CN115254089A - Carbon nanotube-based-TiO2Composite nano material and preparation method and application thereof - Google Patents

Carbon nanotube-based-TiO2Composite nano material and preparation method and application thereof Download PDF

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CN115254089A
CN115254089A CN202210867127.8A CN202210867127A CN115254089A CN 115254089 A CN115254089 A CN 115254089A CN 202210867127 A CN202210867127 A CN 202210867127A CN 115254089 A CN115254089 A CN 115254089A
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tio
carbon nanotube
nano material
nano tube
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刘洪祥
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Hubei Zhanpeng Electronic Materials Co ltd
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a carbon nano tube based-TiO2The preparation method of the composite nano material comprises the following steps: firstly, modifying the carbon nano tube; (2) Dispersing modified carbon nano tubes in ethanol, ultrasonically dispersing uniformly, adding zinc acetate, tetrabutyl titanate and ethylenediamine into the uniformly dispersed modified carbon nano tube mixed solution, stirring and mixing uniformly, carrying out hydrothermal reaction on the mixed solution, and obtaining the product after the reaction is finishedCentrifuging, washing and drying the material to obtain the modified carbon nano tube/titanium dioxide/zinc oxide composite nano material; (3) Adding the modified carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial prepared in the step (2) into zirconia hydrosol for dipping, and then drying and roasting to obtain the carbon nanotube-TiO2A composite nanomaterial. The carbon nanotube-based TiO prepared by the invention2The composite nano material has high catalytic activity and good catalytic degradation effect on automobile exhaust.

Description

Carbon nanotube-based-TiO2Composite nano material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new nano materials, and particularly relates to a carbon nanotube-based-TiO2A composite nano material and a preparation method and application thereof.
Background
With industryThe rapid development of the automobile exhaust technology, the negative problem caused by environmental pollution also becomes the focus of people attention, and the automobile exhaust as a conventional environmental pollution source has a profound influence on the environment of human life. The harmful substances of the automobile exhaust are very complex, and comprise 150 to 200 different compounds, and the main harmful components are as follows: unburned or incompletely combusted CH, NOx, CO2, SO2、H2S and trace aldehyde, phenol, peroxide, organic acid and lead and phosphorus pollution formed by lead and phosphorus-containing gasoline. Among them, carbon monoxide, hydrocarbons, nitrogen oxides, lead compounds and particulate matters are the most harmful to humans. The sulfur dioxide in the tail gas has strong pungent smell, and the sulfur dioxide easily causes the generation of acid rain when reaching a certain concentration, so that soil and water sources are acidified, and the growth of crops and forests is influenced. Carbon monoxide is a product of incomplete combustion of fuel in an engine, and has a much stronger binding force with hemoglobin of a human body than with oxygen. Carbon monoxide impairs the ability of hemoglobin to deliver oxygen to human tissues, affecting the central nervous system and, in severe cases, leading to toxic death. Nitrogen oxides can cause respiratory distress, respiratory infections, asthma, etc. in humans, while simultaneously reducing lung function. Therefore, it is important to develop a method for treating several major harmful components in automobile exhaust.
Nano TiO 22The catalytic material has excellent chemical stability, wear resistance and acid and alkali resistance, and has a large storage capacity worldwide and abundant sources of nano titanium dioxide (TiO)2) Due to the advantages of excellent catalytic performance, high chemical stability, light corrosion resistance, no toxicity, low cost and the like, the catalyst is regarded as the most promising catalytic material and draws wide attention of people. But the industrialization of the titanium dioxide photocatalysis technology is limited to a certain extent due to the self limitation of the titanium dioxide. On one hand, the problem is that the light response range of the titanium dioxide is narrow and is only limited to an ultraviolet light region; on the other hand, the titanium dioxide photo-generated carriers have higher recombination probability and low photon yield, and the reaction activity of the catalyst is reduced. Thus, the titanium dioxide host material is modified or modified to obtainObtaining high-efficiency titanium dioxide composite materials becomes the main research direction. The invention takes the titanium dioxide material with high activity as the base, hopes to obtain the titanium dioxide composite nano material for treating the automobile exhaust with high efficiency through modification and modification, thereby providing a feasible scheme for solving the pollution of the automobile exhaust.
