CN106178982B - 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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- CN106178982B CN106178982B CN201610581538.5A CN201610581538A CN106178982B CN 106178982 B CN106178982 B CN 106178982B CN 201610581538 A CN201610581538 A CN 201610581538A CN 106178982 B CN106178982 B CN 106178982B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052802 copper Inorganic materials 0.000 claims abstract description 61
- 239000010408 film Substances 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000012923 MOF film Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 19
- 229960004756 ethanol Drugs 0.000 claims description 19
- 229940116318 copper carbonate Drugs 0.000 claims description 18
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 239000006260 foam Substances 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000000280 densification Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 3
- -1 basic metal carbonates Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 9
- 239000012528 membrane Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 239000013148 Cu-BTC MOF Substances 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 6
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of preparation method of the metal-organic framework film inverting based on subcarbonate, belongs to technical field of membrane separation.It prepares Porous Cu substrate and it is pre-processed；Configure the precursor solution of different subcarbonates；The copper-based bottom handled well is put into the precursor solution of subcarbonate, under certain condition, in substrate surface in-situ preparation subcarbonate nano-array；The copper-based bottom for being modified with subcarbonate nano-array is put into the ligand solution of different MOF, subcarbonate is slowly dissolved release metal ions in carboxylic acids organic ligand and coordination occurs for ligand, to generate continuous MOF film in substrate surface.The present invention provides a kind of preparation methods of novel metal-organic framework film.Continuous MOF film is generated by the way that subcarbonate nano-array is inverting, effectively increases the binding force between MOF film and substrate, it is simple process, easy to implement, be conducive to large-scale promotion application.
Description
Technical field
The present invention relates to a kind of technologies of preparing of metal-organic framework film, specifically provide one kind and are received with subcarbonate
The method that rice array modifies substrate and prepares metal-organic framework film as unique metal source, belongs to UF membrane field.
Background technique
UF membrane as a kind of novel isolation technics, have easy to operate, low energy consumption, good separating effect, without secondary dirt
The features such as dye, receives more and more attention.The property of membrane material is to influence one of the key factor of membrane separating effect, metal-
Organic backbone (metal-organic framework, MOF) is built by metal ion (or metal cluster) and organic ligand
Crystalline material with periodic network structure has the advantages such as porosity, pore size and surface nature be adjustable, deposits in gas
Storage and separation aspect have potential application value.MOF material is applied to membrane separation technique, distinctive structure can design, hole
Road size adjustable and can functionalization the features such as, to improve film separating property have decisive role.Therefore, MOF is with the shape of film
State is expected to obtain important breakthrough for separating.MOF belongs to crystalline state complex, itself enbrittles, it is necessary to depend on certain machine
The perforated substrate of tool intensity could be used for subsequent gas separation.But heterogeneous nucleation is difficult MOF and inert perforated substrate
Good binding force is formed, so the boundary between MOF and substrate must be solved by preparing continuous fine and close MOF film on perforated substrate
Face combines problem.The present invention provides a kind of novel film-forming method, using subcarbonate nano-array modify substrate and as
The method that unique metal source prepares metal-organic framework film.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 problems, such as the interface cohesion between MOF and substrate,
Improve the stability of MOF film.Different metal base MOF film can be made by changing different subcarbonates in this method, in MOF
The preparation field of film has important scientific value.
Summary of the invention
The preparation method of the object of the present invention is to provide a kind of MOF film inverting based on subcarbonate.By more
In-situ modification subcarbonate nano-array on the copper-based bottom in hole, and as unique metal source and ligand reaction, it is made continuous fine and close
MOF film, this method preparation MOF film gas separation field have potential application.
Method includes the following steps:
(1) if dry plate foam copper is pressed into porous copper-based bottom, ethyl alcohol, hydrochloric acid are used respectively, and 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 into step (2) precursor mixed solution, is added under conditions of 25~200 DEG C
0.5~48h of heat takes out copper-based bottom cleaning, obtains the copper-based bottom for being modified with subcarbonate nano-array；
(4) the corresponding organic ligand solution of MOF is prepared, the copper-based dolly after the modification of subcarbonate nano-array is directly put
Enter wherein, reaction a period of time, subcarbonate nano-array provides metal ion and organic ligand and converted by coordination
Corresponding MOF is generated, forms the MOF film of continuous densification in substrate surface；
(5) MOF film prepared by step (4) is put into impregnate in organic solvent and is activated, vacuum is dry within the scope of 30~100 DEG C
It is dry.
