CN111686776A - Titanium dioxide-shell powder composite material and preparation method and application thereof - Google Patents
Titanium dioxide-shell powder composite material and preparation method and application thereof Download PDFInfo
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- CN111686776A CN111686776A CN202010559973.4A CN202010559973A CN111686776A CN 111686776 A CN111686776 A CN 111686776A CN 202010559973 A CN202010559973 A CN 202010559973A CN 111686776 A CN111686776 A CN 111686776A
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- 239000000843 powder Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 239000010936 titanium Substances 0.000 title claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000009987 spinning Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 18
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000010041 electrostatic spinning Methods 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 25
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 39
- 238000010521 absorption reaction Methods 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 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 11
- 229940043267 rhodamine b Drugs 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000004887 air purification Methods 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000005034 decoration Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000003905 indoor air pollution Methods 0.000 description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J23/74—Iron group metals
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention discloses a titanium dioxide-shell powder composite material and a preparation method thereof, comprising TiO2And shell powder, said TiO2And shell powder in a mass ratio of 1: 0.5-2, the composite material has excellent photocatalytic performance, and the shell powder is used as a carrier of titanium dioxide and plays a role in inhibiting nano TiO2By agglomeration and with TiO2The photocatalysis nano material is compounded into two tubes, and can adsorb and decompose pollutants. Meanwhile, a new way is provided for the development and utilization of waste shell resources, the material has remarkable social, economic and environmental benefits, and is suitable for the field of coatings.
Description
Technical Field
The invention belongs to the technical field of chemical materials, relates to a composite material for coating and a preparation method thereof, and particularly relates to a titanium dioxide-shell powder composite material and a preparation method and application thereof.
Background
As the modern spends 80% -90% of the day indoors, indoor air pollution is harmful to human bodies greatly. In order to reduce indoor air pollution caused by decoration, China has strictly limited the content of harmful substances in various decorations since 2001. Over the past decade, the quality of indoor air in people's lives has improved greatly, but many households are still plagued by indoor air pollution due to the accumulation of pollutants in various materials and the improper selection of individual materials.
In recent years, research on indoor air purification has been actively conducted. At present, a plurality of indoor air purification products, such as active carbon, air purifier, various air treatment agents and functionalityWallpaper, diatom ooze, etc. Among a plurality of air purification products, the interior wall coating has the advantages of low cost, large indoor coating area and no secondary pollution as the most widely applied interior wall decoration product at present, so that the interior wall coating has great potential in air purification and is generally favored by consumers. TiO was discovered by Fujishima et al, Japan scientist since 19722Can decompose water into hydrogen and oxygen under the action of ultraviolet light, and is developed for decades by using nano TiO2The semiconductor photocatalytic material and the photocatalytic technology thereof have achieved great research results. TiO 22Is an important inorganic chemical raw material, has a plurality of excellent characteristics of no toxicity, no harm, strong tinting strength, high covering power, good weather resistance and the like, is widely applied in various fields of the coating industry, and particularly has great development in the directions of organic pollutant degradation, sewage treatment, air purification and the like. TiO 22As an environment-friendly material, TiO is added with the enhancement of environmental consciousness of people2TiO with integrated pigment performance and photocatalysis characteristic2Photocatalytic coatings are also receiving increasing attention from the industry.
But nano TiO2The use in coatings faces several important problems: (1) ordinary nano TiO2The photocatalyst has excellent photocatalytic performance under ultraviolet light, has no obvious effect under visible light, and has extremely weak ultraviolet light intensity in common indoor environment, so that the photocatalyst needs to be applied to nano TiO2And (5) carrying out modification treatment. (2) In TiO2In the process of adding the nano material into the coating, agglomeration and cladding phenomena of nano ions inevitably exist, so that the photocatalysis effect of the photocatalyst is ineffective. (3) TiO 22When organic matters with low concentration are degraded, the adsorption capacity to the organic matters is poor, so that the collision probability with organic matter molecules in the photocatalytic reaction process is reduced, and the photocatalytic degradation efficiency is low.
Disclosure of Invention
Therefore, the present invention is to solve the above technical problems, and to provide a method for improving TiO content2Titanium dioxide-shell powder composite material with excellent visible light absorption and photocatalytic performanceAnd a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a titanium dioxide-shell powder composite material which comprises TiO2And shell powder, said TiO2And shell powder in a mass ratio of 1: 0.5-2.
Further, the composite material also comprises metal ions, and the metal ions are Fe3+Or Cu2+In the composite material, the Fe3+Or Cu2+The molar concentration of (A) is 0.1-0.5%.
In another aspect, the present invention provides a method for preparing the composite material, which comprises the following steps:
s1, uniformly mixing the butyl titanate and the solvent according to TiO2And shell powder in a mass ratio of 1: 0.5-2, adding shell powder, and uniformly stirring to obtain a premix;
s2, adding a high-molecular template agent into the premix, and uniformly stirring to obtain a spinning solution;
s3, carrying out electrostatic spinning operation on the spinning solution to obtain a spinning material;
and S4, calcining the spinning material to obtain the titanium dioxide-shell powder composite material.
Further, the step S1 includes a step of adding iron nitrate or copper nitrate to the mixture of butyl titanate and the solvent at a molar concentration of 0.1 to 0.5%.
Further, in step S3, the processing parameters in the electrospinning process are: the voltage is 10KV, the distance between the spinning nozzle and the collector is 18-20cm, the ambient temperature is 20-24 ℃, and the relative humidity is 30-40%.
Further, in step S4, the calcination process is: placing the spinning material in a high-temperature program temperature control box type furnace at 1 ℃ for min-1The temperature is raised to 500 ℃ at the speed, and the heat is preserved for 3 hours, thus obtaining the titanium dioxide-shell powder composite material.
Further, the solvent is ethanol, and the polymer template agent is polyvinylpyrrolidone.
Further, in the step S1, after adding shell powder, stirring for 20min, and performing ultrasonic dispersion for 30min to obtain a premix.
Further, in step S2, a polymer template is added and stirred for 12 hours to obtain a spinning solution.
The invention also provides an application of the composite material in coating.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the titanium dioxide-shell powder composite material comprises TiO2And shell powder, said TiO2And shell powder in a mass ratio of 1: 0.5-2, the composite material has excellent photocatalytic performance, and the shell powder is used as a carrier of titanium dioxide and plays a role in inhibiting nano TiO2By agglomeration and with TiO2The photocatalysis nano material is compounded into two tubes, and can adsorb and decompose pollutants. Meanwhile, a new way is provided for the development and utilization of waste shell resources, and the method has remarkable social, economic and environmental benefits.
(2) The titanium dioxide-shell powder composite material also comprises metal ions, wherein the metal ions are Fe3+Or Cu2+The composite material doped with metal ions further improves the photocatalytic performance of the composite material, and the composite material modifies the interior wall coating to obtain a novel metal ion doped TiO with low cost, which integrates multiple functions of physical formaldehyde adsorption, photocatalytic formaldehyde decomposition, antibiosis and the like into a whole2Shell powder composite coating.
(3) The preparation method adopts an electrostatic spinning technology, which utilizes a high-voltage electric field to charge the surface of a spinning solution, and the spinning solution is sprayed out from a nozzle under the induction of the electric field and then is stretched to form the nano-fiber. The electrostatic spinning technology has simple equipment operation and low price, and is an ideal method for preparing inorganic substance/polymer composite nano materials and pure inorganic substance nano materials, and the industrial production is easy to realize.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is an XRD pattern of a composite material according to example 1 of the present invention;
FIG. 2 is an infrared spectrum of a composite material according to example 1 of the present invention;
FIG. 3 is a photocatalytic absorption curve of the composite material according to example 1 of the present invention;
FIG. 4 is a graph comparing the degradation rate of the composite material of example 1 of the present invention to rhodamine B;
FIG. 5 shows TiO described in example 2 of the present invention2:x％Fe3+XRD pattern of the shell powder composite material;
FIG. 6 shows TiO described in example 2 of the present invention2:x％Cu2+XRD pattern of the shell powder composite material;
FIG. 7 shows TiO described in example 2 of the present invention2:x％Fe3+An infrared spectrogram of the shell powder composite material;
FIG. 8 shows TiO described in example 2 of the present invention2:x％Cu2+An infrared spectrogram of the shell powder composite material;
FIG. 9 shows TiO described in example 2 of the present invention2:x％Fe3+An absorption curve of the shell powder composite material under photocatalysis;
FIG. 10 shows TiO described in example 2 of the present invention2:x％Fe3+A shell powder composite material is used for comparing the degradation rate of rhodamine B;
FIG. 11 shows TiO described in example 2 of the present invention2:x％Cu2+An absorption curve of the shell powder composite material under photocatalysis;
FIG. 12 shows TiO described in example 2 of the present invention2:x％Cu2+And a comparison graph of the degradation rate of the shell powder composite material on rhodamine B.
Detailed Description
Example 1
The embodiment provides a titanium dioxide-shell powder composite material which comprises TiO2And shell powder, said TiO2The mass ratio of the shell powder to the shell powder is1：0.5-2。
The composite material described in this example was prepared by the following method:
s1, weighing a proper amount of butyl titanate, dissolving the butyl titanate in an ethanol solvent, placing the solution on a magnetic stirrer, stirring the solution until the solution is clear and transparent, and mixing the solution according to a mass ratio (in the embodiment, TiO)2The mass ratio of the shell powder to the shell powder is respectively as follows: 1:0.5, 1:1 and 1:2) adding shell powder, stirring for 20min, and performing ultrasonic dispersion for 30min to obtain a premix.
And S2, slowly adding a proper amount of high molecular template agent polyvinylpyrrolidone (PVP) into the premix, stirring for 12 hours, and standing to obtain milky spinning solution suitable for electrostatic spinning.
S3, carrying out electrostatic spinning operation on the spinning solution: and adding the spinning solution into a spinning device, connecting an aluminum electrode with the positive electrode of a power supply, and connecting the negative electrode of the power supply with a collector (an iron wire net). Adjusting spinning voltage to 10kV, solidifying distance between a spinning nozzle and a collector to 18-20cm, ambient temperature to 20-24 ℃, and relative humidity to 30-40% to obtain a spinning material; in the present embodiment, the distance is preferably 20cm, the ambient temperature is preferably 22 ℃, and the relative humidity is preferably 35%.
S4, calcining the spinning material to obtain a titanium dioxide-shell powder composite material: (ii) Ti (OC) collected on a wire mesh4H9)4+ shell powder]the/PVP composite material (spinning material) is placed in a high-temperature program temperature control box type furnace at 1 ℃ for min-1Heating to 500 ℃ at the rate of (1), and keeping the temperature for 3 hours to obtain TiO2Shell powder composite material.
Example 2
The embodiment provides a titanium dioxide-shell powder composite material which comprises TiO2And shell powder, said TiO2And shell powder in a mass ratio of 1: 0.5-2, in this example, TiO2The mass ratio of the shell powder to the shell powder is respectively as follows: 1:0.5, 1:1 and 1: 2. The composite material also comprises metal ions, and the metal ions are Fe3+Or Cu2+In the composite material, the Fe3+Or Cu2+In the present example, the molar concentration of Fe is 0.1-0.5%3+Or Cu2+The molar concentration of (b) may be 0.1%, 0.3%, 0.5%.
The composite material described in this example was prepared by the following method:
s1, weighing appropriate amount of butyl titanate, dissolving in ethanol solvent (DMF or water can be used as solvent in alternative embodiment), stirring with magnetic stirrer to obtain clear solution4+:Fe3+Or Cu2+)＝99.9:0.1，99.7:0.3，99.5:0.5]An appropriate amount of ferric nitrate or cupric nitrate was weighed and dissolved in the above solution at a mass ratio (in this example, TiO)2The mass ratio of the shell powder to the shell powder is as follows: 1:1) adding shell powder, stirring for 20min, and performing ultrasonic dispersion for 30min to obtain a premix.
And S2, slowly adding a proper amount of high molecular template agent polyvinylpyrrolidone (PVP) into the premix, stirring for 12 hours, and standing to obtain milky spinning solution suitable for electrostatic spinning.
S3, carrying out electrostatic spinning operation on the spinning solution: and adding the spinning solution into a spinning device, connecting an aluminum electrode with the positive electrode of a power supply, and connecting the negative electrode of the power supply with a collector (an iron wire net). Adjusting spinning voltage to 10kV, solidifying distance between a spinning nozzle and a collector to 18-20cm, ambient temperature to 20-24 ℃, and relative humidity to 30-40% to obtain a spinning material; in the present embodiment, the distance is preferably 20cm, the ambient temperature is preferably 22 ℃, and the relative humidity is preferably 35%.
S4, calcining the spinning material to obtain a titanium dioxide-shell powder composite material: (ii) Ti (OC) collected on a wire mesh4H9)4+Fe(NO3)3+ shell powder]/PVP composite material or [ Ti (OC)4H9)4+Cu(NO3)2+ shell powder]the/PVP composite material (spinning material) is placed in a high-temperature program temperature control box type furnace at 1 ℃ for min-1Heating to 500 ℃ at the rate of (1), and keeping the temperature for 3 hours to obtain TiO2:Fe3+Shell powder composite material or TiO2:Cu2+Shell powder composite material.
Examples of the experiments
1. X-ray diffraction (XRD) analysis of the composite material described in example 1
FIG. 1 shows TiO in example 12Shell powder [ m (TiO)2) M (shell powder) 1:0.5, 1:1 and 1:2]XRD spectrum of the composite material. As can be seen from the figure, CaCO3The strongest peak (111) occurs at 2 ═ 28.588 °, the second strongest peak occurs at 47.555 ° (220), while the distinct cacos also occur at 33.129 ° (200), 56.429 ° (311), 59.181 ° (222), 76.829 ° (331), 79.210 ° (420), 88.586 ° (422)3Characteristic diffraction peak, with CaCO3(PDF #47-1743, cubic, space group Fm-3m) substantially congruent and TiO2Four main diffraction peaks (101), (004), (200) and (211) of (1), (004), and (211), and the d value and relative intensity and TiO2The PDF cards (21-1272) are matched with the value listed and belong to anatase type TiO2The crystal is tetragonal system, and the space group is I41/amd. Shows that the shell powder is loaded with TiO2And TiO 22The crystal structure of the shell powder is not changed when the shell powder is loaded on the surface of the shell powder. As can be seen from the figure, all three samples had significant TiO2And CaCO3Characteristic diffraction peak, peak shape is not changed, only TiO2And CaCO3There is a difference in the intensity of the characteristic diffraction peaks, which may be TiO in the sample2Different mass ratio with shell powder. XRD analysis showed that pure phase TiO has been prepared2Shell powder composite material.
2. Infrared spectroscopic analysis of the composite material of example 1
FIG. 2 is TiO2Shell powder [ m (TiO)2) M (shell powder) 1:1]Infrared spectrum of the composite material. As can be seen from the figure, 3451cm-1，2986cm-1，2828cm-1And 1000cm-1The absorption peak is caused by vibration of organic matter containing C-H and-OH and is 2369cm-1、1617cm-1、1384cm-1、870cm-1、781cm-1Is treated with CO3 2-Wherein 1617cm, of-1And 1384cm-1Is CO3 2-Has an antisymmetric telescopic vibration absorption peak of 870cm-1Is out-of-plane bend absorption peak, 781cm-1The in-plane bend absorption peak. Thus, in the composite materialShell powder containing calcite crystal form. 562cm-1In the presence of TiO2Characteristic absorption peak of (A), indicating that the composite material contains TiO2. Combined XRD analysis showed that TiO had been prepared2Shell powder composite material.
3. Photocatalytic Performance testing of the composite material described in example 1
The photocatalytic degradation reaction is carried out under the irradiation of a 400W metal halide lamp. The suspension comprised 0.03g TiO2Shell powder composite material and organic dye solution. The suspension was stirred in the dark for 30min, and the organic dye and the catalyst surface reached equilibrium of adsorption-desorption. FIG. 3 shows rhodamine B solution in TiO2Shell powder [ m (TiO)2) M (shell powder) 1:1]As can be seen from FIG. 3, the absorption curve of the composite material under photocatalysis shows that the maximum absorption peak of the rhodamine B solution is gradually reduced and the degradation rate is gradually increased along with the extension of the ultraviolet irradiation time under the catalysis. When the illumination time is 100min, TiO2Shell powder [ m (TiO)2) M (shell powder) 1:1]The degradation rate of the composite material to rhodamine B is 84.5 percent. FIG. 4 is TiO2Shell powder [ m (TiO)2) M (shell powder) 1:0.5, 1:1 and 1:2]According to a comparison graph of the degradation rates of the composite material rhodamine B, the degradation rates of three samples on the rhodamine B are 63.5%, 85% and 73.5%, respectively. It can be seen that TiO2Shell powder [ m (TiO)2) M (shell powder) 1:1]The composite material has optimal photocatalytic efficiency. The composite material is described as being useful in coatings, particularly interior wall coatings. In order to ensure the photocatalytic performance and antibacterial performance of the coating, TiO with good photocatalytic performance is selected2Shell powder [ m (TiO)2) M (shell powder) 1:1]Composite material as metal ion doped TiO2A substrate of shell powder composite material.
4. X-ray diffraction (XRD) analysis of the composite material described in example 2
FIG. 5 is TiO2:x％Fe3+Shell powder (x ═ 0.1, 0.3, and 0.5) composites, fig. 6 for TiO2:x％Cu2+XRD pattern of/shell powder (x ═ 0.1, 0.3 and 0.5) composite. As can be seen from the figure, the d value and the relative intensity of the diffraction peak are respectively equal to those of CaCO3Standard of (2)Card (PDF #47-1743, cubic system, space group Fm-3m) and anatase TiO2The standard card (PDF #21-1272, tetragonal system, space group I41/amd) is consistent, which shows that the shell powder is loaded with TiO2And TiO 22The surface loaded to the shell powder does not change the crystal structure of the shell powder and is accompanied by Fe3+And Cu2+The doping concentration is increased, and other diffraction peaks do not appear, which indicates that Fe3+And Cu2+Has been successfully doped into TiO2Among the crystal lattices. XRD analysis shows that pure phase metal ion doped TiO has been prepared2Shell powder composite material.
5. Infrared spectroscopic analysis of the composite material of example 2
FIG. 7 and FIG. 8 are TiO, respectively2:0.3％Fe3+Shell powder composite material and TiO2:0.3％Cu2+An infrared spectrogram of the shell powder composite material. As can be seen from the figure, 3438cm-1(3458cm-1)，2989cm-1(2986cm-1)，2831cm-1(2830cm-1) And 1003cm-1(1006cm-1) The absorption peak is caused by vibration of organic matter containing C-H and-OH and is at 2364cm-1(2347cm-1)、1615cm-1(1602cm-1)、1398cm-1(1396cm-1)、871cm-1、771cm-1(779cm-1) Is treated with CO3 2-Wherein 1615cm, of-1(1602cm-1) And 1398cm-1(1396cm-1) Is CO3 2-Has an antisymmetric telescopic vibration absorption peak of 871cm-1The absorption peak of out-of-plane bending is 771cm-1(779cm-1) The in-plane bend absorption peak. Therefore, the composite material contains the shell powder with calcite crystal form. 554cm-1(523cm-1) In the presence of TiO2Characteristic absorption peak of (A), indicating that the composite material contains TiO2. Combined XRD analysis showed that metal ion doped TiO had been prepared2Shell powder composite material.
6. Photocatalytic Performance testing of the composite material described in example 2
The photocatalytic degradation reaction is carried out under the irradiation of a 400W metal halide lamp. The suspension comprised 0.03g TiO2:Fe3+Shell powder composite material and TiO2:Cu2+Shell powder composite material and organic dye solution. The suspension was stirred in the dark for 30min, and the organic dye and the catalyst surface reached equilibrium of adsorption-desorption. FIGS. 9 to 12 show TiO, respectively2:x％Fe3+Shell powder (x ═ 0.1, 0.3, and 0.5) composite material and TiO2:x％Cu2+The degradation absorption curve and degradation rate of the composite material (x ═ 0.1, 0.3 and 0.5) for RB are compared with the change of illumination time. As can be seen from FIGS. 9 and 11, the maximum absorption peak of the rhodamine B solution is gradually reduced and the degradation rate is gradually increased with the extension of the ultraviolet light irradiation time under the catalysis. When the illumination time is 100min, TiO2:x％Fe3+The degradation rate of the/shell powder (x ═ 0.1, 0.3 and 0.5) composite material to rhodamine B is 85.48%, 88.57% and 86.97%, respectively. TiO 22:x％Cu2+The degradation rate of the/shell powder (x ═ 0.1, 0.3 and 0.5) composite material to rhodamine B is 88.2%, 91.05% and 68.7%, respectively. As shown in FIGS. 10 and 12, when Fe3+And Cu2+When the doping concentration is 0.3 percent, the two composite materials have the best photocatalytic performance, and TiO2The photocatalytic efficiency of the shell powder composite material is higher than that of TiO2:Fe3+Shell powder composite material. In order to ensure the photocatalytic performance and antibacterial performance of the coating, TiO with good photocatalytic performance is selected2:0.3％Fe3+Shell powder composite material and TiO2:0.3％Cu2+Method for preparing metal ion doped TiO by shell powder composite material2/Shell powder composite coating.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The titanium dioxide-shell powder composite material is characterized by comprising TiO2And shell powder, said TiO2And shell powder in a mass ratio of 1: 0.5-2.
2. The composite material of claim 1, further comprising a metal ion, wherein the metal ion is Fe3+Or Cu2+In the composite material, the Fe3+Or Cu2+The molar concentration of (A) is 0.1-0.5%.
3. A method of preparing a composite material according to claim 1 or 2, comprising the steps of:
s1, uniformly mixing the butyl titanate and the solvent according to TiO2And shell powder in a mass ratio of 1: 0.5-2, adding shell powder, and uniformly stirring to obtain a premix;
s2, adding a high-molecular template agent into the premix, and uniformly stirring to obtain a spinning solution;
s3, carrying out electrostatic spinning operation on the spinning solution to obtain a spinning material;
and S4, calcining the spinning material to obtain the titanium dioxide-shell powder composite material.
4. The method according to claim 3, wherein the step S1 further comprises a step of adding iron nitrate or copper nitrate to the mixture of butyl titanate and the solvent at a molar concentration of 0.1 to 0.5%.
5. The method according to claim 3 or 4, wherein in the step S3, the processing parameters in the electrostatic spinning process are as follows: the voltage is 10KV, the distance between the spinning nozzle and the collector is 18-20cm, the ambient temperature is 20-24 ℃, and the relative humidity is 30-40%.
6. The preparation method according to claim 5, wherein in the step S4, the calcination process is: spinning the filamentsThe material is placed in a high-temperature program temperature control box type furnace at 1 ℃ for min-1The temperature is raised to 500 ℃ at the speed, and the heat is preserved for 3 hours, thus obtaining the titanium dioxide-shell powder composite material.
7. The method according to claim 6, wherein the solvent is ethanol, DMF or water, and the polymer template is polyvinylpyrrolidone.
8. The preparation method according to claim 7, wherein in the step S1, the shell powder is added, stirred for 20min and ultrasonically dispersed for 30min to obtain the premix.
9. The method according to claim 8, wherein the polymer template is added and stirred for 12 hours to obtain the spinning solution in step S2.
10. Use of a composite material according to claim 1 or 2 in a coating.
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