CN108816264B - Ultrathin g-C3N4Coated TiO2Homogeneous special-shaped array film and preparation method thereof - Google Patents
Ultrathin g-C3N4Coated TiO2Homogeneous special-shaped array film and preparation method thereof Download PDFInfo
- Publication number
- CN108816264B CN108816264B CN201810569379.6A CN201810569379A CN108816264B CN 108816264 B CN108816264 B CN 108816264B CN 201810569379 A CN201810569379 A CN 201810569379A CN 108816264 B CN108816264 B CN 108816264B
- Authority
- CN
- China
- Prior art keywords
- tio
- special
- homogeneous
- fto glass
- film
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011521 glass Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002073 nanorod Substances 0.000 claims abstract description 21
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 35
- 239000002135 nanosheet Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 230000001788 irregular Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 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 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HFDCVHDLKUZMDI-UHFFFAOYSA-N sulfuric acid titanium Chemical compound [Ti].OS(O)(=O)=O HFDCVHDLKUZMDI-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/59—
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses an ultrathin g-C3N4Coated TiO2A homogeneous and special-shaped array film and a preparation method thereof. Characterized in that the film is made of ultra-thin g-C3N4Coated rutile TiO2TiO with two allotypes of nanorod array and spike-shaped rod bundle2The method comprises the steps of taking inorganic titanium sulfate as a raw material, depositing a precursor film on FTO glass through one-step hydrothermal reaction under an acidic condition, and roasting to obtain rutile TiO2The homogeneous special-shaped array film is formed by depositing gas generated by decomposing melamine on TiO through chemical vapor deposition2Depositing a layer of ultrathin curled g-C on the homogeneous special-shaped array film3N4. The preparation method of the invention has simple operation and mild reaction condition, and can be used as lightThe electrode has important application prospect in the field of photoelectrocatalysis water organic dye degradation and photoelectrocatalysis water decomposition hydrogen production.
Description
Technical Field
The invention belongs to the field of photoelectric catalytic materials, and relates to ultrathin g-C3N4Coated TiO2A method for preparing a homogeneous special-shaped array film, in particular to an ultrathin g-C3N4Coated TiO2A method for preparing homogeneous special-shaped array film photoelectric catalytic material.
Background
Rutile type TiO2The forbidden band width of the intrinsic semiconductor is 3.0eV, the light absorption is mainly concentrated in an ultraviolet region, the response to visible light is poor, and the problems of high recombination rate of photo-generated electron-hole pairs and low quantum efficiency exist, so that the TiO is greatly limited2The application in the field of photocatalysis. g-C3N4The band gap of the light emitting diode is 2.7e V, the adjustable band gap width is environment-friendly, the thermal stability is excellent, and the light emitting diode is responsive to visible light. G to C3N4And TiO2The recombination is favorable for widening photoresponse, reducing the recombination of photo-generated electron-hole pairs and greatly improving the photocatalytic efficiency. At present, g-C3N4The preparation method of (1) mainly comprises a thermal polycondensation method. The use of thermal polymerization generally gives g-C of bulk structure3N4Small specific surface area and few active sites. Thin nanosheets can be obtained only by adopting a chemical stripping method or a liquid-phase ultrasonic stripping method, and the thin nanosheets are complex in operation steps, low in stripping efficiency and low in yield, and large-area ultrathin nanosheets are difficult to prepare. Preparation of large areas of g-C3N4The ultrathin nanosheets are beneficial to improving the light utilization rate.
Disclosure of Invention
The invention aims at the existing preparation of g-C3N4/TiO2The synthesis process is complex, the reaction conditions are harsh, large-area ultrathin nanosheets are difficult to prepare, and the like, and discloses ultrathin g-C3N4Coated TiO2A homogeneous and special-shaped array film and a preparation method thereof. Characterized in that the film is formed by ultra-thin curling g-C3N4Coated rutile TiO2The method takes inorganic titanium sulfate as a raw material, and grows rutile TiO on the surface of the FTO glass by a one-step hydrothermal reaction and roasting process under an acidic condition2The homogeneous special-shaped array film is formed by depositing gas generated by decomposing melamine on TiO through chemical vapor deposition2Depositing a layer of ultrathin curled g-C on the homogeneous special-shaped array film3N4. The invention is realized by adopting the following technical scheme:
(1) pretreating FTO glass: cutting FTO glass into pieces of 1cm × 2.5cm, sequentially soaking in acetone, anhydrous ethanol, and deionized water, respectively performing ultrasonic treatment for 2-5min, cleaning, and drying at 70 deg.C for 2 hr.
(2)TiO2Preparing a nanorod and spike-shaped bundle staggered array: dissolving 0.2-0.3g of titanium sulfate in deionized water, and then adding 4-8ml of concentrated hydrochloric acid to prepare 20ml of uniform and transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing the two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure kettle, and heating at the temperature of 120-200 ℃ for 1-12 h. After the reaction is finished, the high-pressure autoclave is naturally cooled to room temperature, the FTO glass is taken out, washed for three times by deionized water and ethanol in sequence, and dried for 2 hours at 70 ℃. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500-600 ℃ at the heating rate of 1-10 ℃/min, and the temperature is preserved for 1-4h to obtain TiO2The nano-rods and the spike-shaped rod bundles are of the same shape and shape array film.
(3) Will grow TiO2The FTO conductive glass of the homogeneous irregular array film is placed in a reaction tank, the reaction tank is placed in a container, 100-300mg melamine (urea or dicyandiamide) is placed in the container, and the container is sealed. Putting into a tube furnace, heating to 500-600 ℃ at the speed of 2-10 ℃/min, and keeping the temperature for 1-3 h.
The invention has the advantage that large-area g-C can be prepared3N4The ultrathin curled nanosheets are adjustable in thickness. Preparation of large areas of g-C3N4Ultra-thin crimpThe nano sheet is beneficial to improving the utilization rate of visible light, simultaneously improves the transmittance of ultraviolet light, and ensures TiO2Fully utilizes ultraviolet light and prepares large-area g-C3N4Ultrathin curled nanosheet and TiO2The contact area of the nanorods and the spike-shaped cluster homogeneous and special-shaped array is increased, which is beneficial to improving the separation efficiency of photon-generated carriers; the rutile TiO prepared by the method2The nano-rod array and the spike-shaped rod bundle have two homomorphic and special-shaped nano structures with heterojunction structures, and can further improve TiO2The photocatalytic performance of (a). The catalyst is applied to the fields of photocatalytic electrolyzed water hydrogen production and organic dye photoelectrocatalytic degradation in water, and shows excellent catalytic performance.
Drawings
FIG. 1 is an ultra-thin g-C film made in example one3N4Coated TiO2XRD spectrogram of homogeneous and special-shaped array film sample.
FIG. 2 shows TiO prepared in the first example2Homogeneous and heterogeneous array film samples and ultrathin g-C3N4Coated TiO2SEM photographs of the homogeneous heterogeneous array thin film samples.
FIG. 3 is a drawing of an ultra-thin g-C film made in accordance with example one3N4Coated TiO2And (3) performing photoelectric degradation on the UV-Vis absorption spectrum of the rhodamine B solution by using the homogeneous special-shaped array film sample.
Detailed Description
The invention is illustrated in more detail below by way of examples:
the first embodiment is as follows:
(1) cutting the FTO glass into pieces with the specification of 10mm multiplied by 25mm, sequentially immersing the pieces into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 2min, fully cleaning, and drying at 70 ℃ for 2 h.
(2) 0.24g of titanium sulfate was dissolved in deionized water, and then 5ml of concentrated hydrochloric acid was added to prepare 20ml of a uniform transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure reaction kettle, and heating at 180 ℃ for 2h. After the reaction is finished, the high-pressure autoclave is naturally cooled to room temperature, the FTO glass is taken out, washed for three times by deionized water and ethanol in sequence, and dried for 2 hours at 70 ℃. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 2h to obtain TiO2The nano-rods and the spike-shaped rod cluster allotrope are staggered in array.
(3) Will grow TiO2And (3) placing the FTO conductive glass of the homogeneous irregular array film into a reaction tank, placing the reaction tank into a container, placing 250mg of melamine into the container, and sealing. Putting into a tube furnace, heating to 500 deg.C at a speed of 10 deg.C/min, and maintaining for 2 hr.
Example two:
(1) cutting the FTO glass into pieces with the specification of 10mm multiplied by 25mm, sequentially immersing the pieces into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 2min, fully cleaning, and drying at 70 ℃ for 2 h.
(2) 0.24g of titanium sulfate was dissolved in deionized water, and then 5ml of concentrated hydrochloric acid was added to prepare 20ml of a uniform transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure reaction kettle, and heating at 180 ℃ for 2 hours. After the reaction is finished, the high-pressure autoclave is naturally cooled to room temperature, the FTO glass is taken out, washed for three times by deionized water and ethanol in sequence, and dried for 2 hours at 70 ℃. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 2h to obtain TiO2The nano-rods and the spike-shaped rod cluster allotrope are staggered in array.
(3) Will grow TiO2And (3) placing the FTO conductive glass of the homogeneous irregular array film into a reaction tank, placing the reaction tank into a container, placing 250mg of melamine into the container, and sealing. Putting into a tube furnace, heating to 550 ℃ at the speed of 10 ℃/min, and keeping the temperature for 2 h.
Example three:
(1) cutting the FTO glass into pieces with the specification of 10mm multiplied by 25mm, sequentially immersing the pieces into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 2min, fully cleaning, and drying at 70 ℃ for 2 h.
(2) 0.24g of titanium sulfate was dissolved in deionized water, and then 5ml of concentrated hydrochloric acid was added to prepare 20ml of a uniform transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure reaction kettle, and heating at 180 ℃ for 1 h. After the reaction is finished, the high-pressure autoclave is naturally cooled to room temperature, the FTO glass is taken out, washed for three times by deionized water and ethanol in sequence, and dried for 2 hours at 70 ℃. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 2h to obtain TiO2The nano-rods and the spike-shaped rod cluster allotrope are staggered in array.
(3) Will grow TiO2And (3) placing the FTO conductive glass of the homogeneous irregular array film into a reaction tank, placing the reaction tank into a container, placing 250mg of melamine into the container, and sealing. Putting into a tube furnace, heating to 500 deg.C at a speed of 10 deg.C/min, and maintaining for 1 h.
Example four:
(1) cutting the FTO glass into pieces with the specification of 10mm multiplied by 25mm, sequentially immersing the pieces into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 2min, fully cleaning, and drying at 70 ℃ for 2 h.
(2) 0.24g of titanium sulfate was dissolved in deionized water, and then 5ml of concentrated hydrochloric acid was added to prepare 20ml of a uniform transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure reaction kettle, and heating at 150 ℃ for 6 hours. After the reaction is finished, the high-pressure autoclave is naturally cooled to room temperature, the FTO glass is taken out, washed for three times by deionized water and ethanol in sequence, and dried for 2 hours at 70 ℃. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 2h to obtain TiO2The nano-rods and the spike-shaped rod cluster allotrope are staggered in array.
(3) Will grow TiO2FTO conductive glass of the homogeneous special-shaped array film is placed in a reaction tank, andthe reaction tank is placed in a container, 100mg of melamine is placed in the container, and the container is sealed. Putting into a tube furnace, heating to 500 deg.C at a speed of 10 deg.C/min, and maintaining for 2 hr.
Example five:
(1) cutting the FTO glass into pieces with the specification of 10mm multiplied by 25mm, sequentially immersing the pieces into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 2min, fully cleaning, and drying at 70 ℃ for 2 h.
(2) 0.24g of titanium sulfate was dissolved in deionized water, and then 5ml of concentrated hydrochloric acid was added to prepare 20ml of a uniform transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure reaction kettle, and heating at 200 ℃ for 2 hours. After the reaction is finished, the high-pressure autoclave is naturally cooled to room temperature, the FTO glass is taken out, washed for three times by deionized water and ethanol in sequence, and dried for 2 hours at 70 ℃. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 1h to obtain TiO2The nano-rods and the spike-shaped rod cluster allotrope are staggered in array.
(3) Will grow TiO2And (3) placing the FTO conductive glass of the homogeneous irregular array film into a reaction tank, placing the reaction tank into a container, taking 300mg of melamine into the container, and sealing. Putting into a tube furnace, heating to 500 deg.C at a speed of 10 deg.C/min, and maintaining for 1 h.
Example six:
(1) cutting the FTO glass into pieces with the specification of 10mm multiplied by 25mm, sequentially immersing the pieces into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 5min, fully cleaning, and drying at 70 ℃ for 2 h.
(2) 0.3g of titanium sulfate was dissolved in deionized water, and then 6ml of concentrated hydrochloric acid was added to prepare 20ml of a uniform transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure reaction kettle, and heating at 180 ℃ for 3 hours. After the reaction is finished, naturally cooling the high-pressure kettle to room temperature, taking out the FTO glassWashing with deionized water and ethanol for three times, and drying at 70 deg.C for 2 hr. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min, and the temperature is preserved for 4h to obtain TiO2The nano-rods and the spike-shaped rod cluster allotrope are staggered in array.
(3) Will grow TiO2And (3) placing the FTO conductive glass of the homogeneous irregular array film into a reaction tank, placing the reaction tank into a container, placing 200mg of melamine into the container, and sealing. Putting into a tube furnace, heating to 500 deg.C at a speed of 10 deg.C/min, and maintaining for 3 hr.
Example seven:
(1) cutting the FTO glass into pieces with the specification of 10mm multiplied by 25mm, sequentially immersing the pieces into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 2min, fully cleaning, and drying at 70 ℃ for 2 h.
(2) 0.24g of titanium sulfate was dissolved in deionized water, and then 5ml of concentrated hydrochloric acid was added to prepare 20ml of a uniform transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure reaction kettle, and heating at 180 ℃ for 2 hours. After the reaction is finished, the high-pressure autoclave is naturally cooled to room temperature, the FTO glass is taken out, washed for three times by deionized water and ethanol in sequence, and dried for 2 hours at 70 ℃. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 2h to obtain TiO2The nano-rods and the spike-shaped rod cluster allotrope are staggered in array.
(3) Will grow TiO2And (3) placing the FTO conductive glass of the homogeneous special-shaped array film into a reaction tank, placing the reaction tank into a container, placing 400mg of urea into the container, and sealing. Putting into a tube furnace, heating to 500 deg.C at a speed of 5 deg.C/min, and maintaining for 2 h.
Example eight:
(1) cutting the FTO glass into pieces with the specification of 10mm multiplied by 25mm, sequentially immersing the pieces into acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic treatment for 2min, fully cleaning, and drying at 70 ℃ for 2 h.
(2) 0.24g of sulfuric acidTitanium is dissolved in deionized water, and then 5ml of concentrated hydrochloric acid is added to prepare 20ml of uniform and transparent mixed solution. Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure reaction kettle, and heating at 180 ℃ for 2 hours. After the reaction is finished, the high-pressure autoclave is naturally cooled to room temperature, the FTO glass is taken out, washed for three times by deionized water and ethanol in sequence, and dried for 2 hours at 70 ℃. Finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 2h to obtain TiO2The nano-rods and the spike-shaped rod cluster allotrope are staggered in array.
(3) Will grow TiO2And (3) placing the FTO conductive glass of the homogeneous special-shaped array film into a reaction tank, placing the reaction tank into a container, placing 400mg of dicyandiamide into the container, and sealing. Putting into a tube furnace, heating to 500 deg.C at a speed of 10 deg.C/min, and maintaining for 2 hr.
FIG. 1 is an ultra-thin g-C film made in example one3N4Coated TiO2XRD spectrogram of homogeneous and special-shaped array film sample. It can be seen from the figure that the diffraction peaks corresponding to the rutile crystalline phase TiO, except for the diffraction peaks of FTO glass tin dioxide determined according to standard diffraction JCPDS No.46-10882Diffraction peaks (JCPDS number 21-1276) of (101) crystal plane and (002) crystal plane of (A) were detected, but g-C was not detected3N4Is probably due to g-C3N4The crystallinity of (2) is low.
FIG. 2a shows TiO prepared in the first embodiment2SEM photographs of the homogeneous heterogeneous array thin film samples. As can be seen from the photograph of FIG. 2a, TiO2The nano-rods are densely grown on the surface of the FTO glass, and TiO2The protrusions on the surface of the nano-rod film are TiO formed by thinner nano-rods2Cluster of spikes of TiO2The cluster of spikes is higher than TiO2The nano-rod array forms a composite film with homogeneous, special-shaped, staggered height. FIG. 2b is the ultrathin g-C film obtained in the first example3N4Coated TiO2SEM photographs of the homogeneous heterogeneous array thin film samples. As can be seen from the photograph of FIG. 2b, TiO2Nano-rodg-C with ultrathin curled surface of array and spike-shaped rod cluster homogeneous special-shaped nano structure array film3N4Covering, and making the plate transparent to obtain ultrathin g-C3N4Coated TiO2Homogeneous and special-shaped array films.
FIG. 3 is a drawing of an ultra-thin g-C film made in accordance with example one3N4Coated TiO2The homogeneous special-shaped array film sample is used for photoelectrocatalysis degradation of UV-Vis absorption spectrum of rhodamine B in water solution. As can be seen, after the reaction is carried out for 60min, the degradation rate of rhodamine B in the solution is close to 100 percent, which indicates that g-C3N4Coated TiO2The homogeneous special-shaped array film electrode is suitable for the photoelectric catalytic efficient degradation of rhodamine B in an aqueous solution.
Ultra-thin g-C made in example one3N4Coated TiO2The homogeneous special-shaped array film is used as a photoelectrode for preparing hydrogen by photoelectrocatalysis decomposition of water, and experimental results show that from minus 0.3V relative to the bias of an Ag/AgCl electrode, the density of photocurrent generated by the photoelectrode is rapidly increased along with the rise of voltage, and when the voltage is 0.2V relative to the bias of the Ag/AgCl electrode, the density of the photocurrent is up to 1.1mA/cm2. The higher the photocurrent density is, the higher the efficiency of producing hydrogen by photoelectrochemically decomposing water is, and the better the photoelectrochemical property is, so the ultrathin g-C3N4Coated TiO2The homogeneous special-shaped array film as a photoelectrode has excellent performance of hydrogen production by photoelectrocatalysis water decomposition. The reason why the saturation photocurrent of the electrode is large is that large area g-C is prepared3N4The ultrathin curled nano-sheets are beneficial to improving the utilization rate of visible light, simultaneously improving the transmittance of ultraviolet light and ensuring TiO2Fully utilizes ultraviolet light and prepares large-area g-C3N4Ultra-thin curled nano-sheet is added with TiO2The contact area of the nanorod and the spike-shaped bundle homogeneous and special-shaped staggered array is beneficial to improving the separation efficiency of photo-generated carriers, so that the photocurrent density is improved.
Prepared g-C prepared by the invention3N4/TiO2The film photoelectrocatalysis material not only has high photoelectrocatalysis water decomposition hydrogen production efficiency, but also has high photoelectrocatalysis water decomposition hydrogen production efficiencyHas good photoelectrocatalysis performance on the degradation of organic dye in water.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, substitutions, simplifications, etc. without departing from the principle and process of the present invention are all equivalent substitutions and shall be included in the protection scope of the present invention.
Claims (1)
1. Ultrathin g-C3N4Coated TiO2The homogeneous special-shaped array film is characterized in that the film is g-C formed by ultrathin curling3N4Coated rutile TiO2The nano-rod array and spike-shaped rod bundle homogeneous and special-shaped array nanostructure comprises the following steps:
(1) pretreating FTO glass: cutting FTO glass into pieces of specification 1cm × 2.5cm, sequentially immersing into acetone, anhydrous ethanol and deionized water, respectively performing ultrasonic treatment for 2-5min, cleaning, and drying at 70 deg.C for 2 hr; (2) TiO 22Preparing a nanorod and spike bundle homogeneous and special-shaped array: dissolving 0.2-0.3g of titanium sulfate in deionized water, and then adding 4-8ml of concentrated hydrochloric acid to prepare 20ml of uniform and transparent mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, vertically placing the two pieces of FTO glass pretreated in the step (1) in the solution relatively, sealing the high-pressure kettle, and heating at the temperature of 120-; after the reaction is finished, naturally cooling the high-pressure kettle to room temperature, taking out the FTO glass, sequentially washing the FTO glass with deionized water and ethanol for three times, and drying the FTO glass for 2 hours at 70 ℃; finally, the dried FTO glass is put into a tube furnace, the temperature is raised to 500-600 ℃ at the heating rate of 1-10 ℃/min, and the temperature is preserved for 1-4h to obtain TiO2The nano-rods and the spike-shaped rod bundles are of the same-shaped array film;
(3) will support TiO2The FTO conductive glass of the homogeneous special-shaped array film is placed in a reaction tank, the reaction tank is placed in a container, 100 plus 500mg of melamine or urea or dicyandiamide is placed in the container, the container is sealed, the container is placed in a tube furnace to be heated to 500-600 ℃ at the speed of 2-10 ℃/min,and preserving the heat for 1-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810569379.6A CN108816264B (en) | 2018-06-05 | 2018-06-05 | Ultrathin g-C3N4Coated TiO2Homogeneous special-shaped array film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810569379.6A CN108816264B (en) | 2018-06-05 | 2018-06-05 | Ultrathin g-C3N4Coated TiO2Homogeneous special-shaped array film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108816264A CN108816264A (en) | 2018-11-16 |
| CN108816264B true CN108816264B (en) | 2021-07-30 |
Family
ID=64143886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810569379.6A Active CN108816264B (en) | 2018-06-05 | 2018-06-05 | Ultrathin g-C3N4Coated TiO2Homogeneous special-shaped array film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108816264B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110302418B (en) * | 2019-07-30 | 2021-08-20 | 西南大学 | Artificial tooth root with synergistic antibacterial coating and preparation method thereof |
| CN110656350B (en) * | 2019-11-13 | 2021-11-19 | 苏州大学 | Ferroelectric film ternary composite photoelectrode and preparation method thereof |
| CN114682242B (en) * | 2022-03-31 | 2024-02-27 | 武汉理工大学 | Large-area photocatalytic device with built-in electric field and porous structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102122577A (en) * | 2010-12-28 | 2011-07-13 | 复旦大学 | Titanium dioxide (TiO2) nano-rod single-crystal array thin film as well as preparation method and application thereof |
| CN106848494A (en) * | 2017-02-21 | 2017-06-13 | 陕西师范大学 | A kind of simple preparation method of carbon auto-dope nano carbon nitride film electrode |
| CN107675200A (en) * | 2017-08-23 | 2018-02-09 | 肇庆市华师大光电产业研究院 | A kind of modified g C3N4Quantum dot/TiO2Nano wire light anode and its application |
-
2018
- 2018-06-05 CN CN201810569379.6A patent/CN108816264B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102122577A (en) * | 2010-12-28 | 2011-07-13 | 复旦大学 | Titanium dioxide (TiO2) nano-rod single-crystal array thin film as well as preparation method and application thereof |
| CN106848494A (en) * | 2017-02-21 | 2017-06-13 | 陕西师范大学 | A kind of simple preparation method of carbon auto-dope nano carbon nitride film electrode |
| CN107675200A (en) * | 2017-08-23 | 2018-02-09 | 肇庆市华师大光电产业研究院 | A kind of modified g C3N4Quantum dot/TiO2Nano wire light anode and its application |
Non-Patent Citations (2)
| Title |
|---|
| "Improvement in photo voltaic performance of rutile-phased TiO2 nanorod/nanoflower-based dye-sensitized solar cell";M. K. Ahmad et al.;《J Aust Ceram Soc》;20180425;第54卷;第633-670页 * |
| "Modification of TiO2 nanorod arrays by graphite-like C3N4 with high visible light photoelectrochemical activity";Juan Wang et al.;《Electrochimica Acta》;20120327;第71卷;第10-16页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108816264A (en) | 2018-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109621979B (en) | Preparation method of ZnO/zinc indium sulfide nano heterojunction | |
| CN108816264B (en) | Ultrathin g-C3N4Coated TiO2Homogeneous special-shaped array film and preparation method thereof | |
| Li et al. | Hydrothermal growth of well-aligned TiO 2 nanorod arrays: Dependence of morphology upon hydrothermal reaction conditions | |
| CN102125863A (en) | Preparation method of graphite phase carbon nitride/rutile monocrystal titanium dioxide (TiO2) nanowire array | |
| CN107185580B (en) | g-C3N4/ZnO nanosheet multilevel heterostructure photocatalyst | |
| CN109338391B (en) | Preparation method of substrate for hydrogen production by photoelectrochemical decomposition of water, product and application thereof | |
| CN103361631B (en) | A kind of preparation method for light-catalysed Zinc oxide doped thin film of titanium oxide | |
| CN102085482A (en) | Preparation method of p-CoO/n-CdS/TiO2 composite semiconductor photocatalyst | |
| CN106540673A (en) | A kind of three-dimensional TiO2The synthetic method of/ZnO heterojunction array | |
| Khan et al. | Hierarchical nanostructures of titanium dioxide: synthesis and applications | |
| Motola et al. | Anodic TiO2 nanotube walls reconstructed: Inner wall replaced by ALD TiO2 coating | |
| CN101834068A (en) | Core-shell structure positive electrode for dye sensitization solar battery and preparation method thereof | |
| CN111921550A (en) | MXene/titanium dioxide nanotube composite material photocatalyst and preparation method thereof | |
| US20140291142A1 (en) | Photoelectrode for photoelectrochemical cell, method of manufacturing the same, and photoelectrochemical cell including the same | |
| CN106512985A (en) | Synthetic method of ZnO/WO3 heterojunction arrays | |
| CN110735151A (en) | Preparation method of titanium carbide composite indium zinc sulfide photo-anode | |
| CN111041523B (en) | Copper-doped titanium dioxide photoelectrode, preparation method thereof and application thereof in photoelectrocatalysis decomposition of water | |
| CN103352211A (en) | Preparation method of low-dimensional tantalum-based nano-array photo-electrode | |
| CN108579775B (en) | Silver phosphate/silver/titanium dioxide nanoflower composite material and preparation method and application thereof | |
| CN103877964A (en) | Preparation method of heterojunction between perovskite-phase lead titanate monocrystal nanowire and anatase-phase titanium dioxide | |
| CN108277501A (en) | A kind of preparation method of Si doped titanium dioxide nanotube arrays light anode | |
| CN105568309A (en) | Preparation method for photoelectrode of photoelectrochemical cell | |
| Xiao et al. | Mesoporous TiO2 nanowire film for dye-sensitized solar cell | |
| CN108751739B (en) | TiO22Nanorod and spike-shaped rod bundle staggered array film and preparation method thereof | |
| CN107937969A (en) | A kind of GN Sb2Se3The preparation method of laminated film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 266000 Qingdao University of Science & Technology, 99 Songling Road, Laoshan District, Qingdao, Shandong Applicant after: Qingdao University Of Science And Technology Address before: No. 53, Zhengzhou Road, North District, Qingdao, Shandong Applicant before: Qingdao University Of Science And Technology |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220922 Address after: 230000 Room 203, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Hefei Jiuzhou Longteng scientific and technological achievement transformation Co.,Ltd. Address before: 266000 Qingdao University of Science & Technology, 99 Songling Road, Laoshan District, Qingdao, Shandong Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221107 Address after: Room 302, Building C2, Qingdao National University Science Park, No. 127, Huizhiqiao Road, High tech Zone, Qingdao, Shandong 266000 Patentee after: Qingdao Zhonghai Blue Marine Biological Resources Development Co.,Ltd. Address before: 230000 Room 203, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee before: Hefei Jiuzhou Longteng scientific and technological achievement transformation Co.,Ltd. |
|
| TR01 | Transfer of patent right |