CN105753890A - Method for synthesizing metal organic framework material by adopting electrostatic spraying method - Google Patents
Method for synthesizing metal organic framework material by adopting electrostatic spraying method Download PDFInfo
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- CN105753890A CN105753890A CN201610082272.XA CN201610082272A CN105753890A CN 105753890 A CN105753890 A CN 105753890A CN 201610082272 A CN201610082272 A CN 201610082272A CN 105753890 A CN105753890 A CN 105753890A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
- B05B5/03—Discharge apparatus, e.g. electrostatic spray guns characterised by the use of gas, e.g. electrostatically assisted pneumatic spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/16—Arrangements for supplying liquids or other fluent material
- B05B5/1608—Arrangements for supplying liquids or other fluent material the liquid or other fluent material being electrically conductive
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
Abstract
The invention provides a method for synthesizing a metal organic framework material by adopting an electrostatic spraying method. The method adopts double electrostatic spraying devices, namely a first electrostatic spraying device and a second electrostatic spraying device to synthesize an MOF (metal-organic framework) material. The method comprises the following steps: spraying a metal salt solution used for synthesizing the MOF material through the first electrostatic spraying device to obtain charged metal salt solution fog drops; spraying a ligand solution used for synthesizing the MOF material through the second electrostatic spraying device to obtain charged ligand solution fog drops; and joining the sprayed-out metal salt solution fog drops with the sprayed-out ligand solution fog drops to react, thereby forming an MOF crystal. The method for synthesizing the metal organic framework material by adopting the electrostatic spraying method can stop synthesis reaction at any time according to the synthesis conditions, can carry out mass synthesis, and also can carry out micro synthesis. The method has the advantages of being green, environmentally-friendly, high in efficiency, low in cost, high in yield, miniaturized, good in dispersion, simple to operate, and the like.
Description
Technical field
The invention belongs to Material Field, in particular to a kind of method adopting electrostatic spraying processes synthesis metal-organic framework material, the method has environmental protection, high efficiency, low cost, high yield, microminiaturization, good dispersion, simple operation and other advantages.
Background technology
In recent years, metal organic frame (metal-organicframework, be called for short MOF) material be always up people pay close attention to focus, it has high porosity, bigger serface, aperture is adjustable, can the performance such as modification after functionalization, simultaneously can the multiple functional group of load in duct, MOF material is made to have wider application prospect than other porous materials, it is mainly manifested in the following aspects: topological structure and interspersed grid, enrich constantly topological knowledge, also make this just complicated structure become more glamorous simultaneously；2. unique optical, electrical, magnetic property；3. potential using value: absorption, catalysis, gas storage, optical sensing, elimination toxic gas, separation, CO2Seizure, fluorescence etc..
For MOF material, synthetic method conventional at present mainly includes volatility process, diffusion method, hydro-thermal method, solvent-thermal method, microwave-assisted and grinding auxiliary etc., at field of scientific study, they perhaps play huge effect, but its production cycle and production equipment but govern industrial development.Meanwhile, these methods cause again the waste of resource, the increasing the weight of etc. of greenhouse effect.Now, on the basis of protection environment, reduction production cycle, use simply produce equipment efficiently, and efficient, high yield generates product and just more meets industrial requirement.
Summary of the invention
In view of the above problems, a kind of method that it is an object of the invention to provide new synthesis metal-organic framework material, namely the method adopting electrostatic spraying processes synthesis metal-organic framework material, the method has environmental protection, high efficiency, low cost, high yield, microminiaturization, good dispersion, simple operation and other advantages.
Another object of the present invention is to provide a kind of double; two electrostatic atomizers for metal-organic framework material synthesis.
According to an aspect of the present invention, the method of employing electrostatic spraying processes provided by the invention synthesis metal-organic framework material, double, two electrostatic atomizer i.e. the first electrostatic atomizer and the second electrostatic atomizer is adopted to synthesize MOF material, the method includes: the metal salt solution for synthesizing MOF material ejects charged metal salt solution droplet by the first electrostatic atomizer, ligand solution for synthesizing MOF material ejects charged ligand solution droplet by the second electrostatic atomizer, the ligand solution droplet simultaneously making the metal salt solution droplet ejected and eject merges together and reacts, form MOF crystal.
