CN107413325A - A kind of rare earth/carbon co-doped flexible TiO2Nano fibrous membrane and preparation method thereof - Google Patents

A kind of rare earth/carbon co-doped flexible TiO2Nano fibrous membrane and preparation method thereof Download PDF

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CN107413325A
CN107413325A CN201710670266.0A CN201710670266A CN107413325A CN 107413325 A CN107413325 A CN 107413325A CN 201710670266 A CN201710670266 A CN 201710670266A CN 107413325 A CN107413325 A CN 107413325A
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rare earth
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丁彬
崔福海
宋骏
武晓会
张猛
俞建勇
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Donghua University
National Dong Hwa University
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Abstract

The present invention relates to a kind of rare earth/carbon co-doped flexible TiO2Nano fibrous membrane and preparation method thereof, step are as follows:Precursor solution is prepared first, and precursor solution is made up of titanium source, rare earth metal salt, carbon source, nonionic surfactant and solvent;Electrostatic spinning is carried out again and obtains precursor fibre film, and it is 10~0 DEG C to apply 50~100 DEG C of constant temperature thermal field in spinning section during electrostatic spinning and control the temperature of reception device;Finally calcining obtains rare earth/carbon co-doped flexible TiO in air atmosphere2Nano fibrous membrane.The pliability of final obtained product 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, without adding polymer or aging, without post processing, technique is simple, and cost is cheap, and product has good tensile break strength, flexibility and visible light catalytic performance.

Description

A kind of rare earth/carbon co-doped flexible TiO2Nano fibrous membrane and preparation method thereof
Technical field
The invention belongs to field of new materials, is related to a kind of rare earth/carbon co-doped flexible TiO2Nano fibrous membrane and its preparation Method.
Background technology
Titanium dioxide (TiO2) monodimension nanometer material is because of spies such as its photocatalysis property is stable, cheap, no biotoxicities Point, the volatile organic matter (VOCs) in photocatalysis hydrogen production, industry, and caused in terms of the degraded such as indoor, in-car VOCs Extensive concern.But a kind of wide variety of catalysis material is used as, it has following subject matter:1)TiO2Greater band gap (Eg=3.0~3.2eV), can only be low by the ultraviolet excitation below 400 nano wave lengths, solar energy utilization ratio.2) light induced electron- Hole to easily it is compound, cause light quantum utilization rate low, so as to reduce the catalytic activity of material.3) most of one-dimensional titanium dioxides Titanium nano material generally existing fragility it is big, low intensity the problem of.The problem of above-mentioned, turns into limitation nano titanium dioxide photocatalysis The wide variety of bottleneck problem of material.Therefore, people utilize element doping, absorption of the titanium dioxide to visible ray is realized, and Effectively suppress the compound of photo-generate electron-hole pair, so as to improve catalytic activity, and prepared by the flexibility for realizing 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. reports to be responded by the titania-doped visible light catalytic that makes it have of transition metal (Fe, Ni etc.), Asahi etc. reports N substitutions TiO2In lattice after a small amount of O, it can make catalyst that there is visible light catalytic response, then Lettmann etc. chances on when doing N doping, also has visible light catalysis activity in the sample of no doping, so as to find carbon Dopen Nano TiO2Visible light catalysis activity, for this exploitation with visible light catalytic response titania-doped research just Attract wide attention.
Patent CN 104607171 discloses a kind of preparation side of praseodymium doped dioxide composite nanofiber photocatalyst Method, (2014) 1191-1201 of Applied Physics A 117 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 Close, while enhance the interaction between crystal boundary, while improving catalytic activity, also expanded its visible absorption scope, but Its visible absorption wavelength focuses mostly in below 500nm.
Patent CN 102021676A disclose 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, doped energy-band is formed, its energy gap is narrowed, is advantageous to its absorption to visible ray, although C introducing can make catalysis The light abstraction width of agent becomes big, expands to more than 700nm, but C presence result in the catalytic activity reduction of catalyst.
In recent years, multi-element doping is of increased attention.Especially carbon is more favored with rare earth doped. Improve fibre strength.However, on rare earth/carbon co-doped flexible titanium dioxide nanofiber preparation and research report still It is rare.Therefore, a kind of rare earth/carbon co-doped flexible TiO is developed2Nano-fiber material tool is of great significance.
The content of the invention
The purpose of the present invention is to overcome that technique in the prior art is complex, costly and bad properties of product lacks Falling into, there is provided a kind of simple production process, cost are cheap, product photocatalysis performance and its flexible preferably rare earth/and it is carbon co-doped soft Property TiO2Nano fibrous membrane and preparation method thereof.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that:
A kind of rare earth/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, step 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) carry out electrostatic spinning and obtain precursor fibre film, apply constant temperature thermal field in spinning section during the electrostatic spinning And the temperature of reception device is controlled, 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 flexible TiO in air atmosphere2Nano fibrous membrane.
As preferable technical scheme:
A kind of rare earth/carbon co-doped flexible TiO as described above2The preparation method of nano fibrous membrane, the preparation forerunner The concrete operations of liquid solution are:Titanium source and rare earth metal salt dissolving are stirred into 30~150min in a solvent, then sequentially added Carbon source and nonionic surfactant stir 10~90min and are well mixed.
On the one hand it is first to make titanium source carry out partial hydrolysis to produce hydroxyl by titanium source, the purpose of rare earth metal salt dissolving in a solvent Base, on the other hand it is to be well 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 influenceed the growth of micelle, is unfavorable for uniformly dividing for rare earth ion Cloth.
Rare earth/carbon co-doped flexible TiO as described above2The preparation method of nano fibrous membrane, in the precursor solution The mol 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 mol ratio of agent is 1:0.001~0.1:0.05~0.25.
Rare earth/carbon co-doped flexible 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 ethanol, 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, activated carbon or carbon black;
The nonionic surfactant is PEO-PPOX-PEO triblock copolymer, gathered Oxygen ethene polyoxypropylene, glycerine polyoxyethylene polyoxypropylene blocked copolymer, ethylenediamine polyoxyethylene oxypropylene block Formula polyethers or propane diols polyoxyethylene poly-oxygen propylene aether.
A kind of rare earth/carbon co-doped flexible 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 flexible TiO as described above2The preparation method of nano fibrous membrane, the electrostatic spinning Parameter be: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 is metal roller or metal plate.
A kind of rare earth/carbon co-doped flexible TiO as described above2The preparation method of nano fibrous membrane, the temperature of the calcining Degree progressively rises to 400~1000 DEG C from room temperature, and heating rate is 0.1~10 DEG C/min, and is kept under highest calcining heat 10~360min.
The present invention also provides one kind rare earth as made from method produced above/carbon co-doped flexible TiO2Nano fibrous membrane, Rare earth/carbon co-doped flexible TiO2The pliability of nano fibrous membrane is 10~50mN, rare earth/carbon co-doped flexible TiO2Nanowire The tensile break strength for tieing up film is 3~5MPa, and absorbable light abstraction width is expanded to 550~700nm.
As preferable technical scheme:
Rare earth/carbon co-doped flexible TiO as described above2Nano fibrous membrane, the rare earth/carbon co-doped flexible TiO2Receive The average diameter of fiber be 10~400nm in rice tunica fibrosa, and relative standard deviation is 1~5%, internal grain size for 10~ 80nm.Fiber diameter range shows fiber thickness, and fibre diameter is smaller, and single fiber pliability is preferable, is advantageous to tunica fibrosa softness The raising of degree;For relative standard deviation to characterize the uniformity of 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 lifting 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, adds rare earth The purpose of metal salt is during subsequent calcination, reduces fiber surface microdefect, suppresses TiO2Grain growth, crystallite dimension are got over Small, crystal grain is higher than surface, and surface-active bits number is more, and photocatalytic activity is improved accordingly, is adding carbon source After surfactant, hydrogen bond can be formed between titanium source, carbon source and surfactant, 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 during electrostatic spinning, promote The quick volatilization of solvent in spinning jet so that surfactant concentration reaches critical micelle concentration, then passes through self assembly shape Into micella, and arranged under the quick drawing-off effect of electric field force along fiber axial direction direction gage entire row, micella unit phase each other in 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 so that TiO2Presoma and the uniform Assembled distribution of carbon source exist Micellar surface., can be with wink because reception device has relatively low temperature (- 10~0 DEG C) when fiber is collected into reception device Between consolidate and retain the orderly self-assembled structures inside precursor fibre.
Beneficial effect:
(1) a kind of rare earth/carbon co-doped flexible TiO of the invention2The preparation method of nano fibrous membrane, it polymerize without adding Thing or aging, without post processing, by applying constant temperature thermal field in spinning process, and reception substrate temperature is reduced, make carbon source 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, and cost is cheap;
(2) a kind of rare earth/carbon co-doped flexible TiO of the invention2Nano fibrous membrane, have good tension failure strong Degree, flexible and visible light catalytic performance.
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 Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.
Embodiment 1
A kind of rare earth/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, step are as follows:
(1) titanium source isopropyl titanate and rare earth metal salt lanthanum nitrate hexahydrate are dissolved in etoh solvent and stir 30min, so After sequentially add carbon source graphite alkene and nonionic surfactant PEO-PPOX-PEO three block Copolymer stirring 90min is well mixed with obtaining precursor solution, titanium source wherein in solution, rare earth metal salt, solvent, carbon source with it is non- The mol ratio of ionic surface active agent 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 during electrostatic spinning Section apply 50 DEG C constant temperature thermal field and control metal roller reception device temperature be 0 DEG C;The parameter of electrostatic spinning is:Relatively Humidity 20%, rate of flooding 15mL/h, voltage 10kV, the distance 40cm between reception device and spinning nozzle;
(3) above-mentioned precursor fibre film is placed in calcining in air atmosphere and obtains rare earth/carbon co-doped flexible TiO2Nanometer Tunica fibrosa, calcining refer to that the temperature of calcining progressively 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 obtained rare earth/carbon co-doped flexible TiO2The average diameter of fiber is 200nm in nano fibrous membrane, and phase It is 1% to standard deviation, fibrous inside crystallite dimension is 10nm, rare earth/carbon co-doped flexible TiO2The softness of nano fibrous membrane Spend for 10mN, tensile break strength 5MPa, the absorption region of visible ray is expanded to 700nm.
Comparative example 1
A kind of rare earth/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, its basic step and parameter and implementation Example 1 is identical, and difference is to be not provided with constant temperature thermal field during electrostatic spinning, and reception device temperature is set into normal temperature.
Its obtained rare earth/carbon co-doped flexible TiO2The average diameter of fiber is 300nm in nano fibrous membrane, and relatively Standard deviation is 3%, and fibrous inside crystallite dimension is 45nm, the rare earth/carbon co-doped flexible TiO2The softness of nano fibrous membrane Spend for 50mN, tensile break strength 0.8MPa, the absorption region of visible ray is expanded to 500nm, passes through pair with embodiment 1 Than it can be found that obtained rare earth/carbon co-doped flexible TiO in embodiment 12Nano fibrous membrane ensure that it is certain flexible Meanwhile its absorption region to visible ray is substantially increased, photocatalysis performance is far superior to rare earth/carbon co-doped flexible TiO2Receive Rice tunica fibrosa.
Embodiment 2
A kind of rare earth/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, step 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 well mixed With precursor solution, titanium source wherein in solution, rare earth metal salt, solvent, the mol ratio of carbon source and nonionic surfactant 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 during electrostatic spinning Section apply 100 DEG C constant temperature thermal field and control metal plate reception device temperature be -10 DEG C;The parameter of electrostatic spinning is: Relative humidity 70%, rate of flooding 0.1mL/h, voltage 60kV, the distance 20cm between reception device and spinning nozzle;
(3) above-mentioned precursor fibre film is placed in calcining in air atmosphere and obtains rare earth/carbon co-doped flexible TiO2Nanometer Tunica fibrosa, calcining refer to that the temperature of calcining progressively rises to 1000 DEG C from room temperature, and heating rate is 0.1 DEG C/min, and in highest 360min is kept under calcining heat.
Final obtained rare earth/carbon co-doped flexible TiO2The average diameter of fiber is 300nm in nano fibrous membrane, and phase It is 5% to standard deviation, fibrous inside crystallite dimension is 80nm, rare earth/carbon co-doped flexible TiO2The softness of nano fibrous membrane Spend for 50mN, tensile break strength 3MPa, the absorption region of visible ray is expanded to 580nm.
Embodiment 3
A kind of rare earth/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, step are as follows:
(1) titanium source titanium tetrachloride and the hydrated lanthanum chloride of rare earth metal salt seven are stirred into 90min in solvent ethylene glycol, then Sequentially add carbon source multi-walled carbon nanotube and nonionic surfactant glycerine polyoxyethylene polyoxypropylene blocked copolymer Stir 50min and be well mixed and match somebody with somebody to obtain precursor solution, titanium source, rare earth metal salt, solvent, carbon source and nonionic table wherein in solution The mol ratio of face activating agent 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 during electrostatic spinning Section apply 75 DEG C constant temperature thermal field and control metal roller reception device temperature be -5 DEG C;The parameter of electrostatic spinning is:Phase To humidity 45%, rate of flooding 7.5mL/h, voltage 35kV, the distance 30cm between reception device and spinning nozzle;
(3) above-mentioned precursor fibre film is placed in calcining in air atmosphere and obtains rare earth/carbon co-doped flexible TiO2Nanometer Tunica fibrosa, calcining refer to that the temperature of calcining progressively 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 obtained rare earth/carbon co-doped flexible TiO2The average diameter of fiber is 205nm in nano fibrous membrane, and phase It is 3% to standard deviation, fibrous inside crystallite dimension is 45nm, rare earth/carbon co-doped flexible TiO2The softness of nano fibrous membrane Spend for 40mN, tensile break strength 3.5MPa, the absorption region of visible ray is expanded to 650nm.
Embodiment 4~27
The preparation process of embodiment 4~27 prepares parameter, electrospinning parameters, calcining with embodiment 1, wherein precursor solution Parameter and rare earth/carbon co-doped flexible TiO2Nano fibrous membrane performance parameter (note as shown in 1~table of table 6:Mixing time 1 is titanium Source and rare earth metal salt are dissolved in the mixing time after solvent, after mixing time 2 is adds carbon source and nonionic surfactant The time of stirring)
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6

Claims (9)

  1. A kind of 1. rare earth/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, it is characterized in that, step is as follows:
    (1) prepare precursor solution, the precursor solution by titanium source, rare earth metal salt, carbon source, nonionic surfactant and Solvent forms;
    (2) carry out electrostatic spinning and obtain precursor fibre film, apply constant temperature thermal field in spinning section and control during the electrostatic spinning The temperature of reception device processed, the temperature of the constant temperature thermal field is 50~100 DEG C, and the temperature of the reception device is -10~0 DEG C;
    (3) calcining obtains rare earth/carbon co-doped flexible TiO in air atmosphere2Nano fibrous membrane.
  2. A kind of 2. rare earth according to claim 1/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, its feature It is, the concrete operations of the preparation precursor solution are:By titanium source and rare earth metal salt dissolving in a solvent stirring 30~ 150min, then sequentially adds carbon source and nonionic surfactant stirs 10~90min and is well mixed.
  3. A kind of 3. rare earth according to claim 1/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, its feature It is, the mol ratio of titanium source, rare earth metal salt and solvent is 1 in the precursor solution:0.001~0.1:10~100, titanium The mol ratio in source, carbon source and nonionic surfactant is 1:0.001~0.1:0.05~0.25.
  4. A kind of 4. rare earth according to claim 3/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, its 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, strontium salt or neodymium salt;
    The solvent is ethanol, 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, activated carbon or carbon black;
    The nonionic surfactant is PEO-PPOX-PEO triblock copolymer, polyoxy second Alkene polyoxypropylene, glycerine polyoxyethylene polyoxypropylene blocked copolymer, ethylenediamine polyoxyethylene oxypropylene block formula are gathered Ether or propane diols polyoxyethylene poly-oxygen propylene aether.
  5. A kind of 5. rare earth according to claim 4/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, its 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 strontium salt is six chloride hydrates Strontium or six hydration strontium bromides, the neodymium salt is six nitric hydrate neodymiums or six Neodymium chloride hydrates.
  6. A kind of 6. rare earth according to claim 1/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, its feature It is, the parameter of the electrostatic spinning is:Relative humidity 20~70%, 0.1~15mL/h of rate of flooding, 10~60kV of voltage, 20~40cm of distance between reception device and spinning nozzle, the reception device are metal roller or metal plate.
  7. A kind of 7. rare earth according to claim 1/carbon co-doped flexible TiO2The preparation method of nano fibrous membrane, its feature It is, the temperature of the calcining progressively 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 calcining heat.
  8. 8. using rare earth/carbon co-doped flexible TiO made from the preparation method as described in any one of claim 1~72Nanowire Film is tieed up, it is characterized in that:Rare earth/carbon co-doped flexible 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. 9. rare earth according to claim 8/carbon co-doped flexible TiO2Nano fibrous membrane, it is characterised in that the rare earth/ Carbon co-doped flexible TiO2The average diameter of fiber is 10~400nm in nano fibrous membrane, and relative standard deviation is 1~5%, Internal grain size is 10~80nm.
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CN109853068A (en) * 2019-01-30 2019-06-07 东华大学 A kind of carbon quantum dot/fibroin composite nano fiber and its preparation method and application
CN110473960A (en) * 2019-08-26 2019-11-19 西安电子科技大学 Piezoelectric material, piezoelectric material Preparation method and use
CN111905706A (en) * 2020-07-27 2020-11-10 安徽旭晶粉体新材料科技有限公司 Preparation method of titanium dioxide and rare earth material composite catalyst
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CN104289042A (en) * 2014-09-05 2015-01-21 东华大学 Electrospinning nano-fiber electret filtering material and its preparation method
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CN108004649A (en) * 2017-12-28 2018-05-08 赵文立 A kind of graphene nanocomposite material and preparation method thereof
CN108822840A (en) * 2018-08-29 2018-11-16 济南大学 A kind of fiber crops are the preparation method of carbon source neodymium doped carbon quantum dot composite material
CN109603818A (en) * 2019-01-04 2019-04-12 杭州同净环境科技有限公司 Platinum doped titanium dioxide catalysis material and preparation method
CN109603818B (en) * 2019-01-04 2021-12-21 杭州同净环境科技有限公司 Platinum-doped titanium dioxide photocatalytic material and preparation method thereof
CN109853068A (en) * 2019-01-30 2019-06-07 东华大学 A kind of carbon quantum dot/fibroin composite nano fiber and its preparation method and application
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CN110473960A (en) * 2019-08-26 2019-11-19 西安电子科技大学 Piezoelectric material, piezoelectric material Preparation method and use
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CN111905706A (en) * 2020-07-27 2020-11-10 安徽旭晶粉体新材料科技有限公司 Preparation method of titanium dioxide and rare earth material composite catalyst
CN113737395A (en) * 2021-08-06 2021-12-03 华南理工大学 Flexible titanium dioxide nanofiber membrane and preparation method and application thereof

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