CN106978652A - A kind of preparation method of the sour oxygen titanium precursors colloidal sol spinning solution of poly-vinegar and TiOx nano fiber photocatalyst - Google Patents
A kind of preparation method of the sour oxygen titanium precursors colloidal sol spinning solution of poly-vinegar and TiOx nano fiber photocatalyst Download PDFInfo
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000002121 nanofiber Substances 0.000 title claims abstract description 98
- 239000002243 precursor Substances 0.000 title claims abstract description 85
- 238000009987 spinning Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 13
- 239000000052 vinegar Substances 0.000 title abstract 5
- 229910003087 TiOx Inorganic materials 0.000 title abstract 3
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 title abstract 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 153
- 238000010438 heat treatment Methods 0.000 claims abstract description 108
- 239000000835 fiber Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000010936 titanium Substances 0.000 claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 229960000583 acetic acid Drugs 0.000 claims abstract description 13
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229920000954 Polyglycolide Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004633 polyglycolic acid Substances 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- 208000012886 Vertigo Diseases 0.000 description 26
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 titanium alkoxide Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- SNGQTGWGMDHWHG-UHFFFAOYSA-M [O-2].[Ti+3].C(C)(=O)[O-] Chemical compound [O-2].[Ti+3].C(C)(=O)[O-] SNGQTGWGMDHWHG-UHFFFAOYSA-M 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Fibers (AREA)
Abstract
The present invention relates to the preparation method of a kind of sour oxygen titanium precursors colloidal sol spinning solution of poly-vinegar and TiOx nano fiber photocatalyst.Include preparation, electrostatic spinning, the heat treatment of the sour oxygen titanium precursors colloidal sol spinning solution of poly-vinegar；The sour oxygen titanium precursors of poly-vinegar first are prepared using butyl titanate, glacial acetic acid as raw material, the presoma, auxiliary agent, solvent are well mixed by a certain percentage, spinning solution is obtained；The spinning solution obtains the sour oxygen titanium precursors fiber of poly-vinegar by electrostatic spinning technique；The precursor fibre is placed in Muffle furnace and is heat-treated to obtain solid titanium nanofiber or meso-porous titanium oxide nanofiber.This method has the features such as simple technological process, fiber quality optimization and environmental protection, and beneficial to industrialized production, obtained TiOx nano fiber has excellent catalytic performance, can be used as degradable organic pollutant catalysis material.
Description
Technical Field
The invention relates to a method for preparing titanium oxide nano fibers by combining an electrostatic spinning technology, in particular to a method for preparing a poly (titanium oxyacetate) precursor sol spinning solution, and belongs to the technical field of nano functional materials.
Background
With the rapid development of industry, the pollution of harmful gas, solid waste and sewage to the environment has become one of the huge challenges facing the world. Water resources are one of the essential material bases for human life and economy development. At present, the amount of sewage discharged from industries such as textile and dye is increasing day by day, the water pollution is becoming serious day by day, the degradation and mineralization are very difficult due to the high intractable property and the complex molecular structure of the dye, the survival and development of human beings are seriously influenced, and the effective treatment of the pollutants becomes the problem to be solved at present. The semiconductor photocatalytic oxidation technology can degrade organic pollutants by utilizing clean solar energy, does not need to consume a large amount of other substances except light, and can reduce the consumption of energy and raw materials, thereby showing good development prospect in the field of environmental purification.
In the field of photocatalytic decomposition, titanium oxide materials have been widely used in the environmental management fields of pollutant decomposition, air purification and the like due to the characteristics of high photocatalytic activity and oxidation capacity, good chemical stability and thermal stability, no secondary pollution, no irritation, safety, no toxicity, convenience, easy obtainment and the like, and become one of the most promising green and environment-friendly catalysts at present. Catalytically active titanium oxides have mainly two crystalline phases: anatase and rutile. The difference of crystal structures causes the difference of crystal mass density and electron energy band structures, namely the catalytic activity of two crystal forms has certain difference. The mass density of anatase type is slightly less than that of rutile type, and the band gap is slightly greater than that of rutile type. Rutile titanium oxide has poor oxygen adsorption capacity and small specific surface area, so that photo-generated electrons and holes are easy to recombine, and the catalytic activity is influenced to a certain extent. Therefore, the anatase titanium oxide has higher catalytic activity. CN101314482A provides a method for synthesizing anatase titanium dioxide, and the prepared anatase titanium dioxide fine powder has higher catalytic activity; and carrying out degradation experiments under 365 ultraviolet lamp irradiation, and completely degrading the methyl orange solution within 15 minutes. However, the titanium oxide fine powder is difficult to recover after use, and is easy to cause secondary pollution, so that the popularization and application of the titanium oxide fine powder are severely limited.