In method of the invention, mixed solution described in step (2) is to prepare different metal subcarbonate nano-array
Precursor solution (such as precursor solution of basic copper carbonate, basic cobaltous carbonate)；Alkali can also be used if basic copper carbonate
The mixed solution of formula sodium carbonate and ammonium persulfate obtains basic copper carbonate nano-array using copper-based bottom indirectly.
The preferred copper of metal, cobalt in step (2).
Copper described in step (4), cobalt Metal Substrate MOF are HKUST-1, CuBDC, MOF-110 and Co3(HCOO)6Deng；Step
(4) ligand (such as trimesic acid, terephthalic acid (TPA), the 2,5- thiophene two that the organic ligand described in is the Metal Substrates MOF such as copper, cobalt
Carboxylic acid and formic acid etc.)；The solvent of the organic ligand solution is water, methanol, ethyl alcohol, methylene chloride, N, N- dimethyl formyl
One or more of amine etc..
Step (5) organic solvent is preferably dehydrated alcohol.
The principle of technical solution of the present invention is: modifying the process that copper-based bottom prepares MOF film in subcarbonate nano-array
In, the organic ligand solution of carboxylic acids can promote subcarbonate nano-array dissolution to its surface slow release metal from
Son, metal ion can occur coordination with organic ligand and generate MOF, and the special nano array structure of subcarbonate can make it
It is come into full contact with ligand solution, to form continuous MOF film in substrate surface.
Compared with prior art, present invention has the advantage that
One, subcarbonate nanometer battle array can be made using substrate to be directly placed into subcarbonate presoma under certain condition
Column are grown directly upon substrate surface, are effectively fixed in the MOF film of its inverting generation in substrate, solve MOF film and substrate
Between interface cohesion problem, increase the stability of MOF film；
Two, subcarbonate can be used as unique metal source preparation MOF film；
Three, this method simple process, easy to implement, suitable for the preparation of a variety of MOF films, is conducive to large-scale promotion and answers
With.
Below in conjunction with Detailed description of the invention and specific embodiment, invention is further described in detail.
Detailed description of the invention
Fig. 1 is the film surface scanning electron microscope analysis of embodiment 1.
Fig. 2 is the film surface scanning electron microscope analysis of embodiment 3.
Fig. 3 is the film surface scanning electron microscope analysis of embodiment 5.
Fig. 4 is the film surface scanning electron microscope analysis of embodiment 6.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
It prepares Porous Cu substrate and needs foam copper (specification are as follows: 120PPI, 1mm are thick)；Prepare basic copper carbonate nano-array
Need sodium bicarbonate (NaHCO3, molecular weight 84.01), ammonium persulfate ((NH4)2S2O8, molecular weight 228.2)；Prepare HKUST-1
The organic ligand of film is trimesic acid (C9H6O6, molecular weight 210.14), solvent is second alcohol and water.
Preparation condition and method:
(1) foam copper is pressed into porous copper-based bottom, area of base 4.9cm2, respectively use ethyl alcohol, hydrochloric acid and go from
Sub- water cleaning is stand-by；
(2) the basic carbonate sodium solution of 6mL 0.2mol/L, the ammonium persulfate solution of 6mL 0.02mol/L and 48mL is taken to go
Ionized water is configured to mixed liquor；
(3) step (1) copper-based dolly is directly put into step (2) mixed liquor, under conditions of 25 DEG C for 24 hours, takes out copper-based bottom
It is cleaned with deionized water and ethyl alcohol, obtains the copper-based bottom for being modified with basic copper carbonate nano-array；
(4) 0.105g trimesic acid is dissolved in the in the mixed solvent of 25mL ethyl alcohol and 25mL water, matching for HKUST-1 is made
Liquid solution, the copper-based dolly after basic copper carbonate is modified directly are put into wherein, 3h under conditions of 25 DEG C, and continuous densification is made
HKUST-1 film；
(5) it by step (4) HKUST-1 film, is put into dehydrated alcohol and impregnates activation 2 days, vacuum is dry under conditions of 30 DEG C
Dry 12h.Gas performance test, test condition are carried out to HKUST-1 film obtained are as follows: experimental temperature is 25 DEG C, both sides differential pressure of membrane
For 80KPa.The gas separating property measured are as follows: hydrogen permeability is 5.76 × 10-7mol·m-2·s-1·Pa-1, H2/CO2Reason
Think that separation factor is 4.2.
Embodiment 2
It prepares Porous Cu substrate and needs foam copper (specification are as follows: 120PPI, 1mm are thick)；Prepare basic copper carbonate nano-array
Need sodium bicarbonate (NaHCO3, molecular weight 84.01), ammonium persulfate ((NH4)2S2O8, molecular weight 228.2)；Prepare HKUST-1
The organic ligand of film is trimesic acid (C9H6O6, molecular weight 210.14), solvent is second alcohol and water.
