CN105107548A - Preparation method of porous structure metal/rare earth co-doped inorganic nanofiber photocatalytic material - Google Patents
Preparation method of porous structure metal/rare earth co-doped inorganic nanofiber photocatalytic material Download PDFInfo
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- CN105107548A CN105107548A CN201510567553.XA CN201510567553A CN105107548A CN 105107548 A CN105107548 A CN 105107548A CN 201510567553 A CN201510567553 A CN 201510567553A CN 105107548 A CN105107548 A CN 105107548A
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Abstract
The invention relates to the technical fields of preparation of a high-content titanium dioxide sol disperse system by utilizing a sol-gel method, preparation of a polyvinyl acetate/titanium dioxide nanofiber membrane by using an electrostatic spinning device, ultimate preparation of inorganic nanofiber by an autoclaved sintering process and the like, and particularly relates to a preparation method of a metal co-doped TiO2 inorganic nanofiber photocatalytic material. According to the preparation method provided by the invention, a stable TiO2 sol system co-doped with metal ions is prepared by means of a sol-gel principle, and mixed and hybridized with a PVAc solution, inorganic/polymer hybrid nanofiber is prepared by utilizing an electrostatic spinning technology, and organic components are ultimately removed by sintering to obtain the porous inorganic nanofiber. The preparation method provided by the invention solves the problems of little dispersion quantity of the TiO2 sol system, instability in hydrolysis, incompatibility with the metal ions and the like, and achieves the preparation of the metal co-doped inorganic TiO2 nanofiber with the porous structure. The porous metal doped TiO2 nanofiber membrane prepared by the invention is high in adhesion with a glass substrate, high in photocatalytic performance, small in fiber diameter and uniform in distribution, and can be widely applied to various fields such as self-cleaning materials, photocatalytic materials and dye-sensitized solar cells.
Description
Technical field
The present invention relates to a kind of preparation method of metal/rare earth co-doped inorganic nano fiber film of loose structure, be specifically related to utilize sol-gel technique to prepare TiO 2 sol, and then prepare polyvinyl acetate (PVAc)/titanium dioxide (TiO
2) hybrid collosol, prepare metal-doped polyvinyl acetate (PVAc)/titanium dioxide (TiO finally by electrostatic spinning apparatus
2) nano fibrous membrane, and carry out sintering the method for the metal-doped inorganic titanium dioxide nanofiber obtaining loose structure.
Background technology
Nanofiber refers to the fiber of diameter range in nanoscale (1-100nm), belongs to monodimension nanometer material.When diameter is contracted to sub-micron or nanometer from micron, fiber, compared with corresponding material, just shows a series of special character, and such as (its specific area is 10 of micrometer fibers to very large specific area
3doubly), flexible and superpower mechanical behavior (as hardness and tensile strength) etc.Electrostatic spinning technique be at present can continuous production polymer nanofiber one the most directly, most effective method.Electrostatic spinning technique is a kind of method simply and effectively preparing polymer, pottery and composite material nanometer fiber.In typical electrostatic spinning process, effect due to electric field force makes elongated charged Polymer Solution or melt jet overcome the surface tension of self, accelerate in the electric field to stretch, stand a series of instability, drying, be finally deposited in a nano fiber non-woven fabric felt receiving system being formed arbitrary arrangement.Relative to polymer fiber prepared by conventional method, the standby fiber of electro-spinning has fiber finer, the advantages such as specific area is large, and spinning equipment is simple.Make the nanofiber utilizing electrostatic spinning technique to prepare just because of above advantage, have broad application prospects in filtration, organizational project, hypersensitization sensor, the field such as bionical and medical.But due to reasons such as technology, electrospun nanofibers is existed, and finished product structure is difficult to control, poor, the nanofiber film dynamic performance of continuous spinning and the shortcoming such as heat endurance is poor, and this has become the key factor that govern electrostatic spinning technique development.For above deficiency, the present invention utilizes Inorganic-organic Hybrid Material to propose the strength and stability by using the method for inorganic-organic hybridization nano fiber to strengthen nanofiber with the feature of good elasticity, formability and the lighter weight of organic material and the good intensity of inorganic material, heat endurance and chemical stability, provides new method for preparing high intensity nano fibre.
