CN113578361A - Nano C/N/Si/TiO2Preparation method of photocatalytic composite material - Google Patents
Nano C/N/Si/TiO2Preparation method of photocatalytic composite material Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 9
- 239000000661 sodium alginate Substances 0.000 claims abstract description 9
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 238000007605 air drying Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008188 pellet Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 9
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000011858 nanopowder Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 hydroxyl free radical Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 210000002445 nipple Anatomy 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention relates to a nanometer C/N/Si/TiO2The preparation method of the photocatalytic composite material comprises the steps of mixing and dissolving a carbon source, a nitrogen source and a silicon source into absolute ethyl alcohol, adding nano titanium dioxide, stirring uniformly, and drying to obtain C/N/Si/TiO2Calcining the powder, cooling to room temperature, and grinding to obtain the nano C/N/Si/TiO2Adding the powder into a sodium alginate solution, uniformly stirring in a water bath at 60-70 ℃, dropwise adding the obtained transparent sol into a calcium chloride solution by using an injector to obtain gel balls, cleaning by using distilled water, and naturally air-drying. The invention has simple process and low cost, and the prepared nano material has excellent catalytic performance under visible light, and the starting potential is obviously lower than that of pure TiO2And can effectively separate the photo-generated electron hole, under the condition of visible light, the efficiency of removing methylene blue for 120 minutes reaches 43.38 percent, and the efficiency is compared with that of pure TIO2Compared with the prior art, the improvement is 27.1%.
Description
Technical Field
The invention relates to a nanometer C/N/Si/TiO2A preparation method of a photocatalytic composite material belongs to the field of inorganic catalytic materials.
Background
Printing and dyeing are the most polluted process in the textile industry, the discharge amount of the wastewater accounts for 60-80% of the total discharge amount of the wastewater in the industry, and the process is a key link influencing and restricting the development of the textile industry and is also the important factor in industrial pollution prevention and water saving. The traditional physical method, chemical method and biological method for treating the printing and dyeing sewage have the problems of high cost and low efficiency, and most of the currently adopted biological-physical treatment methods can only meet the basic discharge requirement.
Inorganic semiconductor photocatalytic material nano TiO2The stability is strong, the cost is low, and no toxicity is caused to human body, under the irradiation of ultraviolet light, the hydroxyl free radical with high activity can be generated, and the hydroxyl free radical can almost degrade and mineralize all organic pollutants due to the super oxidation characteristic of the hydroxyl free radical. Has better application prospect in the advanced treatment of the printing and dyeing wastewater difficult to degrade. But nano TiO2The photocatalyst has the defects of no visible light excitation, difficult recovery and the like. In order to solve the problem, the nanometer titanium dioxide is doped and modified and is loaded on a stable carrier, so that the method becomes an effective solution.
For example, the chinese patent with application number 201310204442.3 describes a titanium dioxide/activated carbon photocatalyst, and a preparation method and application thereof, wherein the photocatalyst is prepared by using a method of modifying titanium dioxide with activated carbon, but the prepared photocatalyst has no degradation capability under visible light; the invention patent of China with application number 201310168522.8 introduces a preparation method of titanium dioxide coated nano-copper with a core-shell structure, the titanium dioxide is coated outside copper oxide to form the core-shell structure, but the copper oxide can not completely play a promoting role in photocatalysis and can only be used for degrading organic matters, and the prepared sample has larger particles and small specific surface and can not effectively utilize illumination; the Chinese invention patent with the application number of 201310226774.1 introduces a modified titanium dioxide/bamboo charcoal composite material and a method for decoloring dye wastewater under sunlight, the composite material is prepared by adopting modified titanium dioxide and bamboo charcoal, the process is too complex, and the degradation effect caused by adsorption or photocatalysis is difficult to explain; the invention discloses a high-activity two-dimensional doped modified titanium dioxide nano powder photocatalytic material and a preparation method thereof, which are disclosed in the Chinese invention patent with the application number of 201310102282.1. Most of the materials manufactured by the prior art are powdery, which is not beneficial to secondary recycling of the materials.
In summary, the present modified TiO2The photocatalyst has the problems of unsatisfactory photocatalytic performance under the condition of visible light, complex preparation process, high preparation cost, difficulty in recycling and the like. Therefore, a high-efficiency photocatalyst which is reliable, low in cost, simple in preparation process and easy to recycle is urgently needed.
Disclosure of Invention
The invention aims at the modified TiO in the prior art2The photocatalyst is insufficient, and provides a nano C/N/Si/TiO2The preparation method of the photocatalytic composite material has the advantages of simple process and low cost, and the prepared photocatalytic composite material has excellent catalytic performance under visible light and is easy to recycle.
Technical scheme
Nano C/N/Si/TiO2The preparation method of the photocatalytic composite material comprises the following steps:
(1) mixing and dissolving a carbon source, a nitrogen source and a silicon source into absolute ethyl alcohol to obtain an absolute ethyl alcohol solution of the carbon source/the nitrogen source/the silicon source, adding nano titanium dioxide, and uniformly stirring to obtain a carbon source/nitrogen source/silicon source/titanium dioxide mixed solution;
(2) drying the mixed solution of carbon source/nitrogen source/silicon source/titanium dioxide to obtain C/N/Si/TiO2Powder;
(3) mixing C/N/Si/TiO2Calcining the powder, cooling to room temperature, and grinding to obtain the nano C/N/Si/TiO2Powder;
(4) mixing nano C/N/Si/TiO2Adding the powder into a sodium alginate solution, and uniformly stirring in a water bath at 60-70 ℃ to obtain transparent sol;
(5) dripping transparent sol into calcium chloride solution dropwise with injector to obtain gel pellet with uniform particle diameter, cleaning gel pellet with distilled water, and naturally air drying to obtain nanometer C/N/Si/TiO2A photocatalytic composite material.
In the invention, the nano titanium dioxide is commercial P25 or prepared by the following method: dropwise adding tetrabutyl titanate into deionized water to hydrolyze tetrabutyl titanate, and then centrifugally separating and drying to obtain the product.
Further, in the step (1), the carbon source is citric acid, the nitrogen source is ammonium chloride, and the silicon source is sodium silicate nonahydrate.
Further, in the step (1), the mass ratio of C, N and Si in the carbon source, the nitrogen source and the silicon source is (1-3) to (3-5) to (1-3).
Further, in the step (1), the mass of Si in the silicon source accounts for 0.5-1.5% of the mass of the nano titanium dioxide.
Further, in the step (1), the usage relationship between the absolute ethyl alcohol and the nano titanium dioxide is as follows: the dosage of the nano titanium dioxide corresponding to each 80-120mL of absolute ethyl alcohol is 2-5 g.
Further, in the step (2), the drying temperature is 65 ℃.
Further, in the step (3), the calcining temperature is 600 ℃ and the calcining time is 2 h.
Further, in the step (4), the concentration of the sodium alginate solution is 0.02 g/mL.
Further, in the step (5), the mass concentration of the calcium chloride solution is 1-2%.
The invention has the following beneficial effects: the invention provides a nano C/N/Si/TiO2The preparation method of the photocatalytic composite material has simple process and low cost, and the prepared nano C/N/Si/TiO material2The photocatalytic composite material has excellent catalytic performance under visible light. Nano C/N/Si/TiO2The starting potential of the photocatalytic composite material is obviously less than that of pure TiO2The starting potential of the device can effectively separate the photo-generated electron holes. Under the condition of visible light, the efficiency of removing methylene blue for 120 minutes reaches 43.38 percent, and the efficiency is compared with that of pure TIO2Compared with the prior art, the improvement is 27.1%.
Drawings
FIG. 1 shows the nano-titanium dioxide of comparative example 1 and the C/N/Si/TiO obtained in example 12SEM image of nanopowder;
FIG. 2 shows the nano-titanium dioxide of comparative example 1 and the C/N/Si/TiO obtained in example 12XRD pattern of nanopowder.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.
In the following examples, the preparation method of the adopted nano titanium dioxide comprises the following steps: dissolving 10mL of butyl titanate in 40mL of absolute ethyl alcohol at room temperature to obtain a mixed solution, slowly adding nitric acid to adjust the pH value of the solution to 2.0, uniformly stirring and mixing to obtain a dispersion liquid, standing the dispersion liquid for 24 hours, putting the dispersion liquid into an oven, drying the dispersion liquid for 10 hours at 80 ℃, and then grinding the dispersion liquid to obtain powder; and finally, putting the powder into a muffle furnace, and heating for 3h at 450 ℃ to obtain the nano titanium dioxide.
Comparative example 1
Loaded pure TiO2The preparation method of the gel pellet comprises the following steps:
(1) adding 2g of nano titanium dioxide into 100mL of absolute ethyl alcohol, magnetically stirring for 2h, putting into a 65 ℃ drying oven for drying, putting the dried solid into a crucible, heating in a muffle furnace at 600 ℃ for 2h, and taking out after natural cooling;
(2) weighing 2g of sodium alginate, adding 100mL of deionized water, stirring and dissolving to obtain a sodium alginate solution, grinding the solid obtained in the step (1), adding the ground solid into the sodium alginate solution, and uniformly stirring in a water bath at 65 ℃ to obtain transparent sol;
(3) vertically fixing a 10mL syringe barrel on an iron support, placing a calcium chloride solution with the mass concentration of 1.5% under the syringe, enabling the nipple of the syringe to be 5cm away from the liquid level of the calcium chloride solution, pouring the transparent sol obtained in the step (2) into the syringe barrel, and enabling the transparent sol to naturally fall into the calcium chloride solution below the syringe barrel to form gel pellets;
(4) washing the gel pellet with distilled water for 3 times, and naturally air drying to obtain pure TiO load2The gel beads of (4).
Example 1
Nano C/N/Si/TiO2The preparation method of the photocatalytic composite material comprises the following steps:
(1) mixing and dissolving 0.0699g of citric acid, 0.1831g of ammonium chloride and 0.1218g of sodium silicate nonahydrate into 100mL of absolute ethyl alcohol to obtain an absolute ethyl alcohol solution of a carbon source/nitrogen source/silicon source, adding 2g of nano titanium dioxide, and uniformly stirring to obtain a carbon source/nitrogen source/silicon source/titanium dioxide mixed solution;
(2) drying the mixed solution of carbon source/nitrogen source/silicon source/titanium dioxide at 65 ℃ to obtain C/N/Si/TiO2Powder;
(3) mixing C/N/Si/TiO2Calcining the powder at 600 ℃ for 2h, cooling to room temperature, and grinding to obtain the nano C/N/Si/TiO2Powder;
(4) mixing nano C/N/Si/TiO2Adding the powder into 40mL of sodium alginate solution with the concentration of 0.02g/mL, and uniformly stirring in a water bath at 65 ℃ to obtain transparent sol;
(5) vertically fixing a 10mL syringe cylinder on an iron support, placing a calcium chloride solution with the mass concentration of 1.5% under the syringe, enabling the nipple of the syringe to be 5cm away from the liquid level of the calcium chloride solution, and carrying out the step (4)Pouring the transparent sol into a syringe cylinder, allowing the transparent sol to naturally fall into a calcium chloride solution below the syringe cylinder to obtain gel beads with uniform particle size, washing the gel beads with distilled water for 3 times, and naturally drying to obtain the nano C/N/Si/TiO2A photocatalytic composite material.
FIG. 1 shows the nano-titanium dioxide of comparative example 1 and the C/N/Si/TiO obtained in example 12SEM image of nanopowder, in which FIG. 1A is the nano-titania of comparative example 1 and FIG. 1B is the C/N/Si/TiO obtained in example 12Nanopowder, it can be seen that C/N/Si/TiO2The nano powder has smaller particle size, larger porosity and larger specific surface area.
FIG. 2 shows the nano-titanium dioxide of comparative example 1 and the C/N/Si/TiO obtained in example 12XRD patterns of the nanopowder, it can be seen that three elements have been successfully doped.
Application test:
testing of pure TiO Supported from comparative example 12Gel pellets and the nano-C/N/Si/TiO prepared in example 12The removal efficiency of the photocatalytic composite material to methylene blue is measured by a spectrophotometer, firstly 0.7478g of methylene blue is weighed, 1L of deionized water is added for dissolution, 1mL of the methylene blue solution is diluted by 1000 times, and 250mL of the methylene blue solution is put into a capped conical flask; 10g of the pure TiO support obtained in comparative example 1 were weighed2Gel pellets or nano C/N/Si/TiO prepared in example 12Adding the photocatalytic composite material into the capped conical bottle, and covering the conical bottle cap; placing the conical flask in a dark environment, and turning on a long-arc xenon lamp 20cm away from the long-arc xenon lamp to irradiate the conical flask; at intervals of 30 minutes, the flask was shaken, 4mL of the methylene blue solution in the flask was aspirated by a syringe, and the absorbance A of the solution was measured by a spectrophotometeriThen, the degradation efficiency eta is calculated, and the formula is as follows:
in the formula, A0Absorbance of methylene blue solution at initial time, AiWhen isAbsorbance at moment i.
The test results are shown in table 1:
TABLE 1
As can be seen from the test results in Table 1, the nano-C/N/Si/TiO prepared in example 1 of the present invention is irradiated by a long-arc xenon lamp2The efficiency of removing methylene blue of the photocatalytic composite material can reach 43.38 percent, compared with pure TiO2The improvement is 27.08 percent.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as effective replacements within the protection scope of the present invention.
Claims (9)
1. Nano C/N/Si/TiO2The preparation method of the photocatalytic composite material is characterized by comprising the following steps of:
(1) mixing and dissolving a carbon source, a nitrogen source and a silicon source into absolute ethyl alcohol to obtain an absolute ethyl alcohol solution of the carbon source/the nitrogen source/the silicon source, adding nano titanium dioxide, and uniformly stirring to obtain a carbon source/nitrogen source/silicon source/titanium dioxide mixed solution;
(2) drying the mixed solution of carbon source/nitrogen source/silicon source/titanium dioxide to obtain C/N/Si/TiO2Powder;
(3) mixing C/N/Si/TiO2Calcining the powder, cooling to room temperature, and grinding to obtain the nano C/N/Si/TiO2Powder;
(4) mixing nano C/N/Si/TiO2Adding the powder into a sodium alginate solution, and uniformly stirring in a water bath at 60-70 ℃ to obtain transparent sol;
(5) dripping transparent sol into calcium chloride solution dropwise with injector to obtain gel pellet with uniform particle diameter, cleaning gel pellet with distilled water, and naturally air drying to obtain nanometer C/N/Si/TiO2A photocatalytic composite material.
2. The nano-C/N/Si/TiO as claimed in claim 12The preparation method of the photocatalytic composite material is characterized in that in the step (1), the carbon source is citric acid, the nitrogen source is ammonium chloride, and the silicon source is sodium silicate nonahydrate.
3. The nano-C/N/Si/TiO as claimed in claim 12The preparation method of the photocatalytic composite material is characterized in that in the step (1), the mass ratio of C to N to Si in the carbon source, the nitrogen source and the silicon source is (1-3) to (3-5) to (1-3).
4. The nano-C/N/Si/TiO as claimed in claim 12The preparation method of the photocatalytic composite material is characterized in that in the step (1), the mass of Si in the silicon source accounts for 0.5-1.5% of the mass of the nano titanium dioxide.
5. The nano-C/N/Si/TiO as claimed in claim 12The preparation method of the photocatalytic composite material is characterized in that in the step (1), the dosage relationship between the absolute ethyl alcohol and the nano titanium dioxide is as follows: the dosage of the nano titanium dioxide corresponding to every 80-120mL of absolute ethyl alcohol is 2-5 g.
6. The nano-C/N/Si/TiO as claimed in claim 12The preparation method of the photocatalytic composite material is characterized in that in the step (2), the drying temperature is 65 ℃.
7. The nano-C/N/Si/TiO as claimed in claim 12The preparation method of the photocatalytic composite material is characterized in that in the step (3), the calcining temperature is 600 ℃ and the calcining time is 2 hours.
8. The nano-C/N/Si/TiO as claimed in claim 12The preparation method of the photocatalytic composite material is characterized in that in the step (4), the concentration of the sodium alginate solution is 0.02 g/mL.
9. The nano-C/N/Si/TiO as claimed in any one of claims 1 to 82The preparation method of the photocatalytic composite material is characterized in that in the step (5), the mass concentration of the calcium chloride solution is 1-2%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115530183A (en) * | 2022-10-12 | 2022-12-30 | 南方科技大学 | C/N @ titanium dioxide, metal oxide doped C/N @ titanium dioxide, nano fiber thereof, preparation method and sterilization equipment |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014170A1 (en) * | 2003-08-08 | 2005-02-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalyst material being activated by visible light, raw material for the same and method for producing the same |
| US6956006B1 (en) * | 1998-02-24 | 2005-10-18 | Rotem Amfert Negev Ltd. | Modified titanium dioxide and a method for its preparation |
| CN101444724A (en) * | 2008-12-24 | 2009-06-03 | 南开大学 | Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst |
| CN102091644A (en) * | 2010-12-27 | 2011-06-15 | 湖北工业大学 | Method for preparing carbon-nitrogen-chlorine co-doped nano titanium dioxide photocatalysts |
| CN103769188A (en) * | 2013-12-26 | 2014-05-07 | 华北电力大学（保定） | Three-atom-doped titanium dioxide as well as preparation method and application thereof |
| CN104258837A (en) * | 2014-10-21 | 2015-01-07 | 辽宁工业大学 | Preparation method of carbon and silicon co-doped nano titanium dioxide |
| CN106391132A (en) * | 2016-08-30 | 2017-02-15 | 上海交通大学 | Preparation method of hydrogel immobilized TiO2 photocatalyst |
| CN106512977A (en) * | 2016-10-13 | 2017-03-22 | 河海大学 | Preparation method and application of activated carbon doped titanium dioxide nano photocatalyst |
-
2021
- 2021-07-22 CN CN202110831849.3A patent/CN113578361A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6956006B1 (en) * | 1998-02-24 | 2005-10-18 | Rotem Amfert Negev Ltd. | Modified titanium dioxide and a method for its preparation |
| WO2005014170A1 (en) * | 2003-08-08 | 2005-02-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalyst material being activated by visible light, raw material for the same and method for producing the same |
| CN101444724A (en) * | 2008-12-24 | 2009-06-03 | 南开大学 | Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst |
| CN102091644A (en) * | 2010-12-27 | 2011-06-15 | 湖北工业大学 | Method for preparing carbon-nitrogen-chlorine co-doped nano titanium dioxide photocatalysts |
| CN103769188A (en) * | 2013-12-26 | 2014-05-07 | 华北电力大学（保定） | Three-atom-doped titanium dioxide as well as preparation method and application thereof |
| CN104258837A (en) * | 2014-10-21 | 2015-01-07 | 辽宁工业大学 | Preparation method of carbon and silicon co-doped nano titanium dioxide |
| CN106391132A (en) * | 2016-08-30 | 2017-02-15 | 上海交通大学 | Preparation method of hydrogel immobilized TiO2 photocatalyst |
| CN106512977A (en) * | 2016-10-13 | 2017-03-22 | 河海大学 | Preparation method and application of activated carbon doped titanium dioxide nano photocatalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115530183A (en) * | 2022-10-12 | 2022-12-30 | 南方科技大学 | C/N @ titanium dioxide, metal oxide doped C/N @ titanium dioxide, nano fiber thereof, preparation method and sterilization equipment |
| CN115530183B (en) * | 2022-10-12 | 2023-11-07 | 南方科技大学 | C/N@ titanium dioxide, metal oxide doped C/N@ titanium dioxide, nanofiber thereof, preparation method and sterilization equipment |
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