CN114873627A - In-situ preparation method of independently supported cerium oxide nanotube - Google Patents
In-situ preparation method of independently supported cerium oxide nanotube Download PDFInfo
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- 239000002071 nanotube Substances 0.000 title claims abstract description 41
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 40
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- -1 zeolite imidazole ester Chemical class 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- 239000012528 membrane Substances 0.000 claims description 44
- 239000002131 composite material Substances 0.000 claims description 43
- 229920005594 polymer fiber Polymers 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 24
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 23
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 22
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 22
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010041 electrostatic spinning Methods 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- JFRHWQBNJASIQN-UHFFFAOYSA-N CO.CC1=C(N=CN1)C Chemical compound CO.CC1=C(N=CN1)C JFRHWQBNJASIQN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 238000010923 batch production Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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Abstract
The invention belongs to the technical field of novel nano material preparation, and discloses an in-situ preparation method of an independently supported cerium oxide nanotube. The method for preparing the cerium oxide nanotube in situ by using the cobalt-based zeolite imidazole ester framework/polyacrylonitrile as the template agent has the advantages of simple operation, high efficiency, low cost, suitability for large-scale batch production and the like, and is expected to be popularized as controllable preparation of nanotubes with different functions.
Description
Technical Field
The invention relates to the technical field of novel nano material preparation, in particular to an in-situ preparation method of an independently supported cerium oxide nanotube.
Background
Oxidation of hydrogen dioxideCerium (CeO) 2 ) As the rare earth elements with the most abundant storage capacity in the earth crust, the rare earth elements with the most storage capacity in China are also used. Due to the advantages of unique 4f electronic structure, good optical property, excellent oxygen storage and release capacity, higher thermal stability and the like, the catalyst or the carrier is widely applied to the fields of photocatalysis, electrocatalysis, thermocatalysis and the like. With the development of nanotechnology, the researchers turn their eyes to the preparation of CeO with different structural characteristics 2 And (3) functional nano materials. Such as CeO 2 Nanoflower, nanosheet, nanosphere, nanotube, etc., wherein CeO 2 The nanotube has the characteristics of fast and short-range electron transmission channel, large specific surface area, high aspect ratio and the like due to the one-dimensional (1D) nanostructure of the nanotube. In addition, the hollow nanotubes tend to expose more reaction sites, thereby achieving excellent photocatalytic activity. Currently CeO 2 Representative syntheses of nanomaterials include mainly precipitation, sol-gel, microemulsion, sonochemical and hydrothermal methods. The hydrothermal method has the advantages of mild conditions, high purity, good dispersibility, controllable morphology, simple preparation process and simple device, and crystals can grow even at a lower temperature. However, CeO prepared by this method 2 The nano material is mostly a powder material, which is not beneficial to the recovery in the actual reaction process, thereby reducing the catalytic activity. Therefore, the CeO is constructed by developing a process which is simple, convenient, efficient, low in cost, independent in support and easy for large-scale production 2 The nanotube has important theoretical significance and practical application value.
Disclosure of Invention
In view of the prior CeO 2 The invention aims to provide independently supported CeO with high efficiency, simple operation, low cost, high yield and stable material structure 2 Method for in situ preparation of nanotubes for better exploitation of CeO 2 The physicochemical properties and potential applications of nanotubes provide technical support.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an in-situ preparation method of an independently supported cerium oxide nanotube, which comprises the following steps:
(1) mixing dimethylimidazole (2-MI), Polyacrylonitrile (PAN) and N, N-Dimethylformamide (DMF) to obtain a spinning precursor solution;
(2) carrying out electrostatic spinning on the spinning precursor solution prepared in the step (1) to obtain a dimethyl imidazole/polyacrylonitrile composite polymer fiber membrane;
(3) dipping the dimethyl imidazole/polyacrylonitrile composite polymer fiber membrane prepared in the step (2) in a methanol solution of cobalt nitrate to obtain a cobalt-based zeolite imidazole ester framework (ZIF-67)/polyacrylonitrile composite polymer fiber membrane;
(4) and (4) dipping the cobalt-based zeolite imidazole ester framework/polyacrylonitrile composite polymer fiber membrane prepared in the step (3) into a dimethyl imidazole methanol solution of cobalt nitrate and cerium nitrate to obtain the cerium oxide nanotube.
Preferably, in the above method for preparing an independently supported cerium oxide nanotube in situ, the molar ratio of the dimethylimidazole to the acrylonitrile unit in the polyacrylonitrile in step (1) is 1:16 to 1: 28; the mass ratio of polyacrylonitrile to N, N-dimethylformamide is 1: 6-1: 12.
Preferably, in the above method for preparing the cerium oxide nanotubes independently supported in situ, the conditions of the electrospinning process in the step (2) are as follows: the receiving device is an aluminum foil, the voltage is 12-18 kV, and the distance between the spinning needle head and the aluminum foil of the receiving plate is 16-20 cm.