The titanium oxide nano-fiber has the characteristics of unique one-dimensional shape, extremely large specific surface area, high adsorption capacity, high photoelectron transmission speed, anisotropy and the like, is favorable for separation, recovery and reutilization, cannot cause environmental pollution due to easy loss, and can solve the problem of environmental pollutionThe nanometer titanium oxide powder is difficult to recycle and easy to cause secondary pollution, so that the popularization and the application are difficult. CN1584156A proposes a method for preparing titanium dioxide fiber, which comprises using titanium tetrachloride as a titanium source, using acetic acid or acetylacetone as a ligand, selecting a proper precipitation separating agent, preparing a precursor, preparing precursor fiber by a centrifugal spinning or dry spinning method, and obtaining titanium oxide fiber by water vapor pretreatment and high-temperature sintering. The applicant's previous studies have resulted in a minimum diameter>2 mu m titanium oxide fiber, but later researches find that titanium tetrachloride is used as a titanium source, the hydrolytic polycondensation process is difficult to control, impurities which are not completely removed in a precursor cannot influence the polymerization degree and the purity, the length-diameter ratio of the obtained micron-sized fiber is not as large as that of the nano-fiber, the electron transmission efficiency is relatively reduced, and the catalytic activity is to be further optimized. The titanium alkoxide is selected as a titanium source, so that the doping of other impurity ions can be avoided, however, the titanium alkoxide is easy to hydrolyze, and sometimes the pH value of the solution needs to be adjusted to inhibit the hydrolysis. CN100581648A discloses a method for preparing a titanium dioxide fiber membrane by using an electrostatic spinning technology, wherein a spinning solution is prepared by firstly dissolving tetrabutyl titanate in absolute ethyl alcohol, inhibiting hydrolysis of tetrabutyl titanate by using ethyl alcohol, then regulating the pH value of an ethanol solution of tetrabutyl titanate by using hydrochloric acid to control the hydrolysis and polycondensation process of the solution after water is added, but the process of forming a spinnable solution by a series of hydrolysis and polycondensation of the solution is slower, the pH value of the solution is regulated by using hydrochloric acid, and Cl in the prepared fiber membrane is-The fiber is difficult to remove in the post-treatment process, and inevitably has certain influence on the performance of the fiber. Regarding the preparation of spinning solution, generally, titanium alkoxide is selected, a solution with good spinnability is obtained by adding a large amount of spinning aid, and the solid content of the effective component titanium oxide in the precursor fiber is too low due to the large amount of the spinning aid, which has adverse effect on the performance of the obtained titanium oxide nanofiber.
At present, the work on the preparation of titanium oxide nanofibers by electrospinning technology has at least the following two problems: firstly, the specific surface area of the titanium oxide nano fiber obtained by electrospinning is not high, and the application performance is limited to a certain extent, so that the improvement of the porosity and the specific surface area inside the titanium oxide nano fiber becomes a big problem to be solved. Secondly, the electrospun titanium oxide nanofiber prepared after high-temperature treatment has poor mechanical property and is easy to break, often exists in the form of short fiber or nanowire, the advantages of the nanofiber cannot be fully and practically exerted, and the problem of obtaining continuous titanium oxide nanofiber with good mechanical property is also solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing a titanium oxide nano fiber photocatalyst by adopting electrostatic spinning of a titanium acetate precursor sol spinning solution and carrying out heat treatment.
The invention aims to solve the technical problems of improving the solid content of titanium oxide in precursor fiber, avoiding the existence of excessive impurity ions, improving the time of the hydrolytic polycondensation process of solution as much as possible on the premise of not influencing the material performance, and preparing the titanium oxide nano fiber with excellent strength and catalytic performance.
Description of terms:
poly (titanium oxy acetate) (PET), the monomer name is dihydroxy titanium diacetate, the monomer molecular formula is (CH)3COO)2Ti(OH)2. The molecular weight of the monomer is 199.97. Titanium oxide (TiO)2Molecular weight of 79.87). TiO 22The effective solids content is defined by the formula (CH)3COO)2Ti(OH)2Transforming into TiO by heat treatment2The amount ratio of (a) to (b).
Titanium oxide nanofibers: the titanium oxide nano fiber comprises solid titanium oxide nano fiber and mesoporous titanium oxide nano fiber. The mesoporous titanium oxide nanofiber is a nanofiber with a pore channel structure.
P25: the code of the nano titanium oxide powder photocatalyst refers to titanium dioxide white powder of anatase crystal and rutile crystal mixed phase (weight ratio is about 71/29) with the average particle size of 25 nm. Can be purchased in the market.
The technical scheme of the invention is as follows:
a preparation method of a titanium oxyacetate precursor sol spinning solution comprises the following steps:
(1) weighing tetrabutyl titanate according to the molar ratio of tetrabutyl titanate to glacial acetic acid of 1: 1-4, slowly adding the glacial acetic acid, and stirring for reacting for 2-4 h to obtain a solution containing titanium oxyacetate; then, concentrating the solution containing the poly-titanium-oxy-acetate under reduced pressure at the temperature of 40-80 ℃ to prepare powder, thus obtaining a poly-titanium-oxy-acetate precursor;
(2) according to the mass ratio of the precursor of the titanium acetate to the alcohol solvent of 100 (0.4-4) to 100-400, firstly dissolving the precursor of the titanium acetate in the alcohol solvent, then adding the auxiliary agent, and stirring and dissolving at the temperature of 10-60 ℃ to obtain uniform sol spinning solution of the precursor of the titanium acetate;
the auxiliary agent is selected from one or the combination of polyethylene oxide, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, polyacrylamide, polyethylene glycol terephthalate, polyurethane, polyglycolic acid and polylactic acid.
According to the invention, the alcohol solvent is one selected from absolute methanol, absolute ethanol or a combination thereof.
The method of the invention is to prepare the precursor of the poly-titanyl acetate firstly, and dissolve the precursor in the absolute methanol or absolute ethanol solvent, thus adding a small amount of auxiliary agent and preparing the spinning solution with better spinnability in a shorter time. The small amount of the auxiliary agent can prevent the large amount of the auxiliary agent from reducing the solid content of the effective component titanium oxide in the precursor fiber, and has important significance for improving the performance of the obtained titanium oxide nano fiber.
According to the invention, the molar ratio of tetrabutyl titanate to glacial acetic acid is 1: 2.5-3.5.
According to the invention, the mass ratio of the titanium oxyacetate precursor to the auxiliary agent to the solvent is 100 (0.7-2) to 100-300.
According to the invention, the condition that the precursor of the poly-titanyl acetate is dissolved in the alcohol solvent is as follows: stirring and dissolving at the temperature of 0-60 ℃ to form a solution.
A preparation method of the titanium oxide nanofiber photocatalyst comprises the preparation of the titanium oxyacetate precursor sol spinning solution, and further comprises the following steps:
(3) electrostatic spinning: placing the titanium acetate precursor sol spinning solution into an injector with a stainless steel needle head of a spinning device, performing electrostatic spinning by adopting a high-voltage electrostatic spinning method, applying voltage of 8-28 kV under the conditions of ambient temperature of 20-35 ℃ and relative humidity of 30-70%, wherein the flow rate of the spinning solution is 0.5-3.5 mL/h, the inner diameter of the positive stainless steel needle head is 0.19-0.60 mm (model number 4-9 #), and the distance between the needle head and a rotary drum of a fiber collecting device is 8-35 cm, so as to prepare the titanium acetate precursor fiber;
(4) and (3) heat treatment: placing the titanium oxide precursor fiber in a muffle furnace for heat treatment, heating to 300-1000 ℃ at a heating rate of 0.4-5 ℃/min under the air condition, and preserving heat for 1-3 h to fully decompose and crystallize the titanium oxide precursor fiber to prepare the solid titanium oxide nano fiber, or,
placing the titanium oxide precursor fiber in a sintering furnace for heat treatment, heating to 100-200 ℃ at a heating rate of 3-6 ℃/min, starting to introduce steam, heating to 300-900 ℃, preferably 500-750 ℃, further preferably 600-700 ℃ at a heating rate of 0.5-2.5 ℃/min, stopping introducing the steam, and then preserving heat to fully decompose and crystallize the titanium oxide precursor fiber to convert the titanium oxide precursor fiber into mesoporous titanium oxide nano fiber; or,
and (2) placing the titanium oxide precursor fiber in a sintering furnace for heat treatment, heating to 100-200 ℃ at a heating rate of 3-6 ℃/min, starting to introduce steam, heating to 350-550 ℃ at a heating rate of 0.5-1 ℃/min, stopping introducing the steam, heating to 600-700 ℃ at a heating rate of 1.5-2 ℃/min, and preserving heat for 2 hours to obtain the mesoporous titanium oxide nanofiber.
Preferably, in step (3), the electrostatic spinning conditions are as follows: the environment temperature is 20-30 ℃, the relative humidity is 35-60%, the applied voltage is 10-24 kV, the flow rate of the spinning solution is 0.5-2.5 mL/h, the inner diameter of the stainless steel needle is 0.26-0.51 mm (model number 5-8 #), and the distance between the positive stainless steel needle and the rotary drum of the fiber collecting device is 10-30 cm. In the electrostatic spinning step, the flow velocity of the spinning solution is strictly controlled, the flow velocity of the spinning solution has important influence on the quality of the titanium oxide nano-fiber product, a large amount of beads exist in the electrospun fiber when the flow velocity is higher, a large amount of pulverized titanium oxide fibers obtained after heat treatment are pulverized, and the catalytic performance is poorer. The flow rate of the spinning solution is further preferably 1-2 mL/h.
According to the invention, in the step (3), the fiber collecting device is paved with aluminum foil.
According to the invention, in the step (4), the preferable temperature for heat treatment of the poly-titanium-oxy-acetate precursor fiber in the muffle furnace is 600-900 ℃.
Preferably, in the step (4), when the final treatment temperature is 700-800 ℃ in the preparation of the solid titanium oxide nanofiber, a two-stage temperature rise mode is adopted: the temperature is raised to 600-700 ℃ at the heating rate of 0.5 ℃/min, and then raised to 750-800 ℃ at the heating rate of 1 ℃/min, and the temperature is preserved for 2 h.
Preferably, in the step (4), when the final treatment temperature is 900-1000 ℃ in the preparation of the solid titanium oxide nano-fiber, a three-stage heating mode is adopted: heating to 600-700 ℃ at a heating rate of 0.5 ℃/min, heating to 750-800 ℃ at a heating rate of 1 ℃/min, heating to 900-1000 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 2 h. Compared with the method that the temperature is directly increased to 900-1000 ℃ at a constant temperature increasing rate and is kept for 2 hours, the titanium oxide nano-fiber product obtained by the three-stage temperature increasing mode has good fiber crystallization, uniform grain growth and good catalytic degradation activity.
The diameter of the solid titanium oxide nanofiber prepared by the method is 200-800 nm, and the length of the solid titanium oxide nanofiber is 2-8 cm. The specific surface area is 1-12 m2/g。
Preferably, in the step (4), when the final treatment temperature is 600-700 ℃ in the preparation of the mesoporous titanium oxide nanofiber, a two-stage temperature raising mode is adopted after steam is introduced: heating to 300-350 ℃ at a heating rate of 1-1.5 ℃/min, heating to 600-700 ℃ at a heating rate of 1-2.5 ℃/min, stopping introducing steam, and keeping the temperature for 2 hours. The mesoporous titanium oxide nanofiber product obtained by the two-stage heating mode has higher catalytic degradation activity.
According to the invention, the steam is preferably ammonia gas, ethanol, water vapor, mixed steam of water and ethanol or mixed steam of water and hydrogen peroxide. Further preferably, the steam passing amount of the steam is 2.0-3.4L/h.
The mesoporous titanium oxide nanofiber prepared by the method is a nanofiber with an irregular pore structure. The channels are present both on the surface and in the interior of the fibre. See fig. 7. The diameter of the mesoporous titanium oxide fiber obtained by the invention is 300-600 nm, the length is 2-8 cm, and the specific surface area is 20-130 m2The pore size is 1-50 nm. The pore volume is 0.08-0.14 cm3/g。
The titanium oxide nano-fiber prepared by the invention is anatase titanium dioxide.
The invention has the technical characteristics and excellent effects that:
1. the method of the invention is to prepare the precursor of the poly (titanyl acetate) and then dissolve the precursor in the alcohol solvent, thus adding a small amount of auxiliary agent and obtaining the spinning solution with better spinnability. The mass of the auxiliary agent used in the invention is far less than that of a titanium source, the ignition loss is greatly reduced, and the solid content of the effective component titanium oxide in the precursor fiber is prevented from being reduced by a large amount of auxiliary agent; the effective solid content of the titanium oxide fiber converted from the poly (titanium oxyacetate) precursor fiber is 50-55%. Is beneficial to improving the performance of the titanium oxide nano-fiber prepared in the subsequent steps.
2. The titanium oxide nano fiber prepared by the method has excellent mechanical property, single component, no impurity and high purity after high-temperature treatment, and is the titanium oxide nano fiber which can be used for photocatalysis for a long time at higher temperature. The titanium oxide nano-fiber prepared by the method can still maintain anatase crystalline phase with higher catalytic activity at higher temperature. Meanwhile, the prepared titanium oxide nano-fiber has better mechanical property.
3. The titanium oxide precursor fiber obtained by the method can remove most of organic ligands in the precursor fiber at a lower temperature through steam treatment, promotes fiber crystallization, obtains the mesoporous titanium oxide nanofiber, increases the specific surface area, and further improves the catalytic performance of the titanium oxide nanofiber material. In the prior art, a template-induced self-assembly method is generally adopted for preparing mesoporous oxide fibers, for example, block copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene polyether is taken as a template agent to induce self-assembly, so as to form fibers with a worm-like pore channel structure. The disadvantage is that the hydrolytic polycondensation process is not easily controlled. The method successfully prepares the mesoporous titanium oxide nano-fiber with excellent catalytic performance without using a soft template and a hard template.
4. The titanium oxide nano-fiber is easy to recycle as a photocatalytic material, and overcomes the problem that the conventional P25 is difficult to recycle and is easy to generate secondary pollution.
5. In the method of the invention, pH value regulator containing chloride ions such as hydrochloric acid is not used, and Cl does not exist in the fiber membrane-The problem of difficult post-treatment is solved, and the adverse effect on the performance of the titanium oxide nano-fiber is avoided; the invention uses cheap and easily obtained glacial acetic acid as the ligand of the poly (oxytitanium acetate) and simultaneously also as the pH value regulator, is easier to control the hydrolytic polycondensation process, has simple process, reduces the production cost while improving the yield, greatly improves the poly (oxyacetate)Degree of polymerization, purity and stability of titanium.
6. The method has the characteristics of simple process flow, easy adjustment and control of operation conditions, optimized titanium oxide nano-fiber quality, environmental protection and the like, and is beneficial to industrial production.
Drawings
FIG. 1 is an optical photograph of a polyoxotitanium acetate precursor fiber obtained in step (3) of example 1.
FIG. 2 is an SEM photograph of titanium oxide nanofibers heat treated at 900 deg.C for 2 hours according to the method of example 4.
FIG. 3 is an SEM photograph of individual titania nanofibers heat treated at 900 deg.C for 2 hours according to the method of example 4.
FIG. 4 is an SEM photograph of a cross section of a titanium oxide nanofiber heat treated at 900 ℃ for 2 hours according to the method of example 4.
FIG. 5 is an XRD spectrum of titanium oxide nanofibers fabricated according to the method of example 4 under different heat treatment temperature conditions.
FIG. 6 is a graph showing the degradation of 50mL of methyl orange solution with a concentration of 20mg/L under UV irradiation of titanium oxide nanofibers (20mg) prepared according to the methods of examples 4-6 under different heat treatment temperature conditions. The heat treatment temperatures of the curves are 1000 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, 950 deg.C, 700 deg.C, 800 deg.C and 900 deg.C, respectively, from top to bottom.
FIG. 7 is a TEM photograph of mesoporous titanium oxide nanofibers of example 8 heat treated to 650 ℃ and incubated for 2 h. The irregular pore structure runs through the entire fiber.
FIG. 8 is an XRD spectrum of mesoporous titanium oxide nanofibers fabricated by the method of example 8 at different heat treatment temperatures.
FIG. 9 is a graph of 50mL of methyl orange solution with a concentration of 20mg/L degraded by mesoporous titanium oxide nanofibers (20mg) prepared according to the method of example 8 under different heat treatment temperature conditions under irradiation of ultraviolet light.
FIG. 10 shows the isothermal adsorption-desorption curves and pore size distribution curves of mesoporous Titania nanofibers prepared according to the method of example 8 at different heat treatment temperatures (inset).
FIG. 11 is a graph showing the degradation of mesoporous titania nanofibers (20mg) prepared according to the methods of examples 9-11 in 50mL of methyl orange solution at a concentration of 20mg/L under UV irradiation.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The inner diameters of the electrospinning stainless steel needles 5# and 7# used in the examples were 0.26 mm and 0.41mm, respectively.
Example 1: preparation of titanium oxide nanofibers
(1) Preparation of poly (oxytitanium acetate) precursor
Weighing 100g of tetrabutyl titanate and 52.94g of glacial acetic acid, and fully stirring for reacting for 3 hours to obtain a golden yellow solution, namely a titanyl polyacetate solution; placing the mixture into a flask, and concentrating the mixture for 6 hours under reduced pressure at the temperature of 65 ℃ until a dry solid, namely a titanium oxyacetate precursor, is obtained; and (3) stability test of the obtained precursor: the sol formed by dissolving the just prepared titanium oxyacetate precursor powder in an anhydrous methanol solvent can be continuously placed for more than 6 weeks, and still is clear and transparent. The obtained precursor powder is placed for 4 weeks and then dissolved in anhydrous methanol solvent to form sol, and the sol can be continuously placed for more than 6 weeks and still is clear and transparent. Indicating that the stability of the precursor is good.
(2) Preparation of spinning solution
Dissolving 10g of titanium poly-acetate precursor in 23g of anhydrous methanol at 40 ℃, fully stirring to form a solution, adding 0.35g of polyvinylpyrrolidone into the solution, and continuously stirring at 40 ℃ to obtain a uniform transparent spinning solution.
(3) Electrostatic spinning
Putting the precursor spinning solution into an injector with a stainless steel needle head spinning device, applying a voltage value of 20kV and a stainless steel needle head model number 7# to the spinning solution in the injector under the conditions of a temperature of 25 ℃ and a relative humidity of 55%, propelling the spinning solution by gravity, wherein the flow rate is 2mL/h, the distance between a positive stainless steel needle head and a rotating drum of a fiber collecting device with an aluminum foil paved on a negative electrode is 20cm, and drafting and collecting the spun fibers on the rotating drum to obtain the titanium oxyacetate precursor fibers with the diameter of 0.8-1 mu m, as shown in figure 1.
(4) Heat treatment of
Placing the titanium oxide precursor fiber in a muffle furnace for heat treatment, heating to 900 ℃ at a heating rate of 1 ℃/min under the air condition, and preserving heat for 2 hours to ensure that the titanium oxide precursor is fully decomposed, crystallized and converted into titanium oxide nano-fiber, and an anatase phase is maintained, wherein the diameter is 400-600 nm, the length is 2-8 cm, and the specific surface area is 11m2The tensile strength is higher.
Tests show that the effective solid content of the titanium oxide fiber converted from the poly (titanium oxyacetate) precursor fiber is 50-55%.
Comparative example 1:
as described in example 1, except that 100g of tetrabutyl titanate and 15g of glacial acetic acid (molar ratio about 1:0.85) were weighed in step (1), and the mixture was reacted for 3 hours with stirring thoroughly to obtain a golden yellow solution (titanyl polyacetate solution); it was placed in a flask and concentrated under reduced pressure at a temperature of 65 ℃ to give no light yellow solid as described in example 1.
Comparative example 2:
as described in example 1, except that 0.5g of polyvinylpyrrolidone was added in step (2), the diameter of the precursor fiber electrospun in step (3) was 1.5 to 2 μm, and a large amount of the fiber was adhered.
Comparative example 3:
as described in example 1, except that the flow rate of the dope in the gravity-propelled syringe in the step (3) was 4mL/h, a large amount of beading existed in the electrospun fiber, a large amount of pulverization of the titanium oxide fiber was obtained after the heat treatment, and the catalytic performance was poor.
Example 2:
the preparation method is as described in example 1, except that 100g of tetrabutyl titanate and 23.49g of glacial acetic acid are weighed in the step (1), and the mixture is fully stirred and reacted for 3 hours to obtain a golden yellow solution, namely a titanyl polyacetate solution; placing the mixture into a flask, and concentrating the mixture for 9 hours under reduced pressure at the temperature of 65 ℃ to obtain a dry and hard light yellow solid, namely a titanium oxyacetate precursor. The obtained precursor powder is dissolved in alcohol solvent to form sol which can be stably placed for 5 weeks.
Example 3:
the preparation method is as described in example 1, except that 100g of tetrabutyl titanate and 70.5g of glacial acetic acid are weighed in the step (1), and the mixture is fully stirred and reacts for 3 hours to obtain a golden yellow solution, namely a titanyl polyacetate solution; placing the mixture into a flask, and concentrating the mixture under reduced pressure at the temperature of 65 ℃ to obtain a dry and hard light yellow solid, namely a titanium oxyacetate precursor. The obtained precursor powder is dissolved in the alcohol solvent to form sol after being placed for 4 weeks, the sol can be stably placed for 3 weeks, and precipitates gradually begin to form after 3 weeks.
Comparative example 4:
the procedure was as described in example 1 except that 100g of tetrabutyl titanate and 75.5g of glacial acetic acid (molar ratio about 1:4.247) were weighed in step (1) and reacted with stirring thoroughly for 3 hours to give a golden yellow solution, i.e., a titanyl polyacetate solution; placing the mixture into a flask, and concentrating the mixture under reduced pressure at the temperature of 65 ℃ to obtain a dry and hard light yellow solid, namely a titanium oxyacetate precursor. Compared with the precursor of the titanium poly-acetate prepared in the example 1, the stability is poor, and the obtained precursor powder is placed for 4 weeks, and then the sol formed by dissolving the precursor powder in an alcohol solvent is placed for 4 days to gradually form precipitates.
Example 4:
as described in example 1, except that in step (4), the titanium oxide precursor fiber is placed in a muffle furnace for heat treatment, the temperature is raised to 600 ℃ at a heating rate of 0.5 ℃/min, then raised to 800 ℃ at a heating rate of 1 ℃/min, then raised to 900 ℃, 950 ℃ or 1000 ℃ at a heating rate of 2 ℃/min, and then kept for 2h, and finally the temperature is naturally reduced, so that the titanium oxide nanofiber with the diameter of 400-600 nm is obtained. The obtained fiber has small diameter distribution difference and good fiber crystallization.
The SEM photograph of the titanium oxide nano-fiber subjected to heat treatment at 900 ℃ and heat preservation for 2 hours is shown in figure 2, the SEM photograph of a single titanium oxide nano-fiber is shown in figure 3, and the SEM photograph of the cross section of the titanium oxide nano-fiber is shown in figure 4.
The XRD patterns of the titanium oxide nanofibers prepared under different heat treatment temperature conditions are shown in FIG. 5.
Compared with a product which is directly heated to 900 ℃, 950 ℃ or 1000 ℃ and is kept warm for 2 hours, the three-section heating mode has higher catalytic degradation activity. The degradation curve is shown in FIG. 6.
Example 5:
as described in example 1, except that in step (4), the poly (titanium oxide acetate) precursor fiber is placed in a muffle furnace for heat treatment, the temperature is raised to 400 ℃, 500 ℃ or 600 ℃ at a heating rate of 0.5 ℃/min, the temperature is kept for 2h, and the temperature is naturally reduced to obtain the titanium oxide nanofiber. The resulting fiber degradation curve is shown in FIG. 6.
Example 6:
as described in example 1, except that in step (4), the titanium oxide precursor fiber is placed in a muffle furnace for heat treatment, the temperature is raised to 600 ℃ at a heating rate of 0.5 ℃/min, then raised to 700 ℃ or 800 ℃ at a heating rate of 1 ℃/min, and the temperature is kept for 2h, and then the temperature is naturally reduced, so that the titanium oxide nanofiber is obtained. The resulting fiber degradation curve is shown in FIG. 6.
FIG. 6 is a graph showing the degradation curves of the fibers of examples 4-6 at different heat treatment temperatures. The degradation experimental conditions were: the titanium oxide nano-fiber with the concentration of 20mg/L, which is 20mg/L, is degraded by the irradiation of ultraviolet light, and the maximum heat treatment temperature of the curve shown in FIG. 6 from top to bottom is 1000 ℃, 400 ℃, 500 ℃, 600 ℃, 950 ℃, 700 ℃, 800 ℃ or 900 ℃.
Example 7:
as described in example 4, except that the temperature was maintained at 900 ℃ for 5 hours, the obtained titania nanofibers showed rutile phase, and the catalytic activity was reduced.
Example 8: the preparation of the mesoporous titanium oxide nano-fiber has the heat treatment temperature of 350 ℃, 450 ℃, 550 ℃, 650 ℃ and 700 ℃.
As described in example 1, except that:
in the step (4), the poly (titanium oxide acetate) precursor fiber is placed in a sintering furnace for heat treatment, the temperature is raised to 100 ℃ at the heating rate of 3-6 ℃/min, water vapor is introduced, and the vapor introduction amount is 3.1L/h; heating to the heat treatment temperature of 350 ℃, 450 ℃ or 550 ℃ at the heating rate of 1 ℃/min, stopping introducing steam, and keeping the temperature for 2 hours; or,
adopting a two-stage heating mode: heating to 350 deg.C at a heating rate of 1 deg.C/min, heating to 650 deg.C or 700 deg.C at a heating rate of 2 deg.C/min, stopping introducing steam, and maintaining for 2 hr.
The diameter of the obtained mesoporous titanium oxide nano-fiber is 300-600 nm, and the specific surface area is 20-130 m2The pore size is 2-50 nm. The irregular pore structure runs through the entire fiber. As shown in fig. 7.
The XRD spectrum of the mesoporous titania nanofibers prepared at the above different heat treatment temperatures is shown in fig. 8.
Degradation experiments of the mesoporous titanium oxide nanofibers prepared at the different heat treatment temperatures: the prepared mesoporous titanium oxide nano-fiber (20mg) is degraded by 50mL of methyl orange solution with the concentration of 20mg/L under the irradiation of ultraviolet light, and the obtained graph is shown in FIG. 9. Wherein, the mesoporous titanium oxide nano-fiber obtained by heat preservation for 2 hours at 650 ℃ and 700 ℃ has the same catalytic activity with P25 and is slightly better than P25.
The isothermal adsorption-desorption curve and pore size distribution curve (inset) of the mesoporous titania nanofibers prepared under the above different heat treatment temperature conditions are shown in fig. 10.
Example 9:
as described in example 1, except that in step (4), the poly (titanium oxyacetate) precursor fiber is placed in a sintering furnace for heat treatment, the temperature is raised to 100 ℃ at a heating rate of 3-6 ℃/min, water vapor is introduced, the vapor introduction amount is 3.1L/h, the temperature is raised to 350 ℃ at a heating rate of 1 ℃/min, the vapor introduction is stopped, then the temperature is raised to 650 ℃ at a heating rate of 1.5 ℃/min and the temperature is kept for 2h, and the catalytic activity of the obtained mesoporous titanium oxide nanofiber is slightly lower than that of the mesoporous titanium oxide nanofiber obtained in example 8 by directly introducing the vapor to 650 ℃, as shown in fig. 11.
Example 10:
as described in example 1, except that in step (4), the poly (titanium oxyacetate) precursor fiber is placed in a sintering furnace for heat treatment, the temperature is raised to 100 ℃ at a heating rate of 3-6 ℃/min, water vapor is introduced, the vapor flow rate is 3.1L/h, the temperature is raised to 450 ℃ at a heating rate of 1 ℃/min, the vapor introduction is stopped, then the temperature is raised to 650 ℃ at a heating rate of 1.5 ℃/min, and the temperature is kept for 2h, so that the catalytic activity of the obtained mesoporous titanium oxide nanofiber is slightly lower than that of the mesoporous titanium oxide nanofiber obtained in example 8 by directly introducing the vapor to 650 ℃, as shown in fig. 11.
Example 11:
as described in example 1, except that in step (4), the titanium oxyacetate precursor fiber is placed in a sintering furnace for heat treatment, the temperature is raised to 100 ℃ at a heating rate of 3-6 ℃/min, water vapor is introduced, the vapor introduction amount is 3.1L/h, the temperature is raised to 550 ℃ at a heating rate of 1 ℃/min, the vapor introduction is stopped, then the temperature is raised to 650 ℃ at a heating rate of 1.5 ℃/min and the temperature is kept for 2h, and the catalytic activity of the obtained mesoporous titanium oxide nanofiber is equivalent to that of P25, as shown in FIG. 11.
Examples 9-11 above illustrate that treatment of the fiber to 350 ℃ and then to 650 ℃ in a steam atmosphere, or treatment of the fiber to 450 ℃ and then to 650 ℃ in a steam atmosphere, or treatment of the fiber to 550 ℃ and then to 650 ℃ in a steam atmosphere, and treatment in an air atmosphere, facilitates crystallization of the fiber. The rate of grain growth of the fibers in an air atmosphere is higher than in a water vapor atmosphere, the specific surface area of the fibers is reduced, but the crystallinity of the fiber material is improved.
Claims (10)
1. A preparation method of a titanium oxyacetate precursor sol spinning solution comprises the following steps:
(1) according to the weight ratio of tetrabutyl titanate: weighing tetrabutyl titanate and slowly adding the tetrabutyl titanate into glacial acetic acid at a molar ratio of 1: 1-4, and stirring for reacting for 2-4 h to obtain a solution containing the poly (oxytitanium acetate); then, concentrating the solution containing the poly-titanium-oxy-acetate under reduced pressure at the temperature of 40-80 ℃ to prepare powder, thus obtaining a poly-titanium-oxy-acetate precursor;
(2) according to a precursor of the poly (titanium oxyacetate): auxiliary agent: dissolving a titanium oxyacetate precursor in an alcohol solvent according to the mass ratio of (0.4-4) to (100-400), adding an auxiliary agent, and stirring and dissolving at the temperature of 10-60 ℃ to obtain a uniform titanium oxyacetate precursor sol spinning solution;
the auxiliary agent is selected from one or the combination of polyethylene oxide, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, polyacrylamide, polyethylene glycol terephthalate, polyurethane, polyglycolic acid and polylactic acid.
