CN101805019A - Synthesis method of N doped hollow TiO2 microspheres - Google Patents
Synthesis method of N doped hollow TiO2 microspheres Download PDFInfo
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- CN101805019A CN101805019A CN201010153793.2A CN201010153793A CN101805019A CN 101805019 A CN101805019 A CN 101805019A CN 201010153793 A CN201010153793 A CN 201010153793A CN 101805019 A CN101805019 A CN 101805019A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 19
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 239000004793 Polystyrene Substances 0.000 claims abstract description 56
- 229920002223 polystyrene Polymers 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000000839 emulsion Substances 0.000 claims abstract description 34
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 23
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 60
- 238000002156 mixing Methods 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 17
- 238000010189 synthetic method Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 13
- 230000001476 alcoholic effect Effects 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 10
- 229960004418 trolamine Drugs 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 239000003112 inhibitor Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000002019 doping agent Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000004159 Potassium persulphate Substances 0.000 abstract description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 abstract description 2
- -1 1-tert-butyl-1H-tetrazol-5-yl Chemical group 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000005253 cladding Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000005242 forging Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 21
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention discloses a synthesis method of N doped hollow TiO2 microspheres, comprising the following steps of: adding styrene, polyvinylpyrrolidone and water in a reaction vessel for stirring under the protection of N2, heating the materials to 70 DEG C, then adding a potassium persulphate aqueous solution to the heated materials for polymerization reaction to obtain polystyrene emulsion; adding ethanol, ammonia water and the polystyrene emulsion to the reaction vessel for stirring and keeping the temperate of 50 DEG C, then adding a solution with three mixed components of TBT (1-tert-butyl-1H-tetrazol-5-yl), TEA (triethanolamine) and ethanol for carrying out TiO2 cladding polystyrene particle reaction; after finishing the addition, continuously stirring the materials for a while, carrying out the centrifugal separation and drying to obtain polystyrene-TiO2(core-shell) composite microspheres; removing the polystyrene by forging to obtain the N doped hollow TiO2 microspheres. The invention has the advantages that the TEA plays a role of an inhibitor for controlling the generation of TiO2 particles and the coating speed and also an N dopant of hollow TiO2 microspheres in the process of synthesizing the N doped hollow TiO2 microspheres.
Description
Technical field
The present invention relates to a kind of synthetic method of hollow inorganic microspheres, specifically a kind of N doped hollow TiO
2The synthetic method of microballoon.
Background technology
In recent years, the inorganic hollow particle has become the theme of broad research in chemistry and the Materials science.Wherein, TiO
2Tiny balloon has caused concern especially, and it has important use at aspects such as photochemical catalysis, photochemistry solar cell, chemical sensors.By the calcining and dissolution with solvents with polymkeric substance-TiO
2Nuclear in (nuclear-shell) complex microsphere is removed and is just obtained hollow TiO
2Microballoon.Regulate calcination condition and can obtain anatase titanium dioxide, rutile TiO
2Polymkeric substance-TiO
2Self-assembly method and sol-gel method are layer by layer mainly adopted in the complex microsphere preparation.The sol-gel method method is simple, productive rate is high.TiO
2The hydrolysis of presoma and polycondensation are very fast, as suitably not controlling, are difficult to generate TiO
2The even coating of particle.Often select for use mineral acid and complex compound to control as inhibitor.TiO
2Photocatalytic applications owing to its broad band be restricted at interval-ultraviolet light irradiation is photocatalytic activity.And UV-light only accounts for 5% of sunlight total energy, and visible light accounts for 45%.Therefore, the scope from the UV-light to the visible light realizes TiO
2Photochemical catalysis response, have significant role to improving its photocatalysis efficiency.Method has doped metal ion and non-metallic element etc., and wherein N mixes the most general.Synthetic in the past N doped Ti O
2Method will be used inhibitor and N doping agent respectively, and is more numerous and diverse.
Summary of the invention
Goal of the invention: the invention provides a kind of simple to operate, in synthetic system, use trolamine to bear the N doped hollow TiO of the dual function of inhibitor and N doping agent
2The synthetic method of microballoon.
