CN108993473B - Composite photocatalytic material SnO2/TiO2Preparation method of (1) - Google Patents
Composite photocatalytic material SnO2/TiO2Preparation method of (1) Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 67
- 238000001354 calcination Methods 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000227 grinding Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 69
- 238000002156 mixing Methods 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 29
- 235000006408 oxalic acid Nutrition 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 230000007246 mechanism Effects 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 11
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011858 nanopowder Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 73
- 239000000047 product Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 4
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- 239000000049 pigment Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
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- 238000011031 large-scale manufacturing process Methods 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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Images
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B01J35/39—
-
- B01J35/40—
Abstract
The invention discloses a composite photocatalytic material SnO2/TiO2Belonging to the technical field of photocatalytic materials. The method specifically comprises the following steps: 1) adding butyl titanate into ethanol at room temperature, and carrying out ultrasonic treatment for 1h to obtain a solution A; 2) SnO2Dispersing in deionized water to obtain solution B; 3) adding the solution A into the solution B, stirring for 4-6h, and standing for one night; 4) centrifuging, drying, grinding, calcining at the temperature of 400-800 ℃ for a certain time, and grinding again to obtain the composite photocatalytic material. The composite photocatalytic material prepared by the method has the advantages of large specific surface area, good chemical stability, good photocatalytic performance and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a composite photocatalystChemical material SnO2/TiO2The preparation method of (1).
Background
The discharge of industrial waste water is increasing, especially the discharge of various dyes seriously pollutes water resources which human beings rely on for survival, and seriously harms aquatic organisms and human health. In the field of sewage treatment, the conventional methods have failed to satisfy the requirements for efficient and thorough purification of sewage. Through research, people find that organic pollutants can be thoroughly degraded into non-toxic and harmless inorganic matters through a photocatalytic reaction, the reaction can be carried out at normal temperature, and the method has incomparable advantages compared with the traditional method, so that the photocatalytic technology is taken as a technology with an application prospect and provides a new direction for sewage treatment.
SnO2The color of the powder is generally white, light yellow or light gray. Its catalytic activity is superior to that of traditional material, SnO2The catalytic activity of (2) is deeply related to the specific surface area thereof. To obtain SnO having good photocatalytic activity2The preparation of SnO is required2And (3) ultrafine powder.
TiO2Is a pigment with high infrared reflectivity, but its application is limited because it is susceptible to "white light" contamination, if TiO can be used2Effectively compounded with other substrates to synthesize a mesoporous and spheroidal core-shell structure with nano or submicron order, and on the one hand, the TiO is exerted2The high infrared reflection performance of the pigment can play the chromaticity of the color pigment on one hand, and the high infrared reflection color pigment is hopeful to be obtained. The method is a good development direction in combination with the problem that the current building energy consumption has increasingly serious influence on the environment and energy.
The' 201210240596.3 patent application discloses SnO2-TiO2Preparation method of core-shell structure nano composite material SnO prepared by chemical vapor deposition method2Nanowires and atomic vapor deposition on SnO2The surface of the nano wire is coated with rutile phase TiO layer by layer2The invention has the advantages of simple operation process, accurate and controllable thickness of the core-shell structure and uniform size distribution, but the temperature required by the method is lowHigher cost, not beneficial to energy conservation and emission reduction, and not suitable for large-scale production.
Disclosure of Invention
Aiming at the problems, the invention provides a composite photocatalytic material SnO2/TiO2The preparation method of (1).
The technical scheme of the invention is as follows: composite photocatalytic material SnO2/TiO2The preparation method is characterized by comprising the following steps:
1) adding butyl titanate into ethanol at room temperature, and carrying out ultrasonic treatment for 0.5-2h to obtain a solution A;
2) SnO2Dispersing in deionized water to obtain solution B;
3) adding the solution A into the solution B, stirring at a stirring speed of 80-100r/min in a stirring device, and standing overnight, wherein the molar ratio of the butyl titanate to the metal ions is 1: 1;
4) centrifuging, drying and grinding the solution obtained in the step 3), calcining at 400-.
Further, the ultrasonic treatment time in the step 1) is 1 h; when the ultrasonic treatment time is less than 1 hour, the reaction is insufficient, the generated product is not uniform, and the cost is increased due to the overlong reaction time.
Further, the drying conditions in the step 4) are as follows: drying at 80 deg.C for 4 hr, and drying at 90 deg.C for 2 hr; using different temperatures, the product after centrifugation was thoroughly freed of water.
Further, the calcining temperature in the step 4) is 400 ℃, and the calcining time is 4 hours; the optimal calcination temperature is utilized to avoid the influence of over-calcination or incomplete calcination on the use effect of the photocatalytic material.
Further, the SnO2The preparation method comprises the following steps:
step A: SnCl2·2H2Dissolving O in deionized water, and stirring for 30min to form a uniform solution;
and B: dissolving oxalic acid in deionized water to obtain oxalic acid solutionSnCl obtained in the step A is stirred under the condition of magnetic force2·2H2Dropwise adding the O solution into the oxalic acid solution;
and C: b, adding polyvinylpyrrolidone into the solution obtained in the step B, and stirring until a white solution containing milky white precipitates is obtained;
step D: and C, reacting the white solution obtained in the step C at the constant temperature of 160-180 ℃ for 5-7h, and then centrifuging, cleaning, drying and grinding.
Step E: d, calcining the powder obtained after grinding in the step D, wherein the calcining process comprises the following steps: the calcination temperature is 400-600 ℃, and then SnO is obtained2And (4) nano powder.
Further, SnCl added in the step B2·2H2The molar ratio of O to oxalic acid is 1:4, 1:2 or 1: 1.5.
Further, SnCl added in the step B2·2H2The molar ratio of O to oxalic acid is 1: 1.5; is in favor of SnO2With TiO2To form composite particles.
Further, before the polyvinylpyrrolidone is added in the step C, the polyvinylpyrrolidone is treated by using a catalyst, and the catalyst is prepared from the following raw materials: refined diatomite, boehmite, silicic acid gel, polyanionic cellulose and titanium sulfate; the preparation method of the catalyst comprises the following steps: uniformly mixing refined diatomite, boehmite, silicic acid gel, polyanionic cellulose and titanium sulfate, and grinding in a grinding device for 1 h; adding nitric acid with concentration of 0.5mol/L to dilute the ground powder until the powder becomes pasty, and then putting the powder into an extrusion device to repeatedly extrude the powder into a strip-shaped body for 2 hours; placing the obtained strip-shaped body at room temperature for 3h, airing, then adding the strip-shaped body into a low-temperature roasting furnace for low-temperature roasting for 20-30min, wherein the roasting temperature is 400 ℃ at 300-; after the polyvinylpyrrolidone is prepared into a solution by using a solvent, the catalyst is added and stirred for 2 hours, and then the polyvinylpyrrolidone with improved purity is obtained after filtration, drying and grinding, so that the content of residual monomer N-vinyl pyrrolidone in the process of preparing the polyvinylpyrrolidone can be reduced, the purity of the polyvinylpyrrolidone is improved, and the reaction time is shortened.
Further, before the calcination process in step E, the powder obtained in step D is subjected to a preheating calcination process, and the preheating calcination process includes: preheating at low temperature of 150-2After the color of the nano powder is generated, cooling; the first preheating and calcining is carried out at low temperature, so that overburning is avoided, and the incomplete crystallization caused by low temperature is avoided by the second preheating and calcining at higher temperature.
Preferably, the isothermal reaction temperature of the step D is 160 ℃ and the time is 6 hours.
Preferably, the calcination temperature in the step E is 500 ℃ and the calcination time is 2 h.