According to another aspect of the present invention, above-mentioned double; two electrostatic atomizers for metal-organic framework material synthesis provided by the invention, including the first electrostatic atomizer and the second electrostatic atomizer, wherein:
Described first electrostatic atomizer is for ejecting charged metal salt solution droplet by the metal salt solution of synthesis MOF material, and it includes first liquid conveyer device and the first electrostatic atomization apparatus；
Described second electrostatic atomizer is for ejecting charged ligand solution droplet by the ligand solution of synthesis MOF material, and it includes second liquid conveyer device and the second electrostatic atomization apparatus；
Described first electrostatic atomizer and described second electrostatic atomizer are arranged to intersect so that the charged metal salt solution droplet ejected and the charged ligand solution droplet ejected can converge.
Beneficial effect
The present invention adopts the first electrostatic atomizer and the second electrostatic atomizer i.e. double; two electrostatic atomizers to synthesize MOF material, first electrostatic atomizer and the second electrostatic atomizer all include triple channel, triple channel innermost layer is liquid delivery tube, transferring metal saline solution or ligand solution, middle level is air shooter, conveying high-pressure gas, outermost layer is electric installation, liquor charging forms sealing system with gas, liquor charging and conduction each through a three-way connector, form a good airtight entirety, then can surround by the resilient insulant PEEK pipe of apparatus；After energising, metal salt solution and ligand solution are ionized to charged liquid, sputter and go out under the conveying of gases at high pressure, and negative ions combines and forms MOF material, becomes scattered about in an orderly manner on object stage.
Adopt electrostatic spraying processes synthesis MOF material, negative ions is with clearly defined objective, " orientation " combines, rapidly be crystallized product, and product purity is higher, it is possible to the convenient production process promptly controlling product, improve effective utilization of resource simultaneously, decrease the waste of solvent, alleviate the pollution to environment.
Meanwhile, double; two electrostatic atomizers eliminate the incidental a series of devices of atomising device in conventional electrostatic sprayer unit, only realize transporting the purpose of charged ion by air shooter conveying high-pressure gas, simple and convenient, practical.
It addition, the method adopting electrostatic spraying processes synthesis MOF material of the present invention, it is possible to stop synthetic reaction at any time according to the situation of synthesis, both can carry out high-volume synthesis, it is also possible to microsynthesis.The method has environmental protection, high efficiency, low cost, high yield, microminiaturization, good dispersion, simple operation and other advantages.
Accompanying drawing explanation
The above-mentioned purpose of the present invention, feature and advantage can be more clearly understood that by the detailed description below in conjunction with accompanying drawing, wherein:
Fig. 1 is the structural representation of double; two electrostatic atomizers of the present invention；
Fig. 2 is the composition block diagram of double; two electrostatic atomizers of the present invention；
Fig. 3 is the X-ray powder diffraction pattern of the MOF-5 according to embodiments of the invention 1 preparation；With
Fig. 4 is the X-ray powder diffraction pattern of the Cu-BDC according to embodiments of the invention 2 preparation.
Detailed description of the invention
Below, it is more fully described the present invention.
According to the present invention, the method of employing electrostatic spraying processes provided by the invention synthesis metal-organic framework material, double, two electrostatic atomizer i.e. the first electrostatic atomizer and the second electrostatic atomizer is adopted to synthesize MOF material, the method includes: the metal salt solution for synthesizing MOF material ejects charged metal salt solution droplet by the first electrostatic atomizer, ligand solution for synthesizing MOF material ejects charged ligand solution droplet by the second electrostatic atomizer, the ligand solution droplet simultaneously making the metal salt solution droplet ejected and eject merges together and reacts, form MOF crystal.
Below, described pair of electrostatic atomizer is further illustrated.
Described pair of electrostatic atomizer, including the first electrostatic atomizer and the second electrostatic atomizer, wherein:
Described first electrostatic atomizer is for ejecting charged metal salt solution droplet by the metal salt solution of synthesis MOF material, and it includes first liquid conveyer device and the first electrostatic atomization apparatus；
Described second electrostatic atomizer is for ejecting charged ligand solution droplet by the ligand solution of synthesis MOF material, and it includes second liquid conveyer device and the second electrostatic atomization apparatus；
Described first electrostatic atomizer and described second electrostatic atomizer are arranged to intersect so that the charged metal salt solution droplet ejected and the charged ligand solution droplet ejected can converge.
