CN106178982A - A kind of preparation method of the metal organic framework film inverting based on subcarbonate - Google Patents
A kind of preparation method of the metal organic framework film inverting based on subcarbonate Download PDFInfo
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- CN106178982A CN106178982A CN201610581538.5A CN201610581538A CN106178982A CN 106178982 A CN106178982 A CN 106178982A CN 201610581538 A CN201610581538 A CN 201610581538A CN 106178982 A CN106178982 A CN 106178982A
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- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/32—By heating or pyrolysis
Abstract
The preparation method of a kind of metal organic framework film inverting based on subcarbonate, belongs to technical field of membrane separation.Prepare Porous Cu substrate and it is carried out pretreatment；The precursor solution of differently configured subcarbonate；Put in the precursor solution of subcarbonate at the bottom of the cuprio that will handle well, under certain condition, at substrate surface in-situ preparation subcarbonate nano-array；To be modified with at the bottom of the cuprio of subcarbonate nano-array in the ligand solution putting into different MOF, subcarbonate slowly dissolves release metal ions and part generation coordination in carboxylic acids organic ligand, thus generates continuous print MOF film at substrate surface.The invention provides the preparation method of a kind of novel metal organic framework film.By subcarbonate nano-array inverting generation continuous print MOF film, effectively increasing the adhesion between MOF film and substrate, technique is simple, easy to implement, beneficially large-scale promotion application.
Description
Technical field
The present invention relates to the technology of preparing of a kind of metal-organic framework film, specifically provide one and receive with subcarbonate
Rice array modifies substrate the method preparing metal-organic framework film as unique metal source, belongs to membrance separation field.
Background technology
Membrance separation as a kind of novel isolation technics, have simple to operate, energy consumption is low, good separating effect, dirty without secondary
The features such as dye, receive more and more attention.The character of membrane material is one of key factor affecting membrane separating effect, metal-
Organic backbone (metal-organic framework, MOF) is built into organic ligand by metal ion (or metal cluster)
There is the crystalline material of periodic network structure, there is the advantages such as porous, hole dimension and surface nature scalable, deposit at gas
Storage and separation aspect have potential using value.By MOF materials application in membrane separation technique, its distinctive structure can design, hole
Road size adjustable and can the feature such as functionalization, the separating property improving film is had decisive role.Therefore, MOF is with the shape of film
State is used for separating, and is expected to obtain important breakthrough.MOF belongs to crystalline state coordination compound, and itself enbrittles, it is necessary to depended on certain machine
The perforated substrate of tool intensity could be used for follow-up gas and separate.But heterogeneous nucleation makes MOF be difficult to and inert perforated substrate
Form good adhesion, so the MOF film that preparation is the finest and close on perforated substrate must solve the boundary between MOF and substrate
Face combines problem.The invention provides a kind of novel film-forming method, using subcarbonate nano-array modify substrate and as
The method of metal-organic framework film is prepared in unique metal source.Subcarbonate nano-array is grown directly upon on substrate so that
The MOF film of its inverting generation is effectively fixed in substrate, preferably solves the interface cohesion problem between MOF and substrate,
Improve the stability of MOF film.The method can prepare different metal base MOF film, at MOF by changing different subcarbonates
The preparation field of film has important scientific value.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of MOF film inverting based on subcarbonate.By many
In-situ modification subcarbonate nano-array at the bottom of the cuprio of hole, and as unique metal source and ligand reaction, prepare the finest and close
MOF film, MOF film prepared by the method has potential application at gas separation field.
The method comprises the following steps:
(1) if being pressed into by dry tablet foam copper at the bottom of the cuprio of porous, respectively with ethanol, hydrochloric acid, deionized water cleans up；
(2) it is configured to prepare the precursor mixed solution of subcarbonate nano-array；
(3) step (1) substrate is vertically put in step (2) precursor mixed solution, add under conditions of 25～200 DEG C
Heat 0.5～48h, takes out and cleans at the bottom of cuprio, obtains being modified with at the bottom of the cuprio of subcarbonate nano-array；
(4) organic ligand solution corresponding for preparation MOF, the cuprio dolly after being modified by subcarbonate nano-array is directly put
Entering wherein, react a period of time, subcarbonate nano-array provides metal ion to be converted by coordination with organic ligand
Generate corresponding MOF, form the finest and close MOF film at substrate surface；
(5) being put into MOF film prepared by step (4) and soak activation in organic solvent, in the range of 30～100 DEG C, vacuum is done
Dry.
