CN108977935A - Coated with silica lanthanum trifluoride band cuff structure nano band and preparation method thereof - Google Patents

Abstract

The present invention relates to coated with silica lanthanum trifluoride band cuff structure nano bands and preparation method thereof, belong to quasi-one-dimensional nanometer material preparation technical field.The present invention includes three steps: (1) preparing spinning solution；(2) PVP/ [La (NO is prepared using uniaxial electrospinning technology₃)₃+ TEOS] original composite Nano band；(3) LaF is prepared₃@SiO₂Band cuff structure nano band, uses ammonium acid fluoride for fluorization agent, active carbon granule is assistant reducing agent, in air by PVP/ [La (NO₃)₃+ TEOS] original composite Nano band carries out heating fluorination treatment, obtain LaF₃@SiO₂Band cuff structure nano band, width are 4.36 ± 0.14 μm, and with a thickness of 380nm, length is greater than 50 μm.Of the invention preparation method is simple, can produce in batches, and the nano material of this special construction has broad application prospects.

Description

Coated with silica lanthanum trifluoride band cuff structure nano band and preparation method thereof

Technical field

The present invention relates to quasi-one-dimensional nanometer material preparation research fields, in particular relate to coated with silica lanthanum trifluoride band Cuff structure nano band and preparation method thereof.

Background technique

The preparation and property research of inorganic matter nanobelt are currently the disciplinary studies such as material science, Condensed Matter Physics, chemistry One of forward position focus.Nanobelt is a kind of nano material in banded structure synthesized by artificial means, its cross section is One rectangular configuration, thickness is in nanometer scale, and width can reach micron order, and length is up to several hundred microns or even several millimeters. Nanobelt causes the height of people since it is different from the performances such as pipe, the novel structure of wire material and unique light, electricity, magnetic Pay attention to.

Lanthanum trifluoride LaF₃It is widely used in the raw material for preparing lanthanoid metal, non-ferrous metal additive, solid electrolyte, gas It is quick, humidity sensor, rare earth luminescence matrix, lubricant, Laser Crystals of Rare Earth, fluoride glass, optical fiber and rare earth Infrared glass etc..Silica or referred to as silicon oxide sio₂Purposes and its extensively, mainly for the manufacture of glass, waterglass, pottery Device, enamel, refractory material, aerogel blanket, ferrosilicon, molding sand, elemental silicon, cement etc..If by lanthanum trifluoride LaF₃Nanobelt is made For sandwich layer, outside coated silica SiO₂As shell, coated with silica lanthanum trifluoride band cuff can be thus formed Structure nano band is labeled as LaF₃@SiO₂With cuff structure nano band, the substance before@is sandwich layer, and the subsequent substance of@is cladding Layer, i.e.@indicate the substance of subsequent substance cladding front.Due to its special quasi-one dimensional nanostructure, this material will have Wide application prospect, has no LaF at present₃@SiO₂Relevant report with cuff structure nano band.

One related electrospinning process (electrospinning) of the U.S. Patent Publication of Patent No. 1975504 Technical solution, this method is a kind of effective ways for preparing continuous micro nanometer fiber with macro length, by Formhals was proposed first in 1934.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making electrification Polymer solution or melt is sprayed by the traction of electrostatic force by nozzle in electrostatic field, invests the receiving screen on opposite, thus real Existing wire drawing, then solvent evaporation or melt are cooled to room temperature and solidify at normal temperature, obtain micro nanometer fiber.Electrostatic spinning Method can continuously prepare big L/D ratio micrometer fibers or nanofiber.Over the past decade, it is led in inorfil technology of preparing Domain occurs preparing the technical solution of inorganic compound such as oxide nanofiber, the oxygen using uniaxial electrospinning technology Compound includes TiO₂、ZrO₂、Y₂O₃、Y₂O₃:RE³⁺(RE³⁺=Eu³⁺、Tb³⁺、Er³⁺、Yb³⁺/Er³⁺)、NiO、Co₃O₄、Mn₂O₃、 Mn₃O₄、CuO、SiO₂、Al₂O₃、V₂O₅、ZnO、Nb₂O₅、MoO₃、CeO₂、LaMO₃(M=Fe, Cr, Mn, Co, Ni, Al), Y₃Al₅O₁₂、La₂Zr₂O₇Equal metal oxides and composite oxide of metal.Someone utilizes uniaxial electrospinning technology successfully It is prepared for high molecular nanometer band [Materials Letters, 2007,61:2325-2328；Journal of Polymer Science:Part B:Polymer Physics,2001,39:2598–2606].Someone utilizes the organic compound of tin, uses Electrostatic spinning technique combines with metallo-organic compound decomposition technique and is prepared for porous SnO₂Nanobelt [Nanotechnology, 2007,18:435704].It is multiple that someone is prepared for PEO/ stannic hydroxide using electrostatic spinning technique first Nanobelt is closed, is roasted to have obtained porous SnO₂Nanobelt [J.Am.Ceram.Soc., 2008,91 (1): 257-262].Dong Phase court of a feudal ruler etc. using uniaxial electrospinning technology be prepared for titanium dioxide nano-belts [national inventing patent, grant number: ZL200810050948.2] and Gd₃Ga₅O₁₂:Eu³⁺Porous nano-belt [Chemical Journal of Chinese Universities, 2010,31 (7), 1291- 1296], combined using uniaxial electrospinning technology with fluorination technology and be prepared for trifluorides nanobelt [country's invention is special Benefit, grant number: ZL201010108039.7].When preparing inorganic nano band using uniaxial electrospinning technology, it is necessary to by Static Spinning Product inorganic salts/high-molecular composite nanometer band of silk, carries out high-temperature heat treatment in air, obtains inorganic oxide nanobelt, And it cannot be with cuff structure nano band.It is difunctional that Dong Xiangting etc. uses coaxial electrostatic spinning technology to be successfully prepared for photoelectromagnetic With three function coaxial nanoribbons and its array [national inventing patent, grant number: 201410707446.8；RSC Advances, 2015,5(4),2523-2530；Chemical Engineering Journal,2015,260,222-230；Scientific Reports,2015,5:14052].LaF is prepared using uniaxial electrospinning technology currently, having no₃@SiO₂Band cuff structure nano The relevant report of band.

When preparing nano material using electrostatic spinning technique, the type of raw material, the molecular weight of high polymer templates, spinning solution Composition, spinning process parameter, heat treatment process and heat treatment when ambiance to the pattern of final products, size and group Chengdu It has a major impact.The present invention first uses uniaxial electrospinning technology, with lanthana La₂O₃For raw material, evaporated after being dissolved with nitric acid, Obtain lanthanum nitrate La (NO₃)₃, it is poly- that ethyl orthosilicate TEOS, solvent n,N-Dimethylformamide DMF and high polymer templates are added Vinylpyrrolidone PVP, obtains spinning solution, and the viscosity for controlling spinning solution is most important, carries out under the best experimental conditions quiet Electrospun prepares PVP/ [La (NO₃)₃+ TEOS] original composite Nano band, with ammonium acid fluoride NH₄HF₂For fluorization agent, activated carbon Grain is assistant reducing agent, carries out heating fluorination treatment in air, obtains the LaF of structure novel₃@SiO₂Band cuff structure nano Band.

Summary of the invention

Macromolecule, metal oxide, metal composite oxidation are prepared for using uniaxial electrospinning technology in the background technology Object nanofiber and nanobelt, are combined with fluorination technology using uniaxial electrospinning technology and are prepared for rare-earth fluoride nano Band, is prepared for that photoelectromagnetic is difunctional and three function coaxial nanoribbons using coaxial electrostatic spinning technology.Used raw material, template Agent, solvent and method of the invention are different.In order to provide a kind of new material in nanobelt material field, we will be uniaxial Electrostatic spinning technique is combined with fluorination technology, has invented LaF₃@SiO₂Preparation method with cuff structure nano band.

The invention is realized in this way the spinning solution with certain viscosity for uniaxial electrostatic spinning is prepared first, Electrostatic spinning, which is carried out, using uniaxial electrospinning technology prepares PVP/ [La (NO under the best experimental conditions₃)₃+TEOS] Original composite Nano band, uses NH₄HF₂It is assistant reducing agent for fluorization agent, active carbon granule, directly heats be fluorinated in air LaF is arrived₃@SiO₂Band cuff structure nano band.It the steps include:

(1) spinning solution is prepared

Lanthanum source uses lanthana La₂O₃, silicon source uses ethyl orthosilicate TEOS, and high polymer templates are using poly- Vinylpyrrolidone PVP, molecular weight 90000 use n,N-Dimethylformamide DMF for solvent, weigh 0.7223g La₂O₃, With nitric acid HNO₃It is evaporated after dissolution, obtains La (NO₃)₃, 7.8000g DMF, 0.6000g TEOS and 1.6800g PVP is added, in Magnetic agitation 6h at room temperature, and 2h is stood, form spinning solution；

(2) PVP/ [La (NO is prepared₃)₃+ TEOS] original composite Nano band

Using uniaxial electrospinning technology, spinning solution is injected in the 10mL syringe with 1mL plastic spray gun head, It will be connected in a copper wire insertion spinning solution and with the positive terminal of high-voltage DC power supply, the angle of lance head and horizontal plane is It 30 °, using the wire netting that is disposed vertically as reception device and is grounded, with another copper wire by wire netting and high-voltage DC power supply Zero potential binding post is connected, and lance head is 16cm at a distance from receiving screen wire netting, spinning voltage 13kV, and room temperature is 20-25 DEG C, relative humidity 20%-40%, carry out electrostatic spinning can be obtained on wire netting as the solvent evaporates PVP/[La(NO₃)₃+ TEOS] original composite Nano band；

(3) LaF is prepared₃@SiO₂Band cuff structure nano band

Fluorination reagent uses ammonium acid fluoride NH₄HF₂, active carbon granule is assistant reducing agent, ammonium acid fluoride is put into crucible, Active carbon granule is covered above, by the PVP/ [La (NO₃)₃+ TEOS] original composite Nano band is placed on above active carbon granule, covers It is put into tube furnace after upper crucible lid, is warming up to 700 DEG C with the heating rate of 1 DEG C/min and keeps the temperature 4h, then with 1 DEG C/min's Rate of temperature fall is cooled to 200 DEG C, later with furnace body cooled to room temperature, obtains LaF₃@SiO₂Band cuff structure nano band, it is wide Degree is 4.36 ± 0.14 μm, and with a thickness of 380nm, length is greater than 50 μm.

The LaF in above process₃@SiO₂Band cuff structure nano band has good crystallinity, width 4.36 ± 0.14 μm, with a thickness of 380nm, length is greater than 50 μm, realizes goal of the invention.

Detailed description of the invention

Fig. 1 is PVP/ [La (NO₃)₃+ TEOS] original composite Nano band SEM photograph；

Fig. 2 is PVP/ [La (NO₃)₃+ TEOS] original composite Nano band width distribution histogram；

Fig. 3 is LaF₃@SiO₂XRD spectra with cuff structure nano band；

Fig. 4 is LaF₃@SiO₂SEM photograph with cuff structure nano band, the figure double as Figure of abstract；

Fig. 5 is LaF₃@SiO₂The XRD spectra of nanobelt after removing shell with cuff structure nano band；

Fig. 6 is LaF₃@SiO₂Width distribution histogram with cuff structure nano band；

Fig. 7 is LaF₃@SiO₂EDS spectrogram with cuff structure nano band.

Specific embodiment

Lanthana La selected by the present invention₂O₃Purity be 99.99%, polyvinylpyrrolidone PVP, molecular weight is 90000, n,N-Dimethylformamide DMF, active carbon granule, ethyl orthosilicate, ammonium acid fluoride NH₄HF₂, nitric acid HNO₃And hydrofluoric acid HF is commercially available analysis net product；Glass apparatus, crucible and equipment used is common instrument and equipment in laboratory.

Embodiment: 0.7223g La is weighed₂O₃, with nitric acid HNO₃It is evaporated after dissolution, obtains La (NO₃)₃, 7.8000g is added DMF, 0.6000g TEOS and 1.6800g PVP, magnetic agitation 6h at room temperature, and 2h is stood, form spinning solution；Using single shaft Electrostatic spinning technique injects spinning solution in one 10mL syringe with 1mL plastic spray gun head, and a copper wire insertion is spun It is connected in silk liquid and with the positive terminal of high-voltage DC power supply, the angle of lance head and horizontal plane is 30 °, with what is be disposed vertically Wire netting is as reception device and is grounded, with another copper wire by the zero potential binding post phase of wire netting and high-voltage DC power supply Even, lance head is 16cm at a distance from receiving screen wire netting, and spinning voltage 13kV, room temperature is 20-25 DEG C, relative humidity For 20%-40%, carry out electrostatic spinning can be obtained PVP/ [La (NO as the solvent evaporates on wire netting₃)₃+TEOS] Original composite Nano band；Fluorination reagent uses ammonium acid fluoride NH₄HF₂, active carbon granule is assistant reducing agent, and ammonium acid fluoride is put into In crucible, active carbon granule is covered above, by the PVP/ [La (NO₃)₃+ TEOS] original composite Nano band is placed on active carbon granule Above, it is put into tube furnace after covering crucible lid, is warming up to 700 DEG C with the heating rate of 1 DEG C/min and keeps the temperature 4h, then with 1 DEG C/rate of temperature fall of min is cooled to 200 DEG C, later with furnace body cooled to room temperature, obtain LaF₃@SiO₂Band set band structure is received Rice band.PVP/ [La (the NO₃)₃+ TEOS] there is good band-like pattern to see with a thickness of 710nm original composite Nano band Shown in Fig. 1；PVP/[La(NO₃)₃+ TEOS] original composite Nano band width distribution it is uniform, with Shapiro-Wilk method to receiving The width of rice band carries out normal distribution-test, under 95% confidence level, PVP/ [La (NO₃)₃+ TEOS] original composite Nano band Width distribution belong to normal distribution, width is 10.44 ± 0.08 μm, as shown in Figure 2；LaF₃@SiO₂Band cuff structure nano Band has good crystallinity, the d value and relative intensity and LaF of main diffraction peak₃PDF standard card (32-0483) institute The d value of column is consistent with relative intensity, belongs to hexagonal crystal system, shows that amorphous material is LaF₃, the angle of diffraction is 22 ° or so, is had a small Wider diffraction maximum, be unformed SiO₂Diffraction maximum, as shown in Figure 3；LaF₃@SiO₂Band cuff structure nano band has bright Aobvious band set band structure, sandwich layer is LaF₃Nanobelt, shell are SiO₂Nanobelt, LaF₃@SiO₂Thickness with cuff structure nano band Degree is 380nm, and length is greater than 50 μm, as shown in Figure 4；SiO can be dissolved using hydrofluoric acid HF₂Characteristic, can prove LaF₃@ SiO₂Shell is SiO in band cuff structure nano band₂, sandwich layer is LaF₃, by the LaF₃@SiO₂Band cuff structure nano band is put Entering and impregnates 4h in hydrofluoric acid HF, the product after filtration drying is no longer band cuff structure nano band, and its pattern is nanobelt, The d value and relative intensity and LaF of its diffraction maximum₃PDF standard card (32-0483) listed by d value it is consistent with relative intensity, belong to In hexagonal crystal system, show that nanobelt is amorphous material LaF₃, shell SiO₂It is removed by hydrofluoric acid dissolution, thus proves LaF₃@ SiO₂Shell with cuff structure nano band is SiO₂, sandwich layer is LaF₃, as shown in Figure 5；With Shapiro-Wilk method pair LaF₃@SiO₂Width with cuff structure nano band carries out normal distribution-test, under 95% confidence level, LaF₃@SiO₂Band set The width distribution of band structure nanobelt belongs to normal distribution, and width is 4.36 ± 0.14 μm, as shown in Figure 6；LaF₃@SiO₂Band set Band structure nanobelt is made of La, F, Si and O element, the Pt conductive layer of surface plating when Pt derives from SEM sample preparation, as shown in Figure 7.

Certainly, the invention may also have other embodiments, without deviating from the spirit and substance of the present invention, ripe It knows those skilled in the art and makes various corresponding changes and modifications, but these corresponding changes and change in accordance with the present invention Shape all should fall within the scope of protection of the appended claims of the present invention.

Claims (2)

1. coated with silica lanthanum trifluoride band cuff structure nano band, which is characterized in that shell SiO₂, sandwich layer LaF₃It receives Rice band, by shell SiO₂Coat sandwich layer LaF₃Nanobelt forms, and forms LaF₃@SiO₂Band cuff structure nano band, width are 4.36 ± 0.14 μm, with a thickness of 380nm, length is greater than 50 μm.

2. a kind of preparation method of the coated with silica lanthanum trifluoride with cuff structure nano band as described in claim 1, It is characterized in that, the method combined using uniaxial electrospinning technology with fluorination technology, preparing product is LaF₃@SiO₂Band cuff Structure nano band, the steps include:

(1) spinning solution is prepared

Lanthanum source uses lanthana La₂O₃, silicon source uses ethyl orthosilicate TEOS, and high polymer templates use polyethylene Pyrrolidones PVP, molecular weight 90000 use n,N-Dimethylformamide DMF for solvent, weigh 0.7223g La₂O₃, use nitre Sour HNO₃It is evaporated after dissolution, obtains La (NO₃)₃, 7.8000g DMF, 0.6000g TEOS and 1.6800g PVP is added, in room temperature Lower magnetic agitation 6h, and 2h is stood, form spinning solution；

(2) PVP/ [La (NO is prepared₃)₃+ TEOS] original composite Nano band

Using uniaxial electrospinning technology, spinning solution is injected in the 10mL syringe with 1mL plastic spray gun head, by one It is connected in root copper wire insertion spinning solution and with the positive terminal of high-voltage DC power supply, the angle of lance head and horizontal plane is 30 °, It using the wire netting that is disposed vertically as reception device and is grounded, with another copper wire by zero electricity of wire netting and high-voltage DC power supply Gesture binding post is connected, and lance head is 16cm, spinning voltage 13kV, room temperature 20-25 at a distance from receiving screen wire netting DEG C, relative humidity 20%-40%, carry out electrostatic spinning can be obtained PVP/ [La as the solvent evaporates on wire netting (NO₃)₃+ TEOS] original composite Nano band；

(3) LaF is prepared₃@SiO₂Band cuff structure nano band

Fluorination reagent uses ammonium acid fluoride NH₄HF₂, active carbon granule is assistant reducing agent, ammonium acid fluoride is put into crucible, above Active carbon granule is covered, by the PVP/ [La (NO₃)₃+ TEOS] original composite Nano band is placed on above active carbon granule, cover earthenware It is put into tube furnace after crucible lid, is warming up to 700 DEG C with the heating rate of 1 DEG C/min and keeps the temperature 4h, then with the cooling of 1 DEG C/min Rate is cooled to 200 DEG C, later with furnace body cooled to room temperature, obtains LaF₃@SiO₂Band cuff structure nano band, width are 4.36 ± 0.14 μm, with a thickness of 380nm, length is greater than 50 μm.