CN107413325B - A kind of rare earth/carbon co-doped flexibility TiO2Nano fibrous membrane and preparation method thereof - Google Patents
A kind of rare earth/carbon co-doped flexibility TiO2Nano fibrous membrane and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 83
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 77
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000835 fiber Substances 0.000 claims abstract description 30
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 239000010936 titanium Substances 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 150000000917 Erbium Chemical class 0.000 claims description 4
- 150000000921 Gadolinium Chemical class 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001206 Neodymium Chemical class 0.000 claims description 4
- 150000001213 Praseodymium Chemical class 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- XWFVFZQEDMDSET-UHFFFAOYSA-N gadolinium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XWFVFZQEDMDSET-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- ROHFMCNIVFLSTQ-UHFFFAOYSA-K trichloroneodymium;hydrate Chemical class O.Cl[Nd](Cl)Cl ROHFMCNIVFLSTQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 235000010215 titanium dioxide Nutrition 0.000 description 7
- 239000002121 nanofiber Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001523 electrospinning Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 159000000008 strontium salts Chemical class 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- RLDBHKUGRPXFBF-UHFFFAOYSA-N lanthanum;hydrate Chemical compound O.[La] RLDBHKUGRPXFBF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- LMCBEWMQFKWHGU-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O LMCBEWMQFKWHGU-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical class [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- AMGRXJSJSONEEG-UHFFFAOYSA-L strontium dichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Sr]Cl AMGRXJSJSONEEG-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/23—
-
- B01J35/30—
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/58—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
Abstract
The present invention relates to a kind of rare earth/carbon co-doped flexibility TiO2Nano fibrous membrane and preparation method thereof, steps are as follows: preparation precursor solution, precursor solution are made of titanium source, rare earth metal salt, carbon source, nonionic surfactant and solvent first；Electrostatic spinning is carried out again and obtains precursor fibre film, and it is -10~0 DEG C that when electrostatic spinning applies 50~100 DEG C of constant temperature thermal field and control and receive the temperature of device in spinning section；Finally calcining obtains rare earth/carbon co-doped flexibility TiO in air atmosphere2Nano fibrous membrane.The pliability of final product obtained is 10~50mN, and tensile break strength is 3~5MPa, and absorbable light abstraction width is expanded to 550~700nm.Preparation method of the present invention, it is not necessary that polymer or aging is added, without post-processing, simple process and low cost, product has good tensile break strength, flexibility and visible light catalytic performance.
Description
Technical field
The invention belongs to field of new materials, are related to a kind of rare earth/carbon co-doped flexibility TiO2Nano fibrous membrane and its preparation
Method.
Background technique
Titanium dioxide (TiO2) monodimension nanometer material is because of spies such as its photocatalysis property is stable, cheap, no biotoxicities
Point, the degradation aspect such as volatile organic matter (VOCs), and interior, car VOCs in photocatalysis hydrogen production, industry cause
Extensive concern.But it to be used as a kind of widely applied catalysis material, there are following main problems: 1) TiO2Greater band gap
(Eg=3.0~3.2eV), can only be by 400 nano wave lengths ultraviolet excitation below, and solar energy utilization ratio is low.2) light induced electron-
Hole is compound to being easy, and causes light quantum utilization rate low, to reduce the catalytic activity of material.3) most of one-dimensional titanium dioxides
Problem that the generally existing brittleness of titanium nano material is big, that intensity is low.Above-mentioned problem becomes limitation nano titanium dioxide photocatalysis
The widely applied bottleneck problem of material.For this purpose, people utilize element doping, absorption of the titanium dioxide to visible light is realized, and
Effectively inhibit the compound of photo-generate electron-hole pair, to improve catalytic activity, and realizes the flexibility preparation of fiber.
In the research of early stage, mainly with single metal or nonmetal doping, such as C, S, N, Fe, Ni, Zn, La, Ce.
Maruska etc., which is reported, makes it have visible light catalytic response by the way that transition metal (Fe, Ni etc.) is titania-doped,
Asahi etc. reports N and replaces TiO2In lattice after a small amount of O, catalyst can be made to respond with visible light catalytic, then
Lettmann etc. is chanced on when doing N doping, also has visible light catalysis activity in the sample not adulterated, to find carbon
Dopen Nano TiO2Visible light catalysis activity, thus exploitation have visible light catalytic response titania-doped research just
It attracts wide attention.