Preferably, in the above in-situ preparation method of the independently supported cerium oxide nanotube, in the step (3), the mass-to-volume ratio of the dimethylimidazole/polyacrylonitrile composite polymer fiber membrane, cobalt nitrate, and methanol is 0.02-0.08 g: 1.20-1.80 g: 40-80 mL; the dipping time is 12-48 hours, and the temperature is 20-30 ℃.
Preferably, in the above method for in-situ preparation of an independently supported cerium oxide nanotube, the mass-to-volume ratio of the dimethylimidazole/polyacrylonitrile composite polymer fibrous membrane in step (3) to the cobalt nitrate, cerium nitrate, dimethylimidazole, and methanol in step (4) is 0.02-0.08 g: 0.15-0.22 g: 0.25-0.30 g: 0.60-1.20 g: 30-70 mL; the dipping time is 12-48 h, and the temperature is 20-30 ℃.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) in the presence of ligand dimethyl imidazole, the final product is cerium oxide through the ZIF-67 in-situ growth process;
(2) CeO can be realized by an in-situ growth technology 2 The nano tube is generated, the price is low, the reaction process is simple to operate, high in efficiency and short in period, and large-scale production and popularization are facilitated;
(3) CeO prepared by the invention 2 The micro-morphology structure of the nano tube is uniform, the nano tube is in a fiber membrane shape in the macro, and the nano tube is similar to the traditional powder CeO 2 Compared with the nanotube material, the nanotube material has the advantage of independent support, and is favorable for recovery in practical application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below.
FIG. 1 is the independently supported CeO synthesized in example 1 2 Scanning Electron Microscope (SEM) of nanotubes 40000 x.
FIG. 2 is the independently supported CeO synthesized in example 1 2 Scanning Electron Microscope (SEM) of nanotubes 20000 x.
FIG. 3 is the independently supported CeO synthesized in example 1 2 XRD diffraction pattern of nanotubes.
Detailed Description
The invention provides an in-situ preparation method of an independently supported cerium oxide nanotube, which comprises the following steps:
(1) mixing dimethyl imidazole, polyacrylonitrile and N, N-dimethylformamide to obtain a spinning precursor solution;
(2) carrying out electrostatic spinning on the spinning precursor solution prepared in the step (1) to obtain a dimethyl imidazole/polyacrylonitrile composite polymer fiber membrane;
(3) dipping the dimethyl imidazole/polyacrylonitrile composite polymer fiber membrane prepared in the step (2) in a methanol solution of cobalt nitrate to obtain a cobalt-based zeolite imidazole ester framework/polyacrylonitrile composite polymer fiber membrane;
(4) and (4) dipping the cobalt-based zeolite imidazole ester framework/polyacrylonitrile composite polymer fiber membrane prepared in the step (3) into a dimethyl imidazole methanol solution of cobalt nitrate and cerium nitrate to obtain the cerium oxide nanotube.
In the invention, the molar ratio of the dimethylimidazole to the acrylonitrile unit in the polyacrylonitrile in the step (1) is preferably 1:16 to 1:28, more preferably 1:18 to 1:22, and even more preferably 1: 20; the mass ratio of polyacrylonitrile to N, N-dimethylformamide is preferably 1:6 to 1:12, more preferably 1:9 to 1:12, and still more preferably 1: 10.
In the invention, the mixing temperature of the dimethyl imidazole, the polyacrylonitrile and the N, N-dimethylformamide in the step (1) is preferably 20-30 ℃, more preferably 24-28 ℃, and more preferably 25 ℃; the time is preferably 12 to 48 hours, more preferably 20 to 30 hours, and even more preferably 24 hours.
In the present invention, the conditions of the electrospinning process in the step (2) are: the receiving device is an aluminum foil, the voltage is 12-18 kV, the preferred voltage is 14-18 kV, and the preferred voltage is 16 kV; the distance between the spinning needle head and the aluminum foil of the receiving plate is 16-20 cm, preferably 17-19 cm, and more preferably 18 cm.
In the invention, the mass-to-volume ratio of the dimethyl imidazole/polyacrylonitrile composite polymer fiber membrane, the cobalt nitrate and the methanol in the step (3) is preferably 0.02-0.08 g: 1.20-1.80 g: 40-80 mL; more preferably 0.03 to 0.05 g: 1.40-1.70 g: 45-70 mL, more preferably 0.04 g: 1.64 g: 60 mL; the soaking time is preferably 12 to 48 hours, more preferably 20 to 30 hours, and even more preferably 24 hours; the temperature is preferably 20-30 ℃, more preferably 24-27 ℃, and even more preferably 25 ℃.