Preparation condition and method:
(1) foam copper is pressed into porous copper-based bottom, area of base 4.9cm2, respectively use ethyl alcohol, hydrochloric acid and go from
Son cleaning is stand-by；
(2) the basic carbonate sodium solution of 6mL 0.2mol/L, the ammonium persulfate solution of 6mL 0.02mol/L and 48mL is taken to go
Ionized water is configured to mixed liquor；
(3) step (1) copper-based dolly is directly put into step (2) mixed liquor, under conditions of 25 DEG C for 24 hours, takes out copper-based bottom
It is cleaned with deionized water and ethyl alcohol, obtains the copper-based bottom for being modified with basic copper carbonate nano-array；
(4) 0.210g trimesic acid is dissolved in the in the mixed solvent of 25mL ethyl alcohol and 25mL water, matching for HKUST-1 is made
Liquid solution, the copper-based dolly after basic copper carbonate is modified directly are put into wherein, and continuous densification is made in 1.5h under conditions of 25 DEG C
HKUST-1 film；
(5) it by step (4) HKUST-1 film, is put into dehydrated alcohol and impregnates activation 2 days, vacuum is dry under conditions of 30 DEG C
Dry 12h.Gas performance test, test condition are carried out to HKUST-1 film obtained are as follows: experimental temperature is 25 DEG C, both sides differential pressure of membrane
For 80KPa.The gas separating property measured are as follows: hydrogen permeability is 6.82 × 10-7mol·m-2·s-1·Pa-1, H2/CO2Reason
Think that separation factor is 3.9.
Embodiment 3
It prepares Porous Cu substrate and needs foam copper (specification are as follows: 120PPI, 1mm are thick)；Prepare basic cobaltous carbonate nano-array
Need cabaltous nitrate hexahydrate (Co (NO3)·6H2O, molecular weight 291.1), urea (CO (NH2)2, molecular weight 60.06)；Preparation
Co3(HCOO)6The organic ligand of film is formic acid (HCOOH, molecular weight 46.03), and solvent is n,N-Dimethylformamide.
Preparation condition and method:
(1) foam copper is pressed into porous copper-based bottom, area of base 4.9cm2, respectively use ethyl alcohol, hydrochloric acid and go from
Son cleaning is stand-by；
(2) 1.164g cabaltous nitrate hexahydrate, 1.2g urea are dissolved in 40mL deionized water, are configured to mixed liquor；
(3) step (1) copper-based dolly is directly put into step (2) mixed liquor, 10h is heated under conditions of 95 DEG C, take out copper
Substrate is cleaned with deionized water, then is cleaned with ethyl alcohol, is air-dried under room temperature, obtains being modified with basic cobaltous carbonate nano-array
Copper-based bottom；
(4) 1.2mL formic acid is dissolved in n,N-Dimethylformamide solvent, Co is made3(HCOO)6Ligand solution, by alkali
Copper-based dolly after the modification of formula cobalt carbonate is directly put into wherein, heats 3h under conditions of 100 DEG C, the Co of continuous densification is made3
(HCOO)6Film；
(5) by step (4) Co3(HCOO)6Film is put into anhydrous methanol and impregnates activation 2 days, and vacuum is dry under the conditions of 60 DEG C
Dry 12h.To Co obtained3(HCOO)6Film carries out gas performance test, test condition are as follows: experimental temperature is 25 DEG C, two side pressure of film
Difference is 80KPa.The gas separating property measured are as follows: hydrogen permeability is 1.43 × 10-7mol·m-2·s-1·Pa-1, H2/CO2
Gas selectivity is 4.3.
Embodiment 4
It prepares Porous Cu substrate and needs foam copper (specification are as follows: 120PPI, 1mm are thick)；Prepare basic cobaltous carbonate nano-array
Need cabaltous nitrate hexahydrate (Co (NO3)·6H2O, molecular weight 291.1), urea (CO (NH2)2, molecular weight 60.06)；Preparation
Co3(HCOO)6The organic ligand of film is formic acid (HCOOH, molecular weight 46.03), and solvent is n,N-Dimethylformamide.