Technical scheme: N doped hollow TiO of the present invention
2The synthetic method of nanoparticle may further comprise the steps:
(1) adds vinylbenzene (St), polyvinylpyrrolidone (PVP) and water, N in the reaction vessel
220min is stirred in protection down; Its weight ratio is: St is 10～9.71%, and PVP is 0～2.91%, and water is 90～87.38%;
(2) N
2Protection down, with the mixture heating up to 70 of step (1) ℃, add with step (1) in Potassium Persulphate (KPS) aqueous solution (1%, massfraction) the reaction 12h of weight such as St, obtain polystyrene (PS) emulsion;
(3) add the PS emulsion of ethanol, ammoniacal liquor and step (2) gained in the reaction vessel, stir, remain on 50 ℃; Its weight ratio is: ethanol is 93.14～87.96%, and ammoniacal liquor is 1.96～7.41%, and the PS emulsion is 4.90～4.63%;
(4) add tetra-n-butyl titanate (TBT), trolamine (TEA), ethanol three blended mixing solutions in the reaction vessel in step (3), carry out TiO
2Coat PS 1.0～10h, add back continuation stirring 5h and promptly obtain suspension; The consumption of described mixing solutions is 0.4～4.0 times of the middle PS emulsion weight of step (3); When the PVP add-on was 0 in the step (1), TBT, TEA, alcoholic acid weight ratio were 1.0: 0.1～0.4: 1.0 in the mixing solutions; When adding PVP in the step (1), TBT, TEA, alcoholic acid weight ratio are 1.0: 0.1～0.4: 9.0 in the mixing solutions.
(5) suspension to step (4) gained carries out centrifugation, drying obtains polystyrene-TiO
2Complex microsphere, wherein polystyrene is nuclear, TiO
2Be shell;
(6) to the polystyrene-TiO of step (5) gained
2Complex microsphere is removed polystyrene at 500 ℃ of calcining 2h and is promptly obtained N doped hollow TiO
2Microballoon.
In system, TBT generates TiO by sol-gel (sol-gel) reaction
2Particle deposits to the PS particle surface then and forms TiO
2Shell obtains PS-TiO
2(nuclear-shell) complex microsphere.Remove the N doped hollow TiO that PS nuclear obtains anatase titanium dioxide by calcining
2Microballoon.Whether add PVP in the reaction system to N doped hollow TiO
2The size of microballoon is influential.Synthetic PS size of particles is not bigger when adding PVP, and synthetic PS size of particles is less when adding PVP.Therefore, to not using the N doped hollow TiO that PVP synthetic PS coats, calcining obtains
2The microballoon size is greater than the microballoon size to using PVP synthetic PS coating, calcining to obtain.The PVP consumption increases, N doped hollow TiO
2The microballoon size descends.Ammonia volume is to N doped hollow TiO
2The configuration of surface of microballoon is influential.The TEA consumption increases, the shell surface become smooth, TiO
2Doping N content in the shell improves.The TBT consumption increases, TiO
2Shell thickness increases.By the control of calcination condition, make amorphous TiO
2Change anatase titanium dioxide TiO into
2
Beneficial effect: advantage of the present invention is to have adopted trolamine in building-up process, can not only play the inhibitor effect, promptly controls TiO
2Particle generates and coating speed, obtains the TiO of better form
2Shell, and can play the effect of N doping agent, promptly by calcining at TiO
2Forming N in the shell mixes.
Description of drawings
Accompanying drawing 2 is to use the N doped hollow TiO of PVP preparation
2The TEM photo of microballoon.
Embodiment
Below by embodiment the present invention is specifically described, be necessary to be pointed out that at this, following examples only are used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention.
Embodiment 1:
A kind of N doped hollow TiO of the present invention
2The synthetic method of microballoon, it may further comprise the steps:
1, synthetic PS emulsion: add 10.0g St, 90.0g water, N in the 250mL reaction flask
2Protection is stirring at room 20min down, is heated to 70 ℃ then, adds the 10.0g KPS aqueous solution (1%, massfraction) reaction 12h, obtains the PS emulsion.
2, synthetic PS-TiO
2Complex microsphere: add 95.0g ethanol, 5.0g ammoniacal liquor, 5.0g step 1 synthetic PS emulsion in the 250mL reaction flask, adding 5.0g TBT, TEA, ethanol three blended mixing solutions coat 2.5h under 50 ℃, and wherein TBT, TEA, alcoholic acid weight ratio are 1.0: 0.2: 1.0 in the mixing solutions; Add the back and continue to stir 5h; With the reaction product centrifugation, be drying to obtain PS-TiO
2Complex microsphere.
3, under 500 ℃ with step 2 synthetic PS-TiO
2Complex microsphere calcining 2h removes PS nuclear and promptly obtains N doped hollow TiO shown in Figure 1
2Microballoon.
Embodiment 2:
Another kind of N doped hollow TiO of the present invention
2The synthetic method of microballoon, it may further comprise the steps:
1, synthetic PS emulsion: add 10.0g St, 90.0g water, N in the 250mL reaction flask
2Protection is stirring at room 20min down, is heated to 70 ℃ then, adds the 10.0g KPS aqueous solution (1%, massfraction) reaction 12h, obtains the PS emulsion.
2, synthetic PS-TiO
2Complex microsphere: add 95.0g ethanol, 2.0g ammoniacal liquor, 5.0g step 1 synthetic PS emulsion in the 250mL reaction flask, adding 2.0g TBT, TEA, ethanol three blended mixing solutions coat 1.0h under 50 ℃, and wherein TBT, TEA, alcoholic acid weight ratio are 1.0: 0.1: 1.0 in the mixing solutions; Add the back and continue to stir 5h; With the reaction product centrifugation, be drying to obtain PS-TiO
2Complex microsphere, wherein PS is nuclear, TiO
2Be shell.
3, under 500 ℃ with step 2 synthetic PS-TiO
2Complex microsphere calcining 2h removes PS nuclear and promptly obtains N doped hollow TiO
2Microballoon.
Embodiment 3:
Another kind of N doped hollow TiO of the present invention
2The synthetic method of microballoon, it may further comprise the steps:
1, synthetic PS emulsion: add 10.0g St, 90.0g water, N in the 250mL reaction flask
2Protection is stirring at room 20min down, is heated to 70 ℃ then, adds the 10.0g KPS aqueous solution (1%, massfraction) reaction 12h, obtains the PS emulsion;
2, synthetic PS-TiO
2Complex microsphere: add 95.0g ethanol, 8.0g ammoniacal liquor, 5.0g step 1 synthetic PS emulsion in the 250mL reaction flask, adding 8.0g TBT, TEA, ethanol three blended mixing solutions coat 4h under 50 ℃, and wherein TBT, TEA, alcoholic acid weight ratio are 1.0: 0.4: 1.0 in the mixing solutions; Add the back and continue to stir 5h; With the reaction product centrifugation, be drying to obtain PS-TiO
2Complex microsphere.
3, under 500 ℃ with step 2 synthetic PS-TiO
2Complex microsphere calcining 2h removes PS nuclear and promptly obtains N doped hollow TiO
2Microballoon.
Embodiment 4:
Another kind of N doped hollow TiO of the present invention
2The synthetic method of microballoon, it may further comprise the steps:
1, synthetic PS emulsion: add 10.0g St, 1.5g PVP, 90.0g water, N in the 250mL reaction flask
2Protection is stirring at room 20min down, is heated to 70 ℃ then, adds the 10.0g KPS aqueous solution (1%, massfraction) reaction 12, obtains the PS emulsion.
2, synthetic PS-TiO
2Complex microsphere: add 95.0g ethanol, 2.0g ammoniacal liquor, 5.0g step 1 synthetic PS emulsion in the 250mL reaction flask, adding 20.0g TBT, TEA, ethanol three blended mixing solutions coat 10h under 50 ℃, and wherein TBT, TEA, alcoholic acid weight ratio are 1.0: 0.1: 9.0 in the mixing solutions; Add the back and continue to stir 5h; With the reaction product centrifugation, be drying to obtain PS-TiO
2Complex microsphere.
3, under 500 ℃ with step 2 synthetic PS-TiO
2Complex microsphere calcining 2h removes PS nuclear and promptly obtains N doped hollow TiO shown in Figure 2
2Microballoon.
Embodiment 5:
Another kind of N doped hollow TiO of the present invention
2The synthetic method of microballoon, it may further comprise the steps:
1, synthetic PS emulsion: add 10.0g St, 3.0g PVP, 90.0g water, N in the 250mL reaction flask
2Protection is stirring at room 20min down, is heated to 70 ℃ then, adds the 10.0g KPS aqueous solution (1%, massfraction) reaction 12h, obtains the PS emulsion.
2, synthetic PS-TiO
2Complex microsphere: add 95.0g ethanol, 3.0g ammoniacal liquor, 5.0g step 1 synthetic PS emulsion in the 250mL reaction flask, adding 7.5g TBT, TEA, ethanol three blended mixing solutions coat 3.8h under 50 ℃, and wherein TBT, TEA, alcoholic acid weight ratio are 1.0: 0.2: 9.0 in the mixing solutions; Add the back and continue to stir 5h; With the reaction product centrifugation, be drying to obtain PS-TiO
2Complex microsphere.
3, under 500 ℃ with step 2 synthetic PS-TiO
2Complex microsphere calcining 2h removes PS nuclear and promptly obtains N doped hollow TiO
2Microballoon.
Embodiment 6:
Another kind of N doped hollow TiO of the present invention
2The synthetic method of microballoon, it may further comprise the steps:
1, synthetic PS emulsion: add 10.0g St, 2.0g PVP, 90.0g water, N in the 250mL reaction flask
2Protection is stirring at room 20min down, is heated to 70 ℃ then, adds the 10.0g KPS aqueous solution (1%, massfraction) reaction 12h, obtains the PS emulsion.
2, synthetic PS-TiO
2Complex microsphere: add 95.0g ethanol, 4.0g ammoniacal liquor, 5.0g step 1 synthetic PS emulsion in the 250mL reaction flask, adding 10.0g TBT, TEA, ethanol three blended mixing solutions coat 5h under 50 ℃, and wherein TBT, TEA, alcoholic acid weight ratio are 1.0: 0.3: 9.0 in the mixing solutions; Add the back and continue to stir 5h; With the reaction product centrifugation, be drying to obtain PS-TiO
2Complex microsphere.
3, under 500 ℃ with step 2 synthetic PS-TiO
2Complex microsphere calcining 2h removes PS nuclear and promptly obtains N doped hollow TiO
2Microballoon.
Embodiment 7:
Another kind of N doped hollow TiO of the present invention
2The synthetic method of microballoon, it may further comprise the steps:
1, synthetic PS emulsion: add 10.0g St, 2.2g PVP, 90.0g water, N in the 250mL reaction flask
2Protection is stirring at room 20min down, is heated to 70 ℃ then, adds the 10.0g KPS aqueous solution (1%, massfraction) reaction 12, obtains the PS emulsion.
2, synthetic PS-TiO
2Complex microsphere: add 95.0g ethanol, 5.0g ammoniacal liquor, 5.0g step 1 synthetic PS emulsion in the 250mL reaction flask, adding 15.0g TBT, TEA, ethanol three blended mixing solutions coat 7.5h under 50 ℃, and wherein TBT, TEA, alcoholic acid weight ratio are 1.0: 0.4: 9.0 in the mixing solutions; Add the back and continue to stir 5h; With the reaction product centrifugation, be drying to obtain PS-TiO
2Complex microsphere.
3, under 500 ℃ with step 2 synthetic PS-TiO
2Complex microsphere calcining 2h removes PS nuclear and promptly obtains N doped hollow TiO
2Microballoon.
Embodiment 8:
Another kind of N doped hollow TiO of the present invention
2The synthetic method of microballoon, it may further comprise the steps:
1, synthetic PS emulsion: add 10.0g St, 2.5g PVP, 90.0g water, N in the 250mL reaction flask
2Protection is stirring at room 20min down, is heated to 70 ℃ then, adds the 10.0g KPS aqueous solution (1%, massfraction) reaction 12, obtains the PS emulsion.
2, synthetic PS-TiO
2Complex microsphere: add 95.0g ethanol, 2.5g ammoniacal liquor, 5.0g step 1 synthetic PS emulsion in the 250mL reaction flask, adding 13.0g TBT, TEA, ethanol three blended mixing solutions coat 6.5h under 50 ℃, and wherein TBT, TEA, alcoholic acid weight ratio are 1.0: 0.15: 9.0 in the mixing solutions; Add the back and continue to stir 5h; With the reaction product centrifugation, be drying to obtain PS-TiO
2Complex microsphere.
3, under 500 ℃ with step 2 synthetic PS-TiO
2Complex microsphere calcining 2h removes PS nuclear and promptly obtains N doped hollow TiO
2Microballoon.
Claims (3)
1. N doped hollow TiO
2The synthetic method of microballoon is characterized in that this synthetic method may further comprise the steps:
(1) adds vinylbenzene, polyvinylpyrrolidone and water, N in the reaction vessel
220min is stirred in protection down; Its weight ratio is: vinylbenzene is 10～9.71%, and polyvinylpyrrolidone is 0～2.91%, and water is 90～87.38%;
(2) N
2Protection down, with the mixture heating up to 70 of step (1) ℃, add with step (1) in the massfraction of weight such as vinylbenzene be 1% persulfate aqueous solution, reaction 12h obtains polystyrene emulsion;
(3) in another reaction vessel, add the polystyrene emulsion of ethanol, ammoniacal liquor and step (2) gained, stir, remain on 50 ℃; Its weight ratio is: ethanol is 93.14～87.96%, and ammoniacal liquor is 1.96～7.41%, and polystyrene emulsion is 4.90～4.63%;
(4) add tetra-n-butyl titanate, trolamine, ethanol three blended mixing solutions in the reaction vessel in step (3), carry out TiO
2Coat polystyrene 1.0～10h, add back continuation stirring 5h and promptly obtain suspension; The consumption of described mixing solutions is 0.4～4.0 times of the middle polystyrene emulsion weight of step (3);
(5) suspension to step (4) gained carries out centrifugation, drying obtains polystyrene-TiO
2Complex microsphere, wherein polystyrene is nuclear, TiO
2Be shell;
(6) to the polystyrene-TiO of step (5) gained
2Complex microsphere is removed polystyrene at 500 ℃ of calcining 2h and is promptly obtained described N doped hollow TiO
2Microballoon.
2. N doped hollow TiO according to claim 1
2The synthetic method of microballoon is characterized in that: when the add-on of polyvinylpyrrolidone in the step (1) was 0, tetra-n-butyl titanate, trolamine, alcoholic acid weight ratio were 1.0: 0.1～0.4: 1.0 in the step (4).
3. N doped hollow TiO according to claim 1
2The synthetic method of microballoon is characterized in that: when adding polyvinylpyrrolidone in the step (1), tetra-n-butyl titanate, trolamine, alcoholic acid weight ratio are 1.0: 0.1～0.4: 9.0 in the step (4).
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Cited By (5)
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| CN102730755A (en) * | 2012-07-06 | 2012-10-17 | 苏州大学 | Rodlike N-Ag codoped TiO2 and preparation method thereof |
| CN103418416A (en) * | 2013-08-30 | 2013-12-04 | 武汉理工大学 | Preparation method of nitrogen doping titanium dioxide powder, prepared titanium dioxide powder material and purpose thereof |
| CN104707641A (en) * | 2015-02-15 | 2015-06-17 | 山东师范大学 | Metal-nitrogen co-doped titanium dioxide hollow sphere catalyst and preparation method thereof |
| CN110090657A (en) * | 2019-06-04 | 2019-08-06 | 中南大学 | A kind of sepiolite composite catalyst and preparation method thereof, novel Fenton-like and its application |
| CN111834636A (en) * | 2020-07-21 | 2020-10-27 | 陕西师范大学 | Preparation method of nitrogen-doped TiO lithium-sulfur battery positive electrode carrier with large specific surface area |
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| CN104707641A (en) * | 2015-02-15 | 2015-06-17 | 山东师范大学 | Metal-nitrogen co-doped titanium dioxide hollow sphere catalyst and preparation method thereof |
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