Patent CN 104607171 discloses a kind of preparation side of praseodymium doped dioxide composite nanofiber photocatalyst
Method, 117 (2014) 1191-1201 of Applied Physics A report a kind of preparation of cerium doped titanium dioxide nanofiber
Method, a small amount of rare earth metal are incorporated into TiO2Lattice or interstitial void in, effectively inhibit photo-generate electron-hole to answering
It closes, while enhancing the interaction between crystal boundary, while improving catalytic activity, also expanded its visible absorption range, but
Its visible absorption wavelength focuses mostly in 500nm or less.
Patent CN 102021676A discloses a kind of preparation method of titanium dioxide/active carbon composite nanofibrous membrane,
Synthetic Metals 193 (2014) 125-131 reports a kind of preparation side of titanium dioxide/carbon nano tube nano fiber
Method, research are found in C and thulium co-doped nano TiO2In material, a small amount of C enters TiO2In lattice, Ti-C is formed
Key forms doped energy-band, so that its forbidden bandwidth is narrowed, be conducive to its absorption to visible light, although the introducing of C can make to be catalyzed
The light abstraction width of agent becomes larger, and expands to 700nm or more, but the presence of C results in the catalytic activity reduction of catalyst.
In recent years, multi-element doping is receive more and more attention.Especially carbon is more favored with rare earth doped.
Improve fibre strength.However, the report about rare earth/carbon co-doped flexible titanium dioxide nanofiber preparation and research is still
It is rare.Therefore, a kind of rare earth/carbon co-doped flexibility TiO is developed2Nano-fiber material has a very important significance.
Summary of the invention
The purpose of the present invention is overcoming in the prior art, the process is more complicated, expensive and bad properties of product lacks
It falls into, a kind of simple production process, low in cost, product photocatalysis performance and its flexible preferable rare earth/carbon co-doped soft is provided
Property TiO2Nano fibrous membrane and preparation method thereof.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of rare earth/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, steps are as follows:
(1) precursor solution is prepared, the precursor solution is by titanium source, rare earth metal salt, carbon source, non-ionic surface active
Agent and solvent composition；
(2) it carries out electrostatic spinning and obtains precursor fibre film, apply constant temperature thermal field in spinning section when the electrostatic spinning
And the temperature of device is controlled and received, the temperature of the constant temperature thermal field is 50~100 DEG C, and the temperature of the reception device is -10~0
℃；
(3) calcining obtains rare earth/carbon co-doped flexibility TiO in air atmosphere2Nano fibrous membrane.
As a preferred technical scheme:
A kind of rare earth/carbon co-doped flexibility TiO as described above2The preparation method of nano fibrous membrane, the preparation forerunner
The concrete operations of liquid solution are as follows: titanium source and rare earth metal salt dissolution are stirred into 30~150min in a solvent, then sequentially added
Carbon source and nonionic surfactant stir 10~90min and are uniformly mixed.
It is on the one hand first to make titanium source carry out partial hydrolysis to generate hydroxyl by titanium source, the purpose of rare earth metal salt dissolution in a solvent
On the other hand base is to be uniformly mixed rare earth metal salt and titanium source.If simultaneously by titanium source, rare earth metal salt, carbon source and nonionic
Surface-active is added in solvent, is unfavorable for titanium source hydrolysis, is influenced the growth of micelle, and uniformly dividing for rare earth ion is unfavorable for
Cloth.
Rare earth/carbon co-doped flexibility TiO as described above2The preparation method of nano fibrous membrane, in the precursor solution
The molar ratio of titanium source, rare earth metal salt and solvent is 1:0.001~0.1:10~100, titanium source, carbon source and non-ionic surface active
The molar ratio of agent is 1:0.001~0.1:0.05~0.25.
Rare earth/carbon co-doped flexibility TiO as described above2The preparation method of nano fibrous membrane, the titanium source are isopropanol
Titanium, butyl titanate, titanium tetrachloride, titanium trichloride or titanyl sulfate；
The rare earth metal salt is lanthanum salt, cerium salt, gadolinium salt, erbium salt, praseodymium salt, strontium salt or neodymium salt；
The solvent is ethyl alcohol, ethylene glycol, isopropanol, glycerine, acetic acid or N,N-dimethylformamide；
The carbon source is graphene, single-walled carbon nanotube, multi-walled carbon nanotube, carbon quantum dot, active carbon or carbon black；
The nonionic surfactant is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, gathers
Ethylene oxide polyoxypropylene, glycerine polyoxyethylene polyoxypropylene blocked copolymer, ethylenediamine polyoxyethylene oxypropylene block
Formula polyethers or propylene glycol polyoxyethylene poly-oxygen propylene aether.
A kind of rare earth/carbon co-doped flexibility TiO as described above2The preparation method of nano fibrous membrane, the lanthanum salt are six
Nitric hydrate lanthanum, lanthanum acetate or seven hydrated lanthanum chlorides, the cerium salt are six nitric hydrate ceriums or seven chloride hydrate ceriums, the gadolinium salt
For gadolinium nitrate hexahydrate, six chloride hydrate gadoliniums or eight hydrated sulfuric acid gadoliniums, the erbium salt is five nitric hydrate erbiums or six chloride hydrates
Erbium, the praseodymium salt are six nitric hydrate praseodymiums or eight hydrated sulfuric acid praseodymiums, and the strontium salt is that Strontium dichloride hexahydrate or six are hydrated strontium bromides,
The neodymium salt is six nitric hydrate neodymiums or six Neodymium chloride hydrates.
A kind of rare earth/carbon co-doped flexibility TiO as described above2The preparation method of nano fibrous membrane, the electrostatic spinning
Parameter are as follows: relative humidity 20~70%, 0.1~15mL/h of rate of flooding, 10~60kV of voltage, between reception device and spinning nozzle
20~40cm of distance, the reception device be metal roller or metal plate.
A kind of rare earth/carbon co-doped flexibility TiO as described above2The preparation method of nano fibrous membrane, the temperature of the calcining
Degree gradually rises to 400~1000 DEG C from room temperature, and heating rate is 0.1~10 DEG C/min, and is kept under highest calcination temperature
10~360min.
The present invention also provides one kind rare earth as made from method produced above/carbon co-doped flexibility TiO2Nano fibrous membrane,
Rare earth/carbon co-doped flexibility TiO2The pliability of nano fibrous membrane is 10~50mN, rare earth/carbon co-doped flexibility TiO2Nanowire
The tensile break strength for tieing up film is 3~5MPa, and absorbable light abstraction width is expanded to 550~700nm.
As a preferred technical scheme:
Rare earth/carbon co-doped flexibility TiO as described above2Nano fibrous membrane, the rare earth/carbon co-doped flexibility TiO2It receives
The average diameter of fiber is 10~400nm in rice tunica fibrosa, and relative standard deviation is 1~5%, internal grain having a size of 10~
80nm.Fiber diameter range shows fiber thickness, and fibre diameter is smaller, and single fiber pliability is preferable, is conducive to tunica fibrosa softness
The raising of degree；Uniformity of the relative standard deviation to characterize distribution of fiber diameters, deviation is smaller, and Fiber Uniformity is better；
Crystallite dimension and fiber film dynamic performance are closely related, and the reduction of crystallite dimension is also beneficial to the promotion of photocatalysis performance.
Inventive principle:
Titanium source is added in solvent by the first step of the present invention, and hydrolysis-condensation reaction occurs under stirring, and rare earth is added
The purpose of metal salt is to reduce fiber surface microdefect during subsequent calcination, inhibits TiO2Grain growth, crystallite dimension are got over
Small, crystal grain specific surface is higher, and surface-active bits number is more, and photocatalytic activity is improved accordingly, and carbon source is being added
After surfactant, hydrogen bond will form between titanium source, carbon source and surfactant, so that carbon source is evenly distributed on presoma molten
In liquid, the spinning solution of stable homogeneous is obtained；Apply 50~100 DEG C of constant temperature thermal field in spinning section when electrostatic spinning, promotes
The quick volatilization of solvent in spinning jet then passes through self assembly shape so that surfactant concentration reaches critical micelle concentration
It is arranged at micella, and under the quick drawing-off of electric field force effect along fiber axial direction direction gage entire row, micella unit phase each other along fiber
It is mutually parallel, there is one-dimensional order, in addition, thermal field and Electrostatic Field Coupling inducing action can promote TiO in spinning solution2In presoma
Hydroxyl and carbon source between form stronger hydrogen bond or covalent bond effect, to make TiO2Presoma and the uniform Assembled distribution of carbon source exist
Micellar surface.It, can be with wink since reception device has lower temperature (- 10~0 DEG C) when fiber is collected into reception device
Between consolidate and retain the orderly self-assembled structures inside precursor fibre.
The utility model has the advantages that
(1) a kind of rare earth of the invention/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, it is not necessary that polymerization is added
Object or aging by applying constant temperature thermal field during the spinning process, and reduce reception substrate temperature, make carbon source without post-processing
It is uniformly distributed and consolidates in precursor fibre, and Ti content is high in spinning solution, titanium dioxide nanofiber yield is high, prepares work
Skill is simple, low in cost；
(2) a kind of rare earth of the invention/carbon co-doped flexibility TiO2Nano fibrous membrane has good tension failure strong
Degree, flexible and visible light catalytic performance.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of rare earth/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, steps are as follows:
(1) titanium source isopropyl titanate and rare earth metal salt lanthanum nitrate hexahydrate are dissolved in etoh solvent and stir 30min,
Then it sequentially adds carbon source graphite alkene and nonionic surfactant polyethylene oxide-polypropylene oxide-polyethylene oxide three is embedding
Section copolymer stirring 90min is uniformly mixed with to obtain precursor solution, wherein titanium source in solution, rare earth metal salt, solvent, carbon source with
The molar ratio of nonionic surfactant is 1:0.001:100:0.001:0.25；
(2) precursor fibre film is made by electrospinning process in above-mentioned precursor solution, in spinning when electrostatic spinning
It is 0 DEG C that section, which applies 50 DEG C of constant temperature thermal field and controls the temperature of metal roller reception device,；The parameter of electrostatic spinning are as follows: opposite
Humidity 20%, rate of flooding 15mL/h, voltage 10kV, reception device distance 40cm between spinning nozzle；
(3) above-mentioned precursor fibre film is placed in calcining in air atmosphere and obtains rare earth/carbon co-doped flexibility TiO2Nanometer
Tunica fibrosa, calcining refer to that the temperature of calcining gradually rises to 650 DEG C from room temperature, and heating rate is 10 DEG C/min, and is forged in highest
120min is kept at a temperature of burning.
Final rare earth/carbon co-doped flexibility TiO obtained2The average diameter of fiber is 200nm in nano fibrous membrane, and
Relative standard deviation is 1%, and fibrous inside crystallite dimension is 10nm, rare earth/carbon co-doped flexibility TiO2Nano fibrous membrane it is soft
Softness is 10mN, and tensile break strength 5MPa expands to 700nm the absorption region of visible light.
Comparative example 1
A kind of rare earth/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, basic step and parameter and implementation
Example 1 is identical, the difference is that not set constant temperature thermal field during electrostatic spinning, is set as room temperature for reception device temperature.
Its rare earth obtained/carbon co-doped flexibility TiO2The average diameter of fiber is 300nm in nano fibrous membrane, and opposite
Standard deviation is 3%, and fibrous inside crystallite dimension is 45nm, the rare earth/carbon co-doped flexibility TiO2The softness of nano fibrous membrane
Degree is 50mN, and tensile break strength 0.8MPa expands to 500nm the absorption region of visible light, passes through pair with embodiment 1
Than it can be found that rare earth/carbon co-doped flexibility TiO obtained in embodiment 12Nano fibrous membrane ensure that it is certain flexible
Meanwhile its absorption region to visible light is substantially increased, photocatalysis performance is far superior to rare earth/carbon co-doped flexibility TiO2It receives
Rice tunica fibrosa.
Embodiment 2
A kind of rare earth/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, steps are as follows:
(1) titanium source butyl titanate and rare earth metal salt lanthanum acetate are dissolved in solvent ethylene glycol and stir 150min, so
After sequentially add carbon source single-walled carbon nanotube and non-ionic surfactant polyoxyethylene polyoxypropylene stirring 10min be uniformly mixed
With precursor solution, wherein in solution titanium source, rare earth metal salt, solvent, carbon source and nonionic surfactant molar ratio
For 1:0.1:10:0.1:0.05；
(2) precursor fibre film is made by electrospinning process in above-mentioned precursor solution, in spinning when electrostatic spinning
It is -10 DEG C that section, which applies 100 DEG C of constant temperature thermal field and controls the temperature of metal plate reception device,；The parameter of electrostatic spinning are as follows:
Relative humidity 70%, rate of flooding 0.1mL/h, voltage 60kV, reception device distance 20cm between spinning nozzle；
(3) above-mentioned precursor fibre film is placed in calcining in air atmosphere and obtains rare earth/carbon co-doped flexibility TiO2Nanometer
Tunica fibrosa, calcining refer to that the temperature of calcining gradually rises to 1000 DEG C from room temperature, and heating rate is 0.1 DEG C/min, and in highest
360min is kept under calcination temperature.
Final rare earth/carbon co-doped flexibility TiO obtained2The average diameter of fiber is 300nm, and phase in nano fibrous membrane
It is 5% to standard deviation, fibrous inside crystallite dimension is 80nm, rare earth/carbon co-doped flexibility TiO2The softness of nano fibrous membrane
Degree is 50mN, and tensile break strength 3MPa expands to 580nm the absorption region of visible light.
Embodiment 3
A kind of rare earth/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, steps are as follows:
(1) titanium source titanium tetrachloride and seven hydrated lanthanum chloride of rare earth metal salt are stirred into 90min in solvent ethylene glycol, so
After sequentially add carbon source multi-walled carbon nanotube and nonionic surfactant glycerine polyoxyethylene polyoxypropylene blocked copolymerization
Object, which stirs 50min and is uniformly mixed, matches to obtain precursor solution, wherein titanium source, rare earth metal salt, solvent, carbon source and nonionic in solution
The molar ratio of surfactant is 1:0.05:55:0.05:0.15；
(2) precursor fibre film is made by electrospinning process in above-mentioned precursor solution, in spinning when electrostatic spinning
It is -5 DEG C that section, which applies 75 DEG C of constant temperature thermal field and controls the temperature of metal roller reception device,；The parameter of electrostatic spinning are as follows: phase
To humidity 45%, rate of flooding 7.5mL/h, voltage 35kV, reception device distance 30cm between spinning nozzle；
(3) above-mentioned precursor fibre film is placed in calcining in air atmosphere and obtains rare earth/carbon co-doped flexibility TiO2Nanometer
Tunica fibrosa, calcining refer to that the temperature of calcining gradually rises to 700 DEG C from room temperature, and heating rate is 5 DEG C/min, and is calcined in highest
At a temperature of keep 185min.
Final rare earth/carbon co-doped flexibility TiO obtained2The average diameter of fiber is 205nm in nano fibrous membrane, and
Relative standard deviation is 3%, and fibrous inside crystallite dimension is 45nm, rare earth/carbon co-doped flexibility TiO2Nano fibrous membrane it is soft
Softness is 40mN, and tensile break strength 3.5MPa expands to 650nm the absorption region of visible light.
Embodiment 4~27
4~27 preparation step of embodiment is with embodiment 1, and wherein precursor solution prepares parameter, electrospinning parameters, calcining
Parameter and rare earth/carbon co-doped flexibility TiO2(note: mixing time 1 is titanium to nano fibrous membrane performance parameter as shown in 1~table of table 6
Source and rare earth metal salt are dissolved in the mixing time after solvent, and mixing time 2 is after carbon source and nonionic surfactant is added
The time of stirring)
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Claims (9)
1. a kind of rare earth/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, characterized in that steps are as follows:
(1) prepare precursor solution, the precursor solution by titanium source, rare earth metal salt, carbon source, nonionic surfactant and
Solvent composition；
(2) it carries out electrostatic spinning and obtains precursor fibre film, when electrostatic spinning applies constant temperature thermal field in spinning section and controls
The temperature of reception device processed, the temperature of the constant temperature thermal field are 50~100 DEG C, and the temperature of the reception device is -10~0 DEG C；
(3) calcining obtains rare earth/carbon co-doped flexibility TiO in air atmosphere2Nano fibrous membrane.
2. a kind of rare earth according to claim 1/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, feature
Be, it is described prepare precursor solution concrete operations are as follows: by titanium source and rare earth metal salt dissolution in a solvent stirring 30~
150min, then sequentially adds carbon source and nonionic surfactant stirs 10~90min and is uniformly mixed.
3. a kind of rare earth according to claim 1/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, feature
It is, the molar ratio of titanium source, rare earth metal salt and solvent is 1:0.001~0.1:10~100, titanium in the precursor solution
The molar ratio in source, carbon source and nonionic surfactant is 1:0.001~0.1:0.05~0.25.
4. a kind of rare earth according to claim 3/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, feature
It is, the titanium source is isopropyl titanate, butyl titanate, titanium tetrachloride, titanium trichloride or titanyl sulfate；
The rare earth metal salt is lanthanum salt, cerium salt, gadolinium salt, erbium salt, praseodymium salt or neodymium salt；
The solvent is ethyl alcohol, ethylene glycol, isopropanol, glycerine, acetic acid or N,N-dimethylformamide；
The carbon source is graphene, single-walled carbon nanotube, multi-walled carbon nanotube, carbon quantum dot, active carbon or carbon black；
The nonionic surfactant is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyoxy second
Alkene polyoxypropylene, glycerine polyoxyethylene polyoxypropylene blocked copolymer, ethylenediamine polyoxyethylene oxypropylene block formula are poly-
Ether or propylene glycol polyoxyethylene poly-oxygen propylene aether.
5. a kind of rare earth according to claim 4/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, feature
It is, the lanthanum salt is lanthanum nitrate hexahydrate, lanthanum acetate or seven hydrated lanthanum chlorides, and the cerium salt is six nitric hydrate ceriums or seven water
Cerium chloride is closed, the gadolinium salt is gadolinium nitrate hexahydrate, six chloride hydrate gadoliniums or eight hydrated sulfuric acid gadoliniums, and the erbium salt is five hydration nitre
Sour erbium or six chloride hydrate erbiums, the praseodymium salt are six nitric hydrate praseodymiums or eight hydrated sulfuric acid praseodymiums, and the neodymium salt is six nitric hydrates
Neodymium or six Neodymium chloride hydrates.
6. a kind of rare earth according to claim 1/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, feature
It is, the parameter of the electrostatic spinning are as follows: relative humidity 20~70%, 0.1~15mL/h of rate of flooding, 10~60kV of voltage,
Reception device between spinning nozzle at a distance from 20~40cm, the reception device be metal roller or metal plate.
7. a kind of rare earth according to claim 1/carbon co-doped flexibility TiO2The preparation method of nano fibrous membrane, feature
It is, the temperature of the calcining gradually rises to 400~1000 DEG C from room temperature, and heating rate is 0.1~10 DEG C/min, and most
10~360min is kept under high calcination temperature.
8. using rare earth/carbon co-doped flexibility TiO made from preparation method as described in any one of claims 1 to 72Nanowire
Film is tieed up, it is characterized in that: rare earth/carbon co-doped flexibility TiO2The pliability of nano fibrous membrane is 10~50mN, rare earth/carbon co-doped
Flexible TiO2The tensile break strength of nano fibrous membrane is 3~5MPa, and absorbable light abstraction width is expanded to 550~700nm.
9. rare earth according to claim 8/carbon co-doped flexibility TiO2Nano fibrous membrane, which is characterized in that the rare earth/
Carbon co-doped flexibility TiO2The average diameter of fiber is 10~400nm in nano fibrous membrane, and relative standard deviation is 1~5%,
Internal grain is having a size of 10~80nm.
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