CN114433046A - Carbon-based material loaded with titanium oxide nanoparticles and preparation method and application thereof - Google Patents
Carbon-based material loaded with titanium oxide nanoparticles and preparation method and application thereof Download PDFInfo
- Publication number
- CN114433046A CN114433046A CN202111575890.5A CN202111575890A CN114433046A CN 114433046 A CN114433046 A CN 114433046A CN 202111575890 A CN202111575890 A CN 202111575890A CN 114433046 A CN114433046 A CN 114433046A
- Authority
- CN
- China
- Prior art keywords
- carbon
- titanium oxide
- nano
- oxide nanoparticles
- based material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 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
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000010408 sweeping Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000002153 concerted effect Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction 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 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001027 hydrothermal synthesis 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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000011852 carbon nanoparticle Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000010330 laser marking Methods 0.000 description 2
- 238000013532 laser treatment Methods 0.000 description 2
- 239000013335 mesoporous material 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
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 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
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 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 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- CBCIHIVRDWLAME-UHFFFAOYSA-N hexanitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O CBCIHIVRDWLAME-UHFFFAOYSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement 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
- 238000011282 treatment Methods 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
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- 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
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a carbon-based material loaded with titanium oxide nanoparticles, and a preparation method and application thereof, and belongs to the technical field of nano materials. The nano-titanium dioxide 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. The invention utilizes photo-thermal chemical reaction to form the ultra-fine nanometer material which is combined in a chemical or physical mode on the surface of a substrate; meanwhile, the conductive fiber is used as a base material, photoelectric concerted catalysis can be realized, the laser-induced photothermal hydrolysis reaction generates a local heat effect on the carbon-based nano material on the surface of the conductive fiber, and the water desorption of the ultrafine titanium oxide nano particles on the surface is promoted.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to titanium oxide nano particles loaded on the surface of a carbon-based material and having high photocatalytic activity, and a preparation method and application thereof.
Background
At present, titanium oxide nanoparticles with high photocatalytic efficiency can be prepared by various methods, and most of the methods adopt a hydrothermal method. The anatase titanium oxide nano-particles prepared by a hydrothermal method have higher photocatalytic efficiency. And titanium oxide ultrafine nano particles or molecular clusters can be prepared by adopting butyl titanate to hydrolyze at room temperature, the size of the ultrafine nano particles is less than 2 nanometers, and the photocatalytic efficiency is several times higher than that of anatase nano particles. However, since the particle size is small, the general separation technique cannot achieve purification, and thus the solution is a mixture of ultrafine nanoparticles and larger nanoparticles, and the high photocatalytic efficiency of the ultrafine nanoparticles cannot be fully exerted. Meanwhile, ultrafine particles are hardly recyclable due to their very small size. If the mesoporous material or the carbon-based material is loaded, the photocatalytic efficiency can be improved through the coupling effect of charge transfer between heterojunctions, and the purification and recovery of the mesoporous material or the carbon-based material can be conveniently realized.
Titanium oxide nanoparticles are coupled with carbon-based nanomaterials, which can greatly improve the photocatalytic efficiency of titanium oxide (H, Zhang, P25-graphene composite as a high performance photocatalytic system, ACS Nano, 2010, 4, 380-386). The carbon-based nano material has strong infrared absorption characteristic, and 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 instantaneous irradiation on the carbon material is far higher than that of the solution. Therefore, the irradiation of the carbon nano material by the infrared laser only influences the short-term generation of high temperature of the carbon material or the adjacent solution and does not influence the far-zone solution; and the laser irradiation can be locally carried out in a micro-area to form any designable local photochemical reaction.
One of the main applications of photocatalytic nanomaterials is environmental sewage treatment. In order to efficiently utilize the nanomaterial, it is necessary to attach the catalyst to the surface of a base material having a large specific surface area. The fiber material has large specific surface area and becomes a main load base material, and the desorption is easily generated by directly coating the photocatalytic material on the surface of the fiber. The polymer adhesive layer is used for fixing the catalyst, so that the surface coverage is generated, and the photocatalysis efficiency is reduced, so that the superfine nano material with chemical or physical combination is formed in situ on the surface of the substrate by utilizing the photo-thermal chemical reaction, and the problems can be solved.
