CN114433046B - Carbon-based material loaded with titanium oxide nano particles, and preparation method and application thereof - Google Patents
Carbon-based material loaded with titanium oxide nano particles, and preparation method and application 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 51
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002086 nanomaterial Substances 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002109 single walled nanotube Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 3
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- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000009283 thermal hydrolysis Methods 0.000 abstract description 2
- 239000002041 carbon nanotube Substances 0.000 description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
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- 238000000576 coating method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 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 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000010330 laser marking Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- UKKGMDDPINLFIY-UHFFFAOYSA-N [C+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] UKKGMDDPINLFIY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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Abstract
The invention discloses a carbon-based material loaded with titanium oxide nano particles, and a preparation method and application thereof, and belongs to the technical field of nano materials. The preparation method comprises the steps of preparing a carbon nanomaterial and titanium oxide nanoparticles, wherein the titanium oxide nanoparticles are loaded on the surface of the carbon nanomaterial; the titanium oxide nanoparticles have an average particle size of less than 2 nanometers and have enhanced photocatalytic efficiency. The invention utilizes photo-thermal chemical reaction to form superfine nano material combined in chemical or physical mode on the surface of the matrix; meanwhile, the conductive fiber is used as a base material, photoelectric synergistic catalysis can be realized, the laser-induced photo-thermal hydrolysis reaction generates a local thermal effect on the carbon-based nanomaterial on the surface of the conductive fiber, and ultrafine titanium oxide nanoparticles are promoted to be hydrolyzed and separated out on the surface.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to titanium oxide nano particles with high photocatalytic activity loaded on the surface of a carbon-based material, and a preparation method and application thereof.
Background
At present, various methods can be used for preparing titanium oxide nano particles with high photocatalytic efficiency, and a hydrothermal method is mostly adopted. The anatase titanium oxide nano particles prepared by adopting a hydrothermal method have higher photocatalysis efficiency. And the titanium oxide ultrafine nano particles or molecular clusters can be prepared by acidic room temperature hydrolysis of butyl titanate, the size of the ultrafine nano particles is smaller than 2 nanometers, and the photocatalytic efficiency is several times higher than that of anatase nano particles. However, since the particle size is small, purification cannot be achieved by general separation techniques, and thus the solution is a mixture of ultrafine nanoparticles and larger nanoparticles, and the high photocatalytic efficiency of the ultrafine nanoparticles is not fully exerted. Meanwhile, ultrafine particles are very small in size and can hardly be recovered. If the catalyst is loaded on a mesoporous material or a carbon-based material, the photocatalysis efficiency can be improved through the coupling effect of charge transfer between heterojunctions, and the purification and recovery of the catalyst can be conveniently realized.
The titanium oxide Nano particles are coupled with the carbon-based Nano material, so that the photocatalysis efficiency of the titanium oxide can be greatly improved (H.Zhang, P25-graphene composite as a high performance photocatalyst, ACS Nano, 2010, 4, 380-386). The carbon-based nano material has strong infrared absorption characteristic, and the laser irradiation can generate local transient thermal effect on the material. The carbon nano tube and the graphene oxide are dispersed in the aqueous solution at a low concentration, and the thermal effect of the laser instant irradiation on the carbon material is far higher than that of the solution. Therefore, irradiation of the infrared laser to the carbon nanomaterial only affects the carbon material or the adjacent solution to generate high temperature in short time, but does not affect the solution in a far zone; and the laser irradiation can be carried out locally in the micro-area to form any local photochemical reaction which can be designed.
One major application of photocatalytic nanomaterials is environmental wastewater treatment. In order to efficiently use the nanomaterial, it is necessary to attach a catalyst to the surface of a base material having a large specific surface area. The fiber material has a large specific surface area, becomes a main load base material, and is easy to be desorbed when directly coating the photocatalytic material on the surface of the fiber. The catalyst is fixed on the polymer adhesive layer to produce surface coverage and reduce the photocatalysis efficiency, so that the photo-thermal chemical reaction is utilized to form the superfine nano material with chemical or physical combination on the surface of the matrix in situ, and the problems can be solved.
Disclosure of Invention
In order to solve the difficult problem of controlling the hydrothermal reaction heat of the superfine nano particles, the invention adopts infrared laser to irradiate the strong infrared absorption carbon nano material to provide a local instant heating effect, so that butyl titanate forms peptization on the surface of the carbon nano material, and the formation of the superfine nano particles is controlled by the laser irradiation dose, thereby providing a preparation method of the carbon-based material loaded with the titanium oxide superfine nano particles.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the carbon-based material loaded with the titanium oxide nano-particles comprises a carbon nano-material and titanium oxide nano-particles, wherein the titanium oxide nano-particles are loaded on the surface of the carbon nano-material;
the titanium oxide nanoparticles have an average particle size of less than 2 nanometers and have enhanced photocatalytic efficiency.
Further, the carbon nanomaterial is single-walled carbon nanotubes or/and graphene.
The preparation method of the carbon-based material loaded with titanium oxide nano particles comprises the following steps:
step 1, mixing butyl titanate and absolute ethyl alcohol at the temperature of 4-8 ℃, and adding the mixed solution into a nitric acid aqueous solution to obtain a butyl titanate sol precursor;
step 2, mixing a butyl titanate sol precursor with a carbon-based material at the temperature of 4-8 ℃;
and step 3, treating the mixed material obtained in the step 2 by adopting infrared laser at the temperature of 4-8 ℃ and purifying to obtain the carbon-based material loaded with the titanium oxide nano particles.
Further, in the step 1, the molar ratio of butyl titanate, nitric acid, ethanol-free water is 0.2-0.5: 0.10 to 0.22: 0.40-0.60: 15-22.
Further, metal ions are added into the butyl titanate sol precursor in the step 1 for doping.
Further, the metal ion is Fe 3+ 、La 3+ 、Zn 2+ Or Pt (Pt) 4+ One of them is doped with Fe in the amount of titanium 3+ 0.1~0.1mol%、La 3+ 0.5~2mol%、Zn 2+ 0.5~5mol%、Pt 4+ 0.1~3mol%。
Further, in the step 2, the carbon-based material is a single-walled carbon nanotube, graphene oxide or an organic fiber bundle coated with a carbon nanomaterial on the surface.
In the invention, for carbon-based materials such as single-walled carbon nanotubes and graphene oxide, the mixing in step 2 means mixing a butyl titanate sol precursor with an aqueous solution of the single-walled carbon nanotubes or an aqueous solution of the graphene oxide; for the organic fiber bundles with the surfaces coated with the carbon nano materials, the step 2 of mixing refers to that the organic fiber bundles with the surfaces coated with the carbon nano materials are repeatedly passed through a liquid pool of a butyl titanate sol precursor to form infiltration mixing.
Further, the single-walled carbon nanotube is an aqueous solution of single-walled carbon nanotubes with a concentration of 0.01-0.001wt%, and the volume ratio of the aqueous solution of single-walled carbon nanotubes to the butyl titanate sol precursor is 1:3.
Further, the graphene oxide is a graphene oxide aqueous solution with the concentration of 0.01-0.001wt%, and the volume ratio of the graphene oxide aqueous solution to the butyl titanate sol precursor is 1:3.
Further, the conditions for processing by adopting the infrared laser in the step 3 are as follows: focusing laser with the wavelength of 10.6 micrometers to a light spot with the wavelength of 0.1-0.3 millimeter, wherein the energy density is 2 multiplied by 10 4 ~1×10 5 Tile/cm 2 The same sample is repeatedly scanned at a speed of not less than 200 mm/s for a number of 5 to 20 times and repeatedly scanned for 1 to 10 times.
The application of the carbon-based material loaded with titanium oxide nano particles in preparing a photocatalytic material.
Further, the photocatalytic material is a photocatalyst or a photocatalytic fabric.
The beneficial effects are that: the invention can solve the problems by forming the superfine nano material with chemical or physical combination on the surface of the carbon matrix through the photo-thermal chemical reaction; meanwhile, the conductive fiber is used as a base material, photoelectric synergistic catalysis can be realized, the laser-induced photo-thermal hydrolysis reaction generates a local thermal effect on the carbon-based nanomaterial on the surface of the conductive fiber, and ultrafine titanium oxide nanoparticles are promoted to be hydrolyzed and separated out on the surface.
Drawings
Fig. 1 is a schematic structural diagram of a quartz microfluidic flow channel used in the first embodiment.
FIG. 2 is an ultraviolet absorption spectrum of the ultrafine titania-supported carbon nanotubes isolated and purified in the first example.
FIG. 3 is a high-resolution electron microscope image of ultra-fine nano-titania on the surface of a bundle of single-walled carbon nanotubes in accordance with the first embodiment.
FIG. 4 shows the result of the photocatalytic measurement of the ultrafine titania-supported carbon nanotubes isolated and purified in the first example.
Fig. 5 is a schematic diagram of a fibrous liquid pond according to the third embodiment.
Detailed Description
The invention will now be described in further detail with reference to the drawings and specific examples, which should not be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention. The experimental procedures and reagents not shown in the formulation of the examples were all in accordance with the conventional conditions in the art.
Example 1
Step one, mixing 130 ml of butyl titanate with 25 ml of absolute ethyl alcohol at the temperature of 4 ℃, uniformly stirring, and slowly dripping into 340 ml of aqueous nitric acid solution, wherein the aqueous nitric acid solution contains zinc nitrate, and the Zn is calculated according to the dosage of titanium 2+ The concentration was 3.5mol%. Butyl titanate as a final mixed solution: nitric acid: ethanol: the water mole ratio was 0.38:0.11:0.43:18.61. preparing semitransparent butyl titanate sol precursor with the pH value of the system of 3;
step two, an aqueous solution of single-walled carbon nanotubes (manufactured by Naenergy technology Co., ltd. In Chengdu middle-family) having a concentration of 0.001wt% was prepared at 4℃to give a solution of 1:3 volume ratio is mixed with the precursor;
step three, introducing the mixed solution into a quartz micro-fluidic cell (a=50 mm, b=55 mm, h=10 mm, l=5 mm, n=10, shown in fig. 1) at 4 ℃ by a volumetric pump, wherein the flow rate is 2 ml/s;
focusing laser of a carbon dioxide laser marking machine with the wavelength of 10.6 micrometers at 30W to a light spot with the wavelength of 0.2 millimeter at the power of 5 percent, repeatedly scanning liquid in the same flow channel at the speed of 800 millimeters per second, scanning the liquid in the same flow channel for 10 times at the line scanning times at the line interval increment of 0.5 millimeter, moving the light spot to the next flow channel after scanning the same flow channel, repeating the first flow channel after scanning all parallel flow channels, and repeating the scanning for 10 times;
and fifthly, standing 3 milliliters of the laser treated mixed liquid for 24 hours, removing supernatant, taking down sediment, adding absolute ethyl alcohol to 5 times of the volume of the original mixed liquid, dispersing on a vortex dispersing instrument, centrifuging the obtained dispersion liquid at 4000 revolutions per minute, taking sediment, repeatedly adding alcohol for dispersing, and centrifuging to obtain the purified load superfine nano titanium oxide carbon nanotube product.
FIG. 2 is a graph showing that the strong ultraviolet absorption of the carbon nanotubes with ultrafine titanium oxide attached to the surface of the carbon nanotubes shows that a certain amount of ultrafine titanium oxide is attached to the surface of the carbon nanotubes compared with the ultraviolet spectrum of the original carbon nanotube aqueous solution with the same concentration.
FIG. 3 is a high resolution transmission electron micrograph of carbon nanotubes with ultrafine titanium oxide attached thereto, wherein ultrafine titanium oxide nanoparticles are densely attached to the surface of the carbon nanotube bundles, and the average size is less than 2nm.
Photocatalytic activity test:
the purified carbon nanotube superfine titanium oxide product is magnetically stirred and mixed with rhodamine B aqueous solution 100 mL of 2.5 mg/L, and is placed in a dark place for 30 minutes for dark adsorption, and a decolorization test of the product on dye is carried out under the light source of a 300W xenon lamp provided with a 420 nm optical filter. Wherein the illumination intensity of the light source at the liquid level is 6 mu W/cm 2 The duration was 60 min. Taking 4 ml of reaction product at fixed time, centrifuging at 14500 r/min, taking supernatant, measuring Abs value at 665 nm by using a visible light spectrophotometer to obtain absorbance of the solution, and calculating to obtain photocatalytic efficiency.
The purified carbon nano tube superfine titanium oxide product aqueous dispersion is uniformly coated on the surface of a glass sheet with the thickness of 5 cm multiplied by 5 cm, and is repeatedly coated after being dried at 70 ℃ to form a carbon nano tube superfine titanium oxide product layer with the thickness of about 0.1 micrometer. As a control, commercial P25 titania photocatalytic nanomaterial was uniformly coated on the surface of a glass sheet to form a particulate film having a thickness of about 0.2 microns. A frame is used for bonding the edge sealing of the surface of a coating film to form a space of 4 cm (length) multiplied by 4 cm (width) multiplied by 0.2 cm (height), then 2.5ppm of rhodamine B aqueous solution is covered in the space on the surface of the coating film glass, a decolorization test of a product on the dye is carried out under a 300W xenon lamp light source provided with a 420 nm optical filter, wherein the light source is separated from a liquid level by 7 cm for 30 min, the solution is regularly sucked, the Abs value is measured under 665 nm, and the photocatalytic efficiency is calculated.
FIG. 4 shows the results of photocatalytic efficiency measurements of commercial photocatalytic titanium oxide nanoparticles P25 at a concentration of 0.6ppm and a 2.5ppm rhodamine aqueous solution of carbon nanotubes with ultrafine titanium oxide attached at the same concentration, and photocatalytic efficiency measurements of excess P25 coated on the glass surface and carbon nanotubes with ultrafine titanium oxide attached in excess, with a P25 discoloration of 40.45%, 94.4% for carbon nanotubes with ultrafine titanium oxide attached, and far higher for carbon nanotubes with ultrafine titanium oxide attached than for commercial titanium oxide nanoparticles at the same concentration, while the discoloration of the carbon nanotube material on the solid phase surface was significantly higher than for the P25 nanomaterial particle film.
Example two
Step one, the same as in the first embodiment;
step two, at 4 ℃, an aqueous solution of graphene oxide (manufactured by the company of science and technology, sixth element, often) with a concentration of 0.001wt% is prepared by mixing 1:3 volume ratio is mixed with the precursor;
step three, the same as in the first embodiment;
step four, the same as in the first embodiment;
and fifthly, standing 3 milliliters of the laser treated mixed liquid for 24 hours, removing supernatant, taking down sediment, adding absolute ethyl alcohol to 5 times of the volume of the original mixed liquid, dispersing on a vortex dispersing instrument, centrifuging the obtained dispersion liquid at 4000 revolutions per minute, taking sediment, repeatedly adding alcohol for dispersing, and centrifuging to obtain a purified load superfine nano titanium oxide graphene product. According to the photocatalytic activity test of the first reference example, the photocatalytic effect of the product under the liquid phase condition is 77.33%.
Example III
Step one, the same as in the first embodiment;
step two, 16 low-conductive fibers (with specific resistance of 1 kiloohm/cm) and 4 high-conductive fibers (with specific resistance of 100 ohm/cm) coated with single-wall carbon nanotubes are co-woven to form 400D20F conductive bundle wires;
continuously passing the yarns through a liquid pool through a roller, wherein 3-5 yarns are vertically arranged in the liquid pool, the vertical spacing of the yarns is 0.5-1 mm (shown in fig. 5, l=40 cm, d=60 cm), and the yarns are soaked in the solution, and the traversing speed of the yarns is 10 cm/s;
focusing laser of a carbon dioxide laser marking machine with the wavelength of 10.6 microns at 30W to a light spot of 0.2 mm at the power of 10%, repeatedly scanning yarns between rollers at the speed of 1600 mm/s, wherein the scanning times of a row are 10 times, the light spot is moved to the next row of yarns after scanning the yarns, the light spot is moved to the initial position of a first row after scanning all parallel yarns, and repeatedly scanning the yarns of the first row;
and fifthly, guiding the yarns out of the liquid pool, guiding the yarns into a pure water pool, washing off residual liquid on the yarns, drying the yarns with hot air, and winding the yarns to obtain the conductive fiber yarns loaded with the superfine nano titanium oxide.
Claims (10)
1. A carbon-based material loaded with titanium oxide nanoparticles, characterized in that: the preparation method comprises the steps of preparing a carbon nanomaterial and titanium oxide nanoparticles, wherein the titanium oxide nanoparticles are loaded on the surface of the carbon nanomaterial; the average particle size of the titanium oxide nanoparticles is less than 2 nanometers;
the preparation method of the carbon-based material comprises the following steps:
step 1, mixing butyl titanate and absolute ethyl alcohol at the temperature of 4-8 ℃, and adding the mixed solution into a nitric acid aqueous solution to obtain a butyl titanate sol precursor;
step 2, mixing a butyl titanate sol precursor with a carbon-based material at the temperature of 4-8 ℃;
step 3, under the condition of 4-8 ℃, treating the mixed material obtained in the step 2 by adopting infrared laser, and purifying to obtain the carbon-based material loaded with titanium oxide nano particles;
the conditions for processing by adopting infrared laser are as follows: focusing laser with the wavelength of 10.6 micrometers to a light spot with the wavelength of 0.1-0.3 millimeter, wherein the energy density is 2 multiplied by 10 4 ~1×10 5 Tile/cm 2 The same sample is repeatedly scanned at a speed of not less than 200 mm/s for a number of 5 to 20 times and repeatedly scanned for 1 to 10 times.
2. The titanium oxide nanoparticle-supported carbon-based material according to claim 1, wherein: the carbon nanomaterial is single-walled carbon nanotubes or/and graphene.
3. The method for preparing a carbon-based material loaded with titanium oxide nanoparticles according to claim 1, characterized in that: the method comprises the following steps:
step 1, mixing butyl titanate and absolute ethyl alcohol at the temperature of 4-8 ℃, and adding the mixed solution into a nitric acid aqueous solution to obtain a butyl titanate sol precursor;
step 2, mixing a butyl titanate sol precursor with a carbon-based material at the temperature of 4-8 ℃;
and step 3, treating the mixed material obtained in the step 2 by adopting infrared laser at the temperature of 4-8 ℃ and purifying to obtain the carbon-based material loaded with the titanium oxide nano particles.
4. A method of preparation according to claim 3, characterized in that: in the step 1, the molar ratio of butyl titanate, nitric acid, ethanol-free water is 0.2-0.5: 0.10 to 0.22: 0.40-0.60: 15-22.
5. A method of preparation according to claim 3, characterized in that: and (2) adding metal ions into the butyl titanate sol precursor in the step (1) for doping.
6. The method of manufacturing according to claim 5, wherein: the metal ion is Fe 3+ 、La 3+ 、Zn 2+ Or Pt (Pt) 4+ One of them is doped with Fe in the amount of titanium 3+ 0.1~0.1mol%、La 3+ 0.5~2mol%、Zn 2+ 0.5~5mol%、Pt 4+ 0.1~3mol%。
7. A method of preparation according to claim 3, characterized in that: in the step 2, the carbon-based material is a single-walled carbon nanotube, graphene oxide or an organic fiber bundle coated with a carbon nanomaterial on the surface.
8. A method of preparation according to claim 3, characterized in that: the conditions for processing by adopting infrared laser in the step 3 are as follows: focusing laser with the wavelength of 10.6 micrometers to a light spot with the wavelength of 0.1-0.3 millimeter, wherein the energy density is 2 multiplied by 10 4 ~1×10 5 Tile/cm 2 The same sample is repeatedly scanned at a speed of not less than 200 mm/s for a number of 5 to 20 times and repeatedly scanned for 1 to 10 times.
9. Use of the carbon-based material loaded with titanium oxide nanoparticles according to claim 1 for the preparation of photocatalytic materials.
10. The use according to claim 9, characterized in that: the photocatalytic material is a photocatalyst or a photocatalytic fabric.
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