CN115646554A - Titanium dioxide/carbon nanotube composite fiber and preparation method thereof - Google Patents
Titanium dioxide/carbon nanotube composite fiber and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 61
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 61
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 51
- 239000000835 fiber Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010936 titanium Substances 0.000 claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000012159 carrier gas Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000012495 reaction gas Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims abstract description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 9
- 229930192474 thiophene Natural products 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 3
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000003618 dip coating Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000005336 cracking Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- -1 compound titanium dioxide Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a titanium dioxide/carbon nano tube composite fiber and a preparation method thereof, wherein the method comprises the following steps: preparing a catalyst, a cocatalyst and an organic solvent to obtain a carbon source solution, and dissolving a titanium source in the carbon source solution to obtain a titanium source/carbon source mixed solution; heating the reactor to the reaction temperature, and continuously introducing carrier gas and reaction gas into the reactor; and injecting the titanium source/carbon source mixed solution into a reactor, carrying out pyrolysis reaction, cooling, and collecting to obtain the titanium dioxide/carbon nanotube composite fiber. Compared with the prior art, the method adopts an in-situ synthesis method, solves the problems of low photocatalytic activity caused by untight connection between titanium dioxide and carbon nanotubes and low electron transmission efficiency in the traditional dip coating method, and simultaneously improves the problems of non-continuous preparation and difficult product collection of a hydrothermal method.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a titanium dioxide/carbon nano tube composite fiber and a preparation method thereof.
Background
With the shortage of energy and the increasing serious problem of environmental pollution, sewage treatment gradually becomes an increasingly heavy burden in the urban development process. The traditional chemical treatment and electrochemical treatment methods are serious in energy consumption and not environment-friendly, and may bring secondary pollution. Therefore, photocatalysis is becoming popular among scientists as an environmentally friendly and inexpensive means. Pollutants are degraded through the reactivity of the photon-generated carriers, and the products are inorganic micromolecules generally, so that the effect of environment-friendly treatment is achieved. Titanium dioxide is an inorganic substance with moderate band gap width, active electrons generated after sunlight is received are enough to degrade common organic substances in sewage, such as phenol, and the like, but the electron-hole separation efficiency of titanium dioxide is low, and the high decomposition efficiency is difficult to achieve without the help of other materials.
There have been studies to compound titanium dioxide on carbon nanotubes to enhance the overall photocatalytic effect (S. Mallakpour, E.Khadem/Chemical Engineering Journal 302 (2016) 344-367). The interface contact of titanium dioxide and carbon nano tubes is utilized to promote the effective separation of electron-hole, so that the catalytic activity is improved. However, the current efforts generally adopt a coating method or a hydrothermal method to adsorb or grow titanium dioxide on the surface of the carbon nanotube, the titanium dioxide loading rate is low, and the electron transport efficiency between the particles and the carbon nanotube is still limited. Moreover, these methods cannot be used for continuous production, and the production cost of the materials in actual use is very high, so that the method is difficult to be really popularized and used.
Disclosure of Invention
The invention aims to overcome at least one of the defects of low electron transmission efficiency, low titanium dioxide loading rate, incapability of continuous production, high manufacturing cost and the like of titanium dioxide particles and carbon nanotubes in the titanium dioxide/carbon nanotube composite fiber in the prior art, and provides a preparation method of the composite fiber, which has high loading rate and high charge transmission efficiency and can be continuously prepared, so that better photocatalysis efficiency can be obtained, and the large-scale preparation and industrialization process of the titanium dioxide/carbon nanotube composite fiber can be promoted.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of titanium dioxide/carbon nanotube composite fiber comprises the following steps:
preparing a catalyst, a cocatalyst and an organic solvent to obtain a carbon source solution, and dissolving a titanium source in the carbon source solution to obtain a titanium source/carbon source mixed solution;
heating the reactor to the reaction temperature, and continuously introducing carrier gas and reaction gas into the reactor;
and injecting the titanium source/carbon source mixed solution into a reactor, carrying out pyrolysis reaction, cooling, and collecting to obtain the titanium dioxide/carbon nanotube composite fiber.
Further, the catalyst comprises ferrocene, cobaltocene or nickelocene; the cocatalyst is a sulfur-containing organic compound; the organic solvent comprises benzene or ethanol; the titanium source is a titanium-containing organic compound.
Further, the sulfur-containing organic compound includes thiophene; the titanium-containing organic compound comprises titanate and derivatives thereof, organic titanium compound or titanium salt of organic acid with fat solubility, and specifically comprises tetrabutyl titanate or tetraisopropyl titanate.
Furthermore, in the titanium source/carbon source mixed solution, the mass fraction of the catalyst is 0.5-10%, the mass fraction of the cocatalyst is 0.5-10%, and the mass fraction of the titanium source is 0.5-30%.
Further, the reaction temperature is 900-1500 ℃, and the heating rate is 0.5-2 ℃/min.
Further, the volume ratio of the carrier gas to the reaction gas is 1 (5-20); the total flow rate of the gas is 1000-2000sccm.
Further, the carrier gas is an inert gas including argon or helium, and the reaction gas is hydrogen.
Further, the injection rate of the titanium source/carbon source mixed solution is 50-300 mu L/min.
Furthermore, the cooling mode is to draw water, and the drawing speed is 1-20cm/s.
A titanium dioxide/carbon nano tube composite fiber prepared by the method.
Compared with the prior art, the invention has the following advantages:
(1) According to the titanium dioxide/carbon nanotube composite fiber prepared by the invention, titanium dioxide can be uniformly coated around each carbon nanotube, so that the electron transmission efficiency is high, the catalytic activity is strong, and the content of the titanium dioxide can be flexibly adjusted by adjusting the proportion of a titanium source;
(2) The titanium dioxide/carbon nano tube composite fiber is prepared by the technology of growing the titanium dioxide on the surface of the carbon nano tube in situ, the technology can realize continuous production, and the production and preparation efficiency is high and the cost is low.
Drawings
FIG. 1 is a 1 Kd SEM image of a composite fiber prepared in example 1;
FIG. 2 is a SEM photograph at 1 ten thousand times magnification of a composite fiber prepared in example 1;
FIG. 3 is a 1 Kd SEM image of a composite fiber prepared in example 2;
FIG. 4 is a 1 ten thousand magnification SEM image of a composite fiber prepared in example 2;
FIG. 5 is an X-ray photon characteristic energy spectrum (EDS) of the composite fiber prepared in example 1;
FIG. 6 is an X-ray photon characteristic energy spectrum (EDS) of the composite fiber prepared in example 2.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
A preparation method of titanium dioxide/carbon nanotube composite fiber comprises the following steps:
(1) Preparing a catalyst, a cocatalyst and an organic solvent according to a certain proportion to obtain a carbon source solution. And then dissolving a certain proportion of a titanium source in a carbon source solution, and dissolving and dispersing in a heating or ultrasonic mode to obtain a uniform and transparent titanium source/carbon source mixed solution. The catalyst is ferrocene, cobaltocene or nickelocene, and the organic solvent is hydrocarbon, alcohol, ketone or carboxylic acid, including but not limited to benzene, ethanol, etc. The cocatalyst is a sulfur-containing organic compound including, but not limited to, thiophene and the like. The function of the catalyst promoter is to release sulfur element by cracking and restrict the size of the microcrystal formed by the cracking of the catalyst. The mass fraction of the catalyst is 0.5-10%, and the mass fraction of the cocatalyst is 0.5-10%. The titanium source is titanium-containing organic compound, including but not limited to titanate and its derivatives, organic titanium compound, titanium salt containing organic acid with certain lipid solubility, such as tetrabutyl titanate, tetraisopropyl titanate, etc. The mass fraction of the titanium source is 0.5-30%.
(2) Heating the vertical tube furnace to the reaction temperature at a certain heating rate, cleaning the vertical tube furnace with carrier gas at a certain flow rate, adjusting the proportion of the carrier gas and the reaction gas, and continuously keeping for a certain time to ensure that the flow field in the furnace is stable, so that the reaction can be smoothly finished in a reaction area. The temperature rise rate of the vertical tube furnace is 0.5-2 ℃/min, and the reaction temperature is 900-1500 ℃. The carrier gas is inert gas such as argon, helium and the like, and the reaction gas is hydrogen. The carrier gas cleaning flow is 1000-2000sccm. The volume ratio of the carrier gas to the reaction gas after the cleaning is 1.
(3) Injecting the titanium source/carbon source mixed solution prepared in the step (1) into a vertical tubular furnace at a certain flow rate by using an injection pump, and then conveying the mixed solution to a feeding area through a metal thin tube with a certain inner diameter. The mixed solution is rapidly vaporized in the feeding zone and a pyrolysis reaction occurs in the reaction zone. Wherein the carbon source components are assembled into the carbon nano tube on the surface of the catalyst microcrystal after cracking. The titanium source component is cracked into titanium dioxide particles, and a layer of titanium dioxide shell is formed on the surface of the carbon nano tube in a self-assembly mode. The plurality of carbon nanotubes macroscopically form an aggregated state of the carbon nanotube aerogel column. And finally, pulling the carbon nanotube aerogel column through water, connecting the carbon nanotube aerogel column to a rotating shaft with a specific rotating speed, twisting the carbon nanotube aerogel column by using an electric motor to obtain the titanium dioxide/carbon nanotube composite fiber with high orientation degree and mechanical strength, and collecting and winding the titanium dioxide/carbon nanotube composite fiber on a yarn bobbin. The injection speed of the solution is 50-300 mu L/min. The inner diameter of the metal thin tube is 0.1-2mm. The traction speed of the composite carbon nano tube is 1-20cm/s.
The diameter of the prepared titanium dioxide/carbon nano tube composite fiber is 0.01-1mm. The length of the composite fiber is adjusted along with the collection time and can reach more than kilometers. The composite fiber is of a coaxial structure in a microcosmic view, and presents different shapes such as beads, tubes, complete coating and the like along with the increase of the proportion of a titanium source. The titanium dioxide grows uniformly and coats the surface of the carbon nano tube, the coating rate changes along with the increase of the proportion of the titanium source and can change within 0.1-100%, and the atomic proportion of the titanium element in the composite fiber is between 0.1-18%.
In the invention, the room temperature refers to the ambient temperature, and is generally 10-30 ℃.
Example 1
A preparation method of titanium dioxide/carbon nano tube composite fiber comprises the following steps:
(1) Preparing ethanol solution of thiophene and ferrocene, dispersing uniformly, and then adding tetrabutyl titanate to ensure that the mass fractions of thiophene, ferrocene and tetrabutyl titanate are respectively 1%,1% and 3%.
(2) The reaction furnace is of a vertical type, wherein the tubular reactor is vertically arranged in the heating unit and is coated with an insulating layer. The temperature of the tubular reactor was raised to 900 ℃ at 0.5 ℃/min.
(3) And introducing argon into the tubular reactor from an upper end gas inlet, wherein the flow rate is 1000sccm, after introducing the gas for 30min, adjusting the volume ratio of the argon to the hydrogen to be 1.
(4) The reaction solution was injected into the tubular reactor from the injection port at a rate of 300. Mu.L/min. The ethanol in the reaction solution is vaporized at high temperature to generate cracking reaction, under the atmosphere of sulfur generated by thiophene, carbon nano tubes are generated on the surfaces of iron nano particles generated by ferrocene, tetrabutyl titanate is cracked at high temperature, and titanium dioxide is adsorbed and grown on the surfaces of the carbon nano tubes.
(5) The carbon nano tube aerosol column leaves the reaction furnace along with the air flow, the gas which does not participate in the reaction is discharged into a tail gas collecting system along with the air path, the assembly body discharged from the lower end outlet of the aerosol column meets a liquid seal water tank and then shrinks when meeting cold to form carbon nano tube composite fibers, the carbon nano tube composite fibers are twisted and collected through a rotating shaft driven by a motor, and the collecting speed is 20m/min.
The microstructure of the prepared titanium dioxide/carbon nano tube composite fiber is shown in figure 1-2, and the titanium dioxide is arranged around the carbon nano tube in a bead string form, so that the titanium dioxide/carbon nano tube composite fiber has good growth and uniform distribution. The X-ray photon characteristic spectrum scan was performed, and as a result, the atomic ratio of titanium element was 0.72%, as shown in fig. 5.
Example 2
A preparation method of titanium dioxide/carbon nano tube composite fiber comprises the following steps:
(1) Preparing ethanol solution of thiophene and ferrocene, adding tetrabutyl titanate after uniform dispersion, and ensuring that the mass fractions of thiophene, ferrocene and tetrabutyl titanate are respectively 1%,1% and 20%.
(2) The reaction furnace is of a vertical type, wherein the tubular reactor is vertically arranged in the heating unit and is coated with an insulating layer. The temperature of the tubular reactor was raised to 1500 ℃ at 2 ℃/min.
(3) Introducing argon into the tubular reactor from an upper end gas inlet, wherein the flow is 2000sccm, after introducing the argon for 30min, regulating the volume ratio of the argon to the hydrogen to be 1.
(4) The reaction solution was injected into the tubular reactor from the injection port at a rate of 50. Mu.L/min. The ethanol in the reaction solution is vaporized under the high temperature condition to generate cracking reaction, under the atmosphere of sulfur generated by thiophene, a carbon nano tube is generated on the surface of iron nano particles generated by ferrocene, tetrabutyl titanate is cracked at high temperature, and titanium dioxide is adsorbed and grown on the surface of the carbon nano tube.
(5) The carbon nano tube aerosol column leaves the reaction furnace along with the air flow, the gas which does not participate in the reaction is discharged into a tail gas collecting system along with the air path, the assembly body discharged from the lower end outlet of the aerosol column meets a liquid seal water tank and then shrinks when meeting cold to form carbon nano tube composite fibers, the carbon nano tube composite fibers are twisted and collected through a rotating shaft driven by a motor, and the collecting speed is 1.5m/min.
The microstructure of the prepared fiber is shown in fig. 3-4, and titanium dioxide wraps the periphery of the carbon nano tube in the form of a shell, so that the fiber grows well and is distributed uniformly. An X-ray photon characteristic spectrum scan was performed, and as a result, as shown in fig. 5, the atomic ratio of titanium element was 16.26%.
In conclusion, the method of in-situ synthesis is adopted, so that the problems of low photocatalytic activity caused by untight connection between titanium dioxide and carbon nanotubes and low electron transmission efficiency in the traditional dip-coating method are solved, and the problems of non-continuous preparation and difficult product collection of a hydrothermal method are solved. The titanium dioxide/carbon nano tube composite fiber prepared by the method has the advantages of large effective catalytic area and tighter electron transmission between the titanium dioxide and the carbon nano tube, and has a wider application prospect in the fields of photocatalysis, novel lithium battery electrode materials and the like.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of titanium dioxide/carbon nanotube composite fiber is characterized by comprising the following steps:
preparing a catalyst, a cocatalyst and an organic solvent to obtain a carbon source solution, and dissolving a titanium source in the carbon source solution to obtain a titanium source/carbon source mixed solution;
heating the reactor to the reaction temperature, and continuously introducing carrier gas and reaction gas into the reactor;
injecting the titanium source/carbon source mixed solution into a reactor, carrying out pyrolysis reaction, cooling, and collecting to obtain the titanium dioxide/carbon nanotube composite fiber.
2. The method for preparing titanium dioxide/carbon nanotube composite fiber according to claim 1, wherein the catalyst comprises ferrocene, cobaltocene or nickelocene; the cocatalyst is a sulfur-containing organic compound; the organic solvent comprises benzene or ethanol; the titanium source is a titanium-containing organic compound.
3. The method of claim 2, wherein the sulfur-containing organic compound comprises thiophene; the titanium-containing organic compound comprises titanate and derivatives thereof, an organic titanium compound or a titanium salt of an organic acid with fat solubility, and specifically comprises tetrabutyl titanate or tetraisopropyl titanate.
4. The method for preparing titanium dioxide/carbon nanotube composite fiber according to claim 1, wherein in the titanium source/carbon source mixed solution, the mass fraction of the catalyst is 0.5-10%, the mass fraction of the cocatalyst is 0.5-10%, and the mass fraction of the titanium source is 0.5-30%.
5. The method for preparing titanium dioxide/carbon nanotube composite fiber according to claim 1, wherein the reaction temperature is 900-1500 ℃, and the temperature rise rate is 0.5-2 ℃/min.
6. The method for preparing titanium dioxide/carbon nano tube composite fiber according to claim 1, wherein the volume ratio of the carrier gas to the reaction gas is 1 (5-20); the total gas flow is 1000-2000sccm.
7. The method of claim 1, wherein the carrier gas is an inert gas comprising argon or helium, and the reactant gas is hydrogen.
8. The method for preparing titanium dioxide/carbon nanotube composite fiber according to claim 1, wherein the injection rate of the titanium source/carbon source mixed solution is 50 to 300 μ L/min.
9. The method for preparing titanium dioxide/carbon nanotube composite fiber according to claim 1, wherein the cooling mode is drawing water, and the drawing speed is 1-20cm/s.
10. A titanium dioxide/carbon nanotube composite fiber prepared by the method of any one of claims 1 to 9.
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| RU2805730C1 (en) * | 2023-04-06 | 2023-10-23 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | USE OF TiO2/C COMPOSITE AS A SORBENT FOR SELECTIVE EXTRACTION OF COPPER IONS FROM COPPER-NICKEL SOLUTIONS |
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| RU2805730C1 (en) * | 2023-04-06 | 2023-10-23 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | USE OF TiO2/C COMPOSITE AS A SORBENT FOR SELECTIVE EXTRACTION OF COPPER IONS FROM COPPER-NICKEL SOLUTIONS |
| RU2807412C1 (en) * | 2023-08-22 | 2023-11-14 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | METHOD FOR PRODUCING COMPOSITE TiO2/C |
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