CN110605134A - Hollow core-shell structure nitrogen-doped TiO2Method for preparing microspheres - Google Patents
Hollow core-shell structure nitrogen-doped TiO2Method for preparing microspheres Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 66
- 239000011258 core-shell material Substances 0.000 title claims abstract description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 188
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 54
- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 13
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 13
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 13
- 239000007888 film coating Substances 0.000 claims abstract description 3
- 238000009501 film coating Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 238000003837 high-temperature calcination Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 8
- 230000001699 photocatalysis Effects 0.000 abstract description 22
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 229910010443 TiO2-xNx Inorganic materials 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000011806 microball Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
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- 239000002105 nanoparticle Substances 0.000 description 8
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- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011941 photocatalyst 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
- 238000009792 diffusion process Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 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 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Abstract
The invention belongs to the field of photocatalytic nano materials, and provides nitrogen-doped TiO with a hollow core-shell structure2The preparation method of the microsphere comprises the following steps: (1) preparing titanium dioxide sol, (2) preparing PAM @ TiO2Single shell core-shell microball, (3) preparing SiO2@PAM@TiO2Double-shell core-shell microspheres, and (4) preparation of SiO2@@TiO2-xNx hollow core-shell structure microspheres; the invention adopts polyacrylamide and titanium dioxide which provide N element to mix to form single-shell nuclear shell microspheres, and then carries out film coating of silicon dioxide shellThe preparation method is simple, the titanium dioxide modification and the core-shell structure titanium dioxide modification are integrally formed, the cost is reduced, and the photocatalysis efficiency and the stability of a photocatalysis product are improved.
Description
Technical Field
The invention belongs to the field of photocatalytic nano materials, and particularly relates to a hollow core-shell structure nitrogen-doped TiO2A method for preparing microspheres.
Background
Titanium dioxide (chemical formula: TiO)2) The titanium dioxide photocatalyst has the advantages of good photocatalysis, no toxicity, low cost, easy obtaining, simple preparation, stable performance, no occurrence of photo corrosion and the like, so the titanium dioxide photocatalyst is considered to be one of the photocatalysts with the best performance and the most promising development prospect, after the titanium dioxide is excited by ultraviolet light, electrons and holes are separated, the generated strong redox capacity can even break C-H bonds, and therefore the titanium dioxide photocatalyst can be used for decomposing most organic matters and is widely applied to the fields of environmental catalysis, energy storage, sterilization, photocells, sensor devices and the like.
Because titanium dioxide has stronger redox ability, the surface of an organic carrier can be corroded while organic matters are decomposed, and a layer of silicon dioxide is coated on the surface of titanium dioxide nano particles by a common method such as a sol-gel method so as to protect the organic carrier from being corroded by titanium dioxide nano particles; however, since silica is an insulator, electrons or holes cannot reach the surface of the titania nanoparticles, thereby affecting the catalytic activity of the titania nanoparticles. In order to solve the problems, at present, researchers wrap a hollow silica protective layer on the surface of titanium dioxide nano particles, and due to the existence of the hollow layer, the problem that titanium dioxide corrodes an organic carrier is well solved, and meanwhile, certain catalytic activity is kept, but after titanium dioxide is treated, the catalytic activity of the titanium dioxide is reduced to a certain extent, and the catalytic activity of the titanium dioxide is researched to be 60% -80% of that before the titanium dioxide is treated.
In addition, because the titanium dioxide has a large bandwidth, only ultraviolet light with a wavelength less than 400nm can be absorbed and utilized, and the titanium dioxide has no catalytic efficiency under the light irradiation with a wavelength more than 400nm, the absorption and utilization capacity of the titanium dioxide to visible light is limited, so how to further improve the visible light catalytic action of the titanium dioxide becomes a research hotspot and difficulty of new environment-friendly catalytic materials.
The photocatalytic activity of titanium dioxide is affected by factors such as its own crystal structure, specific surface area, particle size, energy band structure, surface hydroxyl concentration, etc., and in order to improve the photocatalytic activity of semiconductors, in the past research, the research of doping various transition metals is widely used for expanding the visible region of the light absorption range, the metal ions can effectively improve the photocatalysis of the titanium dioxide, however, because the thermodynamics of metal ions is unstable, the problem of the compounding of photocarrier ions is easily caused, and in order to effectively improve the problem, researches find that non-metal elements can be added into titanium dioxide to neutralize the reaction of different ions, the non-metal element N is doped into the titanium dioxide, and the solid phase reaction can strengthen the reaction with visible light, so that the titanium dioxide has visible light photocatalytic activity and is considered as a breakthrough of titanium dioxide visible light photocatalysis.
In summary, the modification of titanium dioxide by doping a non-metal N element while performing the structure setting of the silica protective layer on the titanium dioxide is significant for improving the photocatalytic activity of titanium dioxide, and the existing method is to prepare titanium dioxide microspheres with hollow core-shell structures first, and then to dope nitrogen into titanium dioxide particles by using a modification technology, so as to enhance the response of the titanium dioxide microspheres to visible light, and the process is tedious, affects the stability of the product, and needs to be improved urgently.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a hollow core-shell structure nitrogen-doped TiO2 microsphere, which does not need to prepare a template, can prepare a protective shell at one time by construction and N doping, avoids a complicated preparation process, can reduce the cost and improve the stability of a product.
The technical scheme adopted by the invention provides a preparation method of a nitrogen-doped TiO2 microsphere with a hollow core-shell structure, which comprises the following steps:
step 1: preparing titanium dioxide sol, slowly adding a mixed solution of butyl titanate and absolute ethyl alcohol into a nitric acid solution, and uniformly stirring to obtain colorless and transparent titanium dioxide sol;
step 2: preparation of PAM @ TiO2Slowly adding polyacrylic acid into water to dissolve under the conditions that the water temperature is 40 ~ 60 ℃ and the stirring speed is 100 ~ 300r/min, preparing a 0.15% polyacrylic acid aqueous solution, mixing the obtained polyacrylamide aqueous solution with the titanium dioxide sol prepared in the step 1, adding an initiator to perform polymerization reaction, cleaning and drying the polymerization product for multiple times to obtain the single-shell core-shell microspheres with the surfaces of the titanium dioxide coated with the polyacrylamide;
and step 3: preparation of SiO2@PAM@TiO2Carrying out silica film coating on the surface of the single-layer shell-core microsphere obtained in the step 2 by adopting a sol-gel method to obtain PAM @ TiO2The surface of the shell is wrapped with the double-shell core-shell microspheres of silicon dioxide;
and 4, step 4: preparation of SiO2@@TiO2-xNxRemoving the shell obtained in the step 4 by adopting a high-temperature calcination method to form a polyacrylamide intermediate shell layer in the perforated double-shell-layer core-shell microsphere, wherein in the high-temperature calcination process, N element generated by thermal decomposition of polyacrylamide is subjected to thermal diffusion doping and enters TiO2The crystal lattices can be uniformly mixed at the molecular level, and the nitrogen-doped TiO with a hollow core-shell structure is obtained by cooling and grinding after the calcination2And (3) microspheres.
Furthermore, the quantity ratio of the butyl titanate to the absolute ethyl alcohol substance in the mixed solution in the step 1 is 1:3 ~ 8, the concentration of the nitric acid solution is 1 ~ 1.5.5 mol/L, and the volume ratio of the mixed solution to the nitric acid solution is 1:2 ~ 5.
Further, the concentration of the polyacrylamide aqueous solution in step 2 was 0.1 ~ 0.3.3%.
Further, in the step 2, the initiator is one or more of ammonium persulfate, potassium persulfate and sodium bisulfite.
Further, the polymerization product in the step 2 is sequentially subjected to anhydrous formaldehyde cleaning, nitrogen drying, anhydrous acetone cleaning and nitrogen drying.
Further, the anhydrous acetone washing adopts a soxhlet extraction method, a soxhlet extractor is adopted to extract the single-shell core-shell microspheres, and anhydrous acetone is used for condensation and reflux for 24 ~ 48h to remove polymers physically adsorbed on the surfaces of the single-shell core-shell microspheres.
Further, the high-temperature calcination in the step 4 adopts a muffle furnace for calcination, and the calcination temperature is 500 ~ 700 ℃.
Further, before the step 4, the double-shell core-shell microspheres obtained in the step 3 are subjected to corrosion treatment by using corrosive agent steam to remove part of the silica shell to form open pores, and the open pores can enable TiO to be arranged2The inner core is partially exposed, so that the photocatalytic performance is better improved.
Further, the corrosive agent is hydrofluoric acid or inorganic strong base.
Furthermore, the grinding in the step 4 adopts a ball milling method, the hollow titanium dioxide microspheres prepared by the ball milling method have uniform particle size and small size, and the particle size range of the hollow titanium dioxide microspheres is 200 ~ 600 nm.
The invention has the beneficial effects that:
1. the invention adopts polyacrylamide and titanium dioxide which provide N element to mix to form single-shell nuclear shell microsphere, then carries out film covering of silicon dioxide shell to form double-shell nuclear shell microsphere, under high temperature calcination, on one hand, the polyacrylamide which is used as an intermediate shell layer is thermally decomposed to remove and form a cavity, on the other hand, the N element is provided after thermal decomposition to be thermally diffused and doped into the titanium dioxide, and the nitrogen-doped TiO with hollow nuclear shell structure is obtained2The microsphere greatly simplifies the conventional preparation process of firstly modifying the crystal structure and then modifying titanium dioxide by a modification method, the preparation method is simple, the titanium dioxide modification and the core-shell structure are integrally formed, the cost is reduced, and the photocatalytic efficiency and the stability of a photocatalytic product are improved;
2. after the hollow core-shell structure provided by the silicon dioxide is used for protection, the problem that the titanium dioxide corrodes the organic carrier is avoided, the organic carrier can be protected from being damaged, other molecules can be absorbed by the inner cavity part of the hollow core-shell structure, the contact between reactants and the photocatalyst is enhanced, the photocatalytic activity is improved, meanwhile, the band gap of TiO2 can be narrowed by substituting a small amount of lattice oxygen with N element provided by thermal decomposition of polyacrylamide, the visible light catalytic capability of the titanium dioxide is effectively improved under the condition of not sacrificing the ultraviolet light activity, and the application range of the photocatalyst is enlarged.
Detailed Description
The technical solution of the present invention will be further described with reference to the specific embodiments of the present invention.
Example 1
Step 1: preparing titanium dioxide sol, mixing tetrabutyl titanate and absolute ethyl alcohol according to the mass ratio of 1:5, fully shaking up to obtain a mixed solution, dropwise adding 10ml of the mixed solution into 35ml of nitric acid solution with the mass concentration of 1 mol/L, and continuously stirring to prevent condensation in the process until colorless and transparent titanium dioxide sol is formed;
step 2: preparation of PAM @ TiO2Mixing the titanium dioxide sol prepared in the step 1 with a polyacrylamide aqueous solution with the concentration of 0.15%, adding an initiator ammonium persulfate to perform polymerization reaction, and performing anhydrous formaldehyde cleaning, nitrogen drying, anhydrous acetone cleaning and nitrogen drying on a polymerization product to obtain the single-shell core-shell microspheres with the surfaces of the titanium dioxide coated with polyacrylamide;
and step 3: preparation of SiO2@PAM@TiO2Carrying out silicon dioxide coating on the surface of the single-layer shell-core microsphere obtained in the step 2 by adopting a sol-gel method, and coating the PAM @ TiO2Dispersing the single-shell core-shell microspheres in ethanol and aqueous solution, and adding ammonia water to form second mixed solution; adding tetraethoxysilane into the second mixed solution, stirring for reaction, then carrying out vacuum drying, and grinding to obtain PAM @ TiO2The surface of the shell is wrapped with the double-shell core-shell microspheres of silicon dioxide;
and 4, step 4: preparation of SiO2@@TiO2-xNxHollow typeRemoving PAM @ TiO obtained in step 4 by adopting muffle furnace high-temperature calcination of core-shell structure microspheres2Calcining the single-shell core-shell microspheres in a muffle furnace at 600 ℃ for 4h, removing the polyacrylamide intermediate shell in the high-temperature calcining process, and performing thermal diffusion doping on N element generated by thermal decomposition of polyacrylamide to enter TiO2And uniformly mixing the crystal lattices at the molecular level, cooling to room temperature, and grinding by a ball milling method to obtain a final product.
Example 2
Step 1: preparing titanium dioxide sol, mixing butyl titanate and absolute ethyl alcohol according to the amount of substances of 1:3, fully shaking up to obtain a mixed solution, dropwise adding 10ml of the mixed solution into 20ml of nitric acid solution with the substance amount concentration of 0.8mol/L, and continuously stirring to prevent condensation in the process until colorless and transparent titanium dioxide sol is formed;
step 2: preparation of PAM @ TiO2Mixing the titanium dioxide sol prepared in the step 1 with a polyacrylamide aqueous solution with the concentration of 0.1%, adding an initiator potassium persulfate to perform a polymerization reaction, and performing anhydrous formaldehyde cleaning, nitrogen drying, anhydrous acetone cleaning and nitrogen drying on a polymerization product to obtain the single-shell core-shell microspheres with the surfaces of the titanium dioxide coated with polyacrylamide;
and step 3: preparation of SiO2@PAM@TiO2Carrying out silicon dioxide coating on the surface of the single-layer shell-core microsphere obtained in the step 2 by adopting a sol-gel method, and coating the PAM @ TiO2Dispersing the single-shell core-shell microspheres in ethanol and aqueous solution, and adding ammonia water to form second mixed solution; adding tetraethoxysilane into the second mixed solution, stirring for reaction, then carrying out vacuum drying, and grinding to obtain PAM @ TiO2The surface of the shell is wrapped with the double-shell core-shell microspheres of silicon dioxide;
and 4, step 4: preparation of SiO2@@TiO2-xNxRemoving PAM @ TiO obtained in step 4 by adopting muffle furnace high-temperature calcination of hollow core-shell structure microspheres2The single-shell nuclear shell microspheres are placed in a muffle furnace and calcined for 4 hours at 500 ℃, the intermediate shell of polyacrylamide is removed in the high-temperature calcination process,and N element generated by thermal decomposition of polyacrylamide is doped into TiO by thermal diffusion2And uniformly mixing the crystal lattices at the molecular level, cooling to room temperature, and grinding by a ball milling method to obtain a final product.
Example 3
Step 1: preparing titanium dioxide sol, mixing butyl titanate and absolute ethyl alcohol according to the amount of substances of 1:8, fully shaking up to obtain a mixed solution, dropwise adding 10ml of the mixed solution into 50ml of nitric acid solution with the substance amount concentration of 1.5mol/L, and continuously stirring to prevent condensation in the process until colorless and transparent titanium dioxide sol is formed;
step 2: preparation of PAM @ TiO2Mixing the titanium dioxide sol prepared in the step 1 with a polyacrylamide aqueous solution with the concentration of 0.25%, adding an initiator sodium bisulfite to perform polymerization reaction, and performing anhydrous formaldehyde cleaning, nitrogen drying, anhydrous acetone cleaning and nitrogen drying on a polymerization product to obtain the single-shell core-shell microspheres with the surfaces of the titanium dioxide coated with polyacrylamide;
and step 3: preparation of SiO2@PAM@TiO2Carrying out silicon dioxide coating on the surface of the single-layer shell-core microsphere obtained in the step 2 by adopting a sol-gel method, and coating the PAM @ TiO2Dispersing the single-shell core-shell microspheres in ethanol and aqueous solution, and adding ammonia water to form second mixed solution; adding tetraethoxysilane into the second mixed solution, stirring for reaction, then carrying out vacuum drying, and grinding to obtain PAM @ TiO2The surface of the shell is wrapped with the double-shell core-shell microspheres of silicon dioxide;
and 4, step 4: preparation of SiO2@@TiO2-xNxRemoving PAM @ TiO obtained in step 4 by adopting muffle furnace high-temperature calcination of hollow core-shell structure microspheres2Calcining the single-shell core-shell microspheres in a muffle furnace at 700 ℃ for 3h, removing the polyacrylamide intermediate shell in the high-temperature calcining process, and performing thermal diffusion doping on N element generated by thermal decomposition of polyacrylamide to enter TiO2And uniformly mixing the crystal lattices at the molecular level, cooling to room temperature, and grinding by a ball milling method to obtain a final product.
Example 4
The preparation method of this example is the same as example 1, and differs from example 1 in that:
before the step 4, the double-shell core-shell microspheres obtained in the step 3 are subjected to etching treatment by using hydrofluoric acid or inorganic strong base through etchant vapor so as to remove part of the silicon dioxide shell to form open pores.
Comparative example 1
Step 1: preparing titanium dioxide sol, mixing tetrabutyl titanate and absolute ethyl alcohol according to the mass ratio of 1:5, fully shaking up to obtain a mixed solution, dropwise adding 10ml of the mixed solution into 35ml of nitric acid solution with the mass concentration of 1 mol/L, and continuously stirring to prevent condensation in the process until colorless and transparent titanium dioxide sol is formed;
step 2: preparation of SiO2@TiO2Carrying out silicon dioxide coating on the surface of the titanium dioxide sol obtained in the step (1) by adopting a sol-gel method, dispersing the titanium dioxide sol into ethanol and aqueous solution, and adding ammonia water to form mixed solution; adding ethyl orthosilicate into the mixed solution, stirring to react, then drying in vacuum, and grinding by a ball milling method to obtain the single-shell core-shell microspheres with the surfaces of titanium dioxide wrapped by silicon dioxide.
Comparative example 2
Step 1: preparing titanium dioxide sol, mixing tetrabutyl titanate and absolute ethyl alcohol according to the mass ratio of 1:5, fully shaking up to obtain a mixed solution, dropwise adding 10ml of the mixed solution into 35ml of nitric acid solution with the mass concentration of 1 mol/L, and continuously stirring to prevent condensation in the process until colorless and transparent titanium dioxide sol is formed;
step 2: preparation of PAM @ TiO2Mixing the titanium dioxide sol prepared in the step 1 with a polyacrylamide aqueous solution with the concentration of 0.15%, adding an initiator ammonium persulfate to perform polymerization reaction, and performing anhydrous formaldehyde cleaning, nitrogen drying, anhydrous acetone cleaning and nitrogen drying on a polymerization product to obtain the single-shell core-shell microspheres with the surfaces of the titanium dioxide coated with polyacrylamide;
and step 3: preparation of TiO2-xNxRemoving PAM @ TiO obtained in step 2 by adopting muffle furnace high-temperature calcination of core-shell structure microspheres2The single-shell core-shell microspheres are placed in a muffle furnace and calcined for 4 hours at the temperature of 600 ℃, and in the high-temperature calcination process, N element generated by thermal decomposition of polyacrylamide is subjected to thermal diffusion and doping to enter TiO2Uniformly mixing the crystal lattices at the molecular level, cooling to room temperature, and grinding by a ball milling method to obtain the nitrogen-doped TiO2And (3) microspheres.
TiO prepared by the above examples and comparative examples2The microspheres were tested for particle size and photocatalytic effect, and the results are shown in table 1.
The following experimental methods were used for clearance:
(1) preparing a rhodamine B solution with the concentration of 10 mg/L, and placing the prepared solution in a dark place;
(2) weighing 0.1 g of photocatalytic nanoparticles prepared in the embodiment 3, loading the photocatalytic nanoparticles on a fabric, placing the fabric in a photoreactor, adding 100 mL of rhodamine B solution prepared in the step (1), magnetically stirring for 30min, bubbling, carrying out a dark reaction for 1 h, turning on a light source after the nanoparticles are uniformly dispersed, and carrying out a photocatalytic degradation experiment;
(3) irradiating for 30min, 40min, 50min and 60min, measuring the concentration of rhodamine B by taking 1ml of solution, and analyzing the degradation rate.
TABLE 1 results of Performance test of each of examples and comparative examples
As shown by the performance test results of the examples and the comparative examples in the table 1, example 1 ~ 4 shows that the nitrogen-doped TiO with the hollow core-shell structure obtained by the preparation method provided by the invention is example 12The microspheres have the average particle size of 200 ~ 400nm, the degradation rate of the rhodamine B solution within 40min can reach 100%, the photocatalytic effect is excellent, the degradation rate of the rhodamine B solution is only 65% at most due to lack of modification on titanium dioxide in comparative example 1, the photocatalytic effect is poor, and the photocatalytic effect is too high due to lack of protection of a silicon dioxide shell in comparative example 2In the process, organic carriers in the fabric are corroded, the photocatalytic performance is interfered, the degradation rate of the rhodamine B solution is 83%, and the effect is poor.
It should be understood that the above-described embodiments are only preferred embodiments of the present invention, rather than all embodiments, and the embodiments of the present invention are not limited to the above-described embodiments, and all other embodiments obtained by modifications, equivalents, improvements, etc. by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts should fall within the protection scope of the present invention.
Claims (10)
1. Hollow core-shell structure nitrogen-doped TiO2The preparation method of the microsphere is characterized by comprising the following steps:
step 1: preparing titanium dioxide sol, slowly adding a mixed solution of butyl titanate and absolute ethyl alcohol into a nitric acid solution, and uniformly stirring to obtain colorless and transparent titanium dioxide sol;
step 2: preparation of PAM @ TiO2Mixing the titanium dioxide sol prepared in the step 1 with a polyacrylamide aqueous solution, adding an initiator to perform polymerization reaction, and cleaning and drying a polymerization product for multiple times to obtain the single-shell core-shell microspheres with polyacrylamide coated on the surface of titanium dioxide;
and step 3: preparation of SiO2@PAM@TiO2Carrying out silica film coating on the surface of the single-layer shell-core microsphere obtained in the step 2 by adopting a sol-gel method to obtain PAM @ TiO2The surface of the shell is wrapped with the double-shell core-shell microspheres of silicon dioxide;
and 4, step 4: preparation of SiO2@@TiO2Removing a polyacrylamide intermediate shell layer in the double-shell nuclear shell microsphere by adopting a high-temperature calcination method, doping N element generated by thermal decomposition of polyacrylamide into titanium dioxide in the process, cooling and grinding after calcination is finished to obtain the nitrogen-doped TiO with the hollow nuclear shell structure2And (3) microspheres.
2. Such asThe hollow core-shell structure of claim 1, wherein the doped TiO is doped with nitrogen2The preparation method of the microspheres is characterized in that in the step 1, the mass ratio of butyl titanate to absolute ethyl alcohol substances in the mixed solution is 1: 3-8, the concentration of the nitric acid solution is 0.8-1.2 mol/L, and the volume ratio of the mixed solution to the nitric acid solution is 1: 2-5.
3. The preparation method of the nitrogen-doped TiO2 microsphere with the hollow core-shell structure according to claim 1, wherein the concentration of the polyacrylamide aqueous solution in the step 2 is 0.1-0.3%.
4. The hollow core-shell structure of claim 1, wherein said TiO is doped with nitrogen2The preparation method of the microsphere is characterized in that the initiator in the step 2 is one or more of ammonium persulfate, potassium persulfate or sodium bisulfite.
5. The hollow core-shell structure of claim 1, wherein said TiO is doped with nitrogen2The preparation method of the microspheres is characterized in that the polymerization product in the step 2 is sequentially subjected to anhydrous formaldehyde cleaning, nitrogen drying, anhydrous acetone cleaning and nitrogen drying.
6. The hollow core-shell structure of claim 5, wherein the doped TiO is doped with nitrogen2The preparation method of the microspheres is characterized in that the anhydrous acetone cleaning adopts a Soxhlet extraction method.
7. The hollow core-shell structure of claim 1, wherein said TiO is doped with nitrogen2The preparation method of the microspheres is characterized in that in the step 4, the high-temperature calcination is carried out by adopting a muffle furnace, and the calcination temperature is 500-700 ℃.
8. The hollow core-shell structure of claim 1, wherein said TiO is doped with nitrogen2The preparation method of the microsphere is characterized in that before the step 4, the double-shell core-shell microsphere obtained in the step 3 is corroded by corrosive agent steamSo as to remove part of the silicon dioxide shell to form an opening.
9. The hollow core-shell structure of claim 8, wherein the doped TiO is doped with nitrogen2The preparation method of the microsphere is characterized in that the corrosive is hydrofluoric acid or inorganic strong base.
10. The hollow core-shell structure of claim 1, wherein said TiO is doped with nitrogen2The preparation method of the microsphere is characterized in that the grinding in the step 4 adopts a ball milling method.
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