Fig. 1 is the structural representation of double; two electrostatic atomizers of the present invention, and Fig. 2 is the composition block diagram of double; two electrostatic atomizers of the present invention.As depicted in figs. 1 and 2, double; two electrostatic atomizers 1000 include the first electrostatic atomizer 100 and the second electrostatic atomizer 200.
Wherein, the first electrostatic atomizer 100 includes first liquid conveyer device 110 and the first electrostatic atomization apparatus 120.
Described first liquid conveyer device 110 is for being transported to the first electrostatic atomization apparatus 120 by the metal salt solution of synthesis MOF material, first liquid conveyer device 110 includes first liquid conveying pipe 111, this first liquid conveying pipe 111 traverse the first electrostatic atomization apparatus 120, such as, it can be capillary tube, especially quartz capillary.It addition, first liquid conveyer device 110 can also include the device of the auxiliary liquid transmission such as liquid pump.
First electrostatic atomization apparatus 120 is for being atomized and make it charged the metal salt solution that first liquid conveyer device 110 conveying comes, including the first air shooter the 121, first three-way connector the 122, first electrode sleeve pipe the 123, second three-way connector 124 and the first electrode 125, wherein, first air shooter 121 is enclosed within outside first liquid conveying pipe 111 by the first three-way connector 122, and first the 3rd port of three-way connector 122 be arranged to air inlet 1, for passing into gases at high pressure to the first air shooter 121；First electrode sleeve pipe 123 is enclosed within outside the first air shooter 121 by the second three-way connector 124, and second three-way connector 124 the 3rd port for the first electrode 125 connect electric connection, the first electrode 125 is arranged on the outside of the first air shooter 121 and in the inside of the first electrode sleeve pipe 123.Preferably, first air shooter the 121, first electrode sleeve pipe 123 and first liquid carry pipe 111 concentric.
Second electrostatic atomizer 200 includes second liquid conveyer device 210 and the second electrostatic atomization apparatus 220, and they are same or similar with the structure of the first liquid conveyer device 110 in the first electrostatic atomizer 100 and the first electrostatic atomization apparatus 120 respectively.
Specifically, described second liquid conveyer device 210 is for being transported to the second electrostatic atomization apparatus 220 by the ligand solution of synthesis MOF material, second liquid conveyer device 210 includes second liquid conveying pipe 211, this second liquid conveying pipe 211 traverse the second electrostatic atomization apparatus 220, such as, it can be capillary tube, especially quartz capillary.It addition, second liquid conveyer device 210 can also include the device of the auxiliary liquid transmission such as liquid pump.
Second electrostatic atomization apparatus 220 is for being atomized and make it charged the ligand solution that second liquid conveyer device 210 conveying comes, including the second air shooter the 221, the 3rd three-way connector the 222, second electrode sleeve pipe the 223, the 4th three-way connector 224 and the second electrode 225, wherein, second air shooter 221 is enclosed within outside second liquid conveying pipe 211 by the 3rd three-way connector 222, and the 3rd the 3rd port of three-way connector 222 be arranged to air inlet 1, for passing into gases at high pressure to the second air shooter 221；Second electrode sleeve pipe 223 is enclosed within outside the second air shooter 221 by the 4th three-way connector 224, and the 4th three-way connector 224 the 3rd port for the second electrode 225 connect electric connection, the second electrode 225 is arranged on the outside of the second air shooter 221 and in the inside of the second electrode sleeve pipe 223.Preferably, second air shooter the 221, second electrode sleeve pipe 223 and second liquid carry pipe 211 concentric.
Described first electrode 125 and the second electrode 225 can be high pressure resistant electrical filament, are connected with high-voltage positive electrode or negative pole and charged by connecing electric connection.
In double; two electrostatic atomizers 1000, the gases at high pressure inputting the first electrostatic atomizer 100 and the second electrostatic atomizer 200 can be provided by air generator, preferably, the air-flow of described gases at high pressure is pressed within the scope of 0.1MPa～10MPa, it is highly preferred that the air-flow of described gases at high pressure is pressed within the scope of 0.15MPa～5MPa.
Preferably, described first liquid conveying pipe 111, second liquid conveying pipe 211, first air shooter 121 and the second air shooter 221 are quartz capillary, described first electrode sleeve pipe 123 and the second electrode sleeve pipe 223 are PEEK (polyether-ether-ketone) pipe, such as, described first liquid conveying pipe 111 and second liquid conveying pipe 211 are quartz capillary that internal diameter is about 0.25mm, described first air shooter 121 and the second air shooter 221 are quartz capillary that internal diameter is about 0.5mm, described first electrode sleeve pipe 123 and the second electrode sleeve pipe 223 are managed for the PEEK that internal diameter is about 1.0mm.
Preferably, at droplet spout end, the length of described first electrode sleeve pipe 123 and the second electrode sleeve pipe 223 is longer than described first air shooter 121 and the second air shooter 221 respectively, for instance can grow about 1～2mm；The length of described first air shooter 121 and the second air shooter 221 is longer than first liquid conveying pipe 111 and second liquid conveying pipe 211 respectively, for instance can grow about 1～2mm.Thus, form the nozzle that Charged Droplet outwards sprays, promote the atomization of Charged Droplet, control the spray regime of droplet.
Described first electrostatic atomizer 100 and described second electrostatic atomizer 200 are arranged to intersect so that the charged metal salt solution droplet ejected and the charged ligand solution droplet ejected can converge.The angle intersected is determined according to the flow velocity of SOLUTION PROPERTIES and atomization gas, it is preferable that described angle is within the scope of 60 °～180 °, it is further preferred that described angle is within the scope of 70 °～150 °.
As in figure 2 it is shown, double; two electrostatic atomizers 1000 can also include:
Crystal collection device 300, for instance polytetrafluoroethyldisk disk, for collecting the product MOF crystal of synthesis；
Two containers 400, for instance reagent bottle, conical flask or beaker etc., are respectively used to bearing metal saline solution and ligand solution；
Fluid flowmeter 500, for measuring and control the liquid delivery rate of ligand solution in the liquid delivery rate of metal salt solution in the first electrostatic atomizer 100 and the second electrostatic atomizer 200, preferably, described liquid delivery rate is within the scope of 0.1mL/min～50mL/min, it is further preferred that described liquid delivery rate is 4.5mL/min；
Gas flowmeter 600, such as, spinner flowmeter, for measuring and control the gases at high pressure of the first air shooter 121 and the second air shooter 221 and the flow of atomization gas, preferably, the flow of described gases at high pressure and atomization gas is in the scope of 0.1L/min～50L/min, for instance, it is possible to for 336mL/min；
Heater 700, such as liquid heating rod, liquid electric heater etc., for heating metal salt solution and ligand solution, metal salt solution and ligand solution is made to enter the inlet temperature of the first electrostatic atomizer 100 and the second electrostatic atomizer 200 in 100 DEG C～180 DEG C temperature ranges, for instance can be 180 DEG C.
As preferably, described first electrostatic atomizer 100 and the second electrostatic atomizer 200 can be integral with plastics such as teflon seal, wherein the first electrostatic atomizer 100 and the second electrostatic atomizer 200 all include triple channel, triple channel innermost layer is liquid delivery tube, transferring metal saline solution or ligand solution, middle level is air shooter, conveying high-pressure gas, outermost layer is electric installation, this triple channel forms sealing system by three-way connector, then can surround and be sealed to entirety by the resilient insulant PEEK pipe of apparatus, effectively prevent high pressure from getting an electric shock.
Synthesize in the method for metal-organic framework material at the above-mentioned employing electrostatic spraying processes of the present invention,
The described metal salt solution for synthesizing MOF material can be zinc solution or copper salt solution, described zinc solution can be zinc nitrate, zinc acetate or the zinc chloride solution in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or water, preferred zinc nitrate solution in dimethylformamide (DMF), its concentration is not construed as limiting, it is possible to reference to the concentration used in the synthesis hydro-thermal method of MOF material, solvent-thermal method；Described copper salt solution can be copper nitrate or zinc acetate solution in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or water, preferred copper nitrate solution in dimethylformamide (DMF), its concentration is not construed as limiting, it is possible to reference to the concentration used in the synthesis hydro-thermal method of MOF material, solvent-thermal method.
The described ligand solution for synthesizing MOF material can be the solution of p-phthalic acid, specifically, can be p-phthalic acid solution in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or water, it is preferable that p-phthalic acid solution in dimethylformamide (DMF)；And described ligand solution also comprises triethylamine；The concentration of p-phthalic acid and triethylamine is not construed as limiting by described ligand solution, it is possible to reference to the concentration used in the synthesis hydro-thermal method of MOF material, solvent-thermal method.