Disclosure of Invention
The invention aims to provide a carbon nanotube-based-TiO2The titanium dioxide composite nano material prepared by the invention has high catalytic activity and has good catalytic degradation effect on main components of CO and NO in automobile exhaust.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
carbon nano tube based-TiO2The preparation method of the composite nano material comprises the following steps:
(1) Modification of the carbon nanotubes: firstly, immersing a carbon nano tube into concentrated nitric acid, then adding concentrated phosphoric acid and potassium ferrate to carry out oxidation reaction, carrying out centrifugal separation after the reaction is finished, then adding a filter cake into a sodium dodecyl benzene sulfonate aqueous solution, dispersing the carbon nano tube in the solution by using ultrasonic crushing, reacting for 4-6h at 60-70 ℃ under the stirring condition, and carrying out centrifugation, washing and drying after the reaction is finished to obtain a modified carbon nano tube;
(2) Preparing a modified carbon nano tube/titanium dioxide/zinc oxide composite nano material: dispersing the modified carbon nano tube obtained in the step (1) in ethanol, ultrasonically dispersing uniformly, then adding zinc acetate, tetrabutyl titanate and ethylenediamine into the uniformly dispersed modified carbon nano tube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at 120-160 ℃ for 12-24h, centrifuging, washing and drying a product after the reaction is finished, thus obtaining the modified carbon nano tube/titanium dioxide/zinc oxide composite nano material;
(3) Carbon nanotube-based-TiO2Preparing a composite nano material: adding the modified carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial prepared in the step (2) into zirconia hydrosol for dipping, and then drying and roasting to obtain the carbon nanotube-TiO2A composite nanomaterial.
Preferably, the mass ratio of the carbon nano tube, the concentrated nitric acid, the concentrated phosphoric acid, the potassium ferrate and the sodium dodecyl benzene sulfonate in the step (1) is 1: (15-20): (0.1-0.3): (3-6): (0.01-0.05).
Preferably, the immersion temperature in the step (1) is 0 ℃, and the immersion time is 1-2h.
Preferably, the oxidation reaction temperature in the step (1) is-10-60 ℃, and the reaction time is 0.5-24h.
Preferably, the mass ratio of zinc acetate, tetrabutyl titanate and ethylenediamine in the step (2) is 1: (1-3): (1-2).
Preferably, the mass ratio of the carbon nanotubes to the zinc acetate in the step (2) is 1: (0.3-0.6).
Preferably, the preparation method of the zirconia hydrosol comprises the following steps: first, zrOCl is added2Dissolving the zirconium oxide hydrosol in a hydrochloric acid solution to prepare a zirconium salt solution, then dropwise adding ammonia water into the zirconium salt solution under continuous stirring until the pH value of the solution is 5-6, stopping dropwise adding, and then stirring to obtain the zirconium oxide hydrosol.
Preferably, the concentration of the zirconium salt solution is 6-12wt%.
Preferably, the stirring speed is 3500-5500r/min.
In addition, the invention also claims the carbon nano tube-based-TiO prepared by the preparation method2Composite nanomaterial and carbon nanotube-based TiO as described above2The application of the composite nano material in catalyzing and degrading automobile exhaust.
Compared with the prior art, the invention has the following beneficial effects and advantages:
(1) According to the invention, the carbon nano tube is modified, the surface of the carbon nano tube can be oxidized under the action of strong acid, and then the surfactant is added, so that on one hand, the adsorption capacity of the carbon nano tube is improved, on the other hand, the dispersity of the carbon nano tube is also improved, the agglomeration of the carbon nano tube is reduced, and the specific surface area of the whole carbon nano tube is larger;
(2) The carbon nanotube-based TiO of the invention2Composite nanomaterial by, on the one hand, reactingThe carbon nano tube is a carrier, can absorb harmful gases, provides a place for degrading pollutants, prevents titanium dioxide and zinc oxide from agglomerating in the preparation process, and can play a certain catalytic role in the catalytic reaction process;
(3) According to the invention, zinc oxide composite modification is carried out on titanium dioxide, and then the ternary composite oxide catalytic material is formed by loading on zirconium oxide, so that the composite probability of photo-generated electron hole pairs of titanium dioxide can be obviously inhibited, the catalytic effect of the composite material is improved, and the effect is excellent in photocatalytic degradation of automobile exhaust.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The carbon nano-tube used in the invention is a purchased single-wall carbon nano-tube with large specific surface area.