Further, in the step 3), the stirring device comprises a base, a support frame, a mixing mechanism and a stirring mechanism, the support frame is arranged at the upper end of the base, two clamping pieces are arranged on the support frame, the two clamping pieces are respectively positioned at the left side and the right side in the support frame, the mixing mechanism comprises a mixing box and a micro air-adding pump, the mixing box is connected with the support frame through the clamping pieces, the micro air-adding pump is arranged at one end of the support frame, the micro air-adding pump is connected with the mixing box through a vent pipe, an air filter screen and a pressurizing nozzle are arranged at the joint of the micro air-adding pump and the mixing box, the pressurizing nozzle is positioned in the mixing box, a liquid outlet is arranged; the stirring mechanism comprises a rotating motor, a rotating shaft, a clamping seat, a stirring box and a stirring head, wherein the rotating motor provides power for the rotating shaft, the clamping seat is arranged at the upper end of the rotating shaft, a clamping groove is formed in the clamping seat and is positioned right below the liquid outlet, the stirring box is clamped in the clamping groove, and the stirring head is connected with the rotating shaft and is positioned inside the stirring box; through miniature air pump suction air in to the mixing box, utilize mixing mechanism to carry out preliminary mixing to solution, then get into the agitator tank from the liquid outlet with the solution of preliminary mixing, utilize the agitator tank to further stir solution, make the solution after the mixture can reach the requirement of preparation photocatalysis material better, the mixed solution after agitating through agitating unit has certain enhancement to photocatalysis material's chemical stability, photocatalysis moreover.
The invention has the beneficial effects that: in the invention, SnO2Blue pigment and TiO2Compounding, and taking the advantages of the two into full play through the synergistic effect of the two to synthesize the SnO2/TiO2A nano composite photocatalytic material. The composite photocatalytic material obtained by the invention combines SnO2And TiO2The catalyst has the advantages of good performance, good photocatalytic performance, no color change at high temperature and the like. In addition, the preparation method is simple, the raw materials are easy to obtain, the synthesis temperature is low, the process is simple and controllable, and the method is suitable for large-scale production; the obtained product is a low-molecular, low-toxic or even non-toxic organic matter, does not contain toxic elements such as lead, chromium and the like, is green and environment-friendly, and has good product particle dispersibility and uniform particle size distribution.
Drawings
FIG. 1 shows SnO synthesized by different proportions of tin source and oxalic acid according to the invention2X-ray diffraction pattern of (a);
FIG. 2 shows a composite photocatalytic material SnO with different molar amounts of metal ions and butyl titanate according to the present invention2/TiO2X-ray diffraction pattern of (a);
FIG. 3 shows SnO synthesized from a tin source and oxalic acid in a ratio of 1:1.5 according to the present invention2SEM of (2);
FIG. 4 shows the molar ratio of metal ions to butyl titanate of the present invention is 1: composite type photocatalytic material SnO at 1 hour2/TiO2SEM of (2);
FIG. 5 is a diagram of synthetic SnO according to the present invention2/TiO2A composite material degradation methyl orange curve;
FIG. 6 shows SnO synthesized at 1:1 Sn/Ti ratio according to the present invention2/TiO2Degrading a complete curve of methyl orange;
FIG. 7 is a schematic view of the internal structure of the stirring apparatus of the present invention;
the device comprises a base 1, a support 2, a clamping piece 20, a blending mechanism 3, a blending box 30, a liquid outlet 300, a miniature air pump 31, an air filter screen 32, a pressurizing nozzle 33, a stirring mechanism 4, a rotating motor 40, a rotating shaft 41, a clamping seat 42, a stirring box 43 and a stirring head 44.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
SnO2Preparation example 1
First 4.51g of SnCl2·2H2Dissolving O in 20ml deionized water and stirring for 30min to form a uniform solution, and simultaneously dissolving oxalic acid in 40ml deionized water, wherein SnCl2·2H2The molar ratio of O to oxalic acid was 1:2, 0.075g of polyvinylpyrrolidone was added after stirring uniformly, and the solution was stirred until a white solution containing a milky white precipitate was obtained. Then, the white solution was transferred to a 100ml autoclave and reacted at a constant temperature of 180 ℃ for 5 hours, followed by washing, drying, grinding, and calcining at 500 ℃ for 2 hours to obtain tin oxide nanopowder.
SnO2Preparation example 2
First 4.51g of SnCl2·2H2Dissolving O in 20ml deionized water and stirring for 30min to form a uniform solution, and simultaneously dissolving oxalic acid in 40ml deionized water, wherein SnCl2·2H2The molar ratio of O to oxalic acid was 1:4, 0.075g of polyvinylpyrrolidone was added after stirring uniformly, and the solution was stirred until a white solution containing a milky white precipitate was obtained. Thereafter, the white solution was transferred to a 100ml autoclave and reacted at a constant temperature of 175 ℃ for 6 hours, followed by washing, drying, grinding, and then calcining at 400 ℃ for 2 hours to obtain tin oxide nanopowder.
SnO2Preparation example 3
First 4.51g of SnCl2·2H2Dissolving O in 20ml deionized water and stirring for 30min to form a uniform solution, and simultaneously dissolving oxalic acid in 40ml deionized water, wherein SnCl2·2H2The molar ratio of O to oxalic acid was 1:5, 0.075g of polyvinylpyrrolidone was added after stirring well, and the solution was stirred until it reachedA white solution containing a milky white precipitate was obtained. Thereafter, the white solution was transferred to a 100ml autoclave and reacted at a constant temperature of 170 ℃ for 5.5 hours, followed by washing, drying, grinding, and calcining at 450 ℃ for 2 hours to obtain tin oxide nanopowder.
SnO2Preparation example 4
First 4.51g of SnCl2·2H2Dissolving O in 20ml deionized water and stirring for 30min to form a uniform solution, and simultaneously dissolving oxalic acid in 40ml deionized water, wherein SnCl2·2H2The molar ratio of O to oxalic acid is 1:5, then SnCl2·2H2Dropwise adding the O solution into the oxalic acid solution, and uniformly stirring; preparing polyvinylpyrrolidone into a solution with the mass concentration of 30% by using a solvent, adding a catalyst, stirring for 2 hours, filtering, drying, grinding to obtain treated polyvinylpyrrolidone, adding 0.075g of the treated polyvinylpyrrolidone into the uniformly stirred solution, and stirring until a white solution containing milky white precipitates is obtained. Then, transferring the white solution into a 100ml autoclave, reacting for 3 hours at the constant temperature of 160 ℃, then cleaning, drying and grinding, and then carrying out preheating and calcining treatment on the obtained powder, wherein the preheating and calcining treatment process comprises the following steps: preheating at low temperature of 150 ℃ for 30min, cooling to 100 ℃ by using a cooler, carrying out first heating, preheating for 60min after heating to 300 ℃, carrying out second heating, continuously calcining for 2 hours after heating to 600 ℃, and finally cooling to obtain the tin oxide nano powder.
Wherein, the raw materials of the catalyst are as follows: refined diatomite, boehmite, silicic acid gel, polyanionic cellulose and titanium sulfate; the preparation method of the catalyst comprises the following steps: uniformly mixing refined diatomite, boehmite, silicic acid gel, polyanionic cellulose and titanium sulfate, and grinding in a grinding device for 1 h; adding nitric acid with concentration of 0.5mol/L to dilute the ground powder until the powder becomes pasty, and then putting the powder into an extrusion device to repeatedly extrude the powder into a strip-shaped body for 2 hours; and (3) placing the obtained strip-shaped body at room temperature for 3h, airing, then adding the strip-shaped body into a low-temperature roasting furnace for low-temperature roasting for 20min, wherein the roasting temperature is 400 ℃, cooling the strip-shaped body to be below 100 ℃ by using a cooler, then heating, heating to 800 ℃, roasting for 15min, and heating at the rate of 30 ℃/min to obtain the catalyst.
Example 1
Composite photocatalytic material SnO2/TiO2The preparation method mainly comprises the following steps:
1) dissolving 0.68g of butyl titanate in absolute ethyl alcohol with the volume 2 times that of the butyl titanate at room temperature, and carrying out ultrasonic treatment for 0.5h to obtain a solution A;
2) 0.30g of SnO prepared in preparation example 12Dispersing in 50ml of deionized water to obtain a solution B;
3) dropwise adding the solution A into the solution B, stirring at a stirring speed of 80r/min for 4 hours, and standing for 16 hours;
4) centrifuging, drying and grinding the solution obtained in the step 3), and then calcining for a certain time at 400 ℃ for 4 hours to obtain SnO2/TiO2A composite material.
Example 2
Different from the embodiment 1, the composite type photocatalytic material SnO2/TiO2The preparation method mainly comprises the following steps:
1) dissolving 0.68g of butyl titanate in absolute ethyl alcohol with the volume 2 times that of the butyl titanate at room temperature, and carrying out ultrasonic treatment for 0.5h to obtain a solution A;
2) 0.30g of SnO prepared in preparation example 22Dispersing in 50ml of deionized water to obtain a solution B;
3) dropwise adding the solution A into the solution B, stirring for 4 hours in a stirring device at a stirring speed of 80r/min, and standing for 16 hours;
4) centrifuging, drying, grinding and calcining the solution obtained in the step 3), wherein the calcining temperature is 400 ℃, and the calcining time is 4 hours, so that SnO can be obtained2/TiO2A composite material.
The stirring device comprises a base 1, a support frame 2, a mixing mechanism 3 and a stirring mechanism 4, wherein the support frame 2 is arranged at the upper end of the base 1, two clamping pieces 20 are arranged on the support frame 2, the two clamping pieces 20 are respectively positioned at the left side and the right side in the support frame 2, the mixing mechanism 3 comprises a mixing box 30 and a micro air adding pump 31, the mixing box 30 is connected with the support frame 2 through the clamping pieces 20, the micro air adding pump 31 is arranged at one end of the support frame 2, the micro air adding pump 31 is connected with the mixing box 30 through an air pipe, an air filter screen 32 and a pressurizing nozzle 33 are arranged at the joint, the pressurizing nozzle 33 is positioned inside the mixing box 30, a liquid outlet 300 is arranged at the bottom end of the; the stirring mechanism 4 comprises a rotating motor 40, a rotating shaft 41, a clamping seat 42, a stirring box 43 and a stirring head 44, wherein the rotating motor 40 provides power for the rotating shaft 41, the clamping seat 42 is arranged at the upper end of the rotating shaft 41, a clamping groove is arranged on the clamping seat 42 and is positioned at the lower end of the liquid outlet 300, the stirring box 43 is clamped in the clamping groove, and the stirring head 44 is connected with the rotating shaft 41 and is positioned inside the stirring box 43.
The concrete stirring process is as follows: clean air after air filter 32 filters is drawn into mixing box 30 through miniature air pump 31, utilizes the impact force of air to each composition misce bene of solution in mixing box 30, then gets into agitator tank 43 from liquid outlet 300 with the solution of preliminary mixing in mixing box 30, drives rotation axis 41 through rotating electrical machines 40 and rotates to drive stirring head 44 and rotate, further stir the misce bene to solution.
Example 3
Different from the embodiment 2, the composite type photocatalytic material SnO2/TiO2The preparation method mainly comprises the following steps:
1) dissolving 0.34g of butyl titanate in absolute ethyl alcohol with the volume 2 times that of the butyl titanate at room temperature, and carrying out ultrasonic treatment for 0.8h to obtain a solution A;
2) 0.30g of SnO prepared in preparation example 32Dispersing in 50ml of deionized water to obtain a solution B;
3) dropwise adding the solution A into the solution B, stirring for 4.5h in a stirring device at a stirring speed of 85r/min, and standing for 16 h;
4) centrifuging the solution obtained in the step 3), drying at the drying temperature of 80 ℃ for 4h, drying at the drying temperature of 90 ℃ for 2h, grinding, and calcining at the calcining temperature of 500 ℃ for 4h to obtain the catalystSnO2/TiO2A composite material.
Example 4
Different from the embodiment 2, the composite type photocatalytic material SnO2/TiO2The preparation method mainly comprises the following steps:
1) dissolving 0.68g of butyl titanate in absolute ethyl alcohol with the volume 2 times that of the butyl titanate at room temperature, and carrying out ultrasonic treatment for 1 hour to obtain a solution A;
2) 0.30g of SnO prepared in preparation example 12Dispersing in 50ml of deionized water to obtain a solution B;
3) dropwise adding the solution A into the solution B, stirring for 5 hours in a stirring device at a stirring speed of 90r/min, and standing for 16 hours;
4) centrifuging the solution obtained in the step 3), drying at the drying temperature of 80 ℃ for 4h, drying at the drying temperature of 90 ℃ for 2h, grinding, and calcining at the calcining temperature of 600 ℃ for 4h to obtain SnO2/TiO2A composite material.
Example 5
Different from the embodiment 2, the composite type photocatalytic material SnO2/TiO2The preparation method mainly comprises the following steps:
1) dissolving 0.68g of butyl titanate in absolute ethyl alcohol with the volume 2 times that of the butyl titanate at room temperature, and carrying out ultrasonic treatment for 1.5h to obtain a solution A;
2) 0.30g of SnO prepared in preparation example 12Dispersing in 50ml of deionized water to obtain a solution B;
3) dropwise adding the solution A into the solution B, stirring for 5.5h in a stirring device at a stirring speed of 90r/min, and standing for 16 h;
4) centrifuging the solution obtained in the step 3), drying at the drying temperature of 80 ℃ for 4h, drying at the drying temperature of 90 ℃ for 2h, grinding, calcining at the calcining temperature of 700 ℃ for 4h, and thus obtaining SnO2/TiO2A composite material.
Example 6
Different from the embodiment 2, the composite type photocatalytic materialSnO2/TiO2The preparation method mainly comprises the following steps:
1) dissolving 0.68g of butyl titanate in absolute ethyl alcohol with the volume 2 times that of the butyl titanate at room temperature, and carrying out ultrasonic treatment for 2 hours to obtain a solution A;
2) 0.30g of SnO prepared in preparation example 42Dispersing in 50ml of deionized water to obtain a solution B;
3) dropwise adding the solution A into the solution B, stirring for 6 hours in a stirring device at a stirring speed of 100r/min, and standing for 16 hours;
4) centrifuging the solution obtained in the step 3), drying at the drying temperature of 80 ℃ for 4h, drying at the drying temperature of 90 ℃ for 2h, grinding, calcining at the calcining temperature of 800 ℃ for 4h, and thus obtaining SnO2/TiO2A composite material.
Test examples
XRD test
As shown in FIG. 1, is synthesized SnO2XRD pattern of nanocrystals. And comparing with an X-ray diffraction standard card to synthesize a target product. The ratio of the tin dichloride dihydrate to the oxalic acid is 1: 4. 1: 2. 1: SnO synthesized at 1.52The XRD curve of the nano crystal can be obviously seen, and complete diffraction peaks appear. The proportion is 1:4 and 1: the peak shape at 1.5 was narrow and sharp, and the peak value was high, indicating that the crystallinity was good. The ratio of the tin dichloride dihydrate to the oxalic acid in the three proportions is 1: SnO at 1.52The diffraction peaks of the XRD curve of the nanocrystals are clear and free of impurity peaks.
As shown in FIG. 2, is synthetic SnO2/TiO2XRD pattern of composite material wherein (a) represents SnO2A substrate; (b) represents Sn/Ti of 1/0.5; (c) represents Sn/Ti of 1/1. With SnO2Compared with the XRD pattern of the matrix, the modified product SnO2The characteristic peak of (a) still exists, but the peak becomes lower. TiO appears when Sn/Ti is 1/0.52Diffraction peaks, albeit less SnO2The characteristic peak of (A) is very weak, and the SnO in the product is still illustrated2With TiO2Co-exist to form composite particles.
SEM test
As shown in FIG. 3, Sn/oxalic acid is 1: nanocrystalline SnO with different magnification ratios synthesized at 1.5 hours2The SEM image shows that the product has homogeneous particle distribution and excellent dispersivity.
As shown in FIG. 4, the composite product has good dispersibility, uniform particle size and large specific surface area, and is beneficial to the photocatalytic performance of the material.
Photocatalytic testing
As shown in fig. 5, the tin to titanium molar ratio was 1:1 and 1: SnO synthesized at 0.52/TiO2The composite degrades methyl orange at 0, 5, 10, 20, 30, 60, 90 minutes, wherein (a) is a time versus absorbance curve; (b) the absorption value at 465nm wavelength is selected for the relation curve of time and degradation rate, and a line graph is drawn. With SnO2Compared with the matrix, the photocatalytic effect of the compounded product is obviously better than that of the matrix, and when Sn/Ti is 1:1, the photocatalytic effect is better than that of SnO2The catalytic effect of the matrix is better, which shows that the photocatalytic performance of the composite material is improved. When Sn/Ti is 1:1, the synthesized product shows a straight-line descending state from 0 minute, the degradation rate is very fast, the content of methyl orange in the solution is close to zero at 60 minutes, and the degradation rate reaches 96.7 percent at 90 minutes, which shows that the photocatalytic performance is particularly good.
As shown in FIG. 6, SnO synthesized with Sn/Ti of 1:12/TiO2The complete curve of the degraded methyl orange can be visually seen, and the photocatalytic effect of the product can be more visually seen according to the catalytic degradation degree of the methyl orange along with the change of time.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (1)
1. Composite photocatalytic material SnO2/TiO2The preparation method is characterized by comprising the following steps:
1) adding butyl titanate into ethanol at room temperature, and carrying out ultrasonic treatment for 0.5-2h to obtain a solution A;
2) SnO2Dispersing in deionized water to obtain solution B;
3) adding the solution A into the solution B, stirring at a stirring speed of 80-100r/min in a stirring device, and standing overnight, wherein the molar ratio of the butyl titanate to the metal ions is 1: 1;
4) centrifuging, drying and grinding the solution obtained in the step 3), calcining at 400-;
the drying conditions in the step 4) are as follows: drying at 80 deg.C for 4 hr, and drying at 90 deg.C for 2 hr;
the calcination temperature in the step 4) is 400 ℃, and the calcination time is 4 hours;
the SnO2The preparation method comprises the following steps:
step A: SnCl2·2H2Dissolving O in deionized water, and stirring for 30min to form a uniform solution;
and B: dissolving oxalic acid in deionized water to obtain oxalic acid solution, and stirring the SnCl obtained in the step A under the condition of magnetic stirring2·2H2Dropwise adding the O solution into the oxalic acid solution;
and C: b, adding polyvinylpyrrolidone into the solution obtained in the step B, and stirring until a white solution containing milky white precipitates is obtained;
step D: c, reacting the white solution obtained in the step C at the constant temperature of 160-180 ℃ for 5-7h, and then centrifuging, cleaning, drying and grinding;
step E: d, calcining the powder obtained after grinding in the step D, wherein the calcining process comprises the following steps: the calcination temperature is 400-600 ℃, and then SnO is obtained2A nanopowder;
SnCl added in the step B2·2H2The molar ratio of O to oxalic acid is 1:4, 1:2 or 1:1.5；
Before the polyvinylpyrrolidone is added in the step C, the polyvinylpyrrolidone is treated by using a catalyst, wherein the catalyst comprises the following raw materials: refined diatomite, boehmite, silicic acid gel, polyanionic cellulose and titanium sulfate; the preparation method of the catalyst comprises the following steps: uniformly mixing refined diatomite, boehmite, silicic acid gel, polyanionic cellulose and titanium sulfate, and grinding in a grinding device for 1 h; adding nitric acid with concentration of 0.5mol/L to dilute the ground powder until the powder becomes pasty, and then putting the powder into an extrusion device to repeatedly extrude the powder into a strip-shaped body for 2 hours; placing the obtained strip-shaped body at room temperature for 3h, airing, then adding the strip-shaped body into a low-temperature roasting furnace for low-temperature roasting for 20-30min, wherein the roasting temperature is 400 ℃ at 300-;
in the step E, the calcining temperature is 500 ℃, and the calcining time is 2 hours;
in the step 3), the stirring device comprises a base (1), a support frame (2), a mixing mechanism (3) and a stirring mechanism (4), wherein the support frame (2) is arranged at the upper end of the base (1), two clamping pieces (20) are arranged on the support frame (2), the two clamping pieces (20) are respectively arranged at the left side and the right side in the support frame (2), the mixing mechanism (3) comprises a mixing box (30) and a micro air adding pump (31), the mixing box (30) is connected with the support frame (2) through the clamping pieces (20), the micro air adding pump (31) is arranged at one end of the support frame (2), the micro air adding pump (31) is connected with the mixing box (30) through a vent pipe, an air filter screen (32) and a pressurizing nozzle (33) are arranged at the joint, the pressurizing nozzle (33) is arranged inside the mixing box (30), and a liquid outlet (300) is arranged at the bottom end of, a drawing plate is arranged on the liquid outlet (300); rabbling mechanism (4) include rotating electrical machines (40), rotation axis (41), cassette (42), agitator tank (43), stirring head (44), rotating electrical machines (40) do rotation axis (41) provide power, cassette (42) set up in rotation axis (41) upper end, are provided with the draw-in groove on cassette (42), just the draw-in groove is located liquid outlet (300) under, agitator tank (43) joint is in the draw-in groove, stirring head (44) are connected with rotation axis (41), and are located inside agitator tank (43).
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