It is zinc solution or copper salt solution at the described metal salt solution for synthesizing MOF material, when the described ligand solution for synthesizing MOF material can be the solution of p-phthalic acid, ejected the metal salt solution droplet of positively charged by the first electrostatic atomizer for synthesizing the metal salt solution of MOF material, ligand solution for synthesizing MOF material ejects electronegative ligand solution droplet by the second electrostatic atomizer, make to eject the metal salt solution droplet of positively charged simultaneously and eject electronegative ligand solution droplet and merge together and react, form MOF crystal.
In the method for the invention, as preferably, metal salt solution and ligand solution respectively enter the inlet temperature of the first electrostatic atomizer 100 and the second electrostatic atomizer 200 in 100 DEG C～180 DEG C temperature ranges, for instance can be 180 DEG C；
The transporting velocity of metal salt solution and ligand solution is within the scope of 0.1mL/min～50mL/min, for instance can be 4.5mL/min；
For making the flow of gases at high pressure of metal salt solution and ligand solution atomization in the scope of 0.1L/min～50L/min, for instance can be 336mL/min；The air-flow of described gases at high pressure is pressed within the scope of 0.1MPa～10MPa, it is more preferred to, the air-flow of described gases at high pressure is pressed within the scope of 0.15MPa～5MPa；
For making metal salt solution and the charged positive and negative electrode voltage of ligand solution can be such as less than or equal to 10KV.
Being formed after MOF crystal, crystal is collected, it is washed with opposite polarity solvent, separate, the purification procedures such as dry.
Specifically describing the preparation of MOF material MOF-5 and Cu-BDC in the following embodiments, it is provided that these embodiments are only intended to specifically describe the present invention, these embodiments should not be construed as restriction the scope of the present invention.
Embodiment 1
MOF-5 crystal preparation
(1) ten thousand/ analytical balance on accurately weigh 0.6gZn (NO3)2·6H2O, is placed in the beaker of 50mL, measures 20mLDMF in beaker, and stirring and dissolving obtains Zn saline solution；
Analytical balance accurately weighs 0.168g p-phthalic acid, is placed in the beaker of 50mL, measure the triethylamine of DMF and 1.1mL of 20mL in beaker, stirring and dissolving in fume hood, obtain ligand solution；
(2) Zn saline solution ejects the Zn saline solution droplet of positively charged by the first electrostatic atomizer 100, wherein, inlet temperature is 180 DEG C, Zn saline solution transporting velocity is 4.5mL/min, the air-flow pressure of gases at high pressure is 0.4MPa, the flow of gases at high pressure is 336mL/min, and the first electrode 125 is connected with high-voltage positive electrode by connecing electric connection, and cathode voltage is 2500V；
Ligand solution ejects electronegative ligand solution droplet by the second electrostatic atomizer 200, wherein, inlet temperature is 180 DEG C, ligand solution transporting velocity is 4.5mL/min, the air-flow pressure of gases at high pressure is 0.4MPa, the flow of gases at high pressure is 336mL/min, and the second electrode 225 is connected with high voltage negative by connecing electric connection, and cathode voltage is-860V；
First electrostatic atomizer 100 and the second electrostatic atomizer 200 are arranged to intersect 90 ° so that the charged metal salt solution droplet ejected and the charged ligand solution droplet sputtering ejected meet at a place and form white crystals MOF-5.
(3) above-mentioned product is placed in centrifuge tube, measures 10mL methanol, be centrifuged separating；Product after separation washes twice with dichloromethane again, stands and dries to obtain pure MOF-5 crystal.
X-ray powder diffraction (PXRD) collection of illustrative plates of the MOF-5 crystal of above-mentioned preparation as it is shown on figure 3, with MOF-5 single crystal diffraction collection of illustrative plates, utilize Origin software matching, the two curve obtained substantially match that.