Example 1
A preparation method of a titanium dioxide composite nano material comprises the following steps:
(1) Modification of the carbon nanotubes: firstly, 10g of carbon nano tube is immersed in 200ml of concentrated nitric acid, immersed for 1h at 0 ℃, added with 1ml of concentrated phosphoric acid and 40g of potassium ferrate, reacted for 0.5h at-10 ℃, then centrifugally separated, and then added with a filter cake into an aqueous solution containing 0.1g of sodium dodecyl benzene sulfonate, the carbon nano tube is dispersed in the solution by ultrasonic crushing, reacted for 4h at 60 ℃ under the condition of stirring, and centrifuged, washed and dried after the reaction is finished, thus obtaining the modified carbon nano tube;
(2) Preparing a modified carbon nano tube/titanium dioxide/zinc oxide composite nano material: dispersing 10g of the modified carbon nanotube obtained in the step (1) in 150ml of ethanol, ultrasonically dispersing uniformly, then adding 4.6g of zinc acetate, 17g of tetrabutyl titanate and 1.5g of ethylenediamine into the uniformly dispersed modified carbon nanotube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at 120 ℃ for 18h, centrifuging, washing and drying the product after the reaction is finished to obtain the modified carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial;
(3) Carbon nanotube-based-TiO2Preparing a composite nano material: adding 4g of the modified carbon nanotube/titanium dioxide/zinc oxide composite nano material prepared in the step (2) into 20g of zirconium oxide hydrosol for soaking for 2h, then drying at 100 ℃, and roasting at 550 ℃ for 3h to obtain the carbon nanotube-TiO2A composite nanomaterial;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving the zirconium oxide hydrosol in 100mL of 0.05mol/L hydrochloric acid solution to prepare zirconium salt solution, then dropwise adding ammonia water into the zirconium salt solution at a stirring speed of 4000r/min until the pH value of the solution is 6, stopping dropwise adding, and then stirring to obtain the zirconium oxide hydrosol.
Example 2
Carbon nano tube based-TiO2The preparation method of the composite nano material comprises the following steps:
(1) Modification of carbon nanotubes: firstly, 10g of carbon nano tube is immersed in 200ml of concentrated nitric acid, the carbon nano tube is immersed for 1.5h at the temperature of 0 ℃, 1ml of concentrated phosphoric acid and 40g of potassium ferrate are added, the mixture reacts for 5h at the temperature of 10 ℃ and then is centrifugally separated, then a filter cake is added into an aqueous solution containing 0.02g of sodium dodecyl benzene sulfonate, the carbon nano tube is dispersed in the solution by ultrasonic crushing, the mixture reacts for 4.5h at the temperature of 65 ℃ under the stirring condition, and the modified carbon nano tube is obtained by centrifugation, washing and drying after the reaction is finished;
(2) Preparing a modified carbon nano tube/titanium dioxide/zinc oxide composite nano material: dispersing 10g of the modified carbon nanotube obtained in the step (1) in 150ml of ethanol, performing ultrasonic dispersion uniformly, adding 6.1g of zinc acetate, 22.6g of tetrabutyl titanate and 2g of ethylenediamine into the uniformly dispersed modified carbon nanotube mixed solution, stirring and mixing uniformly, performing hydrothermal reaction on the mixed solution at 130 ℃ for 12 hours, centrifuging, washing and drying a product after the reaction is finished to obtain the modified carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial;
(3) Carbon nanotube-based-TiO2Preparing a composite nano material: adding 4g of the modified carbon nanotube/titanium dioxide/zinc oxide composite nano material prepared in the step (2) into 24g of zirconium oxide hydrosol for soaking for 2 hours, then drying at 100 ℃, and roasting at 550 ℃ for 3 hours to obtain the carbon nanotube-TiO2A composite nanomaterial;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving in 100mL of 0.05mol/L hydrochloric acid solution to prepare zirconium salt solution, then dropwise adding ammonia water into the zirconium salt solution at the stirring speed of 4000r/min until the pH value of the solution is 6, stopping dropwise adding, and then stirring to obtain the zirconium oxide hydrosol.
Example 3
Carbon nanotube-based-TiO2The preparation method of the composite nano material comprises the following steps:
(1) Modification of carbon nanotubes: firstly, 10g of carbon nano tube is immersed in 200ml of concentrated nitric acid, the carbon nano tube is immersed for 1.5h at the temperature of 0 ℃, 1ml of concentrated phosphoric acid and 40g of potassium ferrate are added, the mixture reacts for 12h at the temperature of 30 ℃ and then is centrifugally separated, then a filter cake is added into 0.03g of aqueous solution of sodium dodecyl benzene sulfonate, the carbon nano tube is dispersed in the solution by ultrasonic crushing, the mixture reacts for 5h at the temperature of 65 ℃ under the stirring condition, and after the reaction is finished, the mixture is centrifuged, washed and dried, so that the modified carbon nano tube is obtained;
(2) Preparing a modified carbon nano tube/titanium dioxide/zinc oxide composite nano material: dispersing 10g of the modified carbon nanotube obtained in the step (1) in 150ml of ethanol, ultrasonically dispersing uniformly, then adding 7.6g of zinc acetate, 40g of tetrabutyl titanate and 2.5g of ethylenediamine into the uniformly dispersed modified carbon nanotube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at 150 ℃ for 20h, centrifuging, washing and drying the product after the reaction is finished, thus obtaining the modified carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial;
(3) Carbon nanotube-based-TiO2Preparing a composite nano material: the modified carbon nano tube/titanium dioxide/zinc oxide composite nano material prepared in the step (2)Adding 4g of the material into 16g of zirconium oxide hydrosol for soaking for 2h, then drying at 100 ℃ and roasting at 550 ℃ for 3h to obtain the carbon nanotube-TiO2A composite nanomaterial;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving in 100mL of 0.05mol/L hydrochloric acid solution to prepare zirconium salt solution, then dropwise adding ammonia water into the zirconium salt solution at the stirring speed of 4000r/min until the pH value of the solution is 6, stopping dropwise adding, and then stirring to obtain the zirconium oxide hydrosol.
Example 4
Carbon nano tube based-TiO2The preparation method of the composite nano material comprises the following steps:
(1) Modification of carbon nanotubes: firstly, 10g of carbon nano tube is immersed in 200ml of concentrated nitric acid, immersed for 2h at 0 ℃, added with 1ml of concentrated phosphoric acid and 40g of potassium ferrate, reacted for 24h at 60 ℃, centrifugally separated, then added with a filter cake in 0.05g of sodium dodecyl benzene sulfonate aqueous solution, ultrasonically crushed to disperse the carbon nano tube in the solution, reacted for 6h at 70 ℃ under the condition of stirring, centrifuged, washed and dried after the reaction is finished, thus obtaining the modified carbon nano tube;
(2) Preparing a modified carbon nano tube/titanium dioxide/zinc oxide composite nano material: dispersing 10g of the modified carbon nanotube obtained in the step (1) in 150ml of ethanol, ultrasonically dispersing uniformly, then adding 9.0g of zinc acetate, 44g of tetrabutyl titanate and 4.5g of ethylenediamine into the uniformly dispersed modified carbon nanotube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at 160 ℃ for 24 hours, centrifuging, washing and drying the product after the reaction is finished, thus obtaining the modified carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial;
(3) Carbon nanotube-based-TiO2Preparing a composite nano material: adding 4g of the modified carbon nanotube/titanium dioxide/zinc oxide composite nano material prepared in the step (2) into 28g of zirconium oxide hydrosol for soaking for 2 hours, then drying at 100 ℃, and roasting at 550 ℃ for 3 hours to obtain the carbon nanotube-TiO2A composite nanomaterial;
wherein, the preparation method of the zirconia hydrosolComprises the following steps: first, 8g ZrOCl was added2Dissolving in 100mL of 0.05mol/L hydrochloric acid solution to prepare zirconium salt solution, then dropwise adding ammonia water into the zirconium salt solution at the stirring speed of 4000r/min until the pH value of the solution is 6, stopping dropwise adding, and then stirring to obtain the zirconium oxide hydrosol.
Comparative example 1
Carbon nanotube-based-TiO2The preparation method of the composite nano material comprises the following specific steps: dispersing 10g of carbon nano tube (purchased single-walled carbon nano tube with large specific surface area) in 150ml of ethanol, ultrasonically dispersing uniformly, then adding 4.6g of zinc acetate, 17g of tetrabutyl titanate and 1.5g of ethylenediamine into the uniformly dispersed carbon nano tube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at 120 ℃ for 18h, centrifuging, washing and drying the product after the reaction is finished to obtain the carbon nano tube-TiO base2A composite nanomaterial.
Comparative example 2
Carbon nano tube based-TiO2The preparation method of the composite nano material comprises the following steps:
(1) Preparing a carbon nano tube/titanium dioxide composite nano material: firstly, dispersing 10g of carbon nanotubes (purchased single-walled carbon nanotubes with large specific surface area) in 150ml of ethanol, ultrasonically dispersing uniformly, then adding 17g of tetrabutyl titanate and 1.5g of ethylenediamine into the uniformly dispersed carbon nanotube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at 120 ℃ for 18h, and centrifuging, washing and drying the product after the reaction is finished to obtain the carbon nanotube/titanium dioxide composite nanomaterial;
(2) Carbon nanotube-based-TiO2Preparing a composite nano material: adding 4g of the carbon nanotube/titanium dioxide composite nano material prepared in the step (1) into 20g of zirconium oxide hydrosol for soaking for 2h, then drying at 100 ℃, and roasting at 550 ℃ for 3h to obtain the carbon nanotube-TiO2A composite nanomaterial;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving in 100mL of 0.05mol/L hydrochloric acid solution to prepare zirconium salt solution, and then stirring at 4000r/minAnd dropwise adding ammonia water into the zirconium salt solution until the pH value of the solution is 6, stopping dropwise adding, and then stirring to obtain the zirconium oxide hydrosol.
Comparative example 3
A preparation method of a carbon nanotube-based composite nano material comprises the following steps:
(1) Modification of the carbon nanotubes: firstly, 10g of carbon nano tube is immersed in 200ml of concentrated nitric acid, immersed for 1h at 0 ℃, added with 1ml of concentrated phosphoric acid and 40g of potassium ferrate, reacted for 0.5h at-10 ℃, then centrifugally separated, and then added with a filter cake into an aqueous solution containing 0.1g of sodium dodecyl benzene sulfonate, the carbon nano tube is dispersed in the solution by ultrasonic crushing, reacted for 4h at 60 ℃ under the condition of stirring, and centrifuged, washed and dried after the reaction is finished, thus obtaining the modified carbon nano tube;
(2) Preparing a modified carbon nano tube/zinc oxide composite nano material: dispersing 10g of the modified carbon nano tube obtained in the step (1) in 150ml of ethanol, performing ultrasonic dispersion uniformly, adding 4.6g of zinc acetate and 1.5g of ethylenediamine into the uniformly dispersed modified carbon nano tube mixed solution, stirring and mixing uniformly, performing hydrothermal reaction on the mixed solution at 120 ℃ for 18 hours, centrifuging, washing and drying a product after the reaction is finished to obtain the modified carbon nano tube/zinc oxide composite nano material;
(3) Preparing a carbon nanotube-based composite nano material: adding 4g of the modified carbon nanotube/zinc oxide composite nanomaterial prepared in the step (2) into 20g of zirconium oxide hydrosol for soaking for 2h, then drying at 100 ℃ and roasting at 550 ℃ for 3h to obtain the carbon nanotube-based composite nanomaterial;
the preparation method of the zirconium oxide hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving in 100mL of 0.05mol/L hydrochloric acid solution to prepare zirconium salt solution, then dropwise adding ammonia water into the zirconium salt solution at the stirring speed of 4000r/min until the pH value of the solution is 6, stopping dropwise adding, and then stirring to obtain the zirconium oxide hydrosol.
The composite nano-materials prepared in the examples 1 to 4 and the comparative examples 1 to 3 of the invention are evaluated in performance by the following specific method:
evaluation of continuous flow in self-controlThe reaction is carried out in a reaction device which is a quartz glass reactor (with the length of 40mm multiplied by the width of 20mm multiplied by the height of 1.5 mm), the prepared composite nano material is filled in the reaction device, the required temperature is provided for the reactor through a heating device controlled by a temperature programming and controlling instrument, in addition, a light filter (450 nm-760 nm) for exciting a semiconductor and a xenon lamp device are also arranged, and light emitted by the xenon lamp device can reach the composite nano material through the quartz glass reactor. Wherein the particle diameter of the composite nano material is about 100 meshes, the filling amount is 0.5g, the contents of CO and NO in the reaction gas are respectively fixed to be 0.25V percent and 0.25V percent, and N is2As balance make-up gas, the reaction temperature is controlled at 60 ℃ by a temperature controller, the total flow rate of the reaction gas is about 100mL/min, the reaction temperature is controlled by a gas flow controller, a visible light source adopts a 10W LED lamp strip, and the main light-emitting wavelength is 450-550nm. The gas at the gas outlet of the quartz glass reactor adopts AIDE-OW/AI300 to analyze CO, NO and CO in the atmosphere on line2The results of the reaction for 1 hour and 2 hours were used to calculate the CO conversion and the NO conversion. The specific results are shown in the following table:
Figure BDA0003759799970000111
as shown by the above results, the carbon nanotube-based TiO prepared in examples 1 to 4 of the present invention2After the composite nano material is catalyzed for 1 hour, the CO conversion rate and the NO conversion rate are up to 80 percent, the CO conversion rate after 2 hours is up to 97 percent optimally, the NO conversion rate is up to 94 percent optimally, and the effect is far better than that of the comparative examples 1-3.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (10)

1. Carbon nano tube based-TiO2The preparation method of the composite nano material is characterized by comprising the following steps:
(1) Modification of the carbon nanotubes: firstly, immersing a carbon nano tube into concentrated nitric acid, then adding concentrated phosphoric acid and potassium ferrate to carry out oxidation reaction, carrying out centrifugal separation after the reaction is finished, then adding a filter cake into a sodium dodecyl benzene sulfonate aqueous solution, dispersing the carbon nano tube in the solution by using ultrasonic crushing, reacting for 4-6h at 60-70 ℃ under the stirring condition, and carrying out centrifugation, washing and drying after the reaction is finished to obtain a modified carbon nano tube;
(2) Preparing a modified carbon nano tube/titanium dioxide/zinc oxide composite nano material: dispersing the modified carbon nano tube obtained in the step (1) in ethanol, ultrasonically dispersing uniformly, then adding zinc acetate, tetrabutyl titanate and ethylenediamine into the uniformly dispersed modified carbon nano tube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at 120-160 ℃ for 12-24h, centrifuging, washing and drying a product after the reaction is finished, thus obtaining the modified carbon nano tube/titanium dioxide/zinc oxide composite nano material;
(3) Carbon nanotube-based-TiO2Preparing a composite nano material: adding the modified carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial prepared in the step (2) into zirconia hydrosol for dipping, and then drying and roasting to obtain the carbon nanotube-TiO2A composite nanomaterial.
2. The carbon nanotube-based-TiO of claim 12The preparation method of the composite nano material is characterized in that the mass ratio of the carbon nano tube, the concentrated nitric acid, the concentrated phosphoric acid, the potassium ferrate and the sodium dodecyl benzene sulfonate in the step (1) is 1: (15-20): (0.1-0.3): (3-6): (0.01-0.05).
3. The carbon nanotube-based-TiO of claim 12The preparation method of the composite nano material is characterized in that the oxidation reaction temperature in the step (1) is-10-60 ℃, and the reaction time is 0.5-24h.
4. The carbon nanotube-based-TiO of claim 12The preparation method of the composite nano material is characterized in that the substances of zinc acetate, tetrabutyl titanate and ethylenediamine in the step (2)The amount ratio of (A) to (B) is 1: (1-3): (1-2).
5. The carbon nanotube-based-TiO of claim 12The preparation method of the composite nano material is characterized in that the mass ratio of the carbon nano tubes to the zinc acetate in the step (2) is 1: (0.3-0.6).
6. The carbon nanotube-based-TiO of claim 12The preparation method of the composite nano material is characterized by comprising the following steps: first, zrOCl is added2Dissolving the zirconium oxide hydrosol in a hydrochloric acid solution to prepare a zirconium salt solution, then dropwise adding ammonia water into the zirconium salt solution under continuous stirring until the pH value of the solution is 5-6, stopping dropwise adding, and then stirring to obtain the zirconium oxide hydrosol.
7. The carbon nanotube-based-TiO of claim 62The preparation method of the composite nano material is characterized in that the concentration of the zirconium salt solution is 6-12wt%.
8. The carbon nanotube-based-TiO of claim 62The preparation method of the composite nano material is characterized in that the stirring speed is 3500-5500r/min.
9. A carbon nanotube-based-TiO produced by the production method according to any one of claims 1 to 82A composite nanomaterial.
10. A carbon nanotube-based-TiO as described in any one of claims 1 to 82The application of the composite nano material in catalyzing and degrading automobile exhaust.
CN202210867127.8A 2022-07-21 2022-07-21 Carbon nanotube-based-TiO2Composite nano material and preparation method and application thereof Pending CN115254089A (en)

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