional composite membrane
Suction filtration device is installed and leak test link is same as Example 1.Sequentially added into Suction filtration device 5mL solution A and
B, completes 3 circulations.When complete last time circulate and wait drain completely after, continue again plus one layer of 5mL solution A bind, etc.
Treat to drain completely.Complete after preliminary film to convert, it is necessary to add 25mL solution Cs, doping is reoxidized to the cupric oxide in graphene
Nanometer sheet is converted into HKUST-1, obtains composite membrane HKUST-1@GO-3.
(5) sign of film
The test of powder X-ray diffraction collection of illustrative plates, SEM, transmission electron microscope, atomic force microscopy are carried out to it
Mirror characterizes and test is separated with mixed gas, and gas test result is as shown in table 1.
Embodiment 3
Step (1) is same as Example 1 to (3).
(4) layer-by-layer methods prepare two-dimentional composite membrane
Suction filtration device is installed and leak test link is same as Example 1.Sequentially added into Suction filtration device 5mL solution A and
B, completes 4 circulations.When complete last time circulate and wait drain completely after, continue again plus one layer of 5mL solution A bind, etc.
Treat to drain completely.Complete after preliminary film to convert, it is necessary to add 25mL solution Cs, doping is reoxidized to the cupric oxide in graphene
Nanometer sheet is converted into HKUST-1, obtains composite membrane HKUST-1@GO-4.
(5) sign of film
The test of powder X-ray diffraction collection of illustrative plates, SEM, transmission electron microscope, atomic force microscopy are carried out to it
Mirror characterizes and test is separated with mixed gas, and gas test result is as shown in table 1.
Embodiment 4
Step (1) is same as Example 1 to (3).
(4) layer-by-layer methods prepare two-dimentional composite membrane
Suction filtration device is installed and leak test link is same as Example 1.Sequentially added into Suction filtration device 5mL solution A and
B, completes 5 circulations.When complete last time circulate and wait drain completely after, continue again plus one layer of 5mL solution A bind, etc.
Treat to drain completely.Complete after preliminary film to convert, it is necessary to add 25mL solution Cs, doping is reoxidized to the cupric oxide in graphene
Nanometer sheet is converted into HKUST-1, obtains composite membrane HKUST-1@GO-5.
(5) sign of film
The test of powder X-ray diffraction collection of illustrative plates, SEM, transmission electron microscope, atomic force microscopy are carried out to it
Mirror characterizes and test is separated with mixed gas, and gas test result is as shown in table 1.
Comparative example 1
Step (1) is same as Example 1.
(2) pure GO two-dimensional films are prepared
Suction filtration device is installed and leak test link is same as Example 1.25mL solution A is added into Suction filtration device, is waited
Drain completely, obtain pure GO films.
(3) sign of film
Mixed gas separation test is carried out to it, gas test result is as shown in table 1.
Comparative example 2
Step (1) is same as Example 1 to (3).
(4) direct mixing method prepares two-dimentional composite membrane
Suction filtration device is installed and leak test link is same as Example 1.40mL is taken to add after isometric solution A and B are mixed
Enter into Suction filtration device, wait is drained completely.Complete after preliminary film to convert, it is necessary to add 25mL solution Cs, doping is reoxidized
Cupric oxide nano piece in graphene is converted into HKUST-1, obtains composite membrane HKUST-1@GO-m.
(5) sign of film
The test of powder X-ray diffraction collection of illustrative plates, SEM and mixed gas separation test are carried out to it, gas is surveyed
Test result is as shown in table 1.
Table 1：Embodiment 1-4 and comparative example 1-2 films gas separating property data
By contrast it can be found that relative to pure GO films, the gas separation selectivity of HKUST-1@GO-4 membrane materials is lifted
It is 6 times or so, relative with direct method to obtain membrane material and also improve substantially.Compare the membrane material of the different numbers of plies, it can be found that with
Period increase, the selectivity lifting of film is obvious, is optimum value to 4 circulations, declines on the contrary to 5 circulations.
Claims (4)
1. a kind of preparation method of the composite film material based on metal organic framework nanometer sheet and graphene oxide, its step is such as
Under：
(1) graphene oxide solution is prepared
Graphene oxide (analysis is pure) and deionized water are hybridly prepared into concentration for 0.05~0.2gL-1Graphene oxide
Solution, the solution ultrasonic disperse is uniform, labeled as solution A, sealing and standing；
(2) cupric oxide nano piece solution is prepared
Copper nitrate is added into deionized water, concentration is made into for 1~3mmolL-1Copper nitrate solution；By monoethanolamine add go from
Sub- water, is made into concentration for 1~2mmolL-1Ethanolamine solutions；Above two solution is mixed in equal volume, in closed, magnetic force
The lower reaction of stirring 0.5~3 hour, it is then closed at room temperature to stand 20~30 hours, so that cupric oxide nano piece solution is obtained,
Labeled as solution B；
(3) ligand solution is prepared
Trimesic acid is dissolved in the mixed solvent of second alcohol and water, concentration is made into for 0.5~2mmolL-1Trimesic acid solution,
Labeled as solution C；Wherein the volume ratio of second alcohol and water is 1：1, sealing and standing；
(4) layer-by-layer methods prepare two-dimentional composite membrane
Using nylon leaching film as substrate, the solution A and solution B that 5mL is sequentially added into Suction filtration device carry out suction filtration, complete 2~5
Circulation；After completing last time circulation and draining completely, then add one layer of 1~10mL solution A to bind, completed just after draining completely
Step film；Then 10~50mL solution Cs are added into Suction filtration device again, cupric oxide nano piece is converted into HKUST-1, so that
To the composite film material based on metal organic framework nanometer sheet and graphene oxide.
2. a kind of composite film material based on metal organic framework nanometer sheet and graphene oxide, it is characterised in that：It is by right
It is required that the method described in 1 is prepared.
3. a kind of composite film material based on metal organic framework nanometer sheet and graphene oxide described in claim 2 is in gas
Application in separation.
4. a kind of composite film material based on metal organic framework nanometer sheet and graphene oxide as claimed in claim 3 is in gas
Application in body separation, it is characterised in that：For separating hydrogen and carbon dioxide.
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