Compared with routine intravenous electro spinning nanometer fiber membrane material, the metal/rare earth codope TiO of loose structure
2nanofiber sheet has a lot of excellent performance: as a kind of metal/rare earth codoping titanium dioxide nano material, its specific area is large; Light absorption is good, and it is strong to absorb ultraviolet ability; Surface-active is large; Good dispersion, made effect suspension stabilization, photoelectric transformation efficiency is high; Other complete micro/nano fibrous membrane materials without striped crack in surface are different from as a kind of, its surface presentation goes out the porous form of one " be full of cracks " shape, this makes this kind of inorganic nano-fiber sheet have special performance and apply widely, as fine ceramics, electronics, sewage disposal, purification of air, the fields such as energy and material.
The nano-TiO openly reported at present
2preparation method is a lot, mainly contains vapor phase method and liquid phase method.Vapor phase method reaction mostly at high temperature instantaneously completes, and all has very high requirement, so vapor phase method is also in the bench-scale testing stage in China at present to the material of the configuration of reactor, equipment, heating and feeding manner etc.The advantage of Liquid preparation methods nano TiO 2 is a lot, as: raw material sources are extensively, cost is lower, equipment is simple, be convenient to large-scale production.Sol-gel process is synthesis of nano TiO
2one of common methods, be generally presoma with metal alkoxide, through hydrolytie polycondensation gelation gradually, then after ageing, drying nano-TiO
2, but there is complex process, TiO
2the shortcomings such as surface hydroxyl is too much.The present invention proposes to use tetrabutyl titanate to be presoma, and ethanol is that nano titanium oxide prepared by cosolvent.Due to prepare codope TiO2 nanofiber process in need to solve PVAc and TiO
2the compatibility of sol solutions, TiO
2high level in hybrid collosol liquid and the problem such as metal ion and hybrid collosol liquid phase capacitive, the present invention adopts acetylacetone,2,4-pentanedione to be suppress hydrolytic reagent, by using dense HNO
3regulate pH value that system is reached electrostatic spinning and sintering that then stable state carries out next step.The present invention explores some and present the method having better adhesion between the nanofiber sheet of loose structure and matrix after making sintering, the stifling method of final employing steam carries out pre-treatment, and finally obtaining well attached on matrix is cavernous inorganic nano-fiber sheet.
Summary of the invention
The object of the invention is to prepare a kind of novel metal preparing loose structure/rare earth co-doped inorganic nano fiber film.Sol-gel technique is utilized to prepare metal-doped TiO 2 sol, itself and polyvinyl acetate are carried out compound and spins organic and inorganic composite nanofiber by electrostatic spinning technique, then presented the porous TiO of " be full of cracks " shape through pre-treating technology and sintering process
2inorganic nano-fiber sheet.
For achieving the above object, the metal/rare earth co-doped inorganic nano fiber piece preparation method of loose structure of the present invention comprises the following steps:
(1) anhydrous ethanol solvent and tetrabutyl titanate are evenly mixed with volume ratio 1: 1.5 on agitator, add the acetylacetone,2,4-pentanedione of 0.5 volume, be configured to solution A; After configuring the ethanolic solution of the distilled water of 0.5 volume and the absolute ethyl alcohol of 0.5 volume, by appropriate Fe (NO
3)
39H
2o and La (NO
3)
36H
2o adds the ethanolic solution prepared, and makes it fully dissolve, obtains solution B; Solution B is dropwise added in the solution A of magnetic agitation, uses red fuming nitric acid (RFNA) to regulate pH value to equal 3, after stirring 6h, obtain metal co-doped TiO2 sol solutions.
(2) polyvinyl acetate (molecular weight 30000-50000) is dissolved in acetone solvent, is made into the PVAc solution that concentration is 15%; By the metal co-doped TiO prepared
2sol solutions adds in PVAc solution with the ratio of 1: 1, fully stirs normal-temperature reaction 10h, obtains stable Fe
3+and La
3+doping PVAc/TiO
2hybrid collosol liquid.
(3) then the hybrid collosol liquid prepared is placed in electrostatic spinning apparatus to spin uniform nano fibrous membrane and be collected on slide, spinning condition: voltage is 25KV, collecting distance is 20cm, and spinning solution rate of flow of fluid is 1.0ml/h.
(4) load had the slide of Hybrid nanofibers film to carry out steam suffocating treatment, the distance water surface is about 20cm, and fumigation time is 5min, treats that Hybrid nanofibers film is fully fumigated by steam and is attached on slide and stops afterwards, and dry.
(5) be finally placed in high temperature process furnances by spinning and through the nano fibrous membrane of steam pre-treatment to sinter, gained sample is the porous metals co-doped inorganic nano fiber be attached on slide.
