CN114534797A - Continuous flow purification and separation method of nanofiber supported catalyst - Google Patents
Continuous flow purification and separation method of nanofiber supported catalyst Download PDFInfo
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- CN114534797A CN114534797A CN202210230936.8A CN202210230936A CN114534797A CN 114534797 A CN114534797 A CN 114534797A CN 202210230936 A CN202210230936 A CN 202210230936A CN 114534797 A CN114534797 A CN 114534797A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000000926 separation method Methods 0.000 title claims abstract description 43
- 238000000746 purification Methods 0.000 title claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 34
- 229920002678 cellulose Polymers 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 11
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 239000006250 one-dimensional material Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000012065 filter cake Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
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- 238000003917 TEM image Methods 0.000 description 11
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
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- 238000010041 electrostatic spinning Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
The invention discloses a continuous flow purification and separation method of a nanofiber supported catalyst, which comprises the following steps: (1) mixing and stirring the nano-fibers and the metal for loading; (2) sucking the mixed solution into a syringe for filtering; (3) and collecting the solid remained on the mixed cellulose ester membrane after the filtration is finished to obtain the separated nanofiber supported catalyst. The method can be used for carrying out solid-liquid separation, so that the nanofiber supported catalyst with a good separation effect is obtained, the complexity of the preparation process operation is reduced, and the experimental efficiency is remarkably improved; the filter membrane with the proper pore diameter is selected for filtering the nano-fiber, so that the catalyst yield is obviously improved while the operation time is reduced, the problem that the catalyst is easy to agglomerate is solved, and the integral forming of the nano-fiber supported catalyst filter cake is realized.
Description
Technical Field
The invention belongs to catalyst separation and purification, and particularly relates to a continuous flow purification and separation method of a nanofiber supported catalyst.
Background
The metal/nanofiber catalyst prepared by using the nanofiber as a carrier to carry out metal nanoparticle loading has a series of excellent characteristics and catalytic performance, and is an important research direction in the field of catalysts. In the prior art, after metal is loaded on the nano fiber, a solvent washing centrifugation method is usually adopted for removing metal nano particles which cannot be loaded, and the method is relatively complicated in operation process, long in time consumption, high in energy consumption, low in yield, easy to cause agglomeration and not beneficial to efficient development of experiments. The required manpower is more in the experimental process, and the method is an obstacle to the realization of industrialization. Meanwhile, in the prior art, the amount and the variety of the required solvent are more in the separation process, and the energy consumption of the required centrifugal machine is higher, so that the green production and the environmental protection are not facilitated. Therefore, the development of a purification and separation method which is simple and convenient to operate and can effectively improve the experimental efficiency is urgently needed.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a continuous flow purification and separation method of a nanofiber supported catalyst, which is simple in operation, short in time consumption and high in yield.
A second object of the present invention is to provide a nanofiber-supported catalyst that is obtained by a continuous flow purification and separation method of the nanofiber-supported catalyst and is integrally formed.
The third purpose of the invention is to provide the application of the continuous flow purification and separation method of the nanofiber supported catalyst in the nano synthesis with one-dimensional material as a framework.
The technical scheme is as follows: in order to achieve the purpose, the continuous flow purification and separation method of the nanofiber supported catalyst comprises the following specific steps:
(1) mixing and stirring the nano-fiber and the metal in a solvent at room temperature, and carrying out loading;
(2) sucking the loaded mixed solution into a syringe for filtration;
(3) and collecting the solid remained on the mixed cellulose ester membrane after the filtration is finished to obtain the separated nanofiber supported catalyst.
Wherein, the metal in the step (1) can be one or more of Au, Ag, Pt and Pd; the metal nanoparticles have a diameter less than the diameter of the nanofibers.
Preferably, the metal in step (1) is Pt.
Wherein, the nano fiber in the step (1) is TiO2Nanofibers, Al2O3Nanofiber, Al-Ti composite nanofiber or CeO2And (3) nano fibers.
Wherein the mixing and stirring time in the step (1) is 1-3 hours.
Preferably, the stirring time in step (1) is 2 hours.
Preferably, a filter head is connected to the lower part of the injector in the step (2), and a mixed cellulose ester membrane is arranged in the filter head.
Preferably, the filtration in step (3) is carried out using a continuous flow apparatus at a flow rate of 1 to 3 mL/min.
Wherein the mixed cellulose ester membrane has a pore diameter of 0.20-0.50 μm, and the pore diameter of the mixed cellulose ester membrane is between the diameter of the metal nano-particles and the diameter of the nano-fibers.
The invention provides a nanofiber supported catalyst integrally formed into a filter cake, which is obtained by a continuous flow purification and separation method of the nanofiber supported catalyst.
The invention also provides the application of the continuous flow purification and separation method of the nanofiber supported catalyst in the nano synthesis with the one-dimensional material as the framework.
The invention mechanism is as follows: the invention takes the matching degree of the size of the nanometer fiber, the diameter of the metal nanometer particle and the aperture of the mixed cellulose ester membrane as a design idea, adopts the principle of filtration and separation, selects the mixed cellulose ester membrane with the aperture between the diameter of the metal nanometer particle and the diameter of the nanometer fiber, and can pass through the mixed cellulose ester membrane along with liquid during filtration because the diameter of the nanometer particle is smaller than the aperture of the mixed cellulose ester membrane, and the diameter of the nanometer fiber is larger than the aperture of the mixed cellulose ester membrane, and can not pass through and stay on the mixed cellulose ester membrane during filtration, thereby being capable of removing the metal nanometer particle which is not loaded on the fiber, and realizing the separation and purification of the loaded nanometer fiber catalyst. Based on the size matching principle, the technology can be applied to the nano synthesis process taking various one-dimensional materials as the framework, and compared with the centrifugal process, the technology is simple and convenient to operate, labor is reduced, efficiency is high, energy consumption is low, and the technology is beneficial to the industrial process.
Has the advantages that: compared with the prior art, the method has the following advantages:
(1) the method adopts a washing and filtering method to carry out solid-liquid separation, reduces the complexity of the operation of the preparation process while obtaining the nanofiber supported catalyst with better separation effect, obviously improves the experimental efficiency, and needs about two hours for the centrifugal washing process and only ten minutes for the filtering separation when completing a certain amount of the same separation task, wherein the time needed is about one tenth of that of the centrifugal method;
(2) according to the continuous flow separation method for the nanofiber-supported catalyst, the mixed cellulose ester membrane with the pore diameter is selected to filter the nanofiber precipitate, so that the operation time is reduced, the catalyst yield is remarkably improved, and the problem that the catalyst is easy to agglomerate is solved;
(3) the invention realizes the integral molding of the nanofiber-supported catalyst filter cake, and the catalyst obtained by centrifugation is dispersed powder or particle blocks, so that the invention is more convenient for the direct implementation of subsequent catalytic experiments.
Drawings
FIG. 1 is a diagram of a continuous filtration apparatus of the present invention;
FIG. 2 is a view of the construction of the filter tip of the present invention;
FIG. 3 is a diagram of a filtered filter cake of the present invention, where A is a Pt/Al-Ti composite fiber filter cake and B is Pt/CeO2A filter cake;
FIG. 4 shows TiO of the present invention2TEM image of the nanofiber;
FIG. 5 shows TiO of the present invention2TEM image of nanofiber supported Pt catalyst;
FIG. 6 shows Al of the present invention2O3TEM image of nanofiber supported Pt catalyst;
FIG. 7 is a TEM image of the Al-Ti composite nanofiber supported Pt catalyst (molar ratio of titanium to aluminum is 15: 1);
FIG. 8 shows CeO according to the present invention2TEM image of nanofiber supported Pt catalyst.
Detailed Description
The invention is further illustrated by the following figures and examples.
In the examples, PVP is polyvinylpyrrolidone, TTIP is tetraisopropyl titanate, Al (acac)3Is aluminium acetylacetonate, Ce (acac)3Is cerium acetylacetonate. Mixed cellulose ester membranes of different pore sizes were purchased from Shanghai peninsula industrials Inc. clean plant.
Example 1
Separation of TiO by washing filtration2Nanofiber-supported Pt catalyst
(1) Dissolving 0.3g PVP (molecular weight 55000) in 4.5mL ethanol, stirring overnight, adding 3mL acetic acid and 2.5mL TTIP, stirring to obtain clear precursor solution, transferring to a metal head-mounted deviceIn an injector, electrostatic spinning is carried out under the conditions that the voltage is 17.5kV, the distance between a metal needle head and a filament collector is 12.5cm, the flow rate is 0.5mL/h, the prepared nano-fiber is heated to 700 ℃ at the speed of 2.8 ℃/min in the air, and the nano-fiber is roasted for 2h to obtain TiO2And (3) nano fibers.
(2) Preheating 4mL of glycol in an oil bath kettle at 110 ℃ for 30 min; then, 22.5mg of PVP (molecular weight 55000) was dissolved in 2mL of ethylene glycol at room temperature to obtain solution A; then 8.25mg/mL of H is prepared2PtCl6Is solution B. Then 0.5mL of each A, B solution was injected into preheated ethylene glycol simultaneously, and the reaction was continued for about 1h under 110 ℃ oil bath to obtain a Pt suspension.
(3) Weighing 5mg TiO2The nanofibers were dispersed in 1.8mL of pure water, and 0.2mL of Pt suspension (0.392mg/mL) was added dropwise to form 0.0025g/mL TiO2Mixing the nanometer fiber solution with TiO2And (3) loading the nano-fiber and the metal Pt, and mixing and stirring at normal temperature for 2h to complete loading.
(4) As shown in FIG. 1, the solution after stirring and loading (0.0025g/mL, 2mL) was sucked into a syringe, the syringe was fixed to a micro-syringe pump (Shenzhen Riwode Life technologies, Ltd.) with a flow rate set, a filter head was connected to the lower part of the syringe, and a mixed cellulose ester membrane with a pore size of 0.45 μm was filled into the filter head. The filter head can be unscrewed and filled with a mixed cellulose ester membrane, as shown in the configuration of FIG. 2.
(5) And (3) filtering the loaded mixed solution at the flow rate of 3mL/min by using a micro-injection pump in the continuous filtering device, and collecting solids remained on a mixed cellulose ester membrane after the filtration is finished to obtain the nanofiber supported catalyst which is completely separated into filter cakes. According to a transmission electron microscope, the diameter of the Pt nano particle is about 3nm, the diameter of the nano fiber is about 0.1-0.3 μm, the length of the nano fiber is about 0.5-2 μm, and the pore diameter of the mixed cellulose ester film is 0.45 μm, so that the separation of the unsupported Pt nano particle and the nano fiber can be realized.
(6) Observation of the raw, unsupported TiO obtained by electrospinning with a transmission electron microscope2Nanofiber sample to obtain TiO as shown in FIG. 42Nano-fiber TEAnd (5) an M diagram. Observing the TiO loaded with metal Pt by adopting a transmission electron microscope2The nanofiber supported catalyst sample was subjected to TiO modification as shown in FIG. 52TEM image of nanofiber supported Pt catalyst. And the TiO of FIG. 4 without supported metal2Compared with the nano-fiber, it can be seen that the Pt nanoparticles in fig. 5 are successfully loaded on the surface of the fiber, and the background area outside the fiber is clean without residual Pt nanoparticles, which proves that the separation and purification technology is effective.
Example 2
Separating Al by washing and filtering2O3Nanofiber-supported Pt catalyst
(1) 0.3g PVP (molecular weight 55000) was dissolved in 2mL ethanol, stirred overnight, and 0.3g Al (acac) was added3And 3mL of acetone, stirring until the solution is a clear precursor solution, transferring the clear precursor solution into an injector provided with a metal head, performing electrostatic spinning under the conditions that the voltage is 16.5kV, the distance between a metal needle head and a filament collector is 12cm, and the flow rate is 0.3mL/h, heating the prepared nano-fiber to 900 ℃ at the speed of 2.8 ℃/min in the air, and roasting for 2h to obtain Al2O3And (3) nano fibers.
(2) A Pt suspension was prepared as in example 1.
(3) Weighing 5mg of Al2O3The nanofibers were dispersed in 1.8mL of pure water, and 0.2mL of Pt (0.392mg/mL) was added dropwise to form Al at a concentration of 0.0025g/mL2O3Nano fiber solution, mixing and stirring Al2O3And (3) loading the nano-fiber and the metal Pt, and mixing and stirring at normal temperature for 2h to complete loading.
(4) A continuous flow filtration apparatus as described in example 1 was constructed, and the stirred and loaded solution (0.0025g/mL, 2mL) was drawn into a syringe, below which was attached a filter head, into which was loaded a mixed cellulose ester membrane having a pore size of 0.22. mu.m.
(5) And (3) filtering the loaded mixed solution at the flow rate of 1mL/min by using a micro-injection pump in the continuous filtering device, and collecting solids remained on the mixed cellulose ester membrane after the filtration is finished to obtain the separated nanofiber supported catalyst. According to a transmission electron microscope, the diameter of the Pt nano particle is about 3nm, the diameter of the nano fiber is about 0.1-0.3 μm, the length of the nano fiber is about 0.5-2 μm, and the pore diameter of the mixed cellulose ester film is 0.22 μm, so that the separation of the unloaded Pt nano particle and the nano fiber can be realized.
(6) Observing the obtained Al by a transmission electron microscope2O3The nanofiber-supported catalyst sample was subjected to Al as shown in FIG. 62O3TEM image of nanofiber supported Pt catalyst, and TiO not supported with metal in FIG. 42Compared with the nano-fiber, the Pt nano-particles can be successfully loaded on the surface of the fiber, and the back bottom area outside the fiber is clean without residual Pt nano-particles, so that the separation and purification technology is proved to be effective.
Example 3
Method for separating Al-Ti composite nanofiber loaded Pt catalyst by washing and filtering method
(1) 0.6g PVP (molecular weight 55000) was dissolved in ethanol, stirred overnight and then a certain amount of Al (acac) was added3And 5mL of acetone, stirring uniformly, then adding 3mL of acetic acid and 2.5mL of TTIP, stirring until the mixture is clear, transferring the spinning solution into an injector provided with a metal head, carrying out electrostatic spinning under the conditions that the voltage is 18.5kV, the distance between a metal needle and a filament collector is 12.5cm, and the flow rate is 0.3mL/h, heating the obtained nano fiber to 600 ℃ at the speed of 2.0 ℃/min in the air, and roasting for 2h to obtain the Al-Ti composite nano fiber. By adjusting Al (acac)3Was used in an amount of 0.74g to control the titanium to aluminum molar ratio at 15: 1.
(2) A Pt suspension was prepared as in example 1.
(3) Weighing 5mg of Al-Ti composite nanofiber, dispersing the Al-Ti composite nanofiber in 1.8mL of pure water, dropwise adding 0.2mL of Pt (0.392mg/mL) to form an Al-Ti composite nanofiber solution with the concentration of 0.0025g/mL, carrying out mixing and stirring on the Al-Ti composite nanofiber and metal Pt, and carrying out mixing and stirring for 2 hours at normal temperature.
(4) A continuous flow filtration apparatus as described in example 1 was constructed, and the stirred and loaded solution (0.0025g/mL, 2mL) was drawn into a syringe, below which was attached a filter head, into which was loaded a mixed cellulose ester membrane having a pore size of 0.22. mu.m.
(5) And (3) filtering the loaded mixed solution at the flow rate of 2mL/min by using a continuous flow device, collecting the solid remained on the filter membrane after the filtration is finished, and obtaining the separated nanofiber supported catalyst, wherein the filter cake after the filtration is shown as a figure 3 (A). It is known from transmission electron microscopy that Pt nanoparticles have a diameter of about 3nm, nanofibers have a diameter of about 0.1-0.3 μm, a length of about 0.5-2 μm, and mixed cellulose ester membranes have a pore size of 0.22 μm, thus theoretically enabling separation of unsupported Pt nanoparticles and nanofibers.
(6) Observing the obtained Al-Ti composite nanofiber supported catalyst sample by adopting a transmission electron microscope to obtain a TEM image of the Al-Ti composite nanofiber supported Pt catalyst shown in figure 7 and a TEM image of TiO not loaded with metal in figure 42Compared with the nano-fiber, the Pt nano-particles can be successfully loaded on the surface of the Al-Ti composite nano-fiber, and the back bottom area outside the fiber is clean without residual Pt nano-particles, so that the separation and purification technology is proved to be effective.
Example 4
CeO separation by washing and filtering2Nanofiber-supported Pt catalyst
(1) 0.6g PVP (molecular weight 55000) was dissolved in 3mL ethanol, stirred overnight, and 0.3g Ce (acac) was added3And 3mL of acetone, stirring until the solution is a clear precursor solution, transferring the clear precursor solution into an injector provided with a metal head, carrying out electrostatic spinning under the conditions that the voltage is 17kV, the distance between a metal needle head and a filament collector is 12cm, and the flow rate is 0.3mL/h, heating the prepared nano-fiber to 500 ℃ at the speed of 4.2 ℃/min in the air, and roasting for 2h to obtain CeO2And (3) nano fibers.
(2) A Pt suspension was prepared as in example 1.
(3) 5mg of CeO was weighed2The nanofibers were dispersed in 1.8mL of pure water, and 0.2mL of Pt (0.392mg/mL) was added dropwise to form CeO at a concentration of 0.0025g/mL2Nano fiber solution, mixing and stirring CeO2And (3) loading the nano-fiber and metal Pt, and mixing and stirring at normal temperature for 2h to complete loading.
(4) A continuous flow filtration apparatus as described in example 1 was constructed, and the solution loaded with stirring was drawn into a syringe, below which a filtration needle was attached, and the filtration needle was filled with a mixed cellulose ester membrane having a pore size of 0.22. mu.m.
(5) The loaded mixed solution was filtered at a flow rate of 2mL/min using a micro syringe pump in the continuous filtration apparatus, and after the filtration was completed, the precipitate remaining on the mixed cellulose ester membrane was collected to obtain a separated nanofiber-supported catalyst, and the filter cake after filtration was as shown in fig. 3 (B). According to a transmission electron microscope, the diameter of the Pt nano particle is about 3nm, the diameter of the nano fiber is about 0.1-0.3 μm, the length of the nano fiber is about 0.5-2 μm, and the pore diameter of the mixed cellulose ester film is 0.22 μm, so that the separation of the unloaded Pt nano particle and the nano fiber can be realized theoretically.
(6) The nanofiber-supported catalyst sample obtained was observed by a transmission electron microscope to obtain CeO as shown in FIG. 82TEM image of nanofiber supported Pt catalyst, and TiO not supported with metal in FIG. 42Compared with the nano-fiber, the Pt nano-particles can be successfully loaded on the surface of the fiber, and the back bottom area outside the fiber is clean without residual Pt nano-particles, so that the separation and purification technology is proved to be effective.
Comparative example 1
The method of example 1 was employed, except that when a mixed cellulose ester membrane having a pore size of 0.6 μm or more was packed in the filter head, as a result, since the pore size of the mixed cellulose ester membrane was larger than the diameter of the metal nanoparticles and the size of the nanofibers, part or all of the nanofibers passed through the pore size together with the liquid, and the loss of the catalyst occurred, or even the catalyst could not be separated at all. If the pore diameter of the mixed cellulose ester membrane filled in the filter head is too small, the filtration resistance is increased, which increases the difficulty of the filtration process, and meanwhile, the nanofibers continuously accumulated on the mixed cellulose ester membrane during the filtration process influence the pore diameter of the filter membrane to a certain extent, so that the diameter of the filter membrane is smaller, and the possibility of generating the residual nanoparticles is increased. If the separation is not complete, metal nanoparticles appear on the back of the TEM image of the loaded fiber, and the metal nanoparticles which are not loaded on the fiber are more prone to sintering in the catalytic reaction process, so that the catalytic activity is influenced.
