CN110512262A - A kind of in-situ preparation method of optoelectronic pole - Google Patents
A kind of in-situ preparation method of optoelectronic pole Download PDFInfo
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- CN110512262A CN110512262A CN201910801448.6A CN201910801448A CN110512262A CN 110512262 A CN110512262 A CN 110512262A CN 201910801448 A CN201910801448 A CN 201910801448A CN 110512262 A CN110512262 A CN 110512262A
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- carbon nitride
- graphite phase
- phase carbon
- nanometer sheet
- titanium dioxide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 45
- 239000010439 graphite Substances 0.000 claims abstract description 45
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 41
- 239000002127 nanobelt Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 238000010298 pulverizing process Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000007743 anodising Methods 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 230000035807 sensation Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000007517 polishing process Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229960002050 hydrofluoric acid Drugs 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- -1 and cathode Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract description 2
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000010748 Photoabsorption Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of in-situ preparation methods of optoelectronic pole, pure titanium sheet is pre-processed, obtain base material, titanium dioxide nano-belts array is prepared in situ using constant pressure anodizing in base material, it is put into melamine as sample in crucible with cover, calcining, grinding, body phase graphite phase carbon nitride is made, body phase graphite phase carbon nitride is placed under acidic environment, stirring, suspension is taken to be add to deionized water, obtain graphite phase carbon nitride nanometer sheet, by azotized carbon nano piece Ultrasonic Pulverization and constant volume, obtain graphite phase carbon nitride nanometer sheet colloidal solution, taking graphite phase carbon nitride nanometer sheet colloidal solution is electrolyte, make cathode in titanium dioxide nano-belts array photoelectric pole, platinized platinum makees anode, electrochemical deposition, operation of the present invention is simple, mild condition, pass through the modification of graphite phase carbon nitride nanometer sheet, spectral absorption model is widened It encloses, improves the separative efficiency of photo-generated carrier, superior catalytic performance is showed in terms of photocatalysis degradation organic contaminant.
Description
Technical field
The present invention relates to complex light electrode preparation technical fields, in particular to a type graphite phase carbon nitride nanometer
Piece/titanium dioxide nano-belts array photoelectric pole in-situ preparation method.
Background technique
The photocatalysis of semiconductor is widely used in Driven by Solar Energy environment remediation and conversion process of energy such as organic pollutant
Degradation and photodissociation aquatic products H2.Due to the superior optics of titanium dioxide and Electronic Performance, physicochemical properties are stablized, nontoxic secondary work
With, it is cheap and easy to get the advantages that, become one of most widely used photochemical catalyst.In various nanostructures, lead to
Crossing the titanium dioxide nano-belts array photoelectric that high-sequential is made in anodic oxidation great has that surface area is big and nano-band array is accurate
The property of guiding, not only increases charge collection efficiency, and light induced electron/hole is promoted comparatively fast to transmit and slower compound,
The concern of many people is attracted.However, titanium dioxide optical catalyst have the disadvantage in that the recombination rate in light induced electron and hole compared with
It is high；Due to TiO2Forbidden bandwidth is wider, makes it that can only absorb the ultraviolet light that energy is greater than its forbidden bandwidth energy, and in sunlight
Middle ultraviolet light only accounts for 5%, limits the use of sunlight in this way, causes the utilization rate of its sunlight lower.In addition, photocatalysis
Agent titanium dioxide nano-belts array photoelectric recycling rate of waterused extremely with higher when in use.
Carbonitride tool is there are five types of allotrope, wherein graphite phase carbon nitride (g-C3N4) it is most stable in five kinds of carbonitrides
A kind of non-metal semiconductive.It is nontoxic, inexpensive, and preparation method is simple, and structural behaviour is easily controllable to belong to narrow gap semiconductor,
Its band gap width is about 2.7eV, and for maximum absorption wavelength near 460nm, this allows it effectively to absorb visible light.Together
When, g-C3N4Also have many advantages, such as good thermal stability, electronics and optical characteristics.By titanium dioxide nano-belts array and graphite
Phase carbon nitride, which couples the complex light electrode to be formed, can be improved titanium dioxide to visible absorption utilization, and effectively facilitate photoproduction
The separation of electrons and holes, further increases visible light catalytic efficiency.But in the class graphite phase carbon nitride and two reported at present
In titanium oxide composite photocatalyst material, there are some problems in preparation and application aspect.It on the one hand is preparation method complexity, it is raw
At graphite phase carbon nitride it is considerably less or be deposited in the form of quantum dot nanobelt top, absorption and pollution to visible light
The adsorbance of object is low；It on the other hand is catalyst mostly with powdered, complex needs are costly in actual cycle use
Cost seriously hinders its practical application in pollutant process.For example, being disclosed in CN201710471344.4 a kind of compound
The preparation method of the titanium dioxide nano-belts electrode material of carbonitride, first passes through hydro-thermal reaction and calcining prepares nano titania
The titanium dioxide prepared is then added in thiourea solution by band, calcines at a certain temperature after dry and nitrogen is made
The titanium dioxide nano-belts sample of carbon；Disclosed in CN201110028708.4 it is a kind of using infusion process prepare graphite-phase nitridation
Carbon/rutile single crystals titanium dioxide nanowire array method, cyanogen ammoniac compounds or urea are dissolved in solution, then will system
Standby rutile single crystals titanium dioxide nanowire array enters in cyanogen aminated compounds or urea liquid, takes out dry and high temperature and forges
It burns.Therefore, graphite phase carbon nitride modification is carried out to titanium dioxide by the method being simple and efficient in situ, there is good light to urge for preparation
Change activity, it is significant for practical application that the high photochemical catalyst electrode of stability is recycled.
Summary of the invention
The present invention provides a kind of in-situ preparation method of optoelectronic pole, by in-situ preparation graphite phase carbon nitride nanobelt/
Titanium dioxide nano-belts array photoelectric pole, yield and separative efficiency with the raw electron hole of high light, higher visible light benefit
With performance, have a significant effect to the photocatalytic degradation of antibiotic quadracycline (TC).
To achieve the above object, the invention provides the following technical scheme:
A kind of in-situ preparation method of optoelectronic pole, comprising the following steps:
S1: pure titanium sheet is pre-processed, base material is obtained；
S2: titanium dioxide nano-belts array is prepared in situ using constant pressure anodizing in base material；
S3: it is put into melamine as sample in crucible with cover, is calcined in Muffle furnace, ground after calcining with agate
Sample is ground to no granular sensation by alms bowl, and body phase graphite phase carbon nitride is made；
S4: body phase graphite phase carbon nitride is placed under acidic environment, and stirring takes suspension to be add to deionized water, and is surpassed
Sound removing, is washed to neutrality, obtains graphite phase carbon nitride nanometer sheet, by azotized carbon nano piece Ultrasonic Pulverization and constant volume, obtains stone
Black phase carbon nitride nanometer sheet colloidal solution；
S5: taking graphite phase carbon nitride nanometer sheet colloidal solution is electrolyte, and yin is made in titanium dioxide nano-belts array photoelectric pole
Pole, platinized platinum make anode, electrochemical deposition, drying.
Preferably, in the step S1, pretreatment includes but is not limited to cleaning, sanding and polishing and ultrasonic cleaning.
Preferably, the cleaning solution that cleaning process uses is water, hydrofluoric acid or water and hydrofluoric acid mixed solution, sanding and polishing process
It is respectively successively water using 600 mesh, 1000 mesh and 2000 mesh sand paper, the solution of ultrasonic cleaning；The mixing of ethyl alcohol, acetone and water
Liquid, wherein the volume ratio of ethyl alcohol and acetone is 1:1.
Preferably, in the step S2, constant temperature 0.5-1h before anodic oxidation, it is ensured that reaction solution temperature is uniform, keeps oxygen
Temperature is consistent during change, and electrolyte is 0.5%NH4F and 93% ethylene glycol mixture, and voltage 60-65V aoxidizes 2.5-3h.
Preferably, in the step S3, melamine quality is 10-15g, and calcination temperature is 450-550 DEG C, calcination time
For 2-2.5h, 5-6 DEG C of heating rate/min.
Preferably, it in the step S4, takes 3g body phase graphite phase carbon nitride to be placed under acidic environment, is stirred at 25 DEG C
10-24h takes suspension to be add to deionized water, and deionized water volume is 200-400mL, and ultrasound removing 10-24h utilizes pumping
The method of filter is washed, and is washed till neutrality and is obtained graphite phase carbon nitride nanometer sheet, then simultaneously by azotized carbon nano piece Ultrasonic Pulverization
It is settled to 2-3L and obtains graphite phase carbon nitride nanometer sheet colloidal solution, the Ultrasonic Pulverization time is 2-3h.
Preferably, in the step S5, graphite phase carbon nitride nanometer sheet colloidal solution volume is 100mL, electrochemical deposition
30-40min, drying temperature are 101-105 DEG C.
Preferably, the voltage of electrochemical deposition is 1-6V.
The beneficial effects of the present invention are:
Optoelectronic pole is prepared based on electrochemical in-situ deposition method, easy to operate, mild condition, the load of azotized carbon nano piece is
Even, required time is few, save the cost, meanwhile, it improves that TiO 2 visible light utilization rate is low and photogenerated charge hole is easy
Compound disadvantage has widened spectral absorption range by the modification of graphite phase carbon nitride nanometer sheet, improves point of photo-generated carrier
From efficiency, the compound of photo-generate electron-hole is reduced, superior catalytic performance, In are showed in terms of photocatalysis degradation organic contaminant
Quadracycline of degrading under visible light reaches 26.89% in 60min, in addition, the sample that preparation process uses can be weighed directly
It is multiple to utilize, it is convenient and efficient using process, do not need the complicated processes such as the separating-purifying consumption energy.
Detailed description of the invention
Fig. 1 is graphite phase carbon nitride/titanium dioxide nano-belts array photoelectric pole and comparative example two prepared by embodiment one
X-ray diffractogram of the TiOx nano with array photoelectric pole, abscissa indicate that X-ray diffractometer is entire with the angle scanning of 2 θ
Diffraction region, ordinate indicate the unit of relative intensity.
Fig. 2 (b) and Fig. 2 (d) is graphite phase carbon nitride/titanium dioxide nano-belts array photoelectric pole prepared by embodiment two
Scanning electron microscope (SEM) photograph and transmission electron microscope picture, Fig. 2 (a) and Fig. 2 (c) are respectively the scanning of comparative example titanium dioxide nano-belts array photoelectric pole
Electron microscope and transmission electron microscope picture.
Fig. 3 is that embodiment two prepares graphite phase carbon nitride/titanium dioxide nano-belts array photoelectric pole and comparative example dioxy
Change the photo absorption performance schematic diagram of titanium nano-band array optoelectronic pole, abscissa indicates that wavelength, unit nm, ordinate indicate to inhale
Luminosity.
Fig. 4 is graphite phase carbon nitride/titanium dioxide nano-belts array photoelectric pole and comparison prepared by embodiment one and four
Example titanium dioxide nano-belts array photoelectric pole photocatalytic degradation quadracycline degradation property figure under visible light illumination, indulges and sits
Mark indicates degradation rate, unit %.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment one:
A kind of in-situ preparation method of optoelectronic pole, comprising the following steps:
Pure titanium sheet: being cut into the bar shaped paillon of 100 × 10 × 0.2mm by S1, successively passes through hydrofluoric acid clean, 600 mesh, 1000
Mesh and 2000 mesh sand paper sanding and polishings, respectively in deionized water, acetone: being cleaned by ultrasonic in ethyl alcohol=1:1 (vol) and deionized water
After 10min, it is put into and seals to obtain the base material that anodic oxidation prepares titanium dioxide nano-belts array in deionized water up for safekeeping.
S2: using base material as substrate, titanium dioxide nano-belts array, anode are prepared in situ using constant pressure anodizing
Constant temperature 0.5h before aoxidizing, it is ensured that reaction solution temperature is uniform, keeps temperature in oxidation process consistent, electrolyte 0.5%NH4F
With 93% ethylene glycol mixture, 20 DEG C of reaction temperature, voltage 60V, 2.5h is aoxidized, is stirred continuously, has aoxidized in oxidation process
Finish and rinses electrode surface with a large amount of deionized waters immediately.
S3: 10g melamine is put into crucible with cover, 450 DEG C of calcining 2h in Muffle furnace atmosphere of inert gases, heating
Sample is ground to no obvious granular sensation with agate mortar after calcining by 5 DEG C/min of rate, and the nitridation of body phase graphite-phase is made
Carbon.
S4: it takes 3g body phase graphite phase carbon nitride to be placed under acidic environment, stirs 18h at 25 DEG C, suspension is slowly added
Enter into 300mL deionized water, ultrasound removing for 24 hours, is washed using the method for suction filtration, and is cleaned to suspension and be in neutrality
To graphite phase carbon nitride nanometer sheet, then by azotized carbon nano piece Ultrasonic Pulverization 2.5h and it is settled to 2L and obtains graphite phase carbon nitride and receive
Rice piece colloidal solution.
S5: taking 100mL graphite phase carbon nitride nanometer sheet colloidal solution is electrolyte, titanium dioxide nano-belts array photoelectric pole
Make cathode, platinized platinum makees anode, the electrochemical deposition 40min under 3V voltage, at 101 DEG C dry to get to graphite phase carbon nitride/
Titanium dioxide nano-belts array photoelectric pole.
Embodiment two:
The part that the present embodiment is the same as example 1 repeats no more, unlike: in step S4, ultrasound removing 15h.
Embodiment three:
The part that the present embodiment is the same as example 1 repeats no more, unlike: in step S3, it is warming up to 500 DEG C.
Example IV:
The part that the present embodiment is the same as example 1 repeats no more, unlike: in step S5, electrochemical deposition voltage
For 6V.
Testing experiment:
By 4cm2Sample be immersed in 40mL concentration be 20mg/L quadracycline solution in and be stirred continuously dark place
30min is managed, using the 150W xenon lamp of wavelength 420-780nm, photodissociation 60min, which takes out, uses spectrophotometer test record data, makes
As a comparison case with the titanium dioxide nano-belts array photoelectric pole (TNBs) loaded without graphite phase carbon nitride nanometer sheet.
Graphite phase carbon nitride nanometer sheet/titanium dioxide nano-belts array photoelectric pole (g-C prepared by embodiment one3N4/TNBs)
And the X-ray diffractogram of comparative example titanium dioxide nano-belts array photoelectric pole (TNBs), as shown in Figure 1.As can be known from Fig. 1:
Graphite phase carbon nitride nanometer sheet/titanium dioxide nano-belts array (g-C3N4/ TNBs) it is pure anatase phase titanium dioxide, at 28.0 °
Diffraction maximum be due to aroma system feature interlayer stack generate, further prove that the diffraction maximum belongs to hexagonal phase class graphite
(002) crystal face of material stratiform packed structures.
Graphite phase carbon nitride nanometer sheet/titanium dioxide nano-belts array photoelectric pole (g-C prepared by embodiment two3N4/TNBs)
And the scanning electron microscope (SEM) photograph and transmission electron microscope picture of comparative example titanium dioxide nano-belts array photoelectric pole (TNBs), as shown in Figure 2.From
Known in Fig. 2: optoelectronic pole (g-C3N4/ TNBs) surface 1 ties up banded structure, the wherein roomy about 20-50nm of nanobelt, in titanium dioxide
Titanium nanometer belt surface shows g-C3N4Thin layer.Transmission electron microscope also demonstrates g-C3N4With TiO2Between hetero-junctions presence.
Graphite phase carbon nitride nanometer sheet/titanium dioxide nano-belts array photoelectric pole (g-C prepared by embodiment two3N4/
TNBs) and the photo absorption performance of comparative example titanium dioxide nano-belts array photoelectric pole (TNBs), as shown in Figure 3.It can from Fig. 3
Know: optoelectronic pole (g-C3N4/ TNBs) in ultraviolet and visual field absorbing properties it is higher than titanium dioxide nano-belts array photoelectric pole, table
Bright azotized carbon nano piece improves visible absorption performance, and then improves photocatalysis performance.
Graphite phase carbon nitride nanometer sheet/titanium dioxide nano-belts array photoelectric pole prepared by embodiment one is named as g-C3N4/
Graphite phase carbon nitride nanometer sheet/titanium dioxide nano-belts array photoelectric pole of TNBs-3, example IV preparation are named as g-C3N4/
TNBs-6, then g-C3N4/TNBs-3、g-C3N4Photocatalytic degradation quadracycline drops/TNBs-6 and TNBs under visible light illumination
Performance map is solved, as shown in Figure 4.As can be known from Fig. 4: to quadracycline, the removal rate after illumination 60min is 16.19% to TNBs,
g-C3N4/ TNBs-3 and g-C3N4/ TNBs-6 is 26.28% and 23.86% to the removal rate of quadracycline.Experimental result table
Bright azotized carbon nano piece/titanium dioxide nano-belts array photoelectric pole photocatalysis performance significantly improves, and the original of this phenomenon occurs
Visible absorption utilization scope is widened because being primarily due to carbonitride, and effectively facilitates photo-generate electron-hole separation, and then improve
Photocatalysis performance.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (8)
1. a kind of in-situ preparation method of optoelectronic pole, which comprises the following steps:
S1: pure titanium sheet is pre-processed, base material is obtained；
S2: titanium dioxide nano-belts array is prepared in situ using constant pressure anodizing in base material；
S3: being put into melamine as sample in crucible with cover, calcine in Muffle furnace, will with agate mortar after calcining
Sample is ground to no granular sensation, and body phase graphite phase carbon nitride is made；
S4: body phase graphite phase carbon nitride is placed under acidic environment, and stirring takes suspension to be add to deionized water, ultrasound stripping
From being washed to neutrality, obtain graphite phase carbon nitride nanometer sheet, by azotized carbon nano piece Ultrasonic Pulverization and constant volume, obtain graphite-phase
Azotized carbon nano piece colloidal solution；
S5: taking graphite phase carbon nitride nanometer sheet colloidal solution is electrolyte, and cathode, platinum are made in titanium dioxide nano-belts array photoelectric pole
Piece makees anode, electrochemical deposition, drying.
2. in-situ preparation method according to claim 1, which is characterized in that in the step S1, pretreatment includes but not
It is limited to cleaning, sanding and polishing and ultrasonic cleaning.
3. in-situ preparation method according to claim 2, which is characterized in that the cleaning solution that cleaning process uses is water, hydrogen
Fluoric acid or water and hydrofluoric acid mixed solution, sanding and polishing process successively use 600 mesh, 1000 mesh and 2000 mesh sand paper, ultrasonic cleaning
Solution be respectively water；The mixed liquor of ethyl alcohol, acetone and water, wherein the volume ratio of ethyl alcohol and acetone is 1:1.
4. in-situ preparation method according to claim 1, which is characterized in that in the step S2, constant temperature before anodic oxidation
0.5-1h, electrolyte 0.5%NH4F and 93% ethylene glycol mixture, voltage 60-65V aoxidize 2.5-3h.
5. in-situ preparation method according to claim 1, which is characterized in that in the step S3, melamine quality is
10-15g, calcination temperature are 450-550 DEG C, calcination time 2-2.5h, 5-6 DEG C of heating rate/min.
6. in-situ preparation method according to claim 1, which is characterized in that in the step S4, take 3g body phase graphite-phase
Carbonitride is placed under acidic environment, stirs 10-24h at 25 DEG C, suspension is taken to be add to deionized water, deionized water volume
It is washed using the method for suction filtration, and be washed till neutrality and obtain graphite phase carbon nitride for 200-400mL, ultrasound removing 10-24h
Nanometer sheet, then by azotized carbon nano piece Ultrasonic Pulverization and be settled to 2-3L and obtain graphite phase carbon nitride nanometer sheet colloidal solution, surpass
Sound grinding time is 2-3h.
7. according to any in-situ preparation method of claim 2-6, which is characterized in that in the step S5, graphite-phase nitrogen
Change carbon nanosheet colloidal solution volume is 100mL, and electrochemical deposition 30-40min, drying temperature is 101-105 DEG C.
8. in-situ preparation method according to claim 7, which is characterized in that the voltage of electrochemical deposition is 1-6V.
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