CN105817253B - The preparation method of graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material - Google Patents
The preparation method of graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material Download PDFInfo
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- CN105817253B CN105817253B CN201610230592.5A CN201610230592A CN105817253B CN 105817253 B CN105817253 B CN 105817253B CN 201610230592 A CN201610230592 A CN 201610230592A CN 105817253 B CN105817253 B CN 105817253B
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- carbon nitride
- phase carbon
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- nanometer sheet
- titanium dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 70
- 239000010439 graphite Substances 0.000 title claims abstract description 70
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002071 nanotube Substances 0.000 title claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002604 ultrasonography Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 150000007974 melamines Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 63
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 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 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
Abstract
The present invention discloses a kind of preparation method of graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material, including one, thermal polycondensation melamine prepares graphite phase carbon nitride powder；Two, ultrasound stripping body phase graphite phase carbon nitride obtains graphite phase carbon nitride nanometer sheet；Three, azotized carbon nano piece is added in electrolyte, one-step synthesis graphite phase carbon nitride nanometer sheet/unformed Nano tube array of titanium dioxide in anode oxidation process；Four, heat treatment is carried out to the sample that anodic oxidation obtains and prepares graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide material.Graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material is efficiently made in one step of the method for the present invention, it is economic and environment-friendly, obtained photochemical catalyst overcomes the shortcomings that Nano tube array of titanium dioxide and body phase graphite phase carbon nitride, it improves visible light utilization efficiency, reduce photo-generate electron-hole recombination rate, it can high efficiency photocatalysis degradable organic pollutant under visible light illumination.
Description
Technical field
The present invention relates to a kind of preparations of graphite phase carbon nitride nanometer sheet/titanium dioxide nanotube array photocatalyst material
Method belongs to photocatalytic environmental-protection technical field of nano material.
Background technology
There are five types of allotropes for carbon nitride material tool, and wherein graphite phase carbon nitride material is most stable of one kind.From
Antonietti in 2009 etc. report graphite phase carbon nitride can be used in photocatalysis field (Nat.Mater., 2009,8,76-
80.) nonmetallic materials that, this stability is good, environment-protecting and non-poisonous, raw material is cheap have obtained extensive pass in the fields such as photocatalysis
Note.The energy gap of graphite phase carbon nitride is 2.7eV, this allows it effectively to absorb visible light, has to sunlight very high
Utilization ratio.However the body phase graphite-phase that graphite phase carbon nitride presoma is prepared is calcined by high-temperature polycondensation method and is nitrogenized
Carbon, due to the shortcomings of specific surface area is larger, light induced electron and hole-recombination are fast, photocatalysis efficiency is still to be improved.In order to solve
These problems are doped body phase graphite phase carbon nitride, introduce nitrogen vacancy, being coupled with other semi-conducting materials, pattern control
Deng regulation and control, to effectively improve its photocatalysis efficiency.
Nanometer sheet often has high photocatalysis efficiency due to its unique structure, relative to Conventional nano particle.Graphite
Phase carbon nitride has the layer structure of similar graphite, and the graphite phase carbon nitride of nano-sheet can be obtained by lift-off processing to carry
Its high photocatalysis performance.Have many reports at present and graphite phase carbon nitride nanometer is successfully prepared by different stripping means
Piece, for example, liquid phase stripping (Advanced materials, 2013,25,2452-2456；Journal of Materials
Chemistry A, 2014,2,2563-2570.), ultrasound stripping (Applied Catalysis B：Environmental,
2014,152-153,46-50.), oxidation corrosion stripping (Advanced Functional Materials, 2012,22,
4763-4770.), chemical stripping (Journal of Materials Chemistry A, 2013,1,14766-14772) etc..
Graphite phase carbon nitride nanometer sheet after these strippings has the specific surface area of bigger, can provide more reactivity sites simultaneously
Photo-generated carrier combined efficiency is reduced, the efficiency of light-catalyzed reaction can be improved to a certain extent.However, due to component, knot
Structure is single, and photogenerated charge separating capacity and photocatalysis efficiency are still to be improved.
Titanium dioxide is as a kind of traditional n-type semiconductor photochemical catalyst, with economical, nontoxic, stability is good, environment
The advantages that friendly, is widely studied and applied in photocatalysis field, is the most photocatalyst material of current research.So
And energy gap 3.2eV so that it is low to the utilization ratio of sunlight.By the graphite phase carbon nitride of narrow band gap and broadband
The titanium dioxide of gap is compound, can optimize its visible absorption and enhance the separation of photoproduction phone, it is good to obtain visible light catalytic performance
Good catalysis material.Current research is focusing only on graphite phase carbon nitride particle and nano-titania particle is compound.And
The Nano tube array of titanium dioxide of ordered arrangement has the specific surface area of bigger, better electronics than traditional titanic oxide material
Transmittability recycles the advantages that performance is good, by the way that graphite phase carbon nitride nanometer sheet is fixed on titania nanotube battle array
The advantages of the two can be effectively utilized on row, overcome TiO 2 visible light difference in response, light induced electron and hole-recombination rate
The shortcomings of fast, can prepare the efficient visible light catalyst new material convenient for recycling.
Invention content
The present invention provides a kind of simple graphite for the low problem of single azotized carbon nano piece visible light catalytic efficiency
Phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material preparation method.This method can receive graphite phase carbon nitride
Rice piece is efficiently fixed on Nano tube array of titanium dioxide, and the preparation method is simple, quick and easy to operation, is prepared
There is photochemical catalyst preferable visible light catalytic efficiency, the photocatalytic degradation of organic dyestuff rhodamine B to have obvious effects on.
Technical scheme is as follows：
1) 10g melamines being put into crucible with a lid, is positioned in Muffle furnace, heating rate is 10 DEG C/min,
450~550 DEG C of 2~4h of calcining are warming up to,.Room temperature is naturally cooled to after calcining, the sample grind into powder that will be obtained, system
Proper phase graphite phase carbon nitride.
2) the body phase graphite phase carbon nitride that 2g steps 1 are prepared is taken to be added in 30~60ml concentrated sulfuric acids and continue to stir
8h.Then mixture is poured slowly into 200ml deionized waters, ultrasound 6~10h of stripping, then is incited somebody to action after carrying out 1000rmp centrifugations
Sediment rinses 5~15 times with deionized water and obtains colloidal graphite phase carbon nitride nanometer sheet repeatedly, then nanometer sheet colloid is molten
Further 0~the 60min of Ultrasonic Pulverization of liquid obtains smaller graphite phase carbon nitride nanometer sheet；
3) by the titanium sheet of purity > 99% through overpickling, then it is cleaned by ultrasonic 15min respectively in organic solution and water and obtains
Anodic oxidation prepares the base material of Nano tube array of titanium dioxide；
4) the graphite phase carbon nitride nanometer sheet for a concentration of 0.05-0.2g/L being prepared in 30~70ml steps 2 is taken, it will
Graphite phase carbon nitride nanometer sheet aqueous solution, which is added in the anodic oxidation electrolyte configured, to stir evenly, in 20V anodic oxygens
Change 2h, and be stirred continuously in anode oxidation process, mixing speed is 100 revs/min~500 revs/min.
5) taking-up of the Nano tube array of titanium dioxide sample of amorphous state is heat-treated after anodic oxidation, to rise
2 DEG C/min of warm speed is from room temperature to 400 DEG C~500 DEG C 1~3h of heat treatment.
Wherein, pickling solution is water: nitric acid: hydrofluoric acid=5: 4: 1 (V/V/V) mixed solutions in step 3；Ultrasonic cleaning has
Machine solution is acetone, isopropanol, methanol, ethyl alcohol；
Electrolyte is water: glycerine=1: 1 (v/v), 0.27M ammonium fluoride mixed solution in step 4；
Compared with prior art, the beneficial effects of the invention are as follows：Preparation method of the present invention is simple, economical convenient, preparation
Photochemical catalyst has excellent visible light catalytic performance, under visible light illumination can efficient rhodamine B degradation, be pure two
4 times of titanium oxide nanotubes.
Description of the drawings
Fig. 1 is the graphite phase carbon nitride nanometer sheet transmission electron microscope picture that one step 2 of embodiment is prepared；
Fig. 2 is the scanning electricity for graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide that embodiment one is prepared
Mirror figure；
Fig. 3 is the transmission electricity for graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide that embodiment one is prepared
Mirror figure；
Fig. 4 is the XRD diagram for graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide that embodiment one is prepared；
Fig. 5 is the graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide that is prepared of embodiment one in visible light
The lower photocatalytic degradation rhdamine B degradation property figure of irradiation；
Specific implementation mode
It is the specific implementation mode of the present invention below, further illustrates the present invention, but the present invention is not limited to this.
Specific implementation mode one：Present embodiment is that graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide light is urged
Change the easy of material to prepare, be as follows：
1) 10g melamines are put into crucible with a lid, are positioned in Muffle furnace and are forged for 450~550 DEG C in temperature
2~4h is burnt, heating rate is 10 DEG C/min.Room temperature is naturally cooled to after calcining, the sample grind into powder that will be obtained, system
It is standby to have obtained body phase graphite phase carbon nitride；
2) the body phase graphite phase carbon nitride that 2g steps 1 are prepared is taken to be added in 30~50ml concentrated sulfuric acids and continue to stir
8h.Then mixture is poured slowly into 200ml deionized waters, ultrasound 6~10h of stripping, then is incited somebody to action after carrying out 1000rmp centrifugations
Sediment rinses 5~15 times with deionized water and obtains colloidal graphite phase carbon nitride nanometer sheet repeatedly, then nanometer sheet colloid is molten
Further 0~the 60min of Ultrasonic Pulverization of liquid obtains smaller graphite phase carbon nitride nanometer sheet；
3) by the titanium sheet of purity > 99% through overpickling, then at acetone, isopropanol, methanol, ultrasound respectively in second alcohol and water
Cleaning 15min obtains the base material that anodic oxidation prepares Nano tube array of titanium dioxide；
4) the graphite phase carbon nitride nanometer sheet for taking a concentration of 0.1g/L being prepared in 30~70ml step 2, by graphite
Phase carbon nitride nanometer sheet aqueous solution is added to water: glycerine=1: in 1 (v/v), 0.27M ammonium fluoride mixing anodic oxidation electrolyte
Stir evenly, in 20V anodic oxygen 2h, and be stirred continuously in anode oxidation process, mixing speed be 100 revs/min~
500 revs/min.
5) taking-up of the Nano tube array of titanium dioxide sample of amorphous state is heat-treated after anodic oxidation, to rise
2 DEG C/min of warm speed is from room temperature to 400 DEG C~500 DEG C 1~3h of heat treatment.
Specific embodiment two：The present embodiment is different from the first embodiment in that calcination temperature is 520 in step 1
℃.Other are same as the specific embodiment one.
Specific embodiment three：The present embodiment is different from the first embodiment in that being rushed using deionized water in step 2
It is 10 times to wash number.Other are same as the specific embodiment one.
Specific embodiment four：The present embodiment is different from the first embodiment in that the Ultrasonic Pulverization time is in step 2
20~60min.Other are same as the specific embodiment one.
Specific embodiment five：In present embodiment step 2 unlike specific implementation mode one to four when Ultrasonic Pulverization
Between be 60min.Other are same as the specific embodiment one.
Specific embodiment six：The present embodiment is different from the first embodiment in that mixing speed is 200 in step 4
Rev/min.Other are same as the specific embodiment one.
The present invention uses following embodiment verification graphite phase carbon nitride nanometer sheet/titanium dioxide nanotube array photocatalyst
Visual efficiency with raising：
Embodiment one：
A) 10g melamines are put into crucible with a lid, it is 520 DEG C of calcining 2h to be positioned in Muffle furnace in temperature,
Heating rate is 10 DEG C/min.Room temperature is naturally cooled to after calcining, the sample grind into powder that will be obtained is prepared
Body phase graphite phase carbon nitride；
B) it takes the body phase graphite phase carbon nitride that 2g step 1 is prepared to be added in the 40ml concentrated sulfuric acids and continues to stir 8h.
Then mixture is poured slowly into 200ml deionized waters, ultrasound stripping 8h, then carried out sediment after 1000rmp centrifugations
It rinses 10 times repeatedly with deionized water and obtains colloidal graphite phase carbon nitride nanometer sheet, then nanometer sheet colloidal solution is further surpassed
Sound crushes 60min and obtains smaller graphite phase carbon nitride nanometer sheet；
C) by the titanium sheet of purity > 99% through overpickling, then at acetone, isopropanol, methanol, ultrasound respectively in second alcohol and water
Cleaning 15min obtains the base material that anodic oxidation prepares Nano tube array of titanium dioxide；
D) the graphite phase carbon nitride nanometer sheet for taking a concentration of 0.1g/L being prepared in 50ml step 2, by graphite-phase nitrogen
Change carbon nanosheet aqueous solution and be added to water: glycerine=1: being stirred in 1 (v/v), 0.27M ammonium fluoride mixing anodic oxidation electrolyte
Uniformly, it in 20V anodic oxygen 2h, and is stirred continuously in anode oxidation process, mixing speed is 200 revs/min.
E) taking-up of the Nano tube array of titanium dioxide sample of amorphous state is heat-treated after anodic oxidation, to rise
2 DEG C/min of warm speed is from room temperature to 450 DEG C of heat treatment 3h.
The transmission electron microscope picture for the graphite phase carbon nitride nanometer sheet that step 2 obtains through this embodiment is as shown in Figure 1, from figure
In visible obtained graphite phase carbon nitride be nano-sheet；
The scanning electron microscope of the graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide prepared through this embodiment is overlooked
Figure is as shown in Fig. 2, by figure it is observed that the regularly arranged titania nanotube battle array that nozzle diameter is about 50~100nm
Row, and do not covered by a large amount of graphite phase carbon nitride nanometer sheet on nozzle, this is conducive to Nano tube array of titanium dioxide
Absorption to light；
The transmission electron microscope picture of the graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide prepared through this embodiment is such as
Shown in Fig. 3, there is a small amount of graphite phase carbon nitride nanometer sheet close on the tube wall of titania nanotube from being observed in Fig. 3 tri-
Load；
XRD diagram such as Fig. 4 institutes of the graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide prepared through this embodiment
Show, it is observed that embodiment obtained once Overheating Treatment is anatase phase titanium dioxide from XRD diagram, and at 27.4 °
There are one the diffraction maximums that faint peak corresponds to graphite phase carbon nitride nanometer sheet (002) crystal face；
In order to verify graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material that embodiment one obtains
Visible light catalysis activity, be as follows：
It is that graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide that 2cm × 2cm embodiments one obtain is put to take size
It is placed in 30mL beakers, adds the rhodamine B solution of a concentration of 5mg/L of 20mL, be placed under continuous magnetic agitation
It is irradiated under 300W xenon lamps, the optical filter that a 420nm is covered on xenon lamp filters off ultraviolet light, and 4mL is quickly removed at interval of 30min
Rhodamine B solution and the absorbance change that rhodamine B is measured by ultraviolet specrophotometer, refund that the reaction was continued after having measured；
The visible light catalytic of the graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide prepared through this embodiment drops
The degradation effect that changes over time of solution rhodamine B solution is as shown in figure 5, graphite phase carbon nitride nanometer sheet/dioxy as seen from the figure
Changing titanium nano-tube array has good visible light catalytic performance, reaches to degradation of the rhodamine B solution in 300min
88%, 4 times are improved compared to the Nano tube array of titanium dioxide degradation effect without load, there is higher visible light catalytic energy
Power.
Claims (6)
1. a kind of preparation method of graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material, feature exist
In including the following steps：
1) 10g melamines are put into crucible with a lid, are positioned in Muffle furnace and calcine at a certain temperature, heating rate
For 10 DEG C/min；Room temperature is naturally cooled to after calcining, body phase graphite has been prepared in the sample grind into powder that will be obtained
Phase carbon nitride；
2) it takes the body phase graphite phase carbon nitride that 2g steps 1) are prepared to be added in 30~60ml concentrated sulfuric acids and continues to stir 8h；
Then mixture is poured slowly into 200ml deionized waters, ultrasound 6~10h of stripping, then will sunk after carrying out 1000rpm centrifugations
Starch is rinsed with deionized water and obtains colloidal graphite phase carbon nitride nanometer sheet for several times repeatedly, then by nanometer sheet colloidal solution into one
Step Ultrasonic Pulverization certain time obtains smaller graphite phase carbon nitride nanometer sheet；
3) by the titanium sheet of purity > 99% through overpickling, in organic solution and water being cleaned by ultrasonic 15min respectively obtains anode
Oxidation prepares the base material of Nano tube array of titanium dioxide；
4) a certain concentration graphite phase carbon nitride nanometer sheet being prepared in 30~70ml steps 2) is taken, graphite phase carbon nitride is received
Rice piece colloidal solution, which is added in the anodic oxidation electrolyte configured, to stir evenly, in 20V anodic oxygen 2h, and in sun
It is stirred continuously with certain speed in the oxidation process of pole；
5) taking-up of the Nano tube array of titanium dioxide sample of amorphous state is heat-treated after anodic oxidation, with the speed that heats up
2 DEG C/min of degree is heat-treated 1~3h from room temperature to certain temperature.
2. preparation method according to claim 1, it is characterised in that in step 1), the calcination temperature is 450~550
DEG C, calcination time is 2~4 hours.
3. preparation method according to claim 1, it is characterised in that in step 2), the washing time is 5~15 times.
4. preparation method according to claim 1, it is characterised in that in step 2), the Ultrasonic Pulverization time be 10~
70min。
5. preparation method according to claim 1, it is characterised in that in step 4), the graphite phase carbon nitride nanometer sheet is dense
Degree is 0.05-0.2g/L.
6. preparation method according to claim 1, it is characterised in that in step 4), the mixing speed is 100~500
Rev/min.
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| CN113562814A (en) * | 2021-08-09 | 2021-10-29 | 青岛农业大学 | Method for preparing graphite-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode by one-step method |
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