Claims (10)
1. A continuous flow purification and separation method of a nanofiber supported catalyst is characterized by comprising the following specific steps:
(1) mixing and stirring the nano-fibers and the metal, and carrying out loading;
(2) sucking the loaded mixed solution into a syringe for filtration;
(3) and collecting the solid remained on the mixed cellulose ester membrane after the filtration is finished to obtain the separated nanofiber supported catalyst.
2. The continuous flow purification and separation method of the nanofiber supported catalyst according to claim 1, wherein the metal in step (1) is one or more of Au, Ag, Pt, Pd; the metal nanoparticles have a diameter less than the diameter of the nanofibers.
3. The continuous flow purification and separation method of nanofiber-supported catalyst according to claim 1 or 2, wherein the metal in step (1) is Pt.
4. The continuous flow purification and separation process of nanofiber supported catalyst as claimed in claim 1, wherein the nanofiber is TiO in step (1)2Nanofibers, Al2O3Nanofiber, Al-Ti composite nanofiber or CeO2And (3) nano fibers.
5. The continuous flow purification and separation method of the nanofiber supported catalyst according to claim 1, wherein the mixing and stirring time in step (1) is 1-3 hours.
6. The continuous flow purification and separation method of the nanofiber supported catalyst as claimed in claim 1, wherein a filter head is connected below the injector in the step (2), and a mixed cellulose ester membrane is arranged in the filter head.
7. The continuous flow purification and separation method of the nanofiber supported catalyst as claimed in claim 1, wherein the filtration in step (2) is performed by using a continuous flow device and the filtration is performed at a flow rate of 1-3 mL/min.
8. The continuous flow purification and separation method of nanofiber-supported catalyst according to claim 6, wherein the mixed cellulose ester membrane has a pore size of 0.20-0.50 μm, and the pore size of the mixed cellulose ester membrane is between the diameter of metal nanoparticle and the diameter of nanofiber.
9. A monolithic nanofiber supported catalyst obtained by the continuous flow purification and separation process of nanofiber supported catalyst of claim 1.
10. The application of the continuous flow purification and separation method of the nanofiber supported catalyst as claimed in claim 1 in the nano-synthesis of one-dimensional material as a framework.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721705A (en) * | 2014-01-14 | 2014-04-16 | 武汉理工大学 | Porous TiO2 fiber loaded noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN108193500A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Catalyst that composite nano fiber and composite nano fiber support and its preparation and application |
| CN110038452A (en) * | 2019-04-23 | 2019-07-23 | 东南大学 | Load the ceramic nanofibers base compound purifying film and its preparation method and application of silver |
| CN110075834A (en) * | 2019-04-26 | 2019-08-02 | 东南大学 | C-shaped cerium oxide nano fiber of Supported Pt Nanoparticles and its preparation method and application |
-
2022
- 2022-03-09 CN CN202210230936.8A patent/CN114534797B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721705A (en) * | 2014-01-14 | 2014-04-16 | 武汉理工大学 | Porous TiO2 fiber loaded noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN108193500A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Catalyst that composite nano fiber and composite nano fiber support and its preparation and application |
| CN110038452A (en) * | 2019-04-23 | 2019-07-23 | 东南大学 | Load the ceramic nanofibers base compound purifying film and its preparation method and application of silver |
| CN110075834A (en) * | 2019-04-26 | 2019-08-02 | 东南大学 | C-shaped cerium oxide nano fiber of Supported Pt Nanoparticles and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| LEI LIU等: "Concurrent filtration and solar photocatalytic disinfection/degradation using high-performance Ag/TiO2 nanofiber membrane", 《WATER RESEARCH》, pages 1101 - 1112 * |
| YUNQIAN DAI等: "Surface-Functionalized Electrospun Titania Nanofibers for the Scavenging and Recycling of Precious Metal Ions", 《CHEMSUSCHEM》, pages 2912 - 2916 * |
| ZHIHUI LI等: "Porous ceramic nanofibers as new catalysts toward heterogeneous reactions", 《COMPOSITES COMMUNICATIONS》, pages 168 - 178 * |
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