Disclosure of Invention
In order to solve the problem of thermal control of hydrothermal reaction of ultrafine nanoparticles, the invention adopts infrared laser to irradiate the carbon nano material with strong infrared absorption to provide local instantaneous thermal effect, so that butyl titanate forms peptization on the surface of the carbon nano material, and the ultrafine nanoparticles are controlled to form by laser irradiation dose, thereby providing the preparation method of the carbon-based material loaded with the ultrafine titanium oxide nanoparticles.
In order to achieve the purpose, the invention adopts the following technical scheme:
the carbon-based material loaded with the titanium oxide nanoparticles comprises the carbon nanoparticles and the titanium oxide nanoparticles, wherein the titanium oxide nanoparticles are loaded on the surface of the carbon nanoparticles;
the titanium oxide nanoparticles have an average particle size of less than 2 nanometers and have enhanced photocatalytic efficiency.
Further, the carbon nano material is single-walled carbon nano tube or/and graphene.
The preparation method of the carbon-based material loaded with the titanium oxide nanoparticles comprises the following steps:
and 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 alcohol and water is 0.2-0.5: 0.10-0.22: 0.40-0.60: 15 to 22.
Further, metal ions are added into the butyl titanate sol precursor in the step 1 for doping.
Further, the metal ion is Fe3+、La3+、Zn2+Or Pt4+In the formula (I), the doping concentration is Fe based on the dosage of titanium3+ 0.1~0.1mol%、La3+ 0.5~2mol%、Zn2+ 0.5~5mol%、Pt4+ 0.1~3mol%。
Further, in the step 2, the carbon-based material is single-walled carbon nanotubes, graphene oxide or organic fiber bundles coated with carbon nanomaterials on the surface.
In the invention, for carbon-based materials such as single-walled carbon nanotubes and graphene oxide, the mixing in the step 2 is to mix a tetrabutyl titanate sol precursor with an aqueous solution of single-walled carbon nanotubes or an aqueous solution of graphene oxide; for the organic fiber bundle with the surface coated with the carbon nano material, the mixing in step 2 refers to that the organic fiber bundle with the surface coated with the carbon nano material repeatedly passes through a liquid pool of the butyl titanate sol precursor to form infiltration mixing.
Furthermore, the single-walled carbon nanotube is a single-walled carbon nanotube aqueous solution with the concentration of 0.01-0.001 wt%, and the volume ratio of the single-walled carbon nanotube aqueous solution to the butyl titanate sol precursor is 1: 3.
Furthermore, the graphene oxide is a graphene oxide aqueous solution with the concentration of 0.01-0.001 wt%, 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 using the infrared laser in the step 3 are as follows: focusing laser with the wavelength of 10.6 microns to a spot of 0.1-0.3 mm, wherein the energy density is 2 multiplied by 104~1×105Tile/cm2The same sample is repeatedly scanned at a speed of not less than 200 mm/sec for 5 to 20 times, and the scanning is repeated for 1 to 10 times.
The carbon-based material loaded with the titanium oxide nano particles is applied to preparation of a photocatalytic material.
Further, the photocatalytic material is a photocatalyst or a photoelectrocatalytic fabric.
Has the advantages that: the invention utilizes photo-thermal chemical reaction to form the superfine nano material with chemical or physical combination on the surface of the carbon substrate, and can solve the problems; meanwhile, the conductive fiber is used as a base material, photoelectric concerted catalysis can be realized, the laser-induced photothermal hydrolysis reaction generates a local heat effect on the carbon-based nano material on the surface of the conductive fiber, and the water desorption of the ultrafine titanium oxide nano particles on the surface is promoted.
Drawings
Fig. 1 is a schematic structural diagram of a quartz microfluidic flow channel used in the first embodiment.
FIG. 2 is the UV absorption spectrum of the ultrafine titanium oxide-loaded carbon nanotubes separated and purified in the first embodiment.
FIG. 3 is a high resolution electron microscope image of ultrafine nano-titanium oxide on the surface of a single-walled carbon nanotube bundle in the first example.
FIG. 4 shows the result of the photocatalytic measurement of the ultrafine titanium oxide-loaded carbon nanotubes separated and purified in the first embodiment.
FIG. 5 is a schematic structural view of a fiber liquid pool in the third embodiment.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific examples, which should not be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
Example one
Step one, mixing 130 ml of butyl titanate and 25 ml of absolute ethyl alcohol at 4 ℃, uniformly stirring, and slowly dripping into 340 ml of nitric acid aqueous solution, wherein the nitric acid aqueous solution contains zinc nitrate, and the amount of Zn is calculated by the amount of titanium2+The concentration was 3.5 mol%. Final mixed solution butyl titanate: nitric acid: ethanol: the water molar ratio is 0.38: 0.11: 0.43: 18.61. the pH value of the system is 3, and a semitransparent butyl titanate sol precursor is prepared;
step two, under 4 ℃, the single-walled carbon nanotube aqueous solution (produced by Chengdu Kogyo Naneng technology Co., Ltd.) with the concentration of 0.001wt% is mixed with 1:3, mixing with the precursor in a volume ratio;
step three, introducing the mixture into a quartz microfluid tank (shown in fig. 1, a =50 mm, B =55 mm, H =10 mm, L =5 mm, n = 10) at 4 ℃ by using a volumetric pump, and the flow rate is 2 ml/sec;
focusing the laser of a carbon dioxide laser marking machine with the wavelength of 10.6 microns at the power of 5% to a 0.2 mm light spot, repeatedly scanning the liquid in the same flow channel at the speed of 800 mm/s for 10 times, scanning the liquid in the same flow channel at the line spacing increment of 0.5 mm in the same flow channel, moving the light spot to the next flow channel after scanning the same flow channel for repeating, repeating the first flow channel after scanning all parallel flow channels, and repeating the scanning for 10 times;
and step five, standing the mixed liquid after the laser treatment for 24 hours, removing supernatant, taking sediments, adding absolute ethyl alcohol to 5 times of the volume of the original mixed liquid, dispersing on a vortex dispersion instrument, centrifuging the obtained dispersion liquid at 4000 rpm, taking sediments, repeatedly adding ethanol for dispersion and centrifuging to obtain a purified product of the loaded superfine nano titanium oxide carbon nano tube.
FIG. 2 is a comparison of the UV spectra of the carbon nanotube with attached ultrafine titanium oxide and the original aqueous solution of carbon nanotubes with the same concentration, wherein the strong UV absorption indicates that a certain amount of ultrafine titanium oxide is attached to the surface of the carbon nanotube.
FIG. 3 is a high resolution TEM image of carbon nanotubes with ultrafine titanium oxide particles densely adhered to the surface of the carbon nanotube bundle, wherein the average size of the carbon nanotube bundle is less than 2 nm.
Photocatalytic activity test:
and magnetically stirring and mixing the purified carbon nano tube ultrafine titanium oxide product with 100 mL of 2.5 mg/L rhodamine B aqueous solution, placing the mixture in a dark place for dark adsorption for 30 min, and performing a decolorization test of the product on the dye under a 300W xenon lamp light source with a 420 nm optical filter. Wherein the light intensity of the light source at the liquid level is 6 μ W/cm2The duration is 60 min. And (3) taking 4 ml of reaction product at regular time, centrifuging at 14500 r/min, taking supernate, measuring an Abs value at 665 nm by using a visible spectrophotometer to obtain the absorbance of the solution, and calculating to obtain the photocatalytic efficiency.
The purified water dispersion of the carbon nano tube ultrafine titanium oxide product is evenly coated on the surface of a glass sheet with the thickness of 5 cm multiplied by 5 cm, and the carbon nano tube ultrafine titanium oxide product layer with the thickness of about 0.1 micron is formed after the glass sheet is dried at 70 ℃ and repeatedly coated. In contrast, commercial titanium oxide photocatalytic nanomaterial P25 was uniformly coated on the surface of a glass plate to form a particulate film with a thickness of about 0.2 microns. Bonding the edge sealing of the surface of the coated glass by using a frame to form a space of 4 centimeters (length) multiplied by 4 centimeters (width) multiplied by 0.2 centimeter (height), covering 2.5ppm of rhodamine B aqueous solution in the space on the surface of the coated glass, carrying out a decolorization test of the product on dye under a 300W xenon lamp light source provided with a 420 nm optical filter, wherein the light source is 7 cm away from the liquid level, the duration is 30 min, periodically absorbing the solution, measuring the Abs value at 665 nanometers, and calculating to obtain the photocatalytic efficiency.
Fig. 4 shows the result of measuring the photocatalytic efficiency of the commercial photocatalytic titanium oxide nanoparticles P25 with a concentration of 0.6ppm and the photocatalytic efficiency of the carbon nanotubes with attached ultrafine titanium oxide with respect to a 2.5ppm rhodamine aqueous solution, and the results of measuring the photocatalytic efficiency of the carbon nanotubes with excessive P25 and excessive attached ultrafine titanium oxide coated on the glass surface, wherein the discoloration rate of P25 is 40.45%, the discoloration rate of the carbon nanotubes with attached ultrafine titanium oxide is 94.4%, the discoloration rate of the carbon nanotubes with attached ultrafine titanium oxide is much higher than that of the commercial titanium oxide nanopowder with the same concentration, and meanwhile, the discoloration rate of the carbon nanotube material on the solid phase surface is significantly higher than that of the particle film of the P25 nanomaterial.
Example two
Step one, the same as embodiment one;
step two, at 4 ℃, mixing an aqueous solution of graphene oxide (manufactured by hexite materials science and technology ltd., yokozhou) with a concentration of 0.001wt% in a ratio of 1:3, mixing with the precursor in a volume ratio;
step three, the same as the first embodiment;
step four, the same as the first embodiment;
and step five, standing 3 ml of mixed liquid after laser treatment for 24 hours, removing supernatant, taking the sediment, adding absolute ethyl alcohol to 5 times of the volume of the original mixed liquid, dispersing on a vortex dispersion instrument, centrifuging the obtained dispersion liquid at 4000 rpm, taking the sediment, repeatedly adding ethanol for dispersion, and performing centrifugal separation to obtain the purified loaded superfine nano titanium oxide graphene product. Referring to the photocatalytic activity test of example one, the photocatalytic effect of the product under liquid phase condition is 77.33%.
EXAMPLE III
Step one, the same as embodiment one;
step two, doubling 16 low-conductivity fibers (specific resistance 1 kiloohm/cm) coated with single-walled carbon nanotubes on the surface with 4 high-conductivity fibers (specific resistance 100 ohm/cm) to form 400D20F conductive bundle filaments;
step three, continuously enabling the yarns to pass through a liquid pool through rollers, wherein 3-5 yarns are vertically arranged in the precursor solution prepared in the step one in the liquid pool, the vertical distance between the yarns is 0.5-1 mm (shown in figure 5, L =40 cm, D =60 cm), the yarns are soaked in the solution, and the yarn passing speed is 10 cm/s;
focusing laser of a carbon dioxide laser marking machine with the wavelength of 10.6 microns at the power of 10% to a 0.2 mm light spot, repeatedly scanning the yarns between the rollers at the speed of 1600 mm/s, wherein the line scanning times are 10 times, the light spot moves to the next line of yarns after one line of yarns are scanned, the light spots move to the initial position of the first line after all parallel yarns are scanned, and repeatedly scanning the first line of yarns;
and fifthly, leading the yarn out of the liquid pool, leading the yarn into a pure water pool, washing off residual liquid on the yarn, drying by hot air, and rolling to obtain the conductive fiber yarn loaded with the superfine nano titanium oxide.
Claims (10)
1. A carbon-based material loaded with titanium oxide nanoparticles, characterized in that: the nano-titanium dioxide 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.
2. Carbon-based material loaded with titanium oxide nanoparticles according to claim 1, characterized in that: the carbon nano material is a single-walled carbon nanotube or/and graphene.
3. The method for producing a carbon-based material on which titanium oxide nanoparticles are supported 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 the butyl titanate sol precursor with the carbon-based material at the temperature of 4-8 ℃;
and 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 nanoparticles.
4. The production method according to claim 3, characterized in that: in the step 1, the molar ratio of butyl titanate to nitric acid to ethanol-free water is 0.2-0.5: 0.10-0.22: 0.40-0.60: 15 to 22.
5. The production method 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 claim 5, wherein: the metal ion is Fe3+、La3+、Zn2+Or Pt4+In the formula (I), the doping concentration is Fe based on the dosage of titanium3+ 0.1~0.1mol%、La3+ 0.5~2mol%、Zn2+ 0.5~5mol%、Pt4+ 0.1~3mol%。
7. The production method according to claim 3, characterized in that: in the step 2, the carbon-based material is single-walled carbon nanotubes, graphene oxide or organic fiber bundles coated with carbon nano materials on the surface.
8. The production method according to claim 3, characterized in that: the conditions for processing by adopting the infrared laser in the step 3 are as follows: focusing laser with the wavelength of 10.6 microns to a spot of 0.1-0.3 mm, wherein the energy density is 2 multiplied by 104~1×105Tile/cm2Repeatedly sweeping at a speed of not less than 200 mm/sThe same sample is scanned 5 to 20 times, and the scanning is repeated 1 to 10 times.
9. Use of the carbon-based material loaded with titanium oxide nanoparticles of claim 1 for the preparation of a photocatalytic material.
10. Use according to claim 9, characterized in that: the photocatalytic material is a photocatalyst or a photoelectrocatalytic fabric.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111575890.5A CN114433046B (en) | 2021-12-22 | 2021-12-22 | Carbon-based material loaded with titanium oxide nano particles, and preparation method and application thereof |
| PCT/CN2021/140653 WO2023115426A1 (en) | 2021-12-22 | 2021-12-23 | Carbon-based material loaded with titanium oxide nanoparticles, preparation method therefor, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111575890.5A CN114433046B (en) | 2021-12-22 | 2021-12-22 | Carbon-based material loaded with titanium oxide nano particles, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114433046A true CN114433046A (en) | 2022-05-06 |
| CN114433046B CN114433046B (en) | 2023-12-26 |
Family
ID=81363531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111575890.5A Active CN114433046B (en) | 2021-12-22 | 2021-12-22 | Carbon-based material loaded with titanium oxide nano particles, and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114433046B (en) |
| WO (1) | WO2023115426A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115873492A (en) * | 2022-11-17 | 2023-03-31 | 安徽辅朗光学材料有限公司 | Laser-proof coating, preparation method and product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006727A (en) * | 2016-05-17 | 2016-10-12 | 苏州盛丰源新材料科技有限公司 | Homogeneous crystallized TiO2 nano-scale solution, preparation method thereof and crystallization equipment |
| CN108295827A (en) * | 2017-12-23 | 2018-07-20 | 佛山科学技术学院 | A kind of method of graphene-supported visible light-responsible titanium dioxide |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837287B (en) * | 2009-03-21 | 2012-05-30 | 清华大学 | Preparation of carbon nano-tube nano-particle composite material |
| MX360196B (en) * | 2013-09-25 | 2018-10-11 | Mexicano Inst Petrol | Nanostructured titania catalyst with stabilized acidity and process thereof. |
| WO2016098127A1 (en) * | 2014-12-16 | 2016-06-23 | Council Of Scientific & Industrial Research | NOVEL TITANIUM DIOXIDE - GRAPHENE QUANTUM DOTS (TiO2-GQDS) HYBRID MULTIFUNCTIONAL MATERIAL AND PREPARATION THEREOF |
| CN106512939B (en) * | 2016-11-23 | 2019-08-09 | 杭州电子科技大学 | A kind of multi-layer graphene carried titanium dioxide, ferrotitanium duplex metal nano granule and preparation method thereof |
| CN109126756A (en) * | 2018-08-28 | 2019-01-04 | 绍兴文理学院 | A kind of preparation method of high-activity nano titanium dioxide |
| CN110642524B (en) * | 2019-10-31 | 2020-06-30 | 山东大学 | Method for preparing microstructure on glass surface by titanium dioxide nanoparticle assisted infrared nanosecond laser |
-
2021
- 2021-12-22 CN CN202111575890.5A patent/CN114433046B/en active Active
- 2021-12-23 WO PCT/CN2021/140653 patent/WO2023115426A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006727A (en) * | 2016-05-17 | 2016-10-12 | 苏州盛丰源新材料科技有限公司 | Homogeneous crystallized TiO2 nano-scale solution, preparation method thereof and crystallization equipment |
| CN108295827A (en) * | 2017-12-23 | 2018-07-20 | 佛山科学技术学院 | A kind of method of graphene-supported visible light-responsible titanium dioxide |
Non-Patent Citations (1)
| Title |
|---|
| JIN WANG，ET AL: ""Single-Step Preparation of TiO2/MWCNT Nanohybrid Materials by Laser Pyrolysis and Application to Efficient Photovoltaic Energy Conversion"", 《ACS APPL. MATER. INTERFACES》, pages 51 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115873492A (en) * | 2022-11-17 | 2023-03-31 | 安徽辅朗光学材料有限公司 | Laser-proof coating, preparation method and product |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023115426A1 (en) | 2023-06-29 |
| CN114433046B (en) | 2023-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Khan et al. | Morphological influence of TiO2 nanostructures (nanozigzag, nanohelics and nanorod) on photocatalytic degradation of organic dyes | |
| Chen et al. | Synthesis, characterization, and photocatalytic analysis of CNT/TiO2 composites derived from MWCNTs and titanium sources | |
| Hu et al. | Anatase TiO 2 nanoparticles/carbon nanotubes nanofibers: preparation, characterization and photocatalytic properties | |
| Rajput et al. | A review on TiO2/SnO2 heterostructures as a photocatalyst for the degradation of dyes and organic pollutants | |
| Guo et al. | Study on preparation of SnO2-TiO2/Nano-graphite composite anode and electro-catalytic degradation of ceftriaxone sodium | |
| Chuaicham et al. | Importance of ZnTiO3 phase in ZnTi-mixed metal oxide photocatalysts derived from layered double hydroxide | |
| Xiong et al. | Hierarchical pn heterostructure BiOI@ ZnTi-LDH for Cr (VI) reduction under visible light | |
| Zhao et al. | Degradation of rhodamine B and safranin‐T by MoO3: CeO2 nanofibers and air using a continuous mode | |
| Parayil et al. | Naphthalene derivatized TiO2–carbon hybrid materials for efficient photocatalytic splitting of water | |
| Shen et al. | Preparation of doped TiO 2 nanofiber membranes through electrospinning and their application for photocatalytic degradation of malachite green | |
| Xu et al. | Fabrication of polyaniline sensitized grey-TiO2 nanocomposites and enhanced photocatalytic activity | |
| Li et al. | Ag-induced anatase-rutile TiO2− x heterojunction facilitating the photogenerated carrier separation in visible-light irradiation | |
| Liu et al. | Optimizing the interface of C/titania@ reduced graphene oxide nanofibers for improved photocatalytic activity | |
| CN114433046B (en) | Carbon-based material loaded with titanium oxide nano particles, and preparation method and application thereof | |
| Liu et al. | Ionic liquid-induced preparation of novel CNTs/PbBiO2Cl nanosheet photocatalyst with boosted photocatalytic activity for the removal of organic contaminants | |
| Sawal et al. | Si-Ti interaction in unique morphology of fibrous silica titania photoanode for enhanced photoelectrochemical water splitting | |
| Yang et al. | Preparation of graphene-TiO2 photocatalysis materials by laser-induced hydrothermal method | |
| Suppuraj et al. | Novel Ag–TiO2/ZnFe2O4 nanocomposites for effective photocatalytic, electrocatalytic and cytotoxicity applications | |
| Teng et al. | Photocatalytic properties of titania/porous carbon fibers composites prepared by self-template method | |
| Chen et al. | Synthesis of halloysite nanotubes supported Bi-modified BaSnO3 photocatalysts for the enhanced degradation of methylene blue under visible light | |
| Xue et al. | BiOI/Carbon aerogel composite photoanode with enhanced adsorption and Solar-driven photoelectrocatalytic properties | |
| Rabin et al. | A procession on photocatalyst for solar fuel production and waste treatment | |
| Wang et al. | Modified sol-gel synthesis of carbon nanotubes supported titania composites with enhanced visible light induced photocatalytic activity | |
| Zhang et al. | Composite nanoarchitectonics with TiO2 nanocrystals and superior thin Ti3C2Tx nanosheets towards efficient NO removal | |
| Zhao et al. | Fabrication and photocatalytic performance of one-dimensional Ag3PO4 sensitized SrTiO3 nanowire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |