CN113828297B - Nano composite photocatalyst and preparation method thereof - Google Patents
Nano composite photocatalyst and preparation method thereof Download PDFInfo
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- CN113828297B CN113828297B CN202111292471.0A CN202111292471A CN113828297B CN 113828297 B CN113828297 B CN 113828297B CN 202111292471 A CN202111292471 A CN 202111292471A CN 113828297 B CN113828297 B CN 113828297B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 82
- 239000011707 mineral Substances 0.000 claims abstract description 82
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010453 quartz Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 9
- 239000011028 pyrite Substances 0.000 claims abstract description 9
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052622 kaolinite Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000010445 mica Substances 0.000 claims abstract description 7
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 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 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000002076 thermal analysis method Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000007431 microscopic evaluation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000441 X-ray spectroscopy Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 230000035515 penetration Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a nano composite photocatalyst, which comprises the following components: carbon: titanium dioxide, and silicon dioxide: carbon: the mass ratio of the titanium dioxide is 4: (0.5-1): (0.5-1), titanium dioxide and carbon are loaded on the silicon dioxide, and the particle size of the titanium dioxide particles is about 45-55 nm. The preparation takes novel minerals as raw materials, the novel minerals comprise crystalline components and amorphous components, the crystalline components account for 78.61% of the mass fraction of the minerals, and the amorphous components account for 21.39% of the mass fraction of the minerals; the crystalline component comprises quartz, pyrite, kaolinite and mica, wherein the quartz accounts for 91% of the mass fraction of the crystalline component; the amorphous substance comprises water, elemental carbon and organic matters, wherein the elemental carbon accounts for 95.1% of the amorphous component in mass fraction; the preparation process comprises the following steps: roasting the novel minerals to remove organic matters, and grinding the minerals by a wet method; then mixing the absolute ethyl alcohol solution of the butyl titanate with the mixed solution, and drying and calcining the mixed solution.
Description
Technical Field
The invention relates to the technical field of inorganic nonmetallic materials and nano composite photocatalysts, in particular to a nano composite photocatalyst and a preparation method thereof.
Background
With the rapid development of the industrial age, organic pollutants in air and water are increased, and thus a series of environmental problems are brought about. Water resources play a vital role in the development of humans, but in the earth's natural water, fresh water resources account for a small fraction. The industrial water consumption of China is far higher than that of developed countries, and the pollution to water is very serious, so that the method for treating the pollutants is found, which is environment-friendly, low in treatment cost, simple and efficient, and has important significance. TiO 2 photocatalysis has been proved to be a method capable of effectively treating organic pollutants in air and water, has the advantages of low price, stable chemical property, no secondary pollution and the like, and gradually becomes a research hot spot in the photocatalysis field.
Although TiO 2 has many advantages in terms of photocatalysis, there are still some problems in practical production applications: (1) The utilization rate of visible light is low, the forbidden bandwidth of TiO 2 is wide, the response effect to sunlight is poor, the good photocatalysis effect can be achieved only under ultraviolet light, and the degradation cost is high; (2) Agglomeration is easy to occur, so that the specific surface area is reduced, part of the photocatalyst cannot absorb illumination, and the photocatalytic efficiency is reduced; (3) The nano titanium dioxide photocatalyst is difficult to separate, recycle and use in a suspension system, so that waste is caused. Therefore, the problems of low light utilization rate and difficult recycling of the nano TiO 2 are solved, and the method has very important significance for realizing the practical production and application of the photocatalyst.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a nano composite photocatalyst and a preparation method thereof, which are used for solving the problems of low light utilization rate and difficult recycling of nano TiO 2. Compared with the existing method for preparing the photocatalyst, the novel mineral naturally has mesoporous SiO 2 and carbon, no additional carbon source is needed, meanwhile, due to the mesoporous structure in Fengcheng soil, the specific surface area of the composite photocatalyst can be greatly increased, carbon particles in the novel mineral can be doped with TiO 2 to form defects, the composite photocatalyst can red shift the light absorption threshold value, the visible light response is improved, and the characteristic adsorption can be carried out on pollutants, so that the composite photocatalyst has adsorption-degradation performance and the capability of treating the pollutants. The photocatalyst prepared by the method has high photocatalytic activity, does not additionally introduce carbon sources, and is suitable for industrial production.
In order to achieve the above object, the present invention provides a nanocomposite photocatalyst, comprising silica: carbon: titanium dioxide, wherein the silica: carbon: the mass ratio of the titanium dioxide is 4: (0.5-1): (0.5-1), wherein the titanium dioxide and carbon are supported on the silicon dioxide, and the particle size of the titanium dioxide particles is in the range of 45-55 nm.
The invention also provides a preparation method of the nano composite photocatalyst, which takes novel minerals as raw materials, wherein the novel minerals comprise crystalline components and amorphous components, the crystalline components account for 78.61% of the mass fraction of the minerals, and the amorphous components account for 21.39% of the mass fraction of the minerals; the crystalline component comprises quartz, pyrite, kaolinite and mica, wherein the quartz accounts for 91% of the crystalline component in mass fraction; the amorphous substance comprises water, elemental carbon and organic matters, wherein the elemental carbon accounts for 95.1% of the amorphous component in mass fraction; the method comprises the following steps:
S1, taking the novel mineral, drying and roasting to remove trace organic matters, mixing with absolute ethyl alcohol, and grinding in a nano mill to obtain novel mineral slurry;
s2, mixing butyl titanate with absolute ethyl alcohol, and uniformly stirring to obtain a butyl titanate solution;
s3, uniformly mixing the novel mineral slurry in the step S1 and the butyl titanate solution in the step S2, dropwise adding distilled water into the mixture, and slowly stirring until the mixed solution is viscous to obtain gel;
And S4, placing the gel in the step S3 in a blast drying oven for quick drying, placing in a nitrogen atmosphere furnace for calcination for a period of time, and taking out and scattering to obtain the nano composite photocatalyst.
Further, in the step S1, the baking temperature is 250-450 ℃ and the baking time is 3-5h. The purpose of calcination is to remove the organics therein.
Further, in the step S1, the solid particles D 90 in the milled novel mineral slurry are smaller than 2 μm.
Further, in the step S2, the mass ratio of the butyl titanate to the absolute ethyl alcohol is 10% -40%.
Further, in the step S3, the mass ratio of the novel mineral in the novel mineral slurry to the butyl titanate in the butyl titanate solution is 1: (0.5-1).
Further, in the step S4: the drying temperature of the drying box is 105-150 ℃.
Further, the calcination temperature in the step S4 is 400-600 ℃ and the calcination time is 1-6h.
Compared with the prior art, the invention has the advantages that:
The novel mineral raw material used in the invention is a natural mineral dug from underground 10m in Fengcheng city of Jiangxi province, which is named as Fengcheng soil, the Fengcheng soil is a black mineral, the main mineral components are silicon dioxide and carbon, and trace organic matters, wherein the silicon dioxide and the carbon are mesoporous materials, so that the novel mineral raw material has great utilization value. The Fengcheng soil is rich in reserves, can be used as a carrier of a photocatalytic material, wherein silicon dioxide can be used as a carrier of TiO 2, and mesoporous carbon can be used for doping and modifying TiO 2, so that the composite photocatalyst can red shift a light absorption threshold value, improve visible light response, can be used as a characteristic adsorbent of pollutants, improve the concentration of the pollutants near the composite photocatalyst, further improve the catalytic efficiency of the photocatalyst, and achieve the aim of achieving multiple roles of one ore. Meanwhile, the butyl titanate is mixed with Fengcheng soil and then added with distilled water for hydrolysis to generate titanium dioxide, and the newly generated titanium dioxide grows on the titanium dioxide with silicon dioxide as a core, so that the titanium dioxide is more stable and uniform.
Compared with other preparation methods, the method provided by the invention uses natural minerals, can be used after simple purification, does not need to additionally use acid and alkali and carbon sources, is environment-friendly, and enables the minerals to become new cores of titanium dioxide after being added, so that the titanium dioxide is more stable and uniform after being loaded. The whole preparation method is simple, and the prepared photocatalyst has high activity and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a thermal analysis curve of a novel mineral of the present invention;
FIG. 2 is an X-ray diffraction pattern of the novel mineral of the present invention;
FIG. 3 shows a microscopic analysis chart and curve of the novel mineral of the present invention after being dispersed in alcohol, wherein (A) is a scanning electron microscope picture with a magnification (Mag) of 20.00KX, and (B) is a scanning electron microscope picture with a magnification (Mag) of 1.00 KX; (C) An X-ray energy spectrum in a box line area in the (B) graph; (D) is an element mass percentage and atomic percentage table;
FIG. 4 is a scanning electron microscope image of the novel mineral of the present invention after ultrasonic cleaning, wherein (A) magnification (Mag) is 5.40KX; (B) magnification (Mag) 6.00KX;
FIG. 5 is an electron microscopic view of the nanocomposite photocatalyst obtained in example 1 of the present invention;
FIG. 6 is an electron microscopic view of the nanocomposite photocatalyst obtained in example 2 of the present invention;
FIG. 7 is an electron microscopic view of the nanocomposite photocatalyst obtained in example 3 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Novel mineral composition study
The novel mineral is black from Fengcheng city of Jiangxi province. The composition research method and the specific process are as follows.
1. Thermal analysis
The atmosphere for thermal analysis of the sample was air, and the sample was loaded using a Pt crucible as a sample stage. TG, DTG and DSC curves of the sample were obtained at a heating rate of 10℃per minute as shown in FIG. 1. The image clearly shows that the mineral has mainly two decomposition phases during the heating to 1000 ℃. The first stage of sample decomposition is at 25-200 ℃, which is represented as a bump on the DSC curve, an endothermic reaction. This stage involves both the evaporation of a small amount of water from the sample and the dehydroxylation of the sample. As can be seen from the analysis of the image data in FIG. 1, the mass percentage of water and hydroxyl groups contained in the sample was 1.05%. The second stage of sample decomposition is 420-720 ℃, which is represented by a depression on the DSC curve, an exothermic reaction, mainly related to oxidation and combustion of carbon in the sample. As can be seen from DSC curves, the exothermic peak at this stage has a peak value of 625.9 ℃, i.e. the oxidation rate of carbon in the sample is maximum at this temperature, and its exotherm can reach 7.531mW/mg. Meanwhile, the mass percent change rate of the sample reaches the fastest speed at 620.7 ℃ and is-2.17%/min. The loss-to-burn ratio is calculated by a TG curve, and the mass percent loss of the sample at this stage is 20.34%, namely the sample contains the elemental carbon with corresponding proportion.
2. X-ray diffraction analysis
The X-ray diffraction analysis (XRD) is mainly aimed at analyzing crystalline substances in minerals, and components of the crystalline substances in minerals and contents of the components can be obtained by analyzing diffraction peaks of XRD patterns. The invention carries out X-ray diffraction scanning of 10-80 degrees of 2 theta on a mineral sample to obtain a figure 2, and can be determined by the figure 2: among the crystalline substances in minerals are quartz, kaolinite, gypsum and pyrite.
By further analysis of the XRD pattern in FIG. 2, the Miller indices (001), (100), (101), (200), (004), (104), (213), (204), (312), (223), (204), (223) can be identified from the diffraction peaks in the pattern,
(202) (311), (314), (321), (206). The components of the composition are respectively quartz, pyrite, kaolinite and mica can be determined by comparison with an open database. The contents of the components were calculated by analyzing the intensities of the diffraction peaks, and the mass fractions of the components obtained are shown in Table 1.
TABLE 1 crystalline material composition and mass fraction of novel minerals
| Component (A) | Quartz crystal | Pyrite (pyrite) | Kaolinite | Mica |
| Mass fraction | 91％ | 4％ | 4％ | 1％ |
It can be seen that the crystalline component of the mineral is predominantly quartz, with minor amounts of pyrite, kaolinite and mica as impurities.
3. Microscopic analysis
Microscopic analysis is mainly performed on samples using a combination of Scanning Electron Microscopy (SEM) and X-ray spectroscopy (EDS) to test the structure and elemental distribution. The test samples are raw mineral and treated mineral samples, and the treatment method of the mineral comprises ultrasonic cleaning, high Wen Chutan, chemical carbon removal and chemical silica removal. Through observation of the five test samples, the microcomponents of minerals can be comprehensively analyzed, and the suitability of the corresponding treatment method can be explored.
First, the morphology of the raw ore was observed using SEM, and its elemental content was analyzed using EDS. In order to observe the mineral without damaging the basic structure of the mineral, the mineral is dispersed in alcohol as it is, and is simply shaken and then dripped on an aluminum foil to be observed by a scanning electron microscope. As shown in fig. 3 (a) and (B), the mineral is formed by stacking a plurality of fragments, and a large number of voids and holes exist. The presence of circular depressions and streaks on the surface of these block structures may be due to bio-etching. In addition to the bulk structure, the mineral surface also has a large number of rods, with diameters of 50-100nm and lengths of 500nm-1 μm.
EDS spectroscopy was further performed on the region in the block diagram in fig. 3 (B), resulting in fig. 3 (C) and fig. 3 (D). Since the penetration depth of the X-ray spectroscopy analysis was 1.5 μm, elemental analysis was mainly performed on the sample surface layer. As can be seen from FIG. 3 (C), the main elements in the mineral are C, O, al and Si, wherein the content of C is the highest and is 42.51% of the mass percent, and the content of Al is the lowest and is 4.64% of the mass percent.
In combination with thermal analysis and XRD results, the mass percentage of C element obtained by EDS energy spectrum scanning is far higher than 20.34%, and it is known that carbon element is mainly enriched on the surface of the mineral or in some special structures, but is not uniformly distributed in the mineral structure. In which carbon and quartz are grown together, and mesoporous carbon can be obtained by removing silica or the like.
In order to more carefully and clearly observe the inner layer structure of the mineral, the invention uses an ultrasonic cleaning method to separate scraps and impurities on the surface of the mineral particles, disperses a mineral sample in alcohol, ultrasonically cleans for 15min, and drops the mineral sample on a silicon wafer to prepare a scanning electron microscope sample for observation, the obtained scanning electron microscope image is shown as a figure 4, and after ultrasonic cleaning, scraps and rods on the surface of the mineral are basically eliminated, so that the ultrasonic cleaning can effectively separate scraps and impurities on the surface of the mineral. Fig. 4 (a) shows that the mineral particles have circular depressions of varying sizes and that there are mesoporous and microporous structures. Fig. 4 (B) also shows that there are circular depressions in the mineral particles, and that there are scores and cracks.
4. Specific surface area and pore analysis
Specific surface area and pore analysis mainly uses a specific surface area and pore analyzer to detect the specific surface area of a sample and the pore structure of the sample. The algorithm used for detection is mainly BET. The test sample was mineral as such, and after drying the sample at 115 ℃, the BET specific surface area test was performed using nitrogen as an adsorbate.
The resulting minerals were tested as received for BET specific surface area of 5.2684m 2/g, total pore volume of 0.028110cm 3/g, adsorption average pore size of 213.421 angstroms, desorption average pore size of 201.633 angstroms.
In summary, the novel mineral comprises a crystalline component and an amorphous component, wherein the crystalline component accounts for 78.61 percent of the mass fraction of the mineral, and the amorphous component accounts for 21.39 percent of the mass fraction of the mineral; the crystalline component is quartz, pyrite, kaolinite and mica, the quartz accounts for 91% of the crystalline component in mass percent, the amorphous substance is water, simple substance carbon and organic matters, the carbon content is 20.34%, the carbon and the quartz are grown together, and the mesoporous carbon can be obtained by removing the quartz and impurities.
Example 1
A method for preparing a nano composite photocatalyst, comprising the following steps:
1. taking the analyzed novel minerals as raw materials, drying and roasting for 4 hours at the temperature of 250 ℃, removing organic carbon, and scattering to obtain dried mineral powder;
2. butyl titanate and absolute ethyl alcohol are mixed according to the following ratio of 1:10, uniformly stirring to obtain a butyl titanate solution;
3. Mixing mineral powder with butyl titanate in a butyl titanate solution according to a mass ratio of 2:1, uniformly mixing, adding distilled water dropwise into the mixture, and slowly stirring the mixture until the mixture is viscous to obtain gel;
4. Placing the gel in a blast drying oven at 105 ℃ for quick drying, placing the gel in a nitrogen atmosphere furnace at 400 ℃ for calcination for 6 hours, and taking out and scattering the gel to obtain the nano composite photocatalyst;
An electron microscopic image of the composite photocatalyst obtained in example 1 is shown in fig. 5. Wherein the particle size of the titanium dioxide is about 50nm, the adhesion state is good, and the agglomeration phenomenon exists. The photocatalytic activity of the composite photocatalyst is tested by degrading rhodamine B, and the test result is as follows: 50mg of the composite photocatalyst has a degradation rate of 85% for 50ml of 20ppm rhodamine B solution under ultraviolet light for 2 hours.
Example 2
A method for preparing a nano composite photocatalyst, comprising the following steps:
1. Taking the analyzed novel minerals as raw materials, drying and roasting for 3 hours at 450 ℃, removing organic carbon, and scattering to obtain dried mineral powder;
2. butyl titanate and absolute ethyl alcohol are mixed according to the following ratio of 2:5, mixing the materials according to the mass ratio, and uniformly stirring the materials to obtain a butyl titanate solution;
3. mixing mineral powder with butyl titanate in a butyl titanate solution according to a mass ratio of 1:1, uniformly mixing, adding distilled water dropwise into the mixture, and slowly stirring the mixture until the mixture is viscous to obtain gel;
4. placing the gel in a blast drying oven at 150 ℃ for quick drying, placing the gel in a nitrogen atmosphere furnace at 600 ℃ for calcination for 1h, and taking out and scattering the gel to obtain the nano composite photocatalyst;
An electron microscopic image of the composite photocatalyst obtained in example 2 is shown in fig. 6. Wherein the particle size of the titanium dioxide is about 45nm, the adhesion state is good, the titanium dioxide is agglomerated in a large amount, and the titanium dioxide is fully loaded around the silicon dioxide particles. The photocatalytic activity of the composite photocatalyst is tested by degrading rhodamine B, and the test result is as follows: 50mg of the composite photocatalyst has 93% degradation rate to 50ml of 20ppm rhodamine B solution under ultraviolet light for 2 hours.
Example 3
A method for preparing a nano composite photocatalyst, comprising the following steps:
1. taking the analyzed novel minerals as raw materials, drying and roasting for 3 hours at 400 ℃, removing organic carbon, and scattering to obtain dried mineral powder;
2. butyl titanate and absolute ethyl alcohol are mixed according to the following ratio of 1:5, mixing the materials according to the mass ratio, and uniformly stirring the materials to obtain a butyl titanate solution;
3. mixing mineral powder with butyl titanate in a butyl titanate solution according to a mass ratio of 1:0.8, adding distilled water dropwise into the mixture, and slowly stirring until the mixture is viscous to obtain gel;
4. Placing the gel in a blast drying oven at 120 ℃ for quick drying, placing the gel in a nitrogen atmosphere furnace at 500 ℃ for calcination for 3 hours, and taking out and scattering the gel to obtain the nano composite photocatalyst;
An electron microscopic image of the composite photocatalyst obtained in example 1 is shown in fig. 7: wherein the particle size of the titanium dioxide is about 55nm, the adhesion state is good, the agglomeration phenomenon of the titanium dioxide is obviously improved, and the load is uniform. The photocatalytic activity of the composite photocatalyst is tested by degrading rhodamine B, and the test result is as follows: 50mg of the composite photocatalyst has a degradation rate of 97% for 50ml of 20ppm rhodamine B solution under ultraviolet light for 2 hours.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (7)
1. A nanocomposite photocatalyst, characterized in that its composition comprises silica: carbon: titanium dioxide, wherein the silica: carbon: the mass ratio of the titanium dioxide is 4: (0.5-1): (0.5-1), wherein the titanium dioxide and carbon are supported on the silicon dioxide, and the particle size of the titanium dioxide particles is 45-55nm;
the nano composite photocatalyst is prepared by taking minerals as raw materials;
The mineral comprises a crystalline component and an amorphous component, wherein the crystalline component accounts for 78.61% of the mass fraction of the mineral, and the amorphous component accounts for 21.39% of the mass fraction of the mineral; the crystalline component comprises quartz, pyrite, kaolinite and mica, wherein the quartz accounts for 91% of the crystalline component in mass fraction; the amorphous substance comprises water, elemental carbon and organic matters, wherein the elemental carbon accounts for 95.1% of the amorphous component in mass fraction;
the preparation method comprises the following steps:
S1, taking the minerals, drying and roasting to remove trace organic matters, mixing with absolute ethyl alcohol, and grinding in a nano mill to obtain mineral slurry;
s2, mixing butyl titanate with absolute ethyl alcohol, and uniformly stirring to obtain a butyl titanate solution;
S3, uniformly mixing the mineral slurry in the step S1 and the butyl titanate solution in the step S2, dropwise adding distilled water into the mixture, and slowly stirring until the mixed solution is viscous to obtain gel;
And S4, placing the gel in the step S3 in a blast drying oven for quick drying, placing in a nitrogen atmosphere furnace for calcination for a period of time, and taking out and scattering to obtain the nano composite photocatalyst.
2. The method for preparing a nanocomposite photocatalyst according to claim 1, wherein in the step S1, the baking and roasting temperature is 280 ℃ to 450 ℃.
3. The method of preparing a nanocomposite photocatalyst according to claim 1, wherein in step S1, solid particles D 90 in the ground mineral slurry are less than 2 μm.
4. The method for preparing a nanocomposite photocatalyst according to claim 1, wherein in the step S2, the mass ratio of butyl titanate to absolute ethanol in the step S2 is 10% -40%.
5. The method for preparing a nanocomposite photocatalyst according to claim 1, wherein in step S3, the mass ratio of the mineral in the mineral slurry to the butyl titanate in the butyl titanate solution is 1: (0.5-1).
6. The method for preparing a nanocomposite photocatalyst according to claim 1, wherein in the step S4: the drying temperature of the drying box is 105-150 ℃.
7. The method for preparing a nanocomposite photocatalyst according to claim 1, wherein the calcination temperature in step S4 is 400 to 600 ℃ and the calcination time is 1 to 6 hours.
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