Owing to have employed technique scheme, tool of the present invention has the following advantages and effect:
1. the present invention selects acetylacetone,2,4-pentanedione to be suppress hydrolytic reagent both to ensure that dispersion high level TiO
2the stability of colloidal sol in turn ensure that compatibility when mixing with PVAc solution subsequently, and adds the load capacity of nano fibrous membrane when collecting on slide subsequently.
2. the use PVAc that the present invention proposes prepares metal co-doped TiO as organic precursor
2inorganic nano-fiber, due to PVAc itself, to have caking property good, and labile feature, will decompose completely at about 350 DEG C, after sintering process, make TiO
2nanofiber is more easily attached on slide.
3. the present invention proposes steaming, compression technology are to make the metal-doped TiO prepared
2nanofiber is attached on slide preferably, because the vitrification point of PVAc only has about 40 DEG C, so the nanofiber after steaming will be bonded on slide, then in sintering process, uses the technique of pressure that inorganic nano-fiber is heated evenly not easily roll.
Detailed description of the invention
Example 1
The absolute ethyl alcohol of 10ml and 15ml tetrabutyl titanate are added in boiling flask and stirs on magnetic stirring apparatus, use pipette dropwise to add the acetylacetone,2,4-pentanedione of 5ml, stir 10 minutes under normal temperature, be mixed with solution A.5ml distilled water and 5ml absolute ethyl alcohol are added in 50ml beaker, then adds 0.0234 gram of Fe (NO
3)
39H
2o and 0.0186 gram of La (NO
3)
36H
2o is made into Fe
3+: La
3+mol ratio is 1: 1; Ion concentration is the solution B of 0.02%.Solution B is placed in constant pressure funnel and dropwise instills solution A, high-speed stirred 6h, obtain Fe
3+, La
3+codope TiO2 alcosol.PVAc is dissolved in acetone and is made into the solution that concentration is 15%, the alcosol prepared is got 40ml and be placed in the PVAc solution that constant pressure funnel dropwise instills 40ml, fully stir 10h, make PVAc/TiO
2hybrid collosol spinning solution.Spinning solution is inserted homemade electrospinning device, at spinning voltage 25KV, collect distance 15cm, under the process conditions of solution extruded velocity 1ml/h, slide is used to collect nanofiber 7 hours as substrate, low temperature drying half an hour in vacuum drying chamber subsequently, remove residual solvent, obtain PVAc/TiO
2hybrid nanofibers film.Then use steam to carry out stifling 10 minutes, re-use slide pressure and be put into sintering 500 DEG C in tube furnace on the fiber surface, keep 120 minutes, obtain the TiO be attached on slide
2nanofiber.
Example 2
The absolute ethyl alcohol of 10ml and 15ml tetrabutyl titanate are added in boiling flask and stirs on magnetic stirring apparatus, use pipette dropwise to add the acetylacetone,2,4-pentanedione of 5ml, stir 10 minutes under normal temperature, be mixed with solution A.5ml distilled water and 5ml absolute ethyl alcohol are added in 50ml beaker, then adds 0.2921 gram of Fe (NO
3)
39H
2o and 0.0466 gram of La (NO
3)
36H
2o is made into Fe
3+ion concentration is 0.5%, La
3+ion concentration is the solution B of 0.1%.Solution B is placed in constant pressure funnel and dropwise instills solution A, high-speed stirred 8h, obtain Fe
3+, La
3+codope TiO
2alcosol.PVAc is dissolved in acetone and is made into the solution that concentration is 15%, the alcosol prepared is got 40ml and be placed in the PVAc solution that constant pressure funnel dropwise instills 40ml, fully stir 8h, make PVAc/TiO
2hybrid collosol spinning solution.Spinning solution is inserted homemade electrospinning device, at spinning voltage 25KV, collect distance 20cm, under the process conditions of solution extruded velocity 1ml/h, slide is used to collect nanofiber 7 hours as substrate, low temperature drying half an hour in vacuum drying chamber subsequently, remove residual solvent, obtain PVAc/TiO
2hybrid nanofibers film.Then use steam to carry out stifling 10 minutes, re-use slide pressure and be put into sintering 600 DEG C in tube furnace on the fiber surface, keep 120 minutes, obtain the TiO be attached on slide
2nanofiber.
Example 3
The absolute ethyl alcohol of 10ml and 15ml tetrabutyl titanate are added in boiling flask and stirs on magnetic stirring apparatus, use pipette dropwise to add the acetylacetone,2,4-pentanedione of 5ml, stir 10 minutes under normal temperature, be mixed with solution A.5ml distilled water and 5ml absolute ethyl alcohol are added in 50ml beaker, then adds 0.05843 gram of Fe (NO
3)
39H
2o and 0.2331 gram of La (NO
3)
36H
2o is made into Fe
3+ion concentration is 0.1%, La
3+ion concentration is the solution B of 0.5%.Solution B is placed in constant pressure funnel and dropwise instills solution A, high-speed stirred 5h, obtain Fe
3+, La
3+codope TiO
2alcosol.PVAc is dissolved in acetone and is made into the solution that concentration is 17%, the alcosol prepared is got 40ml and be placed in the PVAc solution that constant pressure funnel dropwise instills 40ml, fully stir 8h, make PVAc/TiO
2hybrid collosol spinning solution.Spinning solution is inserted homemade electrospinning device, at spinning voltage 25KV, collect distance 25cm, under the process conditions of solution extruded velocity 0.5ml/h, slide is used to collect nanofiber 7 hours as substrate, low temperature drying half an hour in vacuum drying chamber subsequently, remove residual solvent, obtain PVAc/TiO
2hybrid nanofibers film.Then use steam to carry out stifling 15 minutes, re-use slide pressure and be put into sintering 500 DEG C in tube furnace on the fiber surface, keep 120 minutes, obtain the TiO be attached on slide
2nanofiber.
Claims (4)
1. the preparation method of a metal-doped inorganic titanium dioxide nanofiber, it is characterized in that preparing metal co-doped TiO 2 sol with sol-gel process, metal co-doped polyvinyl acetate/titanium dioxide the spinning solution be mixed evenly is mixed with again with the acetone soln of polyvinyl acetate, utilize electrostatic spinning technique to spin out composite nano-fiber membrane, then carry out sintering and obtain metal co-doped inorganic titanium dioxide nanofiber.
2. a kind of preparation method of metal-doped inorganic titanium dioxide nanofiber as described in right 1, it is characterized in that: when preparing metal co-doped TiO 2 sol, use acetylacetone,2,4-pentanedione to be inhibitor, ensure that butyl titanate mixes with 1: 1.5 volume ratio with alcohol solvent, containing a large amount of titanium elements, and Fe
3+and La
3+the preparation process of metal ion mixing and TiO 2 sol completes simultaneously, ensure that metal ion and TiO 2 sol have good compatibility.
3. a kind of preparation method of metal-doped inorganic titanium dioxide nanofiber as described in right 1, it is characterized in that used TiO 2 sol preparation method can make metal co-doped TiO 2 sol and polyvinyl acetate ester solution well mix and can be applicable to electrostatic spinning process, smooth spinning.
4. a kind of preparation method of metal-doped inorganic titanium dioxide nanofiber as described in right 1, be further characterized in that preparation with slide be the metal co-doped titanium dioxide nanofiber of matrix through steaming, pressure sintering process makes inorganic nano-fiber firmly can be attached to glass surface.
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| CN107974732A (en) * | 2016-10-21 | 2018-05-01 | 苏州今道创业投资有限公司 | The preparation method of zinc oxide hollow Nano fiber in use |
| CN107652669A (en) * | 2017-08-25 | 2018-02-02 | 宁波帅特龙集团有限公司 | A kind of antibacterial reinforced nylon composite and preparation method thereof |
| CN107652669B (en) * | 2017-08-25 | 2020-08-18 | 宁波帅特龙集团有限公司 | Antibacterial enhanced nylon composite material and preparation method thereof |
| WO2019246224A1 (en) * | 2018-06-19 | 2019-12-26 | Flux Photon Corporation | A photocatalytic device based on rare-earth elements, methods of manufacture and use |
| CN111998485A (en) * | 2020-09-02 | 2020-11-27 | 南京信大气象科学技术研究院有限公司 | Wisdom automatically cleaning anion new trend device that disinfects |
| CN115233441A (en) * | 2022-05-16 | 2022-10-25 | 东华大学 | Preparation method of multifunctional wall cloth for indoor air purification |
| CN115233441B (en) * | 2022-05-16 | 2024-04-12 | 东华大学 | Preparation method of multifunctional wallcovering for indoor air purification |
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Application publication date: 20151202 |