CN105944765A - Preparation method of nano photocatalyst - Google Patents
Preparation method of nano photocatalyst Download PDFInfo
- Publication number
- CN105944765A CN105944765A CN201610264753.2A CN201610264753A CN105944765A CN 105944765 A CN105944765 A CN 105944765A CN 201610264753 A CN201610264753 A CN 201610264753A CN 105944765 A CN105944765 A CN 105944765A
- Authority
- CN
- China
- Prior art keywords
- nano
- mixed solution
- photocatalyst
- polypyrrole
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 56
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 37
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000004408 titanium dioxide Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 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 claims description 10
- 229940012189 methyl orange Drugs 0.000 claims description 10
- MOHYOXXOKFQHDC-UHFFFAOYSA-N 1-(chloromethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CCl)C=C1 MOHYOXXOKFQHDC-UHFFFAOYSA-N 0.000 claims description 9
- FYEHYMARPSSOBO-UHFFFAOYSA-N Aurin Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)=C1C=CC(=O)C=C1 FYEHYMARPSSOBO-UHFFFAOYSA-N 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- 235000013877 carbamide Nutrition 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- -1 Methoxyl group Chemical class 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000004298 light response Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 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 8
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 241000220317 Rosa Species 0.000 description 4
- 238000005842 biochemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JOHZPMXAZQZXHR-UHFFFAOYSA-N pipemidic acid Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCNCC1 JOHZPMXAZQZXHR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
- B01J31/0208—Ketones or ketals
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a nano photocatalyst; the photocatalyst is prepared through a plurality of steps: preparation of hollow nano titania, preparation of polypyrrole pipes, polypyrrole pipe surface modification and synthesis of the nano photocatalyst. The catalyst can make full use of solar energy, especially energy of visible light of sun light. The prepared photocatalyst has the advantages of low preparation cost, wide visible light response range, high photocatalytic efficiency and the like.
Description
Technical field
The invention belongs to photocatalyst technology field, relate to the preparation method of a kind of photocatalyst, particularly relate to one
Plant the preparation method of nano-photocatalyst.
Background technology
Environment and the energy are contemporary mankind's Faced In Sustainable Development and significant problem urgently to be resolved hurrily.Solar energy has
Inexpensively, cleaning, the advantage such as renewable, therefore, develop efficiently and rapidly solar energy and convert and memory technology and profit
Realize human kind sustainable development with solar energy decomposing organic pollutant, be the targets made great efforts of people.Photocatalysis technology
Then can realize this target.Photocatalysis technology has can directly utilize that solar energy, secondary pollution be few, reaction condition
The advantage such as gentle, easy and simple to handle, is referred to as a kind of preferably environmental improvement technology and clear energy sources production technology.
Wherein, photocatalyst is the key factor realizing this technology.At present, modal photocatalysis on market
Agent is nano titanium oxide, and it has photocatalysis efficiency height, good stability, the advantage such as cheap.But,
Owing to its energy gap is relatively big, absorption bands is ultraviolet region, and in solar energy only about 5% ultraviolet light,
So the sunlight of more than 95% cannot be utilized effectively.Further, since sunlight can excite titanium dioxide
The ultraviolet ray intensity of titanium is the most weak, causes the effect directly utilizing the photocatalysis degradation organic contaminant that sunlight does light source
Rate is the lowest.Therefore, synthesize and have stronger photocatalytic activity in visible region, sunlight visible light part can be utilized
Effective catalyst, it has also become at present photocatalysis most important meaning and challenging problem.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention discloses the preparation side of a kind of nano-photocatalyst
Method, described photocatalyst can make full use of the visible light part energy in solar energy, especially sunlight, described
Photocatalyst preparation cost wide ranges cheap, visible light-responded, photocatalysis efficiency are high.