Preparation condition and method:
(1) foam copper is pressed into porous copper-based bottom, area of base 4.9cm2, respectively use ethyl alcohol, hydrochloric acid and go from
Son cleaning is stand-by；
(2) 1.164g cabaltous nitrate hexahydrate, 1.2g urea are dissolved in 40mL deionized water, are configured to mixed liquor；
(3) step (1) copper-based dolly is directly put into step (2) mixed liquor, 10h is heated under conditions of 95 DEG C, take out copper
Substrate is cleaned with deionized water, then is cleaned with ethyl alcohol, is air-dried under room temperature, obtains being modified with basic cobaltous carbonate nano-array
Copper-based bottom；
(4) 0.96mL formic acid is dissolved in n,N-Dimethylformamide solvent, Co is made3(HCOO)6Ligand solution, will
Copper-based dolly after basic cobaltous carbonate modification is directly put into wherein, heats 5h under conditions of 100 DEG C, the Co of continuous densification is made3
(HCOO)6Film；
(5) by step (4) Co3(HCOO)6Film is put into anhydrous methanol and impregnates activation 2 days, vacuum under conditions of 60 DEG C
Dry 12h.To Co obtained3(HCOO)6Film carries out gas separating property test, test condition are as follows: experimental temperature is 25 DEG C, film
Two sides pressure difference is 80KPa.The gas separating property measured are as follows: hydrogen infiltration capacity 1.83 × 10-7mol·m-2·s-1·Pa-1, H2/
CO2Gas selectivity is 4.1.
Embodiment 5
It prepares Porous Cu substrate and needs foam copper (specification are as follows: 120PPI, 1mm are thick)；Prepare basic copper carbonate nano-array
Need sodium bicarbonate (NaHCO3, molecular weight 84.01), ammonium persulfate ((NH4)2S2O8, molecular weight 228.2)；Prepare CuBDC film
Organic ligand be terephthalic acid (TPA) (C8H6O4, molecular weight 166.13), solvent is n,N-Dimethylformamide.
Preparation condition and method:
(1) foam copper is pressed into porous copper-based bottom, area of base 4.9cm2, respectively use ethyl alcohol, hydrochloric acid and go from
Son cleaning is stand-by；
(2) the basic carbonate sodium solution of 6mL 0.2mol/L, the ammonium persulfate solution of 6mL0.02mol/L and 48ml is taken to go
Ionized water is configured to mixed liquor；
(3) step (1) copper-based dolly is directly put into step (2) mixed liquor, under conditions of 25 DEG C for 24 hours, takes out copper-based bottom
It is cleaned with deionized water and ethyl alcohol, obtains the copper-based bottom for being modified with basic copper carbonate nano-array；
(4) 0.176g terephthalic acid (TPA) is dissolved in 40mL n,N-Dimethylformamide solvent, the ligand of CuBDC is made
Solution, the copper-based dolly after basic copper carbonate is modified directly are put into wherein, are heated for 24 hours under conditions of 130 DEG C, CuBDC film is made；
(5) it by step (4) CuBDC film, is put into dehydrated alcohol and impregnates activation 2 days, be dried in vacuo under conditions of 30 DEG C
12h obtains the CuBDC film of two-dimensional layered structure.
Embodiment 6
It prepares Porous Cu substrate and needs foam copper (specification are as follows: 120PPI, 1mm are thick)；Prepare basic copper carbonate nano-array
Need sodium bicarbonate (NaHCO3, molecular weight 84.01), ammonium persulfate ((NH4)2S2O8, molecular weight 228.2)；Prepare MOF-110
The organic ligand of film is 2,5- thiophene dicarboxylic acid (C6H4O4S, molecular weight 172.15), solvent is ethyl alcohol and N, N- dimethyl methyl
Amide.
Preparation condition and method:
(1) foam copper is pressed into porous copper-based bottom, area of base 4.9cm2, second is used at resulting copper-based bottom respectively
Alcohol, hydrochloric acid and deionization cleaning are stand-by；
(2) the basic carbonate sodium solution of 6mL 0.2mol/L, the ammonium persulfate solution of 6mL 0.02mol/L and 48mL is taken to go
In ionized water, it is configured to mixed liquor；
(3) step (1) copper-based dolly is directly put into step (2) mixed liquor, under conditions of 25 DEG C for 24 hours, takes out copper-based bottom
It is cleaned with deionized water and ethyl alcohol, obtains the copper-based bottom for being modified with basic copper carbonate nano-array；
(4) mixing for 0.360g 2,5- thiophene dicarboxylic acid being dissolved in 30mL N,N-dimethylformamide and 10mL ethyl alcohol is molten
In agent, the ligand solution of MOF-110 is made, the copper-based dolly after basic copper carbonate is modified directly is put into wherein, 80 DEG C of condition
MOF-110 film is made in lower heating 36h；
(5) it by step (4) MOF-110 film, is put into dehydrated alcohol and impregnates activation 2 days, be dried in vacuo 12h at 30 DEG C,
Obtain the MOF-110 film of two-dimensional layered structure.