In the invention, the mass-to-volume ratio of the dimethylimidazole/polyacrylonitrile composite polymer fiber membrane in the step (3) to the cobalt nitrate, cerium nitrate, dimethylimidazole and methanol in the step (4) is preferably 0.02-0.08 g: 0.15-0.22 g: 0.25-0.30 g: 0.60-1.20 g: 30-70 mL, more preferably 0.03-0.06 g: 0.15-0.20 g: 0.26-0.29 g: 0.80-1.00 g: 45-60 mL, more preferably 0.04 g: 0.18 g: 0.27 g: 0.82 g: 50 mL; the soaking time is preferably 12-48 hours, more preferably 20-30 hours, and even more preferably 24 hours; the temperature is 20 to 30 ℃, more preferably 24 to 27 ℃, and still more preferably 25 ℃.
In the present invention, after completion of the impregnation in step (4), post-treatment is preferably performed; the post-treatment specifically comprises: washing and drying to obtain CeO 2 A nanotube; the washing condition is preferably 3 times by using methanol, and the drying condition is preferably drying for 12h at 60 ℃.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Mixing 0.15g of 2-MI, 2g of PAN and 18g of DMF to form a solution;
(2) stirring the solution in the step (1) at 25 ℃ for 24 hours;
(3) and (3) transferring the spinning precursor solution obtained in the step (2) into a 10mL injector for spinning, controlling the electrostatic spinning voltage to be 16kV, and controlling the distance between a spinning needle head and a receiving plate aluminum foil to be 18 cm.
(4) Soaking 0.04g of the 2-MI/PAN composite polymer fiber membrane obtained in the step (3) in 1.64g of cobalt nitrate and 60mL of methanol solution at 25 ℃ for 24 hours;
(5) soaking the composite polymer fiber membrane obtained in the step (4) in 0.18g of cobalt nitrate, 0.27g of cerium nitrate, 0.82g of 2-MI and 50mL of methanol solution at 25 ℃ for 24 hours; then taking out the composite polymer fiber membrane, washing the composite polymer fiber membrane for 3 times by using methanol, and drying the composite polymer fiber membrane for 12 hours in vacuum at the temperature of 60 ℃.
Example 2
(1) Mixing 0.17g of 2-MI, 1.78g of PAN and 18g of DMF to form a solution;
(2) stirring the solution in the step (1) at 24 ℃ for 20 hours;
(3) and (3) transferring the spinning precursor solution obtained in the step (2) into a 10mL injector for spinning, controlling the electrostatic spinning voltage to be 15kV, and controlling the distance between a spinning needle head and a receiving plate aluminum foil to be 17 cm.
(4) Soaking 0.03g of the 2-MI/PAN composite polymer fiber membrane obtained in the step (3) in a methanol solution of 1.28g of cobalt nitrate and 40mL for 24 hours at 24 ℃;
(5) soaking the composite polymer fiber membrane obtained in the step (4) in 0.15g of cobalt nitrate, 0.29g of cerium nitrate, 0.80g of 2-MI and 55mL of methanol solution at 24 ℃ for 24 hours; then taking out the composite polymer fiber membrane, washing the composite polymer fiber membrane for 3 times by using methanol, and drying the composite polymer fiber membrane for 12 hours in vacuum at the temperature of 60 ℃.
Example 3
(1) Mixing 0.16g of 2-MI, 2.22g of PAN and 17g of DMF to form a solution;
(2) stirring the solution in the step (1) at 26 ℃ for 22 hours;
(3) and (3) transferring the spinning precursor solution obtained in the step (2) into a 10mL injector for spinning, controlling the electrostatic spinning voltage to be 17kV, and controlling the distance between a spinning needle and a receiving plate aluminum foil to be 19 cm.
(4) Soaking 0.05g of the 2-MI/PAN composite polymer fiber membrane obtained in the step (3) in 1.45g of cobalt nitrate and 50mL of methanol solution at 26 ℃ for 24 hours;
(5) soaking the composite polymer fiber membrane obtained in the step (4) in 0.20g of cobalt nitrate, 0.28g of cerium nitrate, 0.86g of 2-MI and 52mL of methanol solution at 26 ℃ for 48 hours; then taking out the composite polymer fiber membrane, washing the composite polymer fiber membrane for 3 times by using methanol, and drying the composite polymer fiber membrane for 12 hours in vacuum at the temperature of 60 ℃.
Example 4
(1) Mixing 0.14g of 2-MI, 2.45g of PAN and 16g of DMF to form a solution;
(2) stirring the solution in the step (1) at 28 ℃ for 26 hours;
(3) and (3) transferring the spinning precursor solution obtained in the step (2) into a 10mL injector for spinning, controlling the electrostatic spinning voltage to be 13kV, and controlling the distance between a spinning needle head and a receiving plate aluminum foil to be 16 cm.
(4) Soaking 0.06g of the 2-MI/PAN composite polymer fiber membrane obtained in the step (3) in 1.74g of cobalt nitrate and 70mL of methanol solution at 27 ℃ for 12 hours;
(5) soaking the composite polymer fiber membrane obtained in the step (4) in 0.17g of cobalt nitrate, 0.26g of cerium nitrate, 0.90g of 2-MI and 46mL of methanol solution at 27 ℃ for 24 hours; then taking out the composite polymer fiber membrane, washing the composite polymer fiber membrane for 3 times by using methanol, and drying the composite polymer fiber membrane for 12 hours in vacuum at the temperature of 60 ℃.
Example 5
(1) Mixing 0.13g of 2-MI, 2g of PAN and 15g of DMF to form a solution;
(2) stirring the solution in the step (1) at 28 ℃ for 30 hours;
(3) and (3) transferring the spinning precursor solution obtained in the step (2) into a 10mL injector for spinning, controlling the electrostatic spinning voltage to be 18kV, and controlling the distance between a spinning needle head and a receiving plate aluminum foil to be 20 cm.
(4) Soaking 0.04g of the 2-MI/PAN composite polymer fiber membrane obtained in the step (3) in a methanol solution of 1.80g of cobalt nitrate and 80mL for 48 hours at 25 ℃;
(5) soaking the composite polymer fiber membrane obtained in the step (4) in 0.19g of cobalt nitrate, 0.27g of cerium nitrate, 0.98g of 2-MI and 48mL of methanol solution at 25 ℃ for 24 hours; then taking out the composite polymer fiber membrane, washing the composite polymer fiber membrane for 3 times by using methanol, and drying the composite polymer fiber membrane for 12 hours in vacuum at the temperature of 60 ℃.
FIGS. 1 and 2 are CeO synthesized in example 1 2 SEM photograph of nanotube, from which CeO can be seen 2 The nanotube is a hollow tubular structure, and has smooth surface and uniform structure.
FIG. 3 shows CeO synthesized in example 1 2 The XRD pattern of the nanotube has characteristic diffraction peaks corresponding to CeO at 28.54 deg., 47.48 deg., 56.34 deg., 69.41 deg. and 76.70 deg 2 The (111), (220), (311), (400) and (331) crystal planes of CeO show that the CeO is successfully prepared 2 A nanotube.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. An in-situ preparation method of an independently supported cerium oxide nanotube is characterized by comprising the following steps:
(1) mixing dimethyl imidazole, polyacrylonitrile and N, N-dimethylformamide to obtain a spinning precursor solution;
(2) carrying out electrostatic spinning on the spinning precursor solution prepared in the step (1) to obtain a dimethyl imidazole/polyacrylonitrile composite polymer fiber membrane;
(3) dipping the dimethyl imidazole/polyacrylonitrile composite polymer fiber membrane prepared in the step (2) in a methanol solution of cobalt nitrate to obtain a cobalt-based zeolite imidazole ester framework/polyacrylonitrile composite polymer fiber membrane;
(4) and (4) dipping the cobalt-based zeolite imidazole ester framework/polyacrylonitrile composite polymer fiber membrane prepared in the step (3) into a dimethyl imidazole methanol solution of cobalt nitrate and cerium nitrate to obtain the cerium oxide nanotube.
2. The in-situ preparation method of the independently supported cerium oxide nanotube according to claim 1, wherein the molar ratio of the dimethylimidazole to the acrylonitrile unit in the polyacrylonitrile in the step (1) is 1:16 to 1: 28; the mass ratio of polyacrylonitrile to N, N-dimethylformamide is 1: 6-1: 12.
3. The in-situ preparation method of the independently supported ceria nanotubes according to claim 2, wherein the conditions of the electrospinning process in the step (2) are as follows: the receiving device is an aluminum foil, the voltage is 12-18 kV, and the distance between the spinning needle head and the aluminum foil of the receiving plate is 16-20 cm.
4. The in-situ preparation method of the independently supported cerium oxide nanotube according to any one of claims 1 to 3, wherein the mass volume ratio of the dimethyl imidazole/polyacrylonitrile composite polymer fiber membrane, the cobalt nitrate and the methanol in the step (3) is 0.02 to 0.08 g: 1.20-1.80 g: 40-80 mL; the dipping time is 12-48 hours, and the temperature is 20-30 ℃.
5. The in-situ preparation method of the independently supported cerium oxide nanotube as claimed in claim 4, wherein the mass-to-volume ratio of the dimethylimidazole/polyacrylonitrile composite polymer fiber membrane in step (3) to the cobalt nitrate, cerium nitrate, dimethylimidazole and methanol in step (4) is 0.02-0.08 g: 0.15-0.22 g: 0.25-0.30 g: 0.60-1.20 g: 30-70 mL; the dipping time is 12-48 h, and the temperature is 20-30 ℃.
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