CN106140242A - A kind of visible-light response type boron nitride modifies carbon nitride photocatalyst and its preparation method and application - Google Patents
A kind of visible-light response type boron nitride modifies carbon nitride photocatalyst and its preparation method and application Download PDFInfo
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- CN106140242A CN106140242A CN201610521036.3A CN201610521036A CN106140242A CN 106140242 A CN106140242 A CN 106140242A CN 201610521036 A CN201610521036 A CN 201610521036A CN 106140242 A CN106140242 A CN 106140242A
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 65
- 230000004044 response Effects 0.000 title claims abstract description 36
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000000975 dye Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 231100001239 persistent pollutant Toxicity 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 24
- 229940106691 bisphenol a Drugs 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance 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
- 206010013786 Dry skin Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 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
- 238000011953 bioanalysis Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000001779 embryotoxic effect Effects 0.000 description 1
- 231100000238 embryotoxicity Toxicity 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 210000002307 prostate Anatomy 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
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- 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
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
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Abstract
The invention provides a kind of visible-light response type boron nitride and modify carbon nitride photocatalyst and its preparation method and application, the carbonitride of this photochemical catalyst is lamellar structure, and boron nitride is that yarn shape is attached to carbonitride sheet surfaces.Its preparation method is first to prepare boron nitride with urea and boric acid for raw material, more block carbonitride is converted into the carbonitride of stratiform, is then doped in carbonitride by ultrasonic wave added by boron nitride, and finally calcining obtains boron nitride and modifies carbon nitride photocatalyst.This photochemical catalyst can be used for the organic matters such as the persistent pollutant in degradation water and dyestuff.The boron nitride of the present invention is modified carbon nitride photocatalyst and is reduced to 2.59eV the band gap of carbonitride from 2.7eV, enhance the utilization rate to visible ray for the carbon nitride photocatalyst, and more fully can utilize solar energy efficiently, this utilizes significant for environmental improvement and green energy resource.
Description
Technical field
The invention belongs to catalysis material technical field, be specifically related to the modified carbon nitride photocatalyst of a kind of boron nitride and
Preparation method and application.
Background technology
At present, persistent pollutant is increasingly subject to people's attention, and bisphenol-A is widely used in daily life, becomes
The material that people are frequently encountered by.Bisphenol-A belongs to hypotoxicity material, is a kind of pollutant simulating female hormone, though very low
Amount can result in the effect such as sex premature, sperm count declines, prostate growth, in addition bisphenol-A also have certain embryotoxicity with
Teratogenesis, hence it is evident that increase cancer morbidity.Bisphenol-A can directly endanger human and livestock health after entering food chain.Traditionally, physics-change
Method, electrochemical process, bioanalysis etc. may serve to carry out the process of waste water from dyestuff, but have that removal efficiency is low, cause
Secondary pollution, shortcoming costly.In view of environmental benefit, it is seen that light degradation dyestuff causes increasingly as a kind of green technology
High attention.
In recent years, conductor photocatalysis material is widely used in fields such as environment, material, the energy, in order to carry
The utilization ratio of high solar, solar energy be converted into storable electric energy, chemical energy is the research topic that the mankind are most interested in
One of.Hydrogen Energy is regenerative resource cleanly and efficiently, has been generally considered a kind of new century preferable green energy resource.Utilize light
Catalysis material carrys out hydrogen manufacturing, and low-density solar energy is converted into Hydrogen Energy.
Carbonitride is to compare popular catalysis material in recent years, relative to pure TiO2Can carry relatively low, wavelength is less than 450nm
When have photoresponse, but carbonitride is still very weak to the absorption of sunshine at visible region, and photoelectron and hole
Easily compound, the utilization rate ratio causing visible ray is relatively low.
Content of the invention
Solve the technical problem that: the present invention is directed to the low technical problem of the visible light-responded rate of carbonitride, provide a kind of visible
Photoresponse type boron nitride modifies carbon nitride photocatalyst and its preparation method and application, and gained photochemical catalyst is not only for ultraviolet light
Produce response, also there is to visible ray response simultaneously.
Technical scheme: a kind of visible-light response type boron nitride modifies carbon nitride photocatalyst, and wherein, carbonitride is lamella knot
Structure, boron nitride is that yarn shape is attached to carbonitride sheet surfaces.
Described visible-light response type boron nitride modifies the preparation method of carbon nitride photocatalyst, comprises the steps:
Boron nitride is added in water by step 1, and ultrasonic disperse 2～4h under room temperature obtains boron nitride dispersion；
Carbonitride is added in water by step 2, and ultrasonic disperse 3～6h under room temperature obtains carbonitride dispersion liquid；
Boron nitride dispersion is dropped in carbonitride dispersion liquid by step 3, stirring, mixed liquor ultrasonic reaction 0.5～1 hour, mistake
Filter, cleans, is dried gained solid；
Step 4, by step 3 gained solid 350 DEG C of reaction 2h under nitrogen atmosphere, to obtain final product.
Further, in step 1, boron nitride is to prepare with boric acid and urea for raw material.Concrete grammar is: by boric acid
Add in water in the ratio of 1:20 with urea, then mixed liquor is put into 18～24h in 60～80 DEG C of baking ovens, obtain white mixing
Thing；Then by white mixture in the tube furnace of full nitrogen 900 DEG C of heating 5～7h, the end product that obtains is ground standby
With.
Further, in step 1, the mass volume ratio of boron nitride and water is 0.3～1.2mg:36～40mL.
Further, in step 2, the mass volume ratio of carbonitride and water is 80～100mg:36～40mL.
Further, in step 3, the mass ratio of boron nitride and carbonitride is 0.3～1.2:100.
Further, step 1, step 2, ultrasonic power is 70～120w in step 3.
Further, in step 3 baking temperature be 60～100 DEG C, the time be 8～12h.
Described visible-light response type boron nitride modifies application in water-treatment technology field for the carbon nitride photocatalyst.
Beneficial effect: compared with prior art, its remarkable advantage is the present invention:
1. compensate for the low shortcoming of carbon nitride photocatalyst band gap length, solar energy utilization ratio, by the band gap of carbonitride from 2.7eV
Reduce to 2.59eV, enhance the utilization rate to visible ray for the carbon nitride photocatalyst；
2. visible-light response type boron nitride modification carbon nitride photocatalyst has good photocatalytic activity under visible light, and
More fully can utilize solar energy efficiently, this utilizes significant for environmental improvement and green energy resource；
3. using conventional urea as reactant, raw material is cheap and easy to get, preparation process is simple, simultaneously preparation method pair
Environmental friendliness, does not produce poisonous and hazardous accessory substance；
4. manufacturing cycle is short, and stability of material is good.
Brief description
Fig. 1 is the SEM figure of the visible-light response type boron nitride modification carbon nitride photocatalyst of embodiment 1 preparation；
Fig. 2 is the DRS figure of the visible-light response type boron nitride modification carbon nitride photocatalyst of embodiment 2 preparation；
Fig. 3 is that the visible-light response type boron nitride of embodiment 2 preparation modifies carbon nitride photocatalyst in different boron nitride dopings
Under degradation effect figure to bisphenol-A；
Fig. 4 is that the visible-light response type boron nitride of embodiment 1 preparation modifies carbon nitride photocatalyst and block carbonitride fluorescence light
Spectrum comparison diagram；
Fig. 5 is that the visible-light response type boron nitride of embodiment 1 preparation modifies carbon nitride photocatalyst degraded bisphenol A catalyst repetition
Utilize figure.
Detailed description of the invention
The present invention provides a kind of visible-light response type boron nitride to modify carbon nitride photocatalyst, and wherein, carbonitride is lamella
Structure, boron nitride is that yarn shape is attached to carbonitride sheet surfaces, and dispersiveness is preferably, and beneficially carbonitride is for the suction of light
Receive.Its preparation method is first to prepare boron nitride with urea and boric acid for raw material, more block carbonitride is converted into stratiform
Carbonitride, then by ultrasonic wave added, boron nitride is doped in carbonitride, finally calcining obtain boron nitride modify carbonitride
Photochemical catalyst.
The present invention, with cheap urea as raw material, first uses the ultrasonic carbonitride that block carbonitride is converted into stratiform,
Then prepare visible-light response type boron nitride modify nitridation through ultrasonic wave added, precipitation, separation, washing, drying, calcining step
Carbon photochemical catalyst, ultrasonic wave added is peeled off not only for carbonitride actively impact, but also introduces oxygen defect, adulterates boron nitride
To carbonitride, utilize quantum limit effect and the skin effect of boron nitride, make graphite phase carbon nitride photocatalysis absorption spectrum open up
Wide to visible region, reduce the band gap of boron nitride to 2.59eV so that it is produce response not only for ultraviolet light, simultaneously to visible
Light also has response.The method preparation manipulation is simple, and the material prepared can make full use of solar energy, can effectively solve the problem that
The problem of environmental pollution.
Boron nitride have improve electron conductivity ability, adulterate less with doping excess all can significantly affect light-catalysed
Degradation effect.During a small amount of doping boron nitride, hence it is evident that improve the absorptivity to light in visible region for the catalyst, but when doping
When boron nitride is excessive, boron nitride can cover the avtive spot above graphite phase carbon nitride, the photoelectron above avtive spot in a large number
The pollutant haptoreaction cannot adsorbed above with catalyst, causes photocatalysis effect to be deteriorated.Boron nitride and nitridation in the present invention
The mass ratio of carbon is 0.3～1.2:100.
The visible-light response type boron nitride of the present invention modifies the continuation dirt that carbon nitride photocatalyst can be used in degradation water
The organic matters such as dye thing and dyestuff.
Embodiment 1
Prepare boron nitride: boric acid and urea are dissolved in 40mL ultra-pure water with the ratio of mass ratio 1:20, put into 80 DEG C of dryings in baking oven
12 hours, obtain the mixture of white.Then by white mixture in the tube furnace of full nitrogen 900 DEG C heat 5 hours, will
The end product obtaining grinds standby.
Preparation is mixed boron nitride and is modified the boron nitride of carbonitride: 0.9mg and be scattered in the ultra-pure water of 36mL, under room temperature ultrasonic 4
Hour, it is thus achieved that boron nitride dispersion；The carbonitride of 99.1mg is added in the ultra-pure water of 36mL, under room temperature ultrasonic 4 hours, it is thus achieved that
Carbonitride dispersion liquid；Boron nitride dispersion is dropwise dropped to carbonitride dispersion liquid, ultrasonic disperse 1 hour；Mixed liquor filters, institute
Obtain after filter residue ultra-pure water cleans 60 DEG C of drying for standby；Will be equipped with the quartz boat of drying sample to put in tube furnace 350 DEG C and add
Heat 2 hours, i.e. prepares 0.9% BN@C of visible-light response type3N4Photochemical catalyst.
Use the 0.9%BN@C to prepared visible-light response type for the SEM3N4Photochemical catalyst carries out Electronic Speculum and sweeps
Retouch, the 0.9%BN@C of the visible-light response type preparing as can be seen from Figure 13N4Photochemical catalyst is Nano microsphere, and there is a small amount of yarn on surface
Shape BN wraps up.
Use the BN@C to prepared visible-light response type for the full-automatic XRF3N4Photochemical catalyst characterizes, from figure
The 2 BN@C that can be seen that prepared visible-light response type3N4Photochemical catalyst is relative to pure C3N4Under excitation wavelength, swashing of generation
Sending out peak lower, therefore advantageously separating with hole in photoelectron, contribute to the degraded for pollutant, this is that boron nitride has
It is effectively conducted the effect of photoelectron ability.
Embodiment 2
The preparation of boron nitride is with embodiment 1.
The carbonitride of different content boron nitride is mixed in preparation: the boron nitride taking 0.3mg, 0.6mg, 0.9mg and 1.2mg respectively divides
Dissipate in the ultra-pure water of 36mL, ultrasonic 4h under room temperature, it is thus achieved that boron nitride dispersion；Respectively by 99.7mg, 99.4mg, 99.1mg and
The carbonitride of 98.8mg adds in the ultra-pure water of 36mL, under room temperature ultrasonic 4 hours, it is thus achieved that carbonitride dispersion liquid；Respectively will nitridation
Boron dispersion liquid dropwise drops to carbonitride dispersion liquid, ultrasonic disperse 1 hour；Mixed liquor filters, and the handy ultra-pure water solid of institute cleans
After 60 DEG C of drying for standby；Will be equipped with the quartz boat of drying sample to put in tube furnace 350 DEG C and heat 2 hours, prepare boron nitride
With carbonitride mass ratio be respectively the 0.3%th, the 0.6%th, 0.9% and 1.2% the BN@C of visible-light response type3N4Photochemical catalyst, remembers respectively
For: 0.3%BN@C3N4、0.6%BN@C3N4、0.9%BN@C3N4、1.2%BN@C3N4。
Use the BN@C to prepared visible-light response type for the UV-vis DRS spectrometer3N4Photochemical catalyst carries out Electronic Speculum
Scanning, as can be seen from Figure 3 the BN@C relative to block carbonitride visible-light response type3N4Photochemical catalyst at visible region to light
Absorption be remarkably reinforced, therefore produce more photoelectron and separate with hole, contribute to the degraded for pollutant.Doped graphite phase
Boron nitride is more, and material is remarkably reinforced in the absorbability to light for the full spectrum, the carbonitride pair of this explanation doping boron nitride
Light-use is substantially strengthened, and absorbs the luminous energy that obtains more, photoelectron-hole to producing more, the sky that can utilize
Cave is more with photoelectron, hole and photoelectron and then generation hydroxyl radical free radical, and hole self also can aoxidize organic contamination
Thing.
Embodiment 3
Use the photochemical catalyst that embodiment 2 prepares for oxidation processes bisphenol-A solution.
Concretely comprise the following steps:
Step 1: accurately weigh the bisphenol-A of 10mg, be dissolved in ultra-pure water, and be settled to 1000mL, prepares the double of 10mg/L
Phenol solution A；
Step 2: accurately pipette the bisphenol-A solution that 40mL step 1 obtains in reactor with pipette, and add 32mg 0.3%
BN@C3N4, 0.6%BN@C3N4, 0.9%BN@C3N4With 1.2%BN@C3N4, reaction system controls at 25 DEG C, first adsorbs flat at half-light
Weigh half an hour so that it is reach adsorption/desorption balance；
Step 2 gained solution is carried out photocatalytic degradation reaction, often by step 3: using 300w xenon lamp as visible light source under light illumination
Interval 5～30min time samples, and with the content of high-efficient liquid phase color spectrometry bisphenol-A, and calculates its conversion ratio.Result is shown in Fig. 4.
As can be seen from Figure 4, when adulterating the boron nitride of 0.9wt%, photocatalysis effect is best, adulterates less and adulterated
Amount all can significantly affect light-catalysed degradation effect.BN has the ability improving electron conductivity, during a small amount of doped graphite phase BN,
Significantly improve the absorptivity to light in visible region for the catalyst, but when the BN that adulterates is excessive, BN can cover nitridation in a large number
Avtive spot above carbon, the pollutant haptoreaction that the photoelectron above avtive spot cannot adsorb above with catalyst, lead
Cause photocatalysis effect to be deteriorated.
Embodiment 4
By the boron nitride in embodiment 1/azotized carbon nano composite (0.9% BN@C3N4) centrifugal drying, it is scattered in 40mL dense
In the bisphenol-A that degree is 10mg/L, put into lucifuge stirring half an hour in light reaction instrument, reach catalyst and adsorb-resolve flat with bisphenol-A
Weighing apparatus, with the xenon lamp of 300w as light source, carries out light degradation experiment, is so repeated twice the photocatalytic degradation weight obtaining as shown in Figure 5
Renaturation curve map, as can be seen from the figure photocatalytic activity keeps constant.
Claims (9)
1. a visible-light response type boron nitride modifies carbon nitride photocatalyst, it is characterised in that: carbonitride is lamellar structure, nitrogen
Changing boron is that yarn shape is attached to carbonitride sheet surfaces.
2. visible-light response type boron nitride described in claim 1 modifies the preparation method of carbon nitride photocatalyst, it is characterised in that:
Comprise the steps:
Boron nitride is added in water by step 1, and ultrasonic disperse 2～4h under room temperature obtains boron nitride dispersion；
Carbonitride is added in water by step 2, and ultrasonic disperse 3～6h under room temperature obtains carbonitride dispersion liquid；
Boron nitride dispersion is dropped in carbonitride dispersion liquid by step 3, stirring, mixed liquor ultrasonic reaction 0.5～1 hour, mistake
Filter, cleans, is dried gained solid；
Step 4, by step 3 gained solid 350 DEG C of reaction 2h under nitrogen atmosphere, to obtain final product.
3. visible-light response type boron nitride modifies the preparation method of carbon nitride photocatalyst, its feature according to claim 2
It is: in step 1, boron nitride is to prepare with boric acid and urea for raw material.
4. visible-light response type boron nitride modifies the preparation method of carbon nitride photocatalyst, its feature according to claim 2
It is: in step 1, the mass volume ratio of boron nitride and water is 0.3～1.2mg:36～40mL.
5. visible-light response type boron nitride modifies the preparation method of carbon nitride photocatalyst, its feature according to claim 2
It is: in step 2, the mass volume ratio of carbonitride and water is 80～100mg:36～40mL.
6. visible-light response type boron nitride modifies the preparation method of carbon nitride photocatalyst, its feature according to claim 2
It is: in step 3, the mass ratio of boron nitride and carbonitride is 0.3～1.2:100.
7. visible-light response type boron nitride modifies the preparation method of carbon nitride photocatalyst, its feature according to claim 2
It is: in step 1, step 2, step 3, ultrasonic power is 70～120w.
8. visible-light response type boron nitride modifies the preparation method of carbon nitride photocatalyst, its feature according to claim 2
Be: in step 3 baking temperature be 60～100 DEG C, the time be 8～12h.
9. the visible-light response type boron nitride described in claim 1 modifies carbon nitride photocatalyst in water-treatment technology field
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