CN112981960A - Preparation method of metal organic framework/nano fiber with beaded structure - Google Patents
Preparation method of metal organic framework/nano fiber with beaded structure Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 38
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- 238000009987 spinning Methods 0.000 claims description 23
- 238000009826 distribution Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011149 active material Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
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- 239000002904 solvent Substances 0.000 claims description 11
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
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- 238000005520 cutting process Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 8
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- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
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- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
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- 239000002086 nanomaterial Substances 0.000 abstract description 2
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- 238000004132 cross linking Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 72
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 36
- 239000000463 material Substances 0.000 description 18
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- 239000002243 precursor Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-O 2-methyl-1h-imidazol-3-ium Chemical compound CC=1NC=C[NH+]=1 LXBGSDVWAMZHDD-UHFFFAOYSA-O 0.000 description 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention provides a preparation method of a metal organic framework/nano fiber with a beaded structure, belonging to the technical field of nano material preparation. Firstly, metal salt nodes on the surface of the metal/PAN nano-fiber are coordinated with 2-methylimidazole bridging in a solution, and ZIF particles distributed along the nano-fiber in a dotted manner are generated in an in-situ one-time growth mode. And adding the metal salt solution again, so that the metal ions enriched on the surface of the fiber and the organic ligand have a strong crosslinking effect, and obtaining the ZIF/PAN nano-fiber composite material with the layered heterostructure through in-situ secondary growth. The method can promote ZIF particles to uniformly grow along the orientation of the nano-fibers, so that more crystal face positions are exposed, the utilization of the crystal faces of the ZIF is maximized, the specific surface area and the activity are greatly improved, and the application field of the ZIF is expanded. The method is simple and controllable in process, the problems of MOF particle agglomeration, MOF derivative structure collapse and the like are solved greatly, and the method can be applied to the field of fuel cell catalysis, so that the catalytic activity and the stability are improved.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method of a metal organic framework/nano fiber with a beaded structure.
Background
The Metal Organic Framework (MOF) is a periodic porous material constructed by self-assembly of metal ions and organic connectors, and has a designable and tailorable rich pore channel structure and a high specific surface area. Among them, Zeolitic Imidazolate Framework (ZIF) is a MOF material with imidazole and its derivatives as ligands, which combines the advantages of both zeolitic and MOF materials, such as: in addition, carbon materials and metal compounds prepared by taking ZIF as a precursor have excellent conductivity, rich pore channel structures and more metal and heteroatom active sites, so that the ZIF material and derivatives thereof have good application prospects in the fields of gas sensing, catalysis, energy storage and the like. However, most MOF materials are in powder form, which is more serious in agglomeration phenomenon, not beneficial to exposing more active sites and pore structures, not beneficial to device integration, and limited in wide application, especially in the field of membranes. Therefore, how to improve the dispersibility of the MOF material and the film forming process, exposing more adsorption and catalytic sites is crucial to improve energy storage and catalytic performance.
The nanofiber has the advantages of small fiber diameter, high porosity, large specific surface area, large length-diameter ratio and the like, is a membrane material, more importantly, the nanofiber is easy to combine with other materials, the unique one-dimensional structure of the nanofiber has flexibility, the dispersibility of the nanofiber can be obviously improved, the conductivity of the nanofiber is increased, the rapid transmission of gas, electrons and ions is ensured, and the nanofiber has wide application prospects in the fields of energy storage, catalysis, sensing and the like. However, the existing binding mode of the ZIF and the nanofiber is generally the mixed spinning of metal salt and high polymer molecules, so that part of the metal salt is wrapped by the polymer on the inner side of the fiber and cannot be bound with an organic ligand, the utilization rate of the metal salt is reduced, the crystal structure and morphology cannot be well controlled, and the maintenance of the polyhedral structure of the MOF derivative is more difficult. The fiber diameter and the metal salt concentration are key factors influencing the nucleation speed and the growth size of the material, so that the metal utilization rate is improved and the nucleation rate is slowed down by regulating the fiber diameter and combining a metal salt in-situ secondary growth method, the MOF particles are ensured to grow slowly and penetrate through the fibers after large particles are formed, the dispersibility and the utilization rate of the MOF particles are greatly improved, and meanwhile, the MOF/nanofiber membrane material is obtained.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a metal organic framework/nano fiber with a beaded structure, and the material prepared by the method can be used in the technical field of fuel cells.
The method realizes the construction of the beaded and monodisperse ZIF nano-particles on the surface of Polyacrylonitrile (PAN) nano-fibers by an electrostatic spinning technology and simultaneously combining an in-situ secondary growth method, can promote the ZIF particles to uniformly grow along the nano-fibers in an oriented manner, enables more crystal face positions to be exposed, maximizes the utilization of crystal faces of ZIF, greatly improves the specific surface area and the activity, and widens the application field of the ZIF. The preparation method is simple and controllable in process, the problems of MOF particle agglomeration, MOF derivative structure collapse and the like are greatly solved, and the method can be applied to the field of fuel cell catalysis, so that the catalytic activity and the stability are improved.
The method comprises the following steps:
(1) preparation of metal/PAN dope: firstly, adding a DMF (dimethyl formamide) organic solvent into a glass bottle, adding metal salt into the solvent under the condition of uniform stirring, slowly adding PAN after the metal salt is dissolved, and uniformly stirring for 8-24 hours in a magnetic stirrer with the rotating speed of 200-1000 rpm to obtain a metal/PAN spinning solution;
(2) synthesis of metal/PAN nanofibers by electrospinning technique: transferring the metal/PAN spinning solution obtained in the step (1) into an injector, adjusting the propelling speed, the receiving distance and the electrostatic spinning voltage, carrying out double-needle spinning, obtaining a metal/PAN nano fiber membrane through the electrostatic spinning technology, and drying the obtained nano fiber membrane in a vacuum drying oven at the temperature of 50-100 ℃ for 12-24 hours;
(3) obtaining a ZIF/PAN active material in dotted distribution by an in-situ one-step growth method: cutting the nanofiber membrane obtained in the step (2) into a strip shape with the length of 4-6 cm and the width of 2-4 cm, putting the strip shape into a prepared 2-methylimidazol solution, and growing in situ for 1-6 hours to obtain a ZIF/PAN active material in a dotted distribution;
(4) obtaining the ZIF/PAN active material with a bead-string structure by an in-situ secondary growth method: adding the prepared metal alcohol solution into the ZIF/PAN active material in the dotted distribution obtained in the step (3) to enrich metal ions on the surface of the metal/PAN nanofiber, carrying out in-situ secondary growth for 1-6 h, taking out the nanofiber membrane, washing the nanofiber membrane for 3-5 times by using methanol, and drying the obtained nanofiber membrane in a vacuum drying oven at 50-100 ℃ for 12-24 h to obtain the ZIF/PAN active material in the bead-string structure.
Wherein, the metal salt in the step (1) is one or two of cobalt nitrate, ferric nitrate, zinc nitrate and nickel nitrate, and the mass ratio of PAN to the metal salt is (0.7-1.0): (0.3-0.6) g.
In the step (2), the propelling speed is 0.01-0.15 mm/min, the receiving distance is 10-25 cm, and the voltage is 15-25 kV.
In the step (3), the molar concentration of the 2-methylimidazole alcohol solution is 0.5-1.0 mol/L, and the selected solvent is methanol.
The molar concentration of the metal alcohol solution in the step (4) is 0.05-0.15 mol/L, the metal salt used for preparing the metal alcohol solution is the same as that in the step (1), and the selected solvent is methanol.
The technical scheme of the invention has the following beneficial effects:
in the scheme, the 'dotted' particles obtained by the in-situ primary growth method and the dimethyl imidazole provide active sites for rapid nucleation and growth for the secondary auxiliary growth of the ZIF nano particles by the in-situ metal salt, so that the growth of the ZIF particles along the orientation direction of the nano fibers is facilitated, and the ZIF/PAN composite material which is uniformly dispersed and grown on the surfaces of the nano fibers is obtained. The in-situ growth of the ZIF on the surface of the nanofiber can improve the utilization efficiency of a crystal face, effectively improve the physicochemical property of the crystal face, increase the specific surface area of the crystal face, provide more active sites, and solve the problems of ZIF particle agglomeration, difficulty in integrated utilization and the like. Meanwhile, the layered heterostructure can be used as a precursor material of carbon materials and metal compounds, can effectively relieve internal stress caused by volume change in the electrochemical reaction process, keeps the structural durability of an electrode material, can greatly improve the catalytic activity of an electrode, increases the contact area of the electrode and electrolyte, is applied to the fields of energy, catalysis, photoelectricity, filtration, protection and the like, and realizes functional application of the layered heterostructure.
Drawings
FIG. 1 is a process flow diagram of a process for preparing a metal-organic framework/nanofiber having a beaded structure according to the present invention;
FIG. 2 is an SEM image of a "dotted" distribution ZIF/PAN prepared according to example 1 of the present invention;
FIG. 3 is an SEM image of a "dotted" distribution ZIF/PAN prepared according to example 2 of the present invention;
FIG. 4 is an SEM image of a "beaded" distribution ZIF/PAN made according to example 3 of the present invention;
FIG. 5 is an SEM image of a "beaded" distribution ZIF/PAN made according to example 4 of the present invention;
FIG. 6 is an XRD pattern of "beaded" distribution ZIF/PAN made in accordance with example 3 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a metal organic framework/nano fiber with a beaded structure.
As shown in fig. 1, the method comprises the steps of:
(1) preparation of metal/PAN dope: firstly, adding a DMF (dimethyl formamide) organic solvent into a glass bottle, adding metal salt into the solvent under the condition of uniform stirring, slowly adding PAN after the metal salt is dissolved, and uniformly stirring for 8-24 hours in a magnetic stirrer with the rotating speed of 200-1000 rpm to obtain a metal/PAN spinning solution;
(2) synthesis of metal/PAN nanofibers by electrospinning technique: transferring the metal/PAN spinning solution obtained in the step (1) into an injector, adjusting the propelling speed, the receiving distance and the electrostatic spinning voltage, carrying out double-needle spinning, obtaining a metal/PAN nano fiber membrane through the electrostatic spinning technology, and drying the obtained nano fiber membrane in a vacuum drying oven at the temperature of 50-100 ℃ for 12-24 hours;
(3) obtaining a ZIF/PAN active material in dotted distribution by an in-situ one-step growth method: cutting the nanofiber membrane obtained in the step (2) into a strip shape with the length of 4-6 cm and the width of 2-4 cm, putting the strip shape into a prepared 2-methylimidazol solution, and growing in situ for 1-6 hours to obtain a ZIF/PAN active material in a dotted distribution;
(4) obtaining the ZIF/PAN active material with a bead-string structure by an in-situ secondary growth method: adding the prepared metal alcohol solution into the ZIF/PAN active material in the dotted distribution obtained in the step (3) to enrich metal ions on the surface of the metal/PAN nanofiber, carrying out in-situ secondary growth for 1-6 h, taking out the nanofiber membrane, washing the nanofiber membrane for 3-5 times by using methanol, and drying the obtained nanofiber membrane in a vacuum drying oven at 50-100 ℃ for 12-24 h to obtain the ZIF/PAN active material in the bead-string structure.
The following description is given with reference to specific examples.
Example 1
A sugarcoated haw type ZIF/PAN nanofiber electrode material with a beaded structure and a preparation method thereof comprise the following steps:
preparing a ZIF-67/PAN nano-fiber composite material with 'dotted' distribution by adopting an in-situ metal salt one-step growth method:
(1) preparation of Co2+PAN/dope: 0.5g of cobalt nitrate (Co (NO) was added separately3)2·6H2O) and 0.9g PAN are dissolved in 10mL DMF and are evenly stirred for 12h at room temperature to obtain Co2+A PAN spinning solution;
(2) preparation of Co2+A/PAN/nanofiber composite membrane: mixing the obtained Co2+the/PAN spinning solution was transferred to two 5mL syringes and double-needle spinning was carried out at a feed rate of 0.08mm/min, a take-up distance of 15cm and a voltage of 17 kV. Subjecting the obtained nanofibers to vacuum at 80 deg.CDrying in an air drying oven for 12h to obtain Co2+a/PAN/nanofiber membrane;
(3) preparation of a methanol solution of 2-methylimidazole: adding 6.6g of 2-methylimidazole into 100mL of methanol solution, and uniformly stirring for 2h to obtain the methanol solution of 2-methylimidazole;
(4) the Co obtained in the step (2) is mixed2+the/PAN nanofiber membrane is cut into a strip shape with the length of about 5cm and the width of about 3cm, put into 12mL of 2-methylimidazol solution, grown in situ for 2h, washed 3 times by using methanol solvent, and dried in a vacuum drying oven at 60 ℃ for 2h to obtain the 'dotted' ZIF-67/PAN composite distributed on the surface of the nanofiber, as shown in figure 2.
Example 2
A grape type ZIF/PAN nanofiber material with a beaded structure and a preparation method thereof comprise the following steps:
preparing a ZIF-67-ZIF-8 bimetal ZIF material in a dotted distribution by adopting an in-situ mixed metal salt one-step growth method:
(1) preparation of Co2+-Zn2+PAN spinning solution: 0.25g of Co (NO) was added3)2·6H2O, 0.25g Zinc nitrate (Zn (NO)3)2·6H2O) and 0.9g PAN are dissolved in 10mL DMF and are evenly stirred for 12h at room temperature to obtain Co2+-Zn2+A PAN spinning solution;
(2) preparation of Co2+-Zn2+PAN nanofiber composite membranes: mixing the obtained Co2+-Zn2+the/PAN spinning solution was transferred to two 5mL syringes and double-needle spinning was carried out at a feed rate of 0.08mm/min, a take-up distance of 15cm and a voltage of 17 kV. Drying the obtained nano-fiber in a vacuum drying oven at 80 ℃ for 12h to obtain Co2+-Zn2+A PAN nanofiber membrane;
(3) preparation of a methanol solution of 2-methylimidazole: adding 6.6g of 2-methylimidazole into 100mL of methanol solution, and uniformly stirring for 2h to obtain the methanol solution of 2-methylimidazole;
(4) the Co obtained in the step (2) is mixed2+-Zn2+PAN nanofiber membrane is cut into long strips with the length of about 5cm and the width of about 3cmAnd putting the mixture into 12mL of 2-methylimidazolium alcohol solution, growing in situ for 2h, then washing the mixture for 3 times by using a methanol solvent, and drying the mixture for 2h in a vacuum drying oven at the temperature of 60 ℃ to obtain the 'dotted' ZIF-67-ZIF-8 bimetal ZIF material distributed on the PAN nanofiber, wherein the material is shown in figure 3.
Example 3
A sugarcoated haw type ZIF/PAN nanofiber electrode material with a beaded structure and a preparation method thereof comprise the following steps:
preparing a sugarcoated haw type beaded ZIF-67/PAN nano-fiber material by adopting an in-situ metal salt secondary auxiliary growth method:
(1) preparation of metal salt/PAN dope: 0.5g of Co (NO) was added3)2·6H2Dissolving O and 0.9g PAN in 10mL DMF, and uniformly stirring at room temperature for 12h to obtain Co2+A PAN spinning solution;
(2) preparation of metal salt/PAN nanofibers: mixing the obtained Co2+the/PAN spinning solution was transferred to two 5mL syringes and double-needle spinning was carried out at a feed rate of 0.08mm/min, a take-up distance of 15cm and a voltage of 17 kV. Drying the obtained nano-fiber in a vacuum drying oven at 80 ℃ for 12h to obtain Co2+A PAN nanofiber membrane;
(3) preparation of a methanol solution of 2-methylimidazole: adding 6.6g of 2-methylimidazole into 100mL of methanol solution, and uniformly stirring for 2h to obtain the methanol solution of 2-methylimidazole;
(4) the Co obtained in the step (2) is mixed2+Cutting the PAN nanofiber membrane into a strip shape with the length of about 5cm and the width of about 3cm, putting the strip shape into 12mL of 2-methylimidazole alcohol solution, and growing in situ for 2 h;
(5) preparation of Co (NO)3)2·6H2Methanol solution of O: 2.91g of Co (NO)3)2·6H2Adding O into 100mL of methanol solution, and uniformly stirring for 2h to obtain Co (NO)3)2·6H2A solution of O in methanol;
(6) after the in-situ growth in the step (4) is carried out for 2 hours, 6mL of Co (NO) obtained in the step (5) is added3)2·6H2Adding the methanol solution of O into the step (4) twice in situGrowing for 2h, washing with methanol solvent for 3 times, and drying in a vacuum drying oven at 60 deg.C for 2h to obtain "beaded" ZIF-67 distributed on the surface of PAN nanofiber, wherein morphology and XRD are shown in FIG. 4 and FIG. 6.