In the method for the present invention, the mixed solution described in step (2) is for preparing different metal subcarbonate nano-array
Precursor solution (such as basic copper carbonate, the precursor solution of basic cobaltous carbonate)；If basic copper carbonate can also use alkali
Formula sodium carbonate and the mixed solution of Ammonium persulfate., utilize and indirectly obtain basic copper carbonate nano-array at the bottom of cuprio.
The preferred copper of metal in step (2), cobalt.
Copper described in step (4), cobalt Metal Substrate MOF are HKUST-1, CuBDC, MOF-110 and Co3(HCOO)6Deng；Step
(4) organic ligand described in is that the part of Metal Substrate MOF such as copper, cobalt is (such as trimesic acid, p-phthalic acid, 2,5-thiophene two
Carboxylic acid and formic acid etc.)；The solvent of described organic ligand solution is water, methanol, ethanol, dichloromethane, N, N-dimethyl formyl
One or more in amine etc..
Step (5) organic solvent is preferably dehydrated alcohol.
The principle of technical solution of the present invention is: prepare the process of MOF film at the bottom of subcarbonate nano-array modifies cuprio
In, the organic ligand solution of carboxylic acids can promote subcarbonate nano-array dissolve thus slowly discharge on its surface metal from
Son, metal ion can generate MOF with organic ligand generation coordination, and the special nano array structure of subcarbonate can make it
It is fully contacted with ligand solution, thus forms continuous print MOF film at substrate surface.
Compared with prior art, present invention have the advantage that
One, use to be directly placed in subcarbonate presoma substrate and subcarbonate nanometer battle array under certain condition, can be made
Row are grown directly upon substrate surface so that it is the MOF film of inverting generation is effectively fixed in substrate, solves MOF film and substrate
Between interface cohesion problem, add the stability of MOF film；
Two, subcarbonate can prepare MOF film as unique metal source；
Three, the method technique is simple, easy to implement, it is adaptable to the preparation of multiple MOF film, beneficially large-scale promotion should
With.
Illustrate with detailed description of the invention, the present invention to be described in further detail below in conjunction with accompanying drawing.
Accompanying drawing explanation
Fig. 1 is the film surface scan electronic microscope photos of embodiment 1.
Fig. 2 is the film surface scan electronic microscope photos of embodiment 3.
Fig. 3 is the film surface scan electronic microscope photos of embodiment 5.
Fig. 4 is the film surface scan electronic microscope photos of embodiment 6.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following example.
Embodiment 1
Prepare Porous Cu substrate and need foam copper (specification is: 120PPI, 1mm are thick)；Prepare basic copper carbonate nano-array
Need sodium bicarbonate (NaHCO3, molecular weight is 84.01), Ammonium persulfate. ((NH4)2S2O8, molecular weight 228.2)；Preparation HKUST-1
The organic ligand of film is trimesic acid (C9H6O6, molecular weight is 210.14), solvent is second alcohol and water.
Preparation condition and method:
(1) being pressed into by foam copper at the bottom of the cuprio of porous, area of base is 4.9cm2, respectively with ethanol, hydrochloric acid and go from
Sub-water cleans stand-by；
(2) take the basic carbonate sodium solution of 6mL 0.2mol/L, the ammonium persulfate solution of 6mL 0.02mol/L and 48mL to go
Ionized water, is configured to mixed liquor；
(3) step (1) cuprio dolly is directly put in step (2) mixed liquor, 24h under conditions of 25 DEG C, takes out at the bottom of cuprio
With deionized water and ethanol purge, obtain being modified with at the bottom of the cuprio of basic copper carbonate nano-array；
(4) 0.105g trimesic acid is dissolved in the mixed solvent of 25mL ethanol and 25mL water, prepares joining of HKUST-1
Liquid solution, directly puts into the cuprio dolly after basic copper carbonate modification wherein, 3h under conditions of 25 DEG C, prepares densification continuously
HKUST-1 film；
(5) by step (4) HKUST-1 film, putting into and soak activation 2 days in dehydrated alcohol, under conditions of 30 DEG C, vacuum is done
Dry 12h.Prepared HKUST-1 film is carried out gas performance test, and test condition is: experimental temperature is 25 DEG C, both sides differential pressure of membrane
For 80KPa.The gas separating property recorded is: hydrogen permeability is 5.76 × 10-7mol·m-2·s-1·Pa-1, H2/CO2Reason
Think that separation factor is 4.2.