Claims (4)
1. a kind of preparation method of the metal-organic framework film inverting based on subcarbonate, which is characterized in that
The following steps are included:
If dry plate foam copper is pressed into porous copper-based bottom, ethyl alcohol, hydrochloric acid are used respectively, and deionized water cleans up；
It is configured to prepare the precursor mixed solution of basic metal carbonates；Using the mixing of basic carbonate sodium and ammonium persulfate
Solution；
Step (1) substrate is vertically put into step (2) precursor mixed solution, under conditions of 25 ~ 200 DEG C heat 0.5 ~
48 h take out copper-based bottom cleaning, obtain the copper-based bottom for being modified with basic copper carbonate nano-array；
Organic ligand solution is prepared, the copper-based dolly after the modification of basic copper carbonate nano-array is directly put into wherein, reacts one section
Time, basic copper carbonate nano-array provide metal ion and are converted into corresponding MOF, In by coordination with organic ligand
Substrate surface forms the MOF film of continuous densification；
MOF film prepared by step (4) is put into organic solvent and impregnates activation, is dried in vacuo within the scope of 30 ~ 100 DEG C；
Organic ligand is trimesic acid, terephthalic acid (TPA), 2,5- thiophene dicarboxylic acid or formic acid.
2. a kind of preparation method of metal-organic framework film inverting based on subcarbonate described in accordance with the claim 1,
It is characterized in that, the solvent of organic ligand solution is one of water, methanol, ethyl alcohol, methylene chloride, n,N-Dimethylformamide
Or it is several.
3. a kind of preparation method of metal-organic framework film inverting based on subcarbonate described in accordance with the claim 1,
It is characterized in that, step (5) organic solvent is dehydrated alcohol.
4. the metal-organic framework film being prepared according to any one of claim 1-3 method.
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| CN112246111B (en) * | 2020-10-11 | 2021-08-06 | 天津工业大学 | Preparation method of metal organic framework film |
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| CN113930782B (en) * | 2021-09-24 | 2023-06-20 | 南京信息工程大学 | Preparation method and application of self-supporting electrode |
| CN114875429B (en) * | 2022-02-17 | 2023-08-04 | 上海应用技术大学 | Flexible thin film electrode and preparation method and application thereof |
| CN115010944A (en) * | 2022-06-16 | 2022-09-06 | 重庆大学 | Method for preparing metal-organic framework structure material by using copper alkaline carbonate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872728A (en) * | 2012-10-11 | 2013-01-16 | 浙江大学 | Method for preparing metal organic framework film by using hydroxide nanowires and organic ligands |
| KR101288279B1 (en) * | 2011-07-20 | 2013-07-26 | 웅진케미칼 주식회사 | Manufacturing method of metallic hollow fiber having porosity |
| CN103406029A (en) * | 2013-07-25 | 2013-11-27 | 大连理工大学 | Preparation method for ZIFs membrane containing zinc adopting sandwich structure and supported by high temperature resistant zinc oxide nanorod |
| CN105126642A (en) * | 2015-07-27 | 2015-12-09 | 北京工业大学 | Preparation of metal organic framework membrane and application in gas separation |
| CN105233702A (en) * | 2015-10-17 | 2016-01-13 | 大连理工大学 | Preparation method for forming metal organic framework ZIF-67 film by utilizing cobalt nano array layer conversion |
| JP2016052620A (en) * | 2014-09-03 | 2016-04-14 | 日本製紙株式会社 | Composite of metal-organic framework and cellulose nanofiber |
-
2016
- 2016-07-21 CN CN201610581538.5A patent/CN106178982B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101288279B1 (en) * | 2011-07-20 | 2013-07-26 | 웅진케미칼 주식회사 | Manufacturing method of metallic hollow fiber having porosity |
| CN102872728A (en) * | 2012-10-11 | 2013-01-16 | 浙江大学 | Method for preparing metal organic framework film by using hydroxide nanowires and organic ligands |
| CN103406029A (en) * | 2013-07-25 | 2013-11-27 | 大连理工大学 | Preparation method for ZIFs membrane containing zinc adopting sandwich structure and supported by high temperature resistant zinc oxide nanorod |
| JP2016052620A (en) * | 2014-09-03 | 2016-04-14 | 日本製紙株式会社 | Composite of metal-organic framework and cellulose nanofiber |
| CN105126642A (en) * | 2015-07-27 | 2015-12-09 | 北京工业大学 | Preparation of metal organic framework membrane and application in gas separation |
| CN105233702A (en) * | 2015-10-17 | 2016-01-13 | 大连理工大学 | Preparation method for forming metal organic framework ZIF-67 film by utilizing cobalt nano array layer conversion |
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