CN106492779A - The preparation method of core shell structure rare earth titanate dioxide composite nanofiber catalysis material - Google Patents
The preparation method of core shell structure rare earth titanate dioxide composite nanofiber catalysis material Download PDFInfo
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- CN106492779A CN106492779A CN201610860551.4A CN201610860551A CN106492779A CN 106492779 A CN106492779 A CN 106492779A CN 201610860551 A CN201610860551 A CN 201610860551A CN 106492779 A CN106492779 A CN 106492779A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 38
- 239000002121 nanofiber Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000011258 core-shell material Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 28
- -1 rare earth titanate Chemical class 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 48
- 238000009987 spinning Methods 0.000 claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960000583 acetic acid Drugs 0.000 claims abstract description 5
- 238000013019 agitation Methods 0.000 claims abstract description 5
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims description 8
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical group [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 12
- 238000007789 sealing Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 39
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000004408 titanium dioxide Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910017582 La2Ti2O7 Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 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
- 239000002070 nanowire Substances 0.000 description 1
- AKMADBIBLGBZQJ-UHFFFAOYSA-N neodymium;nitric acid Chemical compound [Nd].O[N+]([O-])=O AKMADBIBLGBZQJ-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of preparation method of core shell structure rare earth titanate dioxide composite nanofiber catalysis material, comprises the following steps：(1) polyvinyl acetate is dissolved in after absolute ethyl alcohol, is added dropwise over the glacial acetic acid solution of butyl titanate thereto, continued stirring 6h, then stand 3h, form core TiO 2 precursor solution；Polyvinylpyrrolidone is dissolved in N, after N dimethylformamides, the aqueous solution of the inorganic acid salt and rare earth nitrades of titanium, room temperature magnetic agitation 6h under sealing state is added thereto to, then is stood 3h, form shell rare earth titanate precursor solution；(2) newly prepare two kinds of precursor solutions are added separately in core and shell syringe, carry out coaxial electrostatic spinning, collect spinning fibre film；(3) spinning fibre film is calcined using temperature programmed control calcine technology, core shell structure rare earth titanate dioxide composite nanofiber is obtained.Synthesis technique of the present invention is simple, it is possible to obtain structure-controllable, the catalysis material of excellent performance.
Description
Technical field
The present invention relates to a kind of preparation of core shell structure rare earth titanate-dioxide composite nanofiber catalysis material
Method.
Background technology
Today's society economy is developed rapidly, and population is sharply increased, and causes environmental pollution and energy shortage, for early settlement
Environment and energy two large problems, the researchers of various countries' different field are tried to explore.Wherein, Photocatalitic Technique of Semiconductor has been
Become direction sign and normal line that people solve the above problems.In numerous conductor photocatalysis materials, titanium dioxide is because of which
Photocatalytic activity is high, ultraviolet-shielding type is strong, thermal conductance is good, good dispersion and form the advantages of inexpensive, nontoxic, non-secondary pollution
For a kind of most valued photocatalytic semiconductor material.But in actual application, due to titanium dioxide exist band gap width,
Sun light utilization efficiency is low, light induced electron and hole are easily compound, photo-quantum efficiency is poor and titanium dioxide powder is easily suspended in pollution
The shortcomings of in system, not only hinder light to propagate, reduce light transmission, more easy in inactivation is reunited, it is difficult to recycling.These are all tight
Its industrial applications process is hindered again.Therefore, modification is carried out to titanium dioxide, widens its response model to solar spectrum
Enclose, improve the utilization rate of sunshine, effectively suppress light induced electron simple and quick compound with hole pair, improve its photocatalytic activity
The purpose of industrialized production is reached, becomes study hotspot and the key technology in the field.Wherein, risen the thirties in 20th century
Electrostatic spinning technique has abundant raw materials, low cost, process is simple in terms of monodimension nanometer material is constructed, in micron
Material, field of nano material preparation are increasingly widely applied.
Content of the invention
It is an object of the invention to provide a kind of core shell structure rare earth titanate-dioxide composite nanofiber photocatalysis
The preparation method of material, can obtain that material microstructure is controllable, photocatalytic activity strong, sun light utilization efficiency is high by the method,
There is the dioxide composite nanofiber catalysis material of heterojunction characteristics.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of preparation method of core shell structure rare earth titanate-dioxide composite nanofiber catalysis material, including
Following steps：
(1) polyvinyl acetate is dissolved in after absolute ethyl alcohol, is added dropwise over the glacial acetic acid solution of butyl titanate thereto,
6h is continuously stirred, then stands 3h, form core TiO 2 precursor solution；Polyvinylpyrrolidone is dissolved in N, N- dimethyl
Formamide, forms polyvinylpyrrolidonesolution solution, is added thereto to the aqueous solution of the inorganic acid salt and a small amount of rare earth nitrades of titanium,
Room temperature magnetic agitation 6h under sealing state, then 3h is stood, form shell rare earth titanate precursor solution；
(2) precursor solution that newly prepares is added separately in core and shell syringe, carries out coaxial electrostatic spinning,
Collect the spinning fibre film similar to non-woven fabrics；
(3) spinning fibre film is placed in high-temperature atmosphere furnace, is calcined using temperature programmed control calcine technology, core shell structure is obtained
Rare earth titanate-dioxide composite nanofiber.Preferably, in step (1), polyvinyl acetate and polyvinyl pyrrole
The limited compatibility of two kinds of organic high molecular polymers of alkanone is the core for obtaining core shell structure spinning fibre at high proportion, and strict
Concentration range control be the basis to form even thickness spinning fibre, in the invention, polyvinyl acetate with and metatitanic acid four
The mass concentration of butyl ester is controlled between 15-20% and 8-10% respectively.And the control of polyvinylpyrrolidonesolution solution mass concentration
Between 15-25%, titanium ion is 10: 1 with the mol ratio of rare earth ion.
In step (1), the inorganic acid salt of titanium is titanium sulfate or titanium tetrachloride；Rare earth nitrades are lanthanum nitrate, nitric acid
Neodymium or europium nitrate.
In the above-mentioned methods, in step (2), spinning voltage is 15kV, and it is 12cm to receive distance；Surge drum rotating speed control
System is between 500-550 turn/min；Spinning temperature is 60 DEG C, and relative humidity is 50%-60%, and the spinning time is 5-10h.
In step (2), the relative size of two kinds of precursor solution flow rates is to affect spinning fibre core diameter and shell
Thickness degree and the key factor of parcel integrality, and in the invention, the flow rate ratio (u of the flow rate of core solution and shell solutionCore
∶uShell) it is set as 2: 1.
In the step (3), the calcining of spinning fibre is to form rare earth titanium silicate nanometer shell and nano titania
The critical process of fiber core, the invention adopt temperature programmed control calcine technology, are first warming up to 300 DEG C with 25 DEG C/h, constant temperature 5h, then
550 DEG C are warming up to 15 DEG C/h, after constant temperature 10h, room temperature is naturally cooled to.
In the above-mentioned methods, using concentric binary channels composite spray jet head, the solution for making ejection is concentric point to coaxial electrostatic spinning
Laminar flow.As in spinning process, core TiO 2 precursor solution is converged at the mouth of pipe with shell rare earth titanate precursor solution
The conjunction time is shorter, and the diffusion coefficient of two kinds of solution is again all relatively low (forming part compatible system), and therefore two kinds of solution exist
Will not mix before solidification.With the increase of electric field force, the electric charge of core solution gradually moves to shell solution surface, shell layer surface
The quantity of electric charge increase, form compound taylor cone in nozzle, be wrapped in core polymer from the stretched shell of Taylor cone then
Coaxial spinning fibre film.It is removed by organic matters such as high-temperature calcination, the polyvinyl acetate in core, butyl titanate quilt
Oxidation generates titanium dioxide nanofiber core.The organic principles such as the polyvinylpyrrolidone in shell fiber are removed, the nothing of titanium
Machine hydrochlorate generates rare earth titanate with rare earth nitrades reaction, and connects along original fiber stretch direction, ultimately forms rare earth
Titanate cladding titanium dioxide composite nano fiber, in calcination process, shell titanium atom interpenetrates to be formed with core titanium atom
Hetero-junctions, is conducive to the separation of photo-generate electron-hole, can effectively improve its photocatalysis performance.
In the above-mentioned methods, by changing response parameter, such as viscosity, concentration, electrospinning, solvent volatility, flow velocity, electricity
Pressure etc., can be with architectural characteristics such as effective control core diameter, shell thickness and its fiber surface roughness.
It is an advantage of the current invention that：
The present invention is combined to prepare using coaxial electrostatic spinning technology with temperature programmed control calcine technology and there is core shell structure
Dioxide composite nanofiber catalysis material.The primary condition that can be smoothed out according to coaxial electrostatic spinning technology is to produce
The characteristics of giving birth to stable compound taylor cone, is being fully understood by and is grasping core solution continuously entering shell, formed continuous
On the basis of coaxial configuration this key technology, by regulating and controlling such as viscosity, concentration, electrospinning, solvent volatilization in spinning process
The technological parameters such as solution parameter and flow velocity, voltage such as property, in conjunction with temperature programmed control calcine technology to core shell structure composite nano fiber
Pattern control effectively, so as to obtain structure-controllable, excellent performance, the dioxide composite nanofiber with core shell structure
Catalysis material.
Catalysis material prepared by the present invention, synthesis technique are simple；Using the organic contamination in sun light degradation environment
Thing；Photocatalytic activity is high, easily separated recovery and recycling；Energy-conservation, non-secondary pollution, applied range, environmental protection；Market
Prospect is boundless.
Description of the drawings
Fig. 1 is the La obtained by the embodiment of the present invention 12Ti2O7-TiO2The scanning electron microscope (SEM) photograph (a) of composite nano fiber and thoroughly
Penetrate electron microscope (b).
Fig. 2 is the Eu obtained by the embodiment of the present invention 22Ti2O7-TiO2The scanning electron microscope (SEM) photograph (a) of composite nano fiber and thoroughly
Penetrate electron microscope (b).
Specific embodiment
The present invention will be further described by the following examples, but the specific embodiment of the present invention is not limited in
This.
The present invention is combined with temperature programmed control calcine technology using coaxial electrostatic spinning technology, can prepare different covering materials
Core shell structure rare earth titanate-dioxide composite nanofiber with different cladding thickness.The present invention is suitable by selecting
Covering material and optimum reaction condition are conducive to the two to be preferably combined, and rare earth titanium silicate nanometer shell is received with titanium dioxide
Rice core is combined closely, and forms hetero-junctions, can improve the surface area of composite nano fiber, reduces its crystallite dimension, promotes light
Raw electronics is separated with hole.Shell thickness also has important shadow for the photocatalysis performance of core titanium dioxide nanofiber
Ring, the core shell structure composite nano fiber with different shell thicknesses is successfully prepared by controlling shell flow rate.In addition, inorganic acid
Radical ion and nitrate ion all have electric conductivity, so as to cause during rare earth titanate cladding titanium dioxide is prepared,
Spinning jet is highly unstable, is susceptible to the adhesion of fiber and the heterogeneity of fiber during jet flies to receiver board
Property.By the larger macromolecule spinning solution of selection viscosity and adjustment solution concentration, the conductance of effective control spinning solution is to electrostatic
The impact of spinning, prepares structure-controllable, excellent performance, the dioxide composite nanofiber photocatalysis material with core shell structure
Material, reaches the purpose for improving photocatalytic activity.Its conclusion can provide new in a large number for the preparation of titanium dioxide composite photocatalyst
Information, the preparation for inorganic composite nanofiber provide beneficial help.
Material requested and test instrument：
Polyvinylpyrrolidone (PVP, Mw=300000 are analyzed pure)；Polyvinyl acetate (PVAc, Mw=500000, point
Analysis is pure), Beijing Yili Fine Chemicals Co., Ltd..Butyl titanate (Ti (BOu)4, 99%, analyze pure) Shanghai elder brother's row chemical industry
Science and Technology Ltd..Lanthanum nitrate (La (NO3)3, 99.9%, analyze pure)；Europium nitrate (Eu (NO3)3；99.9%, analyze pure), day
Yong great chemical reagent Co., Ltd of Jinshi City.Titanium sulfate (Ti (SO4)2, analyze pure)；Titanium tetrachloride (TiCl4, analyze pure)；Glacial acetic acid
(HAc is analyzed pure)；DMF (DMF is analyzed pure)；Absolute ethyl alcohol (CH3CH2OH, analyzes pure), Tianjin section is close
Europe chemical reagents corporation.
The FM1206 types electrostatic of Beijing Fu Youma Science and Technology Ltd.s production visits silk device；Rigaku Motor Corporation produces
Rigaku D/max type powder x-ray diffractions (XRD)；The S-4800 Flied emissions scanning electricity of Japanese Hitachi companies production
Sub- microscope (SEM)；NEC JEOL companies JEM-1200 types are with, JEL-1400 types and Dutch FEI Co.'s production
Tecnai G2 F20S-TWIN type transmission electron microscopes (HR-TEM)；The TriStar II 3020 of U.S. Micromeritics productions
Analyzer ratio surface area instruments；The U-4100 UV, visible light light splitting light with integrating sphere accessory that Japanese Hitachi companies produce
Degree meter.
Embodiment 1
Accurately weigh 4g PVAc to be dissolved in 12mL absolute ethyl alcohols, dropwise add 6mL Ti (BOu) thereto4HAc solution,
Continue stirring 6h, then stand 3h, form core TiO 2 precursor solution.Accurately weigh 3g PVP to be dissolved in 12mL DMF,
By 2.4g Ti (SO4)2With 0.33g La (NO3)3After being dissolved in 3ml deionized waters respectively, above-mentioned solution is added to, under sealing state
Room temperature magnetic agitation 6h, then 3h is stood, form shell rare earth titanate precursor solution.
Coaxial electrostatic spinning is carried out in the syringe that the precursor solution for preparing is added separately to core and shell, its
Middle spinning voltage is 15kV, receives distance for 12cm, flow rate 0.4mL/h of core solution, and the flow rate of shell solution is 0.2mL/
H, surge drum rotating speed are 550 turns/min, and spinning temperature is 60 DEG C, and relative humidity is 55%, through 5h, collects on surge drum
Spinning fibre film similar to non-woven fabrics.
Spinning fibre film is placed in high-temperature atmosphere furnace and is calcined, first 300 DEG C are warming up to 25 DEG C/h, constant temperature 5h, then
550 DEG C are warming up to 15 DEG C/h, constant temperature 10h naturally cools to room temperature, core shell structure La is obtained2Ti2O7-TiO2Composite Nano is fine
Dimension.
It is illustrated in figure 1 obtained core shell structure La2Ti2O7-TiO2The scanning electron microscope (SEM) photograph of composite nano fiber and transmission electricity
Mirror figure, from scanning electron microscope (SEM) photograph, La2Ti2O7Fiber thickness is uniform, and smooth surface, with good dispersiveness and big major diameter
Than.From transmission electron microscope picture, La2Ti2O7Shell is uniformly coated on TiO2Nanofiber surface, forms core shell structure, and core is straight
Footpath is about 150nm, and shell thickness is about 30nm.
Embodiment 2
Accurately weigh 4g PVAc to be dissolved in 12mL absolute ethyl alcohols, be added dropwise over the glacial acetic acid solution of 6mL butyl titanates,
Continue stirring 6h, then stand 3h, form core TiO 2 precursor solution.Accurately weigh 3g PVP to be dissolved in 12mL DMF,
By 1.9g TiCl4With 0.34g Eu (NO3)3After being dissolved in 3ml deionized waters respectively, it is added in above-mentioned solution, under sealing state
Room temperature magnetic agitation 6h, then 3h is stood, form shell rare earth titanate precursor solution.
Coaxial electrostatic spinning is carried out in the syringe that the precursor solution for preparing is added separately to core and shell, its
Middle spinning voltage is 15kV, and spinning distance is 12cm, and flow rate 0.2mL/h of core solution, the flow rate of shell solution are 0.1mL/
H, surge drum rotating speed are 500 turns/min, and spinning temperature is 60 DEG C, and relative humidity is 55%, through 8h, collects on surge drum
Spinning fibre film similar to non-woven fabrics.
Spinning fibre film is placed in high-temperature atmosphere furnace and is calcined, first 300 DEG C are warming up to 25 DEG C/h, constant temperature 5h, then
550 DEG C are warming up to 15 DEG C/h, constant temperature 10h naturally cools to room temperature, core shell structure Eu is obtained2Ti2O7-TiO2Composite Nano is fine
Dimension.
It is illustrated in figure 2 obtained core shell structure Eu2Ti2O7-TiO2The scanning electron microscope (SEM) photograph of composite nano fiber and transmission electricity
Mirror figure, from scanning electron microscope (SEM) photograph, fiber thickness is uniform, and surface shows slightly coarse, with good dispersiveness and big draw ratio.
From transmission electron microscope picture, Eu2Ti2O7Shell is uniformly coated on TiO2Nanofiber surface, forms core shell structure, and core is straight
Footpath is about 180nm, and shell thickness is about 40nm.
Understand according to Density function theory, TiO2Band structure in, its top of valence band is from O2pState, conduction band bottom is
Ti3dState.The distance between La (Eu)-Ti, La (Eu)-O atom farther out, La (Eu) atom pair Ti3dAnd O2pThe contribution of track is very
Little.And the 4f tracks of La (Eu) are located at the 5-6eV of conduction band, Ti is substantially at3dAnd O2pBetween track, define less than Ti3dLead
The transition energy band of band.As conduction band bottom (the transition energy band) electron energy level of rare earth titanate is less than TiO2Conduction band, top of valence band electricity
Sub- level of energy is higher than TiO2Valence band, TiO2Hole in valence band can be delivered to the valence band of rare earth titanate through interface and tire out
Product, is conducive to TiO2Light induced electron and the separation in hole, enhance the quantum efficiency of system, effectively increase sunshine utilization
Rate, its spectral response range is also by TiO2The ultraviolet region (387.5nm) of nanofiber widen to visible region (473.6nm and
526.3nm).Reacted as pattern with the decolored degradation of rhodamine B, sunshine is light source, investigate embodiment 1, the light of 2 gained samples
Catalytic performance.As a result show：Solar irradiation 6h, the decolored degradation rate of rhodamine B respectively reach 98.7% and 96.5%.And it is identical
Under the conditions of, pure TiO2The decolored degradation rate of nanofiber only has 71.4%, shows that rare earth titanate is coated on TiO2Nanowire dimension table
Face can effectively improve TiO2Photocatalytic activity.
Claims (7)
1. a kind of preparation method of core shell structure rare earth titanate-dioxide composite nanofiber catalysis material, its feature
It is, comprises the following steps：
(1) polyvinyl acetate is dissolved in after absolute ethyl alcohol, is added dropwise over the glacial acetic acid solution of butyl titanate thereto, continuously
Stirring 6h, then 3h is stood, form core TiO 2 precursor solution；Polyvinylpyrrolidone is dissolved in N, N- dimethyl formyls
Amine, forms polyvinylpyrrolidonesolution solution, is added thereto to the aqueous solution of the inorganic acid salt and a small amount of rare earth nitrades of titanium, seals
Room temperature magnetic agitation 6h under state, then 3h is stood, form shell rare earth titanate precursor solution；
(2) precursor solution that newly prepares is added separately in core and shell syringe, carries out coaxial electrostatic spinning, collected
To the spinning fibre film similar to non-woven fabrics；
(3) spinning fibre film is placed in high-temperature atmosphere furnace, is calcined using temperature programmed control calcine technology, core shell structure rare earth is obtained
Titanate-dioxide composite nanofiber.
2. core shell structure rare earth titanate-dioxide composite nanofiber catalysis material according to claim 1
Preparation method, it is characterised in that the mass concentration of polyvinyl acetate and butyl titanate is controlled respectively in step (1)
Between 15-20% and 8-10%；And polyvinylpyrrolidonesolution solution mass concentration control between 15-25%, titanium ion with dilute
The mol ratio of native ion is 10: 1.
3. core shell structure rare earth titanate-dioxide composite nanofiber catalysis material according to claim 1
Preparation method, it is characterised in that the inorganic acid salt of titanium is titanium sulfate or titanium tetrachloride in step (1)；Rare earth nitrades are
Lanthanum nitrate, neodymium nitrate or europium nitrate.
4. core shell structure rare earth titanate-dioxide composite nanofiber catalysis material according to claim 1
Preparation method, it is characterised in that spinning voltage is 15kV in step (2), it is 12cm to receive distance；Surge drum rotating speed is controlled
Between 500-550 turn/min.
5. core shell structure rare earth titanate-dioxide composite nanofiber catalysis material according to claim 1
Preparation method, it is characterised in that spinning temperature is 60 DEG C in step (2), and relative humidity is 50%-60%, spinning time
For 5h-10h.
6. core shell structure rare earth titanate-dioxide composite nanofiber catalysis material according to claim 1
Preparation method, it is characterised in that the flow rate ratio (u of the flow rate of core solution and shell solution in step (2)Core∶uShell) it is 2:
1.
7. core shell structure rare earth titanate-dioxide composite nanofiber catalysis material according to claim 1
Preparation method, it is characterised in that in step (3) spinning fibre film during calcining, using temperature programmed control calciner
Skill, is first warming up to 300 DEG C with 25 DEG C/h, constant temperature 5h, then is warming up to 550 DEG C with 15 DEG C/h, after constant temperature 10h, naturally cools to room
Temperature.
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| CN111330566A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | One-step method for preparing visible light response TiO2@BiVO4Core-shell structure mesoporous nanofiber photocatalytic material |
| CN111330623A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | One-step method for preparing Ag ion modified TiO with high visible light response2/g-C3N4Nanofiber photocatalytic material |
| CN111330623B (en) * | 2020-03-25 | 2022-11-11 | 陕西科技大学 | One-step method for preparing Ag ion modified TiO with high visible light response 2 /g-C 3 N 4 Nanofiber photocatalytic material |
| CN111330566B (en) * | 2020-03-25 | 2024-01-30 | 深圳万知达科技有限公司 | One-step method for preparing visible light response TiO 2 @BiVO 4 Mesoporous nanofiber photocatalytic material with core-shell structure |
| CN113790831A (en) * | 2021-09-18 | 2021-12-14 | 青岛大学 | Ultrafast-response breathable flexible pressure sensor and preparation method thereof |
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