2. The method of preparing a titanyl acetate precursor sol spinning dope according to claim 1, wherein the alcohol solvent is selected from one of absolute methanol, absolute ethanol or a combination thereof.
3. The method for preparing the titanyl acetate precursor sol spinning solution according to claim 1, wherein the molar ratio of tetrabutyl titanate to glacial acetic acid is 1: 2.5-3.5; preferably, the precursor of the poly (titanyl acetate): the mass ratio of the auxiliary agent to the solvent is 100 (0.7-2) to 100-300.
4. A method for preparing a titania nanofiber photocatalyst, comprising the preparation of the titanyl acetate precursor sol spinning solution according to any one of claims 1 to 3, further comprising the steps of:
(3) electrostatic spinning: placing the titanium poly-acetate precursor sol spinning solution into an injector with a stainless steel needle head of a spinning device, performing electrostatic spinning by adopting a high-voltage electrostatic spinning method, applying a voltage of 8-28 kV under the conditions of an ambient temperature of 20-35 ℃ and a relative humidity of 30-70%, wherein the flow speed of the spinning solution is 0.5-3.5 mL/h, the inner diameter of the positive stainless steel needle head is 0.19-0.60 mm, and the distance between the needle head and a rotary drum of a fiber collecting device is 8-35 cm, so as to prepare the titanium poly-acetate precursor fiber;
(4) and (3) heat treatment: placing a titanium oxide precursor fiber in a muffle furnace for heat treatment, heating to 300-1000 ℃ at a heating rate of 0.4-5 ℃/min under the air condition, and preserving heat for 1-3 hours to fully decompose and crystallize the titanium oxide precursor fiber to prepare a solid titanium oxide nanofiber, placing the titanium oxide precursor fiber in a sintering furnace for heat treatment, heating to 100-200 ℃ at a heating rate of 3-6 ℃/min, starting to introduce steam, heating to 300-900 ℃, preferably 500-750 ℃, further preferably 600-700 ℃ at a heating rate of 0.5-2.5 ℃/min, stopping introducing the steam, and preserving heat to fully decompose and crystallize the titanium oxide precursor fiber to convert the titanium oxide nanofiber into mesoporous titanium oxide nanofibers; or,
and (2) placing the titanium oxide precursor fiber in a sintering furnace for heat treatment, heating to 100-200 ℃ at a heating rate of 3-6 ℃/min, starting to introduce steam, heating to 350-550 ℃ at a heating rate of 0.5-1 ℃/min, stopping introducing the steam, heating to 600-700 ℃ at a heating rate of 1.5-2 ℃/min, and preserving heat for 2 hours to obtain the mesoporous titanium oxide nanofiber.
5. The method for preparing the titanium oxide nanofiber photocatalyst according to claim 4, wherein in the step (3), the electrospinning conditions are as follows: the environment temperature is 20-30 ℃, the relative humidity is 35-60%, the applied voltage is 10-24 kV, the flow rate of the spinning solution is 0.5-2.5 mL/h, the inner diameter of the stainless steel needle is 0.26-0.51 mm, and the distance between the positive stainless steel needle and the rotary drum of the fiber collecting device is 10-30 cm; wherein the flow rate of the spinning solution is preferably 1-2 mL/h.
6. The method for preparing the titanium oxide nanofiber photocatalyst according to claim 4, wherein in the step (4), when the maximum treatment temperature is 900 to 1000 ℃ in preparing the solid titanium oxide nanofiber, a three-stage temperature raising mode is adopted: heating to 600-700 ℃ at a heating rate of 0.5 ℃/min, heating to 750-800 ℃ at a heating rate of 1 ℃/min, heating to 900-1000 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 2 h.
7. The method for preparing the titanium oxide nanofiber photocatalyst according to claim 4, wherein the diameter of the solid titanium oxide nanofiber obtained in the step (4) is 200-800 nm, and the length is 2-8 cm.
8. The method for preparing the titanium oxide nanofiber photocatalyst according to claim 4, wherein the steam in the step (4) is ammonia gas, ethanol, water vapor, mixed steam of water and ethanol, or mixed steam of water and hydrogen peroxide.
9. The method for preparing the titanium oxide nanofiber photocatalyst according to claim 4 or 8, wherein the steam aeration amount is 2.0 to 3.4L/h.
10. The method for preparing the titanium oxide nanofiber photocatalyst according to claim 4, wherein the mesoporous titanium oxide nanofiber prepared in the step (4) has a diameter of 300 to 600nm, a length of 2 to 8cm, and a specific surface area of 20 to 130m2The pore size is 1-50 nm.
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| WO2024070019A1 (en) * | 2022-09-30 | 2024-04-04 | Jnc株式会社 | Metal oxide porous fiber |
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