Embodiment 2
Prepare Porous Cu substrate and need foam copper (specification is: 120PPI, 1mm are thick)；Prepare basic copper carbonate nano-array
Need sodium bicarbonate (NaHCO3, molecular weight is 84.01), Ammonium persulfate. ((NH4)2S2O8, molecular weight 228.2)；Preparation HKUST-1
The organic ligand of film is trimesic acid (C9H6O6, molecular weight is 210.14), solvent is second alcohol and water.
Preparation condition and method:
(1) being pressed into by foam copper at the bottom of the cuprio of porous, area of base is 4.9cm2, respectively with ethanol, hydrochloric acid and go from
Son cleans stand-by；
(2) take the basic carbonate sodium solution of 6mL 0.2mol/L, the ammonium persulfate solution of 6mL 0.02mol/L and 48mL to go
Ionized water, is configured to mixed liquor；
(3) step (1) cuprio dolly is directly put in step (2) mixed liquor, 24h under conditions of 25 DEG C, takes out at the bottom of cuprio
With deionized water and ethanol purge, obtain being modified with at the bottom of the cuprio of basic copper carbonate nano-array；
(4) 0.210g trimesic acid is dissolved in the mixed solvent of 25mL ethanol and 25mL water, prepares joining of HKUST-1
Liquid solution, directly puts into the cuprio dolly after basic copper carbonate modification wherein, 1.5h under conditions of 25 DEG C, prepares the finest and close
HKUST-1 film；
(5) by step (4) HKUST-1 film, putting into and soak activation 2 days in dehydrated alcohol, under conditions of 30 DEG C, vacuum is done
Dry 12h.Prepared HKUST-1 film is carried out gas performance test, and test condition is: experimental temperature is 25 DEG C, both sides differential pressure of membrane
For 80KPa.The gas separating property recorded is: hydrogen permeability is 6.82 × 10-7mol·m-2·s-1·Pa-1, H2/CO2Reason
Think that separation factor is 3.9.
Embodiment 3
Prepare Porous Cu substrate and need foam copper (specification is: 120PPI, 1mm are thick)；Prepare basic cobaltous carbonate nano-array
Need cabaltous nitrate hexahydrate (Co (NO3)·6H2O, molecular weight is 291.1), carbamide (CO (NH2)2, molecular weight 60.06)；Preparation
Co3(HCOO)6The organic ligand of film is formic acid (HCOOH, molecular weight is 46.03), and solvent is DMF.
Preparation condition and method:
(1) being pressed into by foam copper at the bottom of the cuprio of porous, area of base is 4.9cm2, respectively with ethanol, hydrochloric acid and go from
Son cleans stand-by；
(2) 1.164g cabaltous nitrate hexahydrate, 1.2g carbamide are dissolved in 40mL deionized water, are configured to mixed liquor；
(3) step (1) cuprio dolly is directly put in step (2) mixed liquor, heat 10h under conditions of 95 DEG C, take out copper
Substrate deionized water cleans, then with ethanol purge, air-dries, obtain being modified with basic cobaltous carbonate nano-array under room temperature condition
At the bottom of cuprio；
(4) 1.2mL formic acid is dissolved in DMF solvent, prepares Co3(HCOO)6Ligand solution, by alkali
Cuprio dolly after formula cobalt carbonate is modified directly is put into wherein, heats 3h, prepare the finest and close Co under conditions of 100 DEG C3
(HCOO)6Film；
(5) by step (4) Co3(HCOO)6Film, puts into and soaks activation 2 days in absolute methanol, and under the conditions of 60 DEG C, vacuum is done
Dry 12h.To prepared Co3(HCOO)6Film carries out gas performance test, and test condition is: experimental temperature is 25 DEG C, film two side pressure
Difference is 80KPa.The gas separating property recorded is: hydrogen permeability is 1.43 × 10-7mol·m-2·s-1·Pa-1, H2/CO2
Gas selectivity is 4.3.
Embodiment 4
Prepare Porous Cu substrate and need foam copper (specification is: 120PPI, 1mm are thick)；Prepare basic cobaltous carbonate nano-array
Need cabaltous nitrate hexahydrate (Co (NO3)·6H2O, molecular weight is 291.1), carbamide (CO (NH2)2, molecular weight 60.06)；Preparation
Co3(HCOO)6The organic ligand of film is formic acid (HCOOH, molecular weight is 46.03), and solvent is DMF.
Preparation condition and method:
(1) being pressed into by foam copper at the bottom of the cuprio of porous, area of base is 4.9cm2, respectively with ethanol, hydrochloric acid and go from
Son cleans stand-by；
(2) 1.164g cabaltous nitrate hexahydrate, 1.2g carbamide are dissolved in 40mL deionized water, are configured to mixed liquor；
(3) step (1) cuprio dolly is directly put in step (2) mixed liquor, heat 10h under conditions of 95 DEG C, take out copper
Substrate deionized water cleans, then with ethanol purge, air-dries, obtain being modified with basic cobaltous carbonate nano-array under room temperature condition
At the bottom of cuprio；
(4) 0.96mL formic acid is dissolved in DMF solvent, prepares Co3(HCOO)6Ligand solution, will
Cuprio dolly after basic cobaltous carbonate is modified directly is put into wherein, heats 5h, prepare the finest and close Co under conditions of 100 DEG C3
(HCOO)6Film；
(5) by step (4) Co3(HCOO)6Film, puts into and soaks activation 2 days, vacuum under conditions of 60 DEG C in absolute methanol
It is dried 12h.To prepared Co3(HCOO)6Film carries out gas separating property test, and test condition is: experimental temperature is 25 DEG C, film
Both sides pressure reduction is 80KPa.The gas separating property recorded is: hydrogen infiltration capacity 1.83 × 10-7mol·m-2·s-1·Pa-1, H2/
CO2Gas selectivity is 4.1.
Embodiment 5
Prepare Porous Cu substrate and need foam copper (specification is: 120PPI, 1mm are thick)；Prepare basic copper carbonate nano-array
Need sodium bicarbonate (NaHCO3, molecular weight is 84.01), Ammonium persulfate. ((NH4)2S2O8, molecular weight 228.2)；Preparation CuBDC film
Organic ligand be p-phthalic acid (C8H6O4, molecular weight is 166.13), solvent is DMF.
Preparation condition and method:
(1) being pressed into by foam copper at the bottom of the cuprio of porous, area of base is 4.9cm2, respectively with ethanol, hydrochloric acid and go from
Son cleans stand-by；
(2) take the basic carbonate sodium solution of 6mL 0.2mol/L, the ammonium persulfate solution of 6mL0.02mol/L and 48ml to go
Ionized water, is configured to mixed liquor；
(3) step (1) cuprio dolly is directly put in step (2) mixed liquor, 24h under conditions of 25 DEG C, takes out at the bottom of cuprio
With deionized water and ethanol purge, obtain being modified with at the bottom of the cuprio of basic copper carbonate nano-array；
(4) 0.176g p-phthalic acid is dissolved in 40mL DMF solvent, prepares the part of CuBDC
Solution, the cuprio dolly after being modified by basic copper carbonate is directly put into wherein, heats 24h, prepare CuBDC film under conditions of 130 DEG C；
(5) by step (4) CuBDC film, put into and dehydrated alcohol soaks activation 2 days, be vacuum dried under conditions of 30 DEG C
12h, obtains the CuBDC film of two-dimensional layered structure.
Embodiment 6
Prepare Porous Cu substrate and need foam copper (specification is: 120PPI, 1mm are thick)；Prepare basic copper carbonate nano-array
Need sodium bicarbonate (NaHCO3, molecular weight is 84.01), Ammonium persulfate. ((NH4)2S2O8, molecular weight 228.2)；Preparation MOF-110
The organic ligand of film is 2,5-thiophene dicarboxylic acid (C6H4O4S, molecular weight is 172.15), solvent is ethanol and N, N-dimethyl methyl
Amide.
Preparation condition and method:
(1) being pressed into by foam copper at the bottom of the cuprio of porous, area of base is 4.9cm2, at the bottom of the cuprio of gained, use second respectively
Alcohol, hydrochloric acid and deionization clean stand-by；
(2) take the basic carbonate sodium solution of 6mL 0.2mol/L, the ammonium persulfate solution of 6mL 0.02mol/L and 48mL to go
In ionized water, it is configured to mixed liquor；
(3) step (1) cuprio dolly is directly put in step (2) mixed liquor, 24h under conditions of 25 DEG C, takes out at the bottom of cuprio
With deionized water and ethanol purge, obtain being modified with at the bottom of the cuprio of basic copper carbonate nano-array；
(4) mixing that 0.360g 2,5-thiophene dicarboxylic acid is dissolved in 30mL N,N-dimethylformamide and 10mL ethanol is molten
In agent, preparing the ligand solution of MOF-110, the cuprio dolly after being modified by basic copper carbonate is directly put into wherein, the condition of 80 DEG C
Lower heating 36h, prepares MOF-110 film；
(5) by step (4) MOF-110 film, put into and dehydrated alcohol soak activation 2 days, at 30 DEG C, be vacuum dried 12h,
Obtain the MOF-110 film of two-dimensional layered structure.
Claims (8)
1. a preparation method based on the inverting metal-organic framework film of subcarbonate, it is characterised in that include following
Step:
(1) if being pressed into by dry tablet foam copper at the bottom of the cuprio of porous, respectively with ethanol, hydrochloric acid, deionized water cleans up；
(2) it is configured to prepare the precursor mixed solution of basic metal carbonates；
(3) step (1) substrate is vertically put in step (2) precursor mixed solution, heat under conditions of 25～200 DEG C
0.5～48h, take out and clean at the bottom of cuprio, obtain being modified with at the bottom of the cuprio of subcarbonate nano-array；
(4) corresponding for preparing metal base MOF organic ligand solution, the cuprio dolly after being modified by subcarbonate nano-array is straight
Putting into wherein, react a period of time, subcarbonate nano-array provides metal ion to be turned by coordination with organic ligand
Metaplasia becomes corresponding MOF, forms the finest and close MOF film at substrate surface；
(5) MOF film prepared by step (4) is put into and organic solvent soaks activation, be vacuum dried in the range of 30～100 DEG C.
2. according to the preparation method of a kind of inverting based on the subcarbonate metal-organic framework film described in claim 1,
It is characterized in that, the mixed solution described in step (2) is the precursor solution preparing different metal subcarbonate nano-array,
For basic copper carbonate, the precursor solution of basic cobaltous carbonate.
3. according to the preparation method of a kind of inverting based on the subcarbonate metal-organic framework film described in claim 2,
It is characterized in that, if basic copper carbonate uses basic carbonate sodium and the mixed solution of Ammonium persulfate., utilize indirect at the bottom of cuprio obtaining
To basic copper carbonate presoma.
4. according to the preparation method of a kind of inverting based on the subcarbonate metal-organic framework film described in claim 1,
It is characterized in that, Metal Substrate MOF described in step (4) is HKUST-1, CuBDC, MOF-110 or Co3(HCOO)6；Step (4) institute
The organic ligand stated is copper, the part of cobalt Metal Substrate MOF.
5. according to the preparation method of a kind of inverting based on the subcarbonate metal-organic framework film described in claim 4,
It is characterized in that, organic ligand be trimesic acid, p-phthalic acid, 2,5-thiophene dicarboxylic acid or formic acid.
6. according to the preparation method of a kind of inverting based on the subcarbonate metal-organic framework film described in claim 1,
It is characterized in that, the solvent of organic ligand solution is in water, methanol, ethanol, dichloromethane, DMF etc.
Plant or several.
7. according to the preparation method of a kind of inverting based on the subcarbonate metal-organic framework film described in claim 4,
It is characterized in that, step (5) organic solvent is preferably dehydrated alcohol.
8. the metal-organic framework film prepared according to claim 1-7 any one method.
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