Embodiment 2
Cu-BDC crystal preparation
(1) ten thousand/ analytical balance on accurately weigh 1.0268gCu (NO3)2·6H2O, is placed in the beaker of 50mL, measures 29.68mLDMF in beaker, and stirring and dissolving obtains Cu saline solution；
Analytical balance accurately weighs 0.7061g p-phthalic acid, is placed in the beaker of 50mL, measure the triethylamine of DMF and 4.68mL of 25mL in beaker, stirring and dissolving in fume hood, obtain ligand solution；
(2) Cu saline solution ejects the Cu saline solution droplet of positively charged by the first electrostatic atomizer 100, wherein, inlet temperature is 180 DEG C, Cu saline solution transporting velocity is 4.5mL/min, the air-flow pressure of gases at high pressure is 0.4MPa, the flow of gases at high pressure is 336mL/min, and the first electrode 125 is connected with high-voltage positive electrode by connecing electric connection, and cathode voltage is 170V；
Ligand solution ejects electronegative ligand solution droplet by the second electrostatic atomizer 200, wherein, inlet temperature is 180 DEG C, ligand solution transporting velocity is 4.5mL/min, the air-flow pressure of gases at high pressure is 0.4MPa, the flow of gases at high pressure is 336mL/min, and the second electrode 225 is connected with high voltage negative by connecing electric connection, and cathode voltage is-230V；
First electrostatic atomizer 100 and the second electrostatic atomizer 200 are arranged to intersect 90 ° so that the charged metal salt solution droplet ejected and the charged ligand solution droplet sputtering ejected meet at a place and form blue crystallization Cu-BDC.
(3) above-mentioned product is placed in centrifuge tube, measures 10mLDMF, be centrifuged separating；Product after separation washes twice with dichloromethane again, and at 150 DEG C, heat drying 24h obtains pure Cu-BDC crystal.
X-ray powder diffraction (PXRD) collection of illustrative plates of the Cu-BDC crystal of above-mentioned preparation as shown in Figure 4, and Cu-BDC single crystal diffraction collection of illustrative plates, utilize Origin software matching, the two curve obtained substantially match that.
Although content disclosed above illustrates the exemplary embodiment of the present invention, it is to be understood that, under the premise without departing substantially from the scope of the claims in the present invention and spirit, it is possible to be variously changed and substitute, these change and substitute in the scope falling into the claims in the present invention.
Claims (10)
1. the method adopting electrostatic spraying processes synthesis metal-organic framework material, it is characterized in that, double, two electrostatic atomizer i.e. the first electrostatic atomizer and the second electrostatic atomizer is adopted to synthesize MOF material, the method includes: the metal salt solution for synthesizing MOF material ejects charged metal salt solution droplet by the first electrostatic atomizer, ligand solution for synthesizing MOF material ejects charged ligand solution droplet by the second electrostatic atomizer, the ligand solution droplet simultaneously making the metal salt solution droplet ejected and eject merges together and reacts, form MOF crystal.
2. the method for synthesis metal-organic framework material according to claim 1, it is characterized in that, described first electrostatic atomizer is for ejecting charged metal salt solution droplet by the metal salt solution of synthesis MOF material, and it includes first liquid conveyer device and the first electrostatic atomization apparatus；
Described second electrostatic atomizer is for ejecting charged ligand solution droplet by the ligand solution of synthesis MOF material, and it includes second liquid conveyer device and the second electrostatic atomization apparatus；
Described first electrostatic atomizer and described second electrostatic atomizer are arranged to intersect so that the charged metal salt solution droplet ejected and the charged ligand solution droplet ejected can converge.
3. the method for synthesis metal-organic framework material according to claim 2, is characterized in that, in the first electrostatic atomizer:
Described first liquid conveyer device is used for the metal salt solution of synthesis MOF material is transported to the first electrostatic atomization apparatus, and first liquid conveyer device includes first liquid conveying pipe, this first liquid conveying pipe traverse the first electrostatic atomization apparatus；
First electrostatic atomization apparatus is for being atomized and make it charged the metal salt solution that the conveying of first liquid conveyer device comes, including the first air shooter, the first three-way connector, the first electrode sleeve pipe, the second three-way connector and the first electrode, wherein, first air shooter is enclosed within first liquid conveying tube outside by the first three-way connector, and first the 3rd port of three-way connector be arranged to air inlet, for passing into gases at high pressure to the first air shooter；First electrode sleeve pipe is enclosed within outside the first air shooter by the second three-way connector, and second three-way connector the 3rd port for the first electrode connect electric connection, the first electrode is arranged on the outside of the first air shooter and in the inside of the first electrode sleeve pipe.
