CN113797911A - Titanium dioxide composite nano material and preparation method and application thereof - Google Patents
Titanium dioxide composite nano material and preparation method and application thereof Download PDFInfo
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- CN113797911A CN113797911A CN202111116478.7A CN202111116478A CN113797911A CN 113797911 A CN113797911 A CN 113797911A CN 202111116478 A CN202111116478 A CN 202111116478A CN 113797911 A CN113797911 A CN 113797911A
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- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 68
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 68
- 229940055360 titanium dioxide / zinc oxide Drugs 0.000 claims abstract description 34
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004246 zinc acetate Substances 0.000 claims abstract description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 3
- 238000006731 degradation reaction Methods 0.000 claims abstract description 3
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 34
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 34
- 150000003754 zirconium Chemical class 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000002109 single walled nanotube Substances 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 102000001554 Hemoglobins Human genes 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010038687 Respiratory distress Diseases 0.000 description 1
- 206010057190 Respiratory tract infections Diseases 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000004199 lung function Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- 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
- B01D53/92—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
-
- 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
- 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
-
- B01J35/23—
-
- B01J35/39—
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of a titanium dioxide composite nano material, which comprises the following steps: (1) firstly, dispersing carbon nano tubes in ethanol, ultrasonically dispersing uniformly, then adding zinc acetate, tetrabutyl titanate and ethylenediamine into the uniformly dispersed carbon nano tube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution, and centrifuging, washing and drying a product after the reaction is finished to obtain the carbon nano tube/titanium dioxide/zinc oxide composite nano material; (2) and (2) adding the carbon nano tube/titanium dioxide/zinc oxide composite nano material prepared in the step (1) into zirconia hydrosol for dipping, and then drying and roasting to obtain the carbon nano tube/titanium dioxide/zinc oxide/zirconia composite nano material. The titanium dioxide composite nano material prepared by the invention has high catalytic activity and good catalytic degradation effect on automobile exhaust.
Description
Technical Field
The invention belongs to the technical field of new nano materials, and particularly relates to a titanium dioxide composite nano material as well as a preparation method and application thereof.
Background
With the rapid development of industry, the negative problems caused by environmental pollution also become the focus of attention, and 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, contain 150-200 different compounds, and are mainly harmfulThe 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, causing 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 considered to be 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. Therefore, it is a main direction of research to modify or modify a titania host material to obtain a high-efficiency titania composite material. 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 titanium dioxide composite nano material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a titanium dioxide composite nano material comprises the following steps:
(1) preparing a carbon nano tube/titanium dioxide/zinc oxide composite nano material: firstly, dispersing carbon nano tubes in ethanol, ultrasonically dispersing uniformly, then adding zinc acetate, tetrabutyl titanate and ethylenediamine into the uniformly dispersed carbon nano tube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at the temperature of 120-160 ℃ for 12-24h, and centrifuging, washing and drying the product after the reaction is finished to obtain the carbon nano tube/titanium dioxide/zinc oxide composite nano material;
(2) preparing a carbon nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material: and (2) adding the carbon nano tube/titanium dioxide/zinc oxide composite nano material prepared in the step (1) into zirconia hydrosol for dipping, and then drying and roasting to obtain the carbon nano tube/titanium dioxide/zinc oxide/zirconia composite nano material.
Preferably, the mass ratio of zinc acetate, tetrabutyl titanate and ethylenediamine in step (1) is 1: (1-3): (1-2).
Preferably, the mass ratio of the carbon nanotubes to the zinc acetate in the step (1) 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 6-12 wt%.
Preferably, the stirring rate is 3500-5500 r/min.
In addition, the invention also claims the titanium dioxide composite nano material prepared by the preparation method and the application of the titanium dioxide composite nano material in the catalytic degradation of automobile exhaust.
Compared with the prior art, the invention has the following beneficial effects and advantages:
(1) on one hand, the titanium dioxide composite nanomaterial can adsorb harmful gas by taking the carbon nano tube as a carrier, provides a place for degrading pollutants, prevents titanium dioxide and zinc oxide from agglomerating in the preparation process, and on the other hand, the carbon nano tube can play a certain catalytic role in the catalytic reaction process;
(2) 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.
Example 1
A preparation method of a titanium dioxide composite nano material comprises the following steps:
(1) preparing a carbon nano tube/titanium dioxide/zinc oxide 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 4.6g of zinc acetate, 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, centrifuging, washing and drying the product after the reaction is finished to obtain the carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial;
(2) preparing a carbon nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material: adding 4g of the carbon nano tube/titanium dioxide/zinc oxide composite nano material prepared in the step (1) into 20g of zirconium oxide hydrosol for soaking for 2 hours, then drying at 100 ℃ and roasting at 550 ℃ for 3 hours to obtain the carbon nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving the zirconium oxide into 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 2
A preparation method of a titanium dioxide composite nano material comprises the following steps:
(1) preparing a carbon nano tube/titanium dioxide/zinc oxide 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 4.6g of zinc acetate, 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, centrifuging, washing and drying the product after the reaction is finished to obtain the carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial;
(2) preparing a carbon nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material: adding 4g of the carbon nano tube/titanium dioxide/zinc oxide composite nano material prepared in the step (1) 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 nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material;
the preparation method of the zirconia hydrosol comprises the following steps: first of all, the first step is to,8g of ZrOCl2Dissolving the zirconium oxide into 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
A preparation method of a titanium dioxide composite nano material comprises the following steps:
(1) preparing a carbon nano tube/titanium dioxide/zinc oxide 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 4.6g of zinc acetate, 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, centrifuging, washing and drying the product after the reaction is finished to obtain the carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial;
(2) preparing a carbon nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material: adding 4g of the carbon nano tube/titanium dioxide/zinc oxide composite nano material prepared in the step (1) into 16g of zirconium oxide hydrosol for soaking for 2 hours, then drying at 100 ℃ and roasting at 550 ℃ for 3 hours to obtain the carbon nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving the zirconium oxide into 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
A preparation method of a titanium dioxide composite nano material comprises the following steps:
(1) preparing a carbon nano tube/titanium dioxide/zinc oxide 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 4.6g of zinc acetate, 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, centrifuging, washing and drying the product after the reaction is finished to obtain the carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial;
(2) preparing a carbon nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material: adding 4g of the carbon nano tube/titanium dioxide/zinc oxide composite nano material prepared in the step (1) 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 nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving the zirconium oxide into 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
A preparation method of a titanium dioxide composite nano material comprises the following specific steps: dispersing 10g of carbon nanotubes (purchased single-walled carbon nanotubes 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 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, thus obtaining the carbon nanotube/titanium dioxide/zinc oxide composite nanomaterial.
Comparative example 2
A preparation method of a titanium dioxide 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) preparing a carbon nano tube/titanium dioxide/zirconium oxide composite nano material: adding 4g of the carbon nano tube/titanium dioxide composite nano material prepared in the step (1) into 20g of zirconia hydrosol for soaking for 2h, then drying at 100 ℃, and roasting at 550 ℃ for 3h to obtain the carbon nano tube/titanium dioxide/zirconia composite nano material;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving the zirconium oxide into 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 3
A preparation method of a composite nano material comprises the following steps:
(1) preparing a carbon nano tube/zinc oxide 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 4.6g of zinc acetate 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/zinc oxide composite nanomaterial;
(2) preparing a carbon nano tube/zinc oxide/zirconium oxide composite nano material: adding 4g of the carbon nano tube/zinc oxide 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 nano tube/zinc oxide/zirconium oxide composite nano material;
the preparation method of the zirconia hydrosol comprises the following steps: first, 8g ZrOCl was added2Dissolving the zirconium salt into 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, and stopping dropwise addingAnd then stirring to obtain the zirconia 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:
the evaluation was carried out in a self-made continuous flow reactor, which was a quartz glass reactor (40 mm long by 20mm wide by 1.5mm high), in which the prepared composite nanomaterial was packed, and the reactor was supplied with a desired temperature by a heating device controlled by a temperature programmed controller, and further, a semiconductor-exciting optical filter (450nm-760nm) and a xenon lamp device were provided, and light emitted from the xenon lamp device was allowed to pass through the quartz glass reactor to the composite nanomaterial. Wherein the particle diameter of the composite nano material is about 100 meshes, the loading 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 supplementary 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 450-550 nm. 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:
the results in the table show that the titanium dioxide composite nanomaterial prepared in the embodiments 1-4 of the invention has the CO conversion rate and the NO conversion rate of more than 70% after being catalyzed for 1 hour, and the CO conversion rate reaches 96% and the NO conversion rate reaches 93% after 2 hours, which is far better than the effects 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 (8)
1. The preparation method of the titanium dioxide composite nano material is characterized by comprising the following steps:
(1) preparing a carbon nano tube/titanium dioxide/zinc oxide composite nano material: firstly, dispersing carbon nano tubes in ethanol, ultrasonically dispersing uniformly, then adding zinc acetate, tetrabutyl titanate and ethylenediamine into the uniformly dispersed carbon nano tube mixed solution, stirring and mixing uniformly, then carrying out hydrothermal reaction on the mixed solution at the temperature of 120-160 ℃ for 12-24h, and centrifuging, washing and drying the product after the reaction is finished to obtain the carbon nano tube/titanium dioxide/zinc oxide composite nano material;
(2) preparing a carbon nano tube/titanium dioxide/zinc oxide/zirconium oxide composite nano material: and (2) adding the carbon nano tube/titanium dioxide/zinc oxide composite nano material prepared in the step (1) into zirconia hydrosol for dipping, and then drying and roasting to obtain the carbon nano tube/titanium dioxide/zinc oxide/zirconia composite nano material.
2. The method for preparing composite nanomaterial according to claim 1, wherein the mass ratio of zinc acetate, tetrabutyl titanate and ethylenediamine in step (1) is 1: (1-3): (1-2).
3. The method for preparing the composite nano material according to claim 1, wherein the mass ratio of the carbon nano tubes to the zinc acetate in the step (1) is 1: (0.3-0.6).
4. The method for preparing the composite nano material according to the claim 1, wherein the method for preparing the zirconium oxide 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.
5. The method for preparing composite nanomaterial according to claim 1, wherein the concentration of the zirconium salt solution is 6-12 wt%.
6. The method for preparing the composite nanomaterial according to claim 4, wherein the stirring rate is 3500-5500 r/min.
7. A titanium dioxide composite nanomaterial produced by the production method according to any one of claims 1 to 6.
8. Use of the titanium dioxide composite nanomaterial of claim 7 in catalytic degradation of automobile exhaust.
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