CN106824247A - A kind of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst and its preparation method and application - Google Patents
A kind of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst and its preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 23
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 23
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 title claims abstract description 23
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 80
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007146 photocatalysis Methods 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 239000008187 granular material Substances 0.000 claims abstract description 12
- 239000000356 contaminant Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 42
- 239000000725 suspension Substances 0.000 claims description 38
- 238000013019 agitation Methods 0.000 claims description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 238000013517 stratification Methods 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000013049 sediment Substances 0.000 claims description 10
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 8
- PPNKDDZCLDMRHS-UHFFFAOYSA-N bismuth(III) nitrate Inorganic materials [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 description 24
- 238000002604 ultrasonography Methods 0.000 description 13
- 229910000474 mercury oxide Inorganic materials 0.000 description 12
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 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
-
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a kind of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst and its preparation method and application, with the Bi of microwave attenuation materials2WO6Powder and BiPO4Powder and burn the C of acquisition altogether by melamine and urea3N4Powder is raw material, and methyl alcohol is solvent, and Bi is synthesized with the step of ultrasonic method paddling process two2WO6/BiPO4/C3N4Composite photo-catalyst, the composite granule crystallinity prepared by the method is high, and heterojunction structure is formed between component, recombination process is carried out at room temperature, reaction condition is gentle, and photocatalysis performance is obviously improved, and has wide practical use in terms of photocatalysis degradation organic contaminant.
Description
Technical field
The invention belongs to field of functional materials, it is related to a