4. the method for synthesis metal-organic framework material according to claim 2, is characterized in that, in the second electrostatic atomizer:
Described second liquid conveyer device is used for the ligand solution of synthesis MOF material is transported to the second electrostatic atomization apparatus, and second liquid conveyer device includes second liquid conveying pipe, this second liquid conveying pipe traverse the second electrostatic atomization apparatus；
Second electrostatic atomization apparatus is for being atomized and make it charged the ligand solution that the conveying of second liquid conveyer device comes, including the second air shooter, the 3rd three-way connector, the second electrode sleeve pipe, the 4th three-way connector and the second electrode, wherein, second air shooter is enclosed within second liquid conveying tube outside by the 3rd three-way connector, and the 3rd the 3rd port of three-way connector be arranged to air inlet, for passing into gases at high pressure to the second air shooter；Second electrode sleeve pipe is enclosed within outside the second air shooter by the 4th three-way connector, and the 4th three-way connector the 3rd port for the second electrode connect electric connection, the second electrode is arranged on the outside of the second air shooter and in the inside of the second electrode sleeve pipe.
5. the method for the synthesis metal-organic framework material according to claim 3 or 4, it is characterized in that, first liquid conveying pipe, second liquid conveying pipe, the first air shooter and the second air shooter are quartz capillary, and the first electrode sleeve pipe and the second electrode sleeve pipe are polyether-ether-ketone pipe；At droplet spout end, the length of the first electrode sleeve pipe and the second electrode sleeve pipe is longer than the first air shooter and the second air shooter respectively, and the length of the first air shooter and the second air shooter is longer than first liquid conveying pipe and second liquid conveying pipe respectively.
6. the method for synthesis metal-organic framework material according to claim 2, is characterized in that, described pair of electrostatic atomizer can also include:
Crystal collection device, for collecting the product MOF crystal of synthesis；And
Two containers, are respectively used to bearing metal saline solution and ligand solution.
7. the method for synthesis metal-organic framework material according to claim 1, it is characterized in that, the described metal salt solution for synthesizing MOF material is zinc solution or copper salt solution, described zinc solution is zinc nitrate, zinc acetate or the zinc chloride solution in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or water, it is preferable that zinc nitrate solution in dimethylformamide (DMF)；Described copper salt solution is copper nitrate or zinc acetate solution in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or water, it is preferable that copper nitrate solution in dimethylformamide (DMF).
8. the method for synthesis metal-organic framework material according to claim 1, it is characterized in that, the described ligand solution for synthesizing MOF material is the solution of p-phthalic acid, specifically, for p-phthalic acid solution in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or water, it is preferable that p-phthalic acid solution in dimethylformamide (DMF)；And described ligand solution also comprises triethylamine.
9. according to claim 1, the method of the synthesis metal-organic framework material described in 7 or 8, it is characterized in that, it is zinc solution or copper salt solution at the described metal salt solution for synthesizing MOF material, when the described ligand solution for synthesizing MOF material is the solution of p-phthalic acid, ejected the metal salt solution droplet of positively charged by the first electrostatic atomizer for synthesizing the metal salt solution of MOF material, ligand solution for synthesizing MOF material ejects electronegative ligand solution droplet by the second electrostatic atomizer, make to eject the metal salt solution droplet of positively charged simultaneously and eject electronegative ligand solution droplet and merge together and react, form MOF crystal.
10. the method for synthesis metal-organic framework material according to claim 9, is characterized in that, described MOF crystal is MOF-5 or Cu-BDC；
Described metal salt solution and ligand solution respectively enter the inlet temperature of the first electrostatic atomizer and the second electrostatic atomizer in 100 DEG C～180 DEG C temperature ranges；
The transporting velocity of described metal salt solution and ligand solution is within the scope of 0.1mL/min～50mL/min；
For making the flow of gases at high pressure of metal salt solution and ligand solution atomization in the scope of 0.1L/min～50L/min；The air-flow of described gases at high pressure is pressed within the scope of 0.1MPa～10MPa；And
For making metal salt solution and the charged positive and negative electrode voltage of ligand solution can be less than or equal to 10KV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610082272.XA CN105753890B (en) | 2016-02-05 | 2016-02-05 | The method for synthesizing metal-organic framework material using electrostatic spraying processes |
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| CN109559971A (en) * | 2018-11-14 | 2019-04-02 | 北京师范大学 | A kind of ionization apparatus and its application |
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