Example 4
A grape type ZIF/PAN nanofiber material with a beaded structure and a preparation method thereof comprise the following steps:
preparing a ZIF-67-ZIF-8 composite material with a grape-type bead structure growing on the surface of the PAN nanofiber by adopting an in-situ metal salt auxiliary secondary growth method:
(1) preparation of a bimetallic/PAN dope: 0.25g of Co (NO) was added3)2·6H2O、0.25g Zn(NO3)2·6H2Dissolving O and 0.9g PAN in 10mL DMF, and uniformly stirring at room temperature for 12h to obtain Co2+-Zn2+A PAN spinning solution;
(2) preparing a bimetal/PAN nanofiber composite membrane: mixing the obtained Co2+-Zn2+the/PAN spinning solution was transferred to two 5mL syringes and double-needle spinning was carried out at a feed rate of 0.08mm/min, a take-up distance of 15cm and a voltage of 17 kV. Drying the obtained nano-fiber in a vacuum drying oven at 80 ℃ for 12h to obtain Co2+-Zn2+A PAN nanofiber membrane;
(3) preparation of a methanol solution of 2-methylimidazole: adding 6.6g of 2-methylimidazole into 100mL of methanol solution, and uniformly stirring for 2h to obtain the methanol solution of 2-methylimidazole;
(4) the Co obtained in the step (2) is mixed2+-Zn2+Cutting the PAN nanofiber membrane into a strip shape with the length of about 5cm and the width of about 3cm, putting the strip shape into 12mL of 2-methylimidazole alcohol solution, and growing in situ for 2 h;
(5) preparation of Co (NO)3)2·6H2O/Zn(NO3)2·6H2Methanol solution of O: 1.455g of Co (NO)3)2·6H2O and 1.480g Zn (NO)3)2·6H2Adding O into 100mL of methanol solution, and uniformly stirring for 2h to obtain Co (NO)3)2·6H2O/Zn(NO3)2·6H2A solution of O in methanol;
(6) after the in-situ growth in the step (4) is carried out for 2 hours, 6mL of Co (NO) obtained in the step (5) is added3)2·6H2O/Zn(NO3)2·6H2And (3) adding a methanol solution of O into the step (4), carrying out in-situ secondary growth for 2h, then washing 3 times by using a methanol solvent, and drying for 2h in a vacuum drying oven at the temperature of 60 ℃ to obtain a grape type beaded structure ZIF/PAN nano fiber material, as shown in figure 5.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A preparation method of metal organic framework/nano fiber with a beaded structure is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of metal/PAN dope: firstly, adding a DMF (dimethyl formamide) organic solvent into a glass bottle, adding metal salt into the solvent under the condition of uniform stirring, slowly adding PAN after the metal salt is dissolved, and uniformly stirring for 8-24 hours in a magnetic stirrer with the rotating speed of 200-1000 rpm to obtain a metal/PAN spinning solution;
(2) synthesis of metal/PAN nanofibers by electrospinning technique: transferring the metal/PAN spinning solution obtained in the step (1) into an injector, adjusting the propelling speed, the receiving distance and the electrostatic spinning voltage, carrying out double-needle spinning, obtaining a metal/PAN nano fiber membrane through the electrostatic spinning technology, and drying the obtained nano fiber membrane in a vacuum drying oven at the temperature of 50-100 ℃ for 12-24 hours;
(3) obtaining a ZIF/PAN active material in dotted distribution by an in-situ one-step growth method: cutting the nanofiber membrane obtained in the step (2) into a strip shape with the length of 4-6 cm and the width of 2-4 cm, putting the strip shape into a prepared 2-methylimidazol solution, and growing in situ for 1-6 hours to obtain a ZIF/PAN active material in a dotted distribution;
(4) obtaining the ZIF/PAN active material with a bead-string structure by an in-situ secondary growth method: adding the prepared metal alcohol solution into the ZIF/PAN active material in the dotted distribution obtained in the step (3) to enrich metal ions on the surface of the metal/PAN nanofiber, carrying out in-situ secondary growth for 1-6 h, taking out the nanofiber membrane, washing the nanofiber membrane for 3-5 times by using methanol, and drying the obtained nanofiber membrane in a vacuum drying oven at 50-100 ℃ for 12-24 h to obtain the ZIF/PAN active material in the bead-string structure.
2. The method for preparing the metal-organic framework/nanofiber with a beaded structure according to claim 1, wherein the method comprises the following steps: in the step (1), the metal salt is one or two of cobalt nitrate, ferric nitrate, zinc nitrate and nickel nitrate, and the mass ratio of PAN to the metal salt is (0.7-1.0): (0.3-0.6) g.
3. The method for preparing the metal-organic framework/nanofiber with a beaded structure according to claim 1, wherein the method comprises the following steps: in the step (2), the propelling speed is 0.01-0.15 mm/min, the receiving distance is 10-25 cm, and the voltage is 15-25 kV.
4. The method for preparing the metal-organic framework/nanofiber with a beaded structure according to claim 1, wherein the method comprises the following steps: the molar concentration of the 2-methylimidazol solution in the step (3) is 0.5-1.0 mol/L, and the selected solvent is methanol.
5. The method for preparing the metal-organic framework/nanofiber with a beaded structure according to claim 1, wherein the method comprises the following steps: the molar concentration of the metal alcohol solution in the step (4) is 0.05-0.15 mol/L, the metal salt used for preparing the metal alcohol solution is the same as that in the step (1), and the selected solvent is methanol.
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