For reaching object above, the technical solution used in the present invention is:
The preparation method of a kind of nano-photocatalyst, comprises the following steps:
1) preparation of hollow Nano titanium dioxide
Titanium tetrachloride, sodium citrate and carbamide are added sequentially in deionized water, magnetic agitation 30-60min
Addition material is made fully to dissolve formation A mixed solution；Polyacrylamide is slowly added into A mixed solution again
In, continue magnetic agitation 60-90min and form B mixed solution；B mixed solution is transferred to hydrothermal reaction kettle
In, after reacting 10-15h at 240-260 DEG C, hydrothermal reaction kettle is taken out and naturally cools to room temperature, by water
After crude product deionized water in thermal response still and dehydrated alcohol are cleaned, in the vacuum drying oven of 70-80 DEG C
It is dried 24-36h products therefrom and is hollow titanium dioxide；
Wherein, the mass ratio of deionized water, titanium tetrachloride, sodium citrate, carbamide and polyacrylamide is
(80-100)∶(1-1.5)∶(2-2.5)∶(0.7-0.8)∶(0.6-0.7)；
2) preparation of polypyrrole pipe
By FeCl3·6H2O is scattered in the chloroform soln containing methyl orange, in time having flocculent substance to generate,
Adding pyrrole monomer, 26-40h is stirred at room temperature, obtains black suspension, after filtration, at 60 DEG C, vacuum is done
Dry 12-24h, the solid matter obtaining black is polypyrrole pipe；
Wherein, FeCl3·6H2O, methyl orange, the mass ratio of pyrrole monomer are 280: (28-35): (14-23), first
Base orange is 1 with the mass ratio of chloroform: (18-20)；
3) polypyrrole tube-surface is modified
By step 2) in the polypyrrole pipe for preparing, KOH powder ultrasonic is scattered in N, N-dimethyl formyl
Forming C mixed solution in amine, the time of ultrasonic disperse is 15-30min；Then to C mixed solution and dripping
P-methoxybenzyl chloride, reacts stopped reaction after 20-30h at 55-65 DEG C, gained crude product is carried out sucking filtration and divides
From obtaining black solid, after being cleaned with acetone by black solid, rotation is evaporated off acetone, then vacuum at 60 DEG C
Dry 12-24h i.e. obtains the polypyrrole pipe of surface modification；
Wherein, polypyrrole pipe, KOH, DMF, the mass ratio of p-methoxybenzyl chloride are
3∶5∶(40-50)∶10；
4) synthesis of nano-photocatalyst
Hollow titanium dioxide nano-particle is distributed in the alcohol solvent of 40-60 DEG C, adds rosolic acid and step
3) the polypyrrole pipe of the surface modification prepared, in 40-60 DEG C of stirring reaction 6-12h, on rosolic acid
Hydroxyl and the polypyrrole pipe modified of surface on the hydroxyl of methoxyl group and hollow titanium dioxide surface there is chemistry
Reaction is chained up, after having reacted successively through sucking filtration, dehydrated alcohol supersound washing, deionized water supersound washing,
Ambient temperature in vacuum obtains nano-photocatalyst after being dried 24-36h；
Wherein, the polypyrrole pipe of described hollow titanium dioxide nano-particle, rosolic acid, ethanol, surface modification
Mass ratio be 10: 3: (50-80): 2.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) nano-photocatalyst of present invention design, prepares raw material and is easy to get, do not contain expensive expensive
Metal, easily operation, less demanding to equipment, with low cost；
(2) nano-photocatalyst of present invention design, has hollow-core construction, beneficially the absorption of material, expansion
Dissipate and light is absorbed, and providing more surface activity site, beneficially light induced electron and hole
Separate；
(3) nano-photocatalyst of present invention design, has modified polypyrrole at hollow Nano titanium dioxide surface
Pipe and rosolic acid, on the one hand, the organic semiconductor of polypyrrole pipe and rosolic acid both conjugated structures can make
Obtain this photocatalyst absorbing light wave-length coverage wider, under ultraviolet light and radiation of visible light, there is decomposition harmful
Learn the effect of material, there is the strongest photocatalytic activity；On the other hand, it is modified with beneficially nanoparticle by surface
The dispersion of son.
Detailed description of the invention
Hereinafter describe and be used for disclosing the present invention so that those skilled in the art are capable of the present invention.In below describing
Preferred embodiment be only used as citing, it may occur to persons skilled in the art that other obvious modification.
Raw material used in the following embodiment of the present invention comes from Haiquan sunrise foreign trade company limited.
The actual application (degraded rhodamine) of visible light catalyst prepared by the present invention: weigh 80mg sample and add
Enter 80mL rhodamine liquor (concentration 8mol/L), lucifuge stirring 1h so that rhodamine liquor is at catalyst table
Face reaches absorption/desorption equilibrium；It is then turned on light source and carries out photocatalysis, take 3mL reactant liquor every 5min,
After being performing centrifugal separation on, supernatant Cary-500 spectrophotometer detects；According to light absorption value at sample 554nm
Determining rhodamine concentration change in degradation process, the light source of reaction is for being placed in double glass jacket (logical condensed water)
In 500W halogen tungsten lamp, use optical filter with ensure incident illumination as visible ray (wave-length coverage: 420-800nm).
Embodiment 1
The preparation method of a kind of nano-photocatalyst, comprises the following steps:
1) preparation of hollow Nano titanium dioxide
12.6g titanium tetrachloride, 23.5g sodium citrate and 7g carbamide are added sequentially in 800g deionized water,
Magnetic agitation 30min makes addition material fully dissolve formation A mixed solution；Again by slow for 6g polyacrylamide
Join in A mixed solution, continue magnetic agitation 60min and form B mixed solution；B mixed solution is turned
Move on in hydrothermal reaction kettle, after reacting 15h at 240 DEG C, hydrothermal reaction kettle is taken out and naturally cools to room
Temperature, after the crude product deionized water in hydrothermal reaction kettle and dehydrated alcohol being cleaned, does in the vacuum of 70 DEG C
Dry case is dried 36h products therefrom and is hollow titanium dioxide；
2) preparation of polypyrrole pipe
30g methyl orange is dissolved in 600g chloroform, wiring solution-forming, then by 280g FeCl3·6H2O
It is scattered in above-mentioned solution, in time having flocculent substance to generate, adds 140g pyrrole monomer, 26h is stirred at room temperature,
Obtaining black suspension, after filtration, be vacuum dried 12h at 60 DEG C, the solid matter obtaining black is
Polypyrrole pipe；
3) polypyrrole tube-surface is modified
By step 2) in the 30g polypyrrole pipe for preparing, 50g KOH powder ultrasonic is scattered in 400g N, N-
Forming C mixed solution in dimethylformamide, the time of ultrasonic disperse is 15min；Then molten to C mixing
Liquid drips 100g p-methoxybenzyl chloride, at 55 DEG C, reacts stopped reaction after 30h, gained crude product is entered
Row sucking filtration isolated black solid, after being cleaned with acetone by black solid, revolves and solvent acetone is evaporated off, then
It is vacuum dried 12h at 60 DEG C and i.e. obtains the polypyrrole pipe of surface modification；
4) synthesis of nano-photocatalyst
Hollow for 20g titanium dioxide nano-particle is distributed in the 1000g alcohol solvent of 40 DEG C, adds 6g
Rosolic acid and 4g step 3) the polypyrrole pipe of surface modification for preparing, in 40 DEG C of stirring reaction 6h,
The hydroxyl of the methoxyl group on polypyrrole pipe that hydroxyl on rosolic acid and surface are modified and hollow titanium dioxide surface
Chemical reaction is occurred to be chained up, successively through sucking filtration, dehydrated alcohol supersound washing, deionized water after having reacted
Supersound washing, ambient temperature in vacuum obtain nano-photocatalyst after being dried 24h.
Embodiment 2
The preparation method of a kind of nano-photocatalyst, comprises the following steps:
1) preparation of hollow Nano titanium dioxide
12g titanium tetrachloride, 25g sodium citrate and 7.5g carbamide are added sequentially in 900g deionized water,
Magnetic agitation 40min makes addition material fully dissolve formation A mixed solution；Again by slow for 7g polyacrylamide
Join in A mixed solution, continue magnetic agitation 70min and form B mixed solution；B mixed solution is turned
Move on in hydrothermal reaction kettle, after reacting 12h at 250 DEG C, hydrothermal reaction kettle is taken out and naturally cools to room
Temperature, after the crude product deionized water in hydrothermal reaction kettle and dehydrated alcohol being cleaned, does in the vacuum of 75 DEG C
Dry case is dried 26h products therefrom and is hollow titanium dioxide；
2) preparation of polypyrrole pipe
32g methyl orange is dissolved in 608g chloroform, wiring solution-forming, then by 280g FeCl3·6H2O
It is scattered in above-mentioned solution, in time having flocculent substance to generate, adds 16g pyrrole monomer, 30h is stirred at room temperature,
Obtaining black suspension, after filtration, be vacuum dried 15h at 60 DEG C, the solid matter obtaining black is
Polypyrrole pipe；
3) polypyrrole tube-surface is modified
By step 2) in the 30g polypyrrole pipe for preparing, 50g KOH powder ultrasonic is scattered in 450g N, N-
Forming C mixed solution in dimethylformamide, the time of ultrasonic disperse is 20min；Then molten to C mixing
Liquid drips 100g p-methoxybenzyl chloride, at 60 DEG C, reacts stopped reaction after 24h, gained crude product is entered
Row sucking filtration isolated black solid, after being cleaned with acetone by black solid, rotation is evaporated off acetone, then at 60 DEG C
Lower vacuum drying 17h i.e. obtains the polypyrrole pipe of surface modification；
4) synthesis of nano-photocatalyst
Hollow for 20g titanium dioxide nano-particle is distributed in the alcohol solvent of 130g 45 DEG C, adds 6g rhodo
Acid and 4g step 3) the polypyrrole pipe of surface modification for preparing, in 45 DEG C of stirring reaction 10h, rose
The hydroxyl of the methoxyl group on polypyrrole pipe that hydroxyl on red acid and surface are modified and hollow titanium dioxide surface is sent out
Biochemical reaction is chained up, and surpasses through sucking filtration, dehydrated alcohol supersound washing, deionized water successively after having reacted
Sound washing, ambient temperature in vacuum obtain nano-photocatalyst after being dried 30h.
Embodiment 3
The preparation method of a kind of nano-photocatalyst, comprises the following steps:
1) preparation of hollow Nano titanium dioxide
15g titanium tetrachloride, 25g sodium citrate and 8g carbamide are added sequentially in 1000g deionized water,
Magnetic agitation 50min makes addition material fully dissolve formation A mixed solution；Again by slow for 7g polyacrylamide
Join in A mixed solution, continue magnetic agitation 80min and form B mixed solution；B mixed solution is turned
Move on in hydrothermal reaction kettle, after reacting 10h at 260 DEG C, hydrothermal reaction kettle is taken out and naturally cools to room
Temperature, after the crude product deionized water in hydrothermal reaction kettle and dehydrated alcohol being cleaned, does in the vacuum of 76 DEG C
Dry case is dried 33h products therefrom and is hollow titanium dioxide；
2) preparation of polypyrrole pipe
28g methyl orange is dissolved in 560g chloroform, wiring solution-forming, then by 280g FeCl3·6H2O
It is scattered in above-mentioned solution, in time having flocculent substance to generate, adds 20g pyrrole monomer, 34h is stirred at room temperature,
Obtaining black suspension, after filtration, be vacuum dried 18h at 60 DEG C, the solid matter obtaining black is
Polypyrrole pipe；
3) polypyrrole tube-surface is modified
By step 2) in the 30g polypyrrole pipe for preparing, 50g KOH powder ultrasonic is scattered in 500g N, N-
Forming C mixed solution in dimethylformamide, the time of ultrasonic disperse is 27min；Then molten to C mixing
Liquid drips 100g p-methoxybenzyl chloride, at 60 DEG C, reacts stopped reaction after 25h, gained crude product is entered
Row sucking filtration isolated black solid, after being cleaned with acetone by black solid, rotation is evaporated off acetone, then at 60 DEG C
Lower vacuum drying 22h i.e. obtains the polypyrrole pipe of surface modification；
4) synthesis of nano-photocatalyst
Hollow for 20g titanium dioxide nano-particle is distributed in the alcohol solvent of 150g 54 DEG C, adds 6g rhodo
Acid and 4g step 3) the polypyrrole pipe of surface modification for preparing, in 54 DEG C of stirring reaction 8h, rose
The hydroxyl of the methoxyl group on polypyrrole pipe that hydroxyl on red acid and surface are modified and hollow titanium dioxide surface is sent out
Biochemical reaction is chained up, and surpasses through sucking filtration, dehydrated alcohol supersound washing, deionized water successively after having reacted
Sound washing, ambient temperature in vacuum obtain nano-photocatalyst after being dried 27h.
Embodiment 4
The preparation method of a kind of nano-photocatalyst, comprises the following steps:
1) preparation of hollow Nano titanium dioxide
11g titanium tetrachloride, 2.2g sodium citrate and 7.6g carbamide are added sequentially in 860g deionized water,
Magnetic agitation 45min makes addition material fully dissolve formation A mixed solution；Again 6.7g polyacrylamide is delayed
Slowly join in A mixed solution, continue magnetic agitation 80min and form B mixed solution；By B mixed solution
Transfer in hydrothermal reaction kettle, after reacting 13h at 250 DEG C, hydrothermal reaction kettle is taken out and naturally cools to
Room temperature, after the crude product deionized water in hydrothermal reaction kettle and dehydrated alcohol being cleaned, in the vacuum of 76 DEG C
Drying baker is dried 29h products therefrom and is hollow titanium dioxide；
2) preparation of polypyrrole pipe
33g methyl orange is dissolved in 660g chloroform, wiring solution-forming, then by 280g FeCl3·6H2O
It is scattered in above-mentioned solution, in time having flocculent substance to generate, adds 21g pyrrole monomer, 33h is stirred at room temperature,
Obtaining black suspension, after filtration, be vacuum dried 20h at 60 DEG C, the solid matter obtaining black is
Polypyrrole pipe；
3) polypyrrole tube-surface is modified
By step 2) in the 30g polypyrrole pipe for preparing, 50g KOH powder ultrasonic is scattered in 480g N, N-
Forming C mixed solution in dimethylformamide, the time of ultrasonic disperse is 28min；Then molten to C mixing
Liquid drips 100g p-methoxybenzyl chloride, at 62 DEG C, reacts stopped reaction after 24h, gained crude product is entered
Row sucking filtration isolated black solid, after being cleaned with acetone by black solid, rotation is evaporated off acetone, then at 60 DEG C
Lower vacuum drying 18h i.e. obtains the polypyrrole pipe of surface modification；
4) synthesis of nano-photocatalyst
Hollow titanium dioxide nano-particle 20g is distributed in the alcohol solvent of 160g 56 DEG C, adds 6g rhodo
Acid and 4g step 3) the polypyrrole pipe of surface modification for preparing, in 60 DEG C of stirring reaction 12h, rose
The hydroxyl of the methoxyl group on polypyrrole pipe that hydroxyl on red acid and surface are modified and hollow titanium dioxide surface is sent out
Biochemical reaction is chained up, and surpasses through sucking filtration, dehydrated alcohol supersound washing, deionized water successively after having reacted
Sound washing, ambient temperature in vacuum obtain nano-photocatalyst after being dried 35h.
Embodiment 5
The preparation method of a kind of nano-photocatalyst, comprises the following steps:
1) preparation of hollow Nano titanium dioxide
15g titanium tetrachloride, 25g sodium citrate and 8g carbamide are added sequentially in 1000g deionized water,
Magnetic agitation 60min makes addition material fully dissolve formation A mixed solution；Again 6.5g polyacrylamide is delayed
Slowly join in A mixed solution, continue magnetic agitation 90min and form B mixed solution；By B mixed solution
Transfer in hydrothermal reaction kettle, after reacting 15h at 260 DEG C, hydrothermal reaction kettle is taken out and naturally cools to
Room temperature, after the crude product deionized water in hydrothermal reaction kettle and dehydrated alcohol being cleaned, in the vacuum of 80 DEG C
Drying baker is dried 24h products therefrom and is hollow titanium dioxide；
2) preparation of polypyrrole pipe
35g methyl orange is dissolved in 630g chloroform, wiring solution-forming, then by 280g FeCl3·6H2O
It is scattered in above-mentioned solution, in time having flocculent substance to generate, adds 23g pyrrole monomer, 40h is stirred at room temperature,
Obtaining black suspension, after filtration, be vacuum dried 24h at 60 DEG C, the solid matter obtaining black is
Polypyrrole pipe；
3) polypyrrole tube-surface is modified
By step 2) in the 30g polypyrrole pipe for preparing, 50g KOH powder ultrasonic is scattered in 500g N, N-
Forming C mixed solution in dimethylformamide, the time of ultrasonic disperse is 30min；Then molten to C mixing
Liquid drips 100g p-methoxybenzyl chloride, at 65 DEG C, reacts stopped reaction after 20h, gained crude product is entered
Row sucking filtration isolated black solid, after being cleaned with acetone by black solid, revolves and solvent acetone is evaporated off, then
It is vacuum dried 24h at 60 DEG C and i.e. obtains the polypyrrole pipe of surface modification；
4) synthesis of nano-photocatalyst
Hollow for 20g titanium dioxide nano-particle is distributed in the alcohol solvent of 160g 60 DEG C, adds 6g rhodo
Acid and 4g step 3) the polypyrrole pipe of surface modification for preparing, in 60 DEG C of stirring reaction 12h, rose
The hydroxyl of the methoxyl group on polypyrrole pipe that hydroxyl on red acid and surface are modified and hollow titanium dioxide surface is sent out
Biochemical reaction is chained up, and surpasses through sucking filtration, dehydrated alcohol supersound washing, deionized water successively after having reacted
Sound washing, ambient temperature in vacuum obtain nano-photocatalyst after being dried 36h；
Comparative example 1
It is not added with any photocatalyst；
Comparative example 2
Described photocatalyst is titanium dioxide nano-particle；
Various embodiments of the present invention and comparative example's photocatalyst catalysis rhodamine degraded test result such as table 1 institute
Show.In table, data are the ratio of rhodamine concentration and initial solubility, as can be seen from the table, the present embodiment
The catalysis activity of organic photocatalyst of preparation is higher than common inorganic photocatalyst titanium dioxide.
Table 1 embodiment photocatalyst catalysis rhodamine degraded test result
| Detection project | After 5min | After 10min | After 15min | After 20min |
| Comparative example 1 | 1 | 1 | 1 | 1 |
| Comparative example 2 | 0.95 | 0.88 | 0.86 | 0.85 |
| Embodiment 1 | 0.19 | 0.02 | 0 | 0 |
| Embodiment 2 | 0.18 | 0.01 | 0 | 0 |
| Embodiment 3 | 0.19 | 0.02 | 0 | 0 |
| Embodiment 4 | 0.17 | 0.02 | 0 | 0 |
| Embodiment 5 | 0.18 | 0.02 | 0 | 0 |
Note: in table, data are the ratio of different time rhodamine concentration and initial concentration
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The industry
Skilled person will appreciate that, the present invention is not restricted to the described embodiments, described in above-described embodiment and description
The principle of the simply present invention, the present invention also has various change without departing from the spirit and scope of the present invention
Changing and improve, these changes and improvements both fall within the range of claimed invention.The guarantor of application claims
Scope of protecting is defined by appending claims and equivalent thereof.
Claims (1)
1. the preparation method of a nano-photocatalyst, it is characterised in that comprise the following steps:
1) preparation of hollow Nano titanium dioxide
Titanium tetrachloride, sodium citrate and carbamide being added sequentially in deionized water, magnetic agitation 30-60min makes addition material
Fully dissolve and form A mixed solution；Again polyacrylamide is slowly added in A mixed solution, continues magnetic agitation
60-90min forms B mixed solution；B mixed solution is transferred in hydrothermal reaction kettle, at 240-260 DEG C, reacts 10-15h
After, hydrothermal reaction kettle is taken out and naturally cools to room temperature, by the crude product deionized water in hydrothermal reaction kettle and anhydrous second
After alcohol is cleaned, the vacuum drying oven of 70-80 DEG C is dried 24-36h products therefrom and is hollow titanium dioxide；
Wherein, the mass ratio of deionized water, titanium tetrachloride, sodium citrate, carbamide and polyacrylamide is
(80-100)∶(1-1.5)∶(2-2.5)∶(0.7-0.8)∶(0.6-0.7)；
2) preparation of polypyrrole pipe
By FeCl3·6H2O is scattered in the chloroform soln containing methyl orange, in time having flocculent substance to generate, adds pyrroles
Monomer, is stirred at room temperature 26-40h, obtains black suspension, after filtration, is vacuum dried 12-24h, obtains at 60 DEG C
The solid matter of black is polypyrrole pipe；
Wherein, FeCl3·6H2O, methyl orange, the mass ratio of pyrrole monomer are 280: (28-35): (14-23), methyl orange and three
The mass ratio of chloromethanes is 1: (18-20)；
3) polypyrrole tube-surface is modified
By step 2) in the polypyrrole pipe for preparing, KOH powder ultrasonic is scattered in DMF formation
C mixed solution, the time of ultrasonic disperse is 15-30min；Then to C mixed solution and dripping p-methoxybenzyl chloride,
React stopped reaction after 20-30h at 55-65 DEG C, gained crude product is carried out sucking filtration isolated black solid, black is solid
After body is cleaned with acetone, rotation is evaporated off acetone, then vacuum drying 12-24h i.e. obtains the poly-of surface modification at 60 DEG C
Pyrroles manages；
Wherein, polypyrrole pipe, KOH, DMF, the mass ratio of p-methoxybenzyl chloride are 3: 5: (40-50): 10；
4) synthesis of nano-photocatalyst
Hollow titanium dioxide nano-particle is distributed in the alcohol solvent of 40-60 DEG C, adds rosolic acid and step 3) it is prepared into
The polypyrrole pipe of the surface modification arrived, in 40-60 DEG C of stirring reaction 6-12h, hydroxyl on rosolic acid and surface are modified
Methoxyl group on polypyrrole pipe is chained up, after having reacted successively with the hydroxyl generation chemical reaction of hollow titanium dioxide surface
Nanometer light is obtained after sucking filtration, dehydrated alcohol supersound washing, deionized water supersound washing, ambient temperature in vacuum are dried 24-36h
Catalyst；
Wherein, the mass ratio of the polypyrrole pipe of described hollow titanium dioxide nano-particle, rosolic acid, ethanol, surface modification
It is 10: 3: (50-80): 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610264753.2A CN105944765B (en) | 2016-04-22 | 2016-04-22 | A kind of preparation method of nano-photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610264753.2A CN105944765B (en) | 2016-04-22 | 2016-04-22 | A kind of preparation method of nano-photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105944765A true CN105944765A (en) | 2016-09-21 |
| CN105944765B CN105944765B (en) | 2018-06-29 |
Family
ID=56915224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610264753.2A Active CN105944765B (en) | 2016-04-22 | 2016-04-22 | A kind of preparation method of nano-photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105944765B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732813A (en) * | 2016-11-30 | 2017-05-31 | 浙江理工大学 | A kind of GO coats hollow TiO2The preparation method of ball supporting nanofibres element |
| CN106732812A (en) * | 2016-11-30 | 2017-05-31 | 浙江理工大学 | It is a kind of new to prepare catalysis TiO high2The method of/cotton cellulose composite |
| CN107983416A (en) * | 2017-12-12 | 2018-05-04 | 成都育芽科技有限公司 | A kind of nano-photocatalyst for the depollution of environment and preparation method thereof |
| CN108031279A (en) * | 2017-12-12 | 2018-05-15 | 成都育芽科技有限公司 | A kind of environmental protection formaldehyde purifying agent and preparation method thereof |
| CN109054361A (en) * | 2018-08-10 | 2018-12-21 | 宁波帝杨电子科技有限公司 | A kind of pulping wastewater treatment environment-friendly materials and preparation method thereof |
| CN114700091A (en) * | 2022-03-11 | 2022-07-05 | 华南理工大学 | Preparation method and application of environment-friendly efficient toluene scavenger |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600907A (en) * | 2012-03-20 | 2012-07-25 | 南京大学 | Polypyrrole-sensitized hollow titanium dioxide nanometer photocatalyst and preparation method thereof |
| JP2013116429A (en) * | 2011-12-01 | 2013-06-13 | Tanaka Kikinzoku Kogyo Kk | Photocatalyst, method for production thereof, and method for treating water containing nitrate nitrogen |
| CN103464213A (en) * | 2013-06-30 | 2013-12-25 | 中北大学 | Polypyrrole-TiO2 magnetically supported photocatalytic composite material and preparation method thereof |
-
2016
- 2016-04-22 CN CN201610264753.2A patent/CN105944765B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013116429A (en) * | 2011-12-01 | 2013-06-13 | Tanaka Kikinzoku Kogyo Kk | Photocatalyst, method for production thereof, and method for treating water containing nitrate nitrogen |
| CN102600907A (en) * | 2012-03-20 | 2012-07-25 | 南京大学 | Polypyrrole-sensitized hollow titanium dioxide nanometer photocatalyst and preparation method thereof |
| CN103464213A (en) * | 2013-06-30 | 2013-12-25 | 中北大学 | Polypyrrole-TiO2 magnetically supported photocatalytic composite material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732813A (en) * | 2016-11-30 | 2017-05-31 | 浙江理工大学 | A kind of GO coats hollow TiO2The preparation method of ball supporting nanofibres element |
| CN106732812A (en) * | 2016-11-30 | 2017-05-31 | 浙江理工大学 | It is a kind of new to prepare catalysis TiO high2The method of/cotton cellulose composite |
| CN107983416A (en) * | 2017-12-12 | 2018-05-04 | 成都育芽科技有限公司 | A kind of nano-photocatalyst for the depollution of environment and preparation method thereof |
| CN108031279A (en) * | 2017-12-12 | 2018-05-15 | 成都育芽科技有限公司 | A kind of environmental protection formaldehyde purifying agent and preparation method thereof |
| CN107983416B (en) * | 2017-12-12 | 2020-12-01 | 湖州达立智能设备制造有限公司 | Nano photocatalyst for environmental purification and preparation method thereof |
| CN109054361A (en) * | 2018-08-10 | 2018-12-21 | 宁波帝杨电子科技有限公司 | A kind of pulping wastewater treatment environment-friendly materials and preparation method thereof |
| CN114700091A (en) * | 2022-03-11 | 2022-07-05 | 华南理工大学 | Preparation method and application of environment-friendly efficient toluene scavenger |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105944765B (en) | 2018-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105944765A (en) | Preparation method of nano photocatalyst | |
| CN105854906B (en) | BiOCl-TiO2/ diatomite photochemical catalyst and preparation method thereof | |
| CN104001504B (en) | Silver and the co-modified TiO of Graphene2the preparation method of nano wire and the effect of photocatalysis degradation of pollutants in waste water | |
| CN105032468A (en) | Cu2O-TiO2/g-C3N4 ternary complex and preparation and application method thereof | |
| CN106914236B (en) | The amorphous state plasma hetero-junctions nano-TiO of efficient visible light response2Colloidal sol | |
| CN104941621A (en) | Composite photocatalyst for efficiently degrading antibiotics as well as preparation method and application thereof | |
| CN103191723A (en) | Hydro-thermal synthesis method of visible light photocatalyst mesoporous Bi2WO6 | |
| CN102302955B (en) | Floating polypyrrole-TiO2/floating bead photocatalyst, and preparation method and application thereof | |
| CN102527381A (en) | Preparation method of nano-sized gold/ titanium dioxide compound mesoporous microspheric photocatalyst | |
| CN107159264A (en) | A kind of high-efficient full-spectrum response CuS/ graphene composite photocatalysts and preparation method thereof | |
| CN105597734A (en) | Preparation method and application of molybdenum doped tungsten trioxide photocatalytic material | |
| CN104826623B (en) | Bismuth oxide photocatalyst, preparation method and applications thereof | |
| CN101579624B (en) | Method for preparing tin dioxide photocatalyst | |
| CN110394178A (en) | Nanometer di-iron trioxide/nanometer titanium dioxide compound photocatalyst and preparation method | |
| CN110075905A (en) | A kind of heterojunction photocatalyst CaSb2O6/g-C3N4Preparation method and applications | |
| CN110227503A (en) | A kind of method of one step of room temperature preparation halogenation oxygen bismuth nanometer sheet | |
| CN105107529A (en) | Preparation of magnetic two-dimensional photocatalysis functional material | |
| CN104148099A (en) | Preparation method for MoS2-BiPO4 composite photocatalyst | |
| CN109317129A (en) | A kind of preparation method of micro-meter scale extra light calcined magnesia photochemical catalyst | |
| CN106040280B (en) | Full spectral response type ammonium tungsten bronze titanium dioxide composite photocatalyst | |
| CN104607214A (en) | Preparation method of AgBr/TiO2 catalyst responding to visible light | |
| CN106807413A (en) | A kind of Ag@AgBr/CaTiO with Plasmon Surface Resonance effect3Photochemical catalyst and preparation method thereof | |
| CN103769175B (en) | A kind of preparation method of composite photo-catalyst and application thereof | |
| CN105944745B (en) | A kind of titanium dioxide nanometer microballoons and its preparation method and application | |
| CN106925252A (en) | A kind of metal doping nano TiO2/ sepiolite composite and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Mingfu Inventor before: Wei Liang |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180326 Address after: Xiangjiang Dong Lu, Qibin District Hebi Henan province 458030 City National Park Photo Applicant after: Zhu Mingfu Address before: 315040 B3 building, hi tech Zone, Zhejiang, Ningbo, China 509-512 Applicant before: High and new technology industrial development zone, Ningbo Xia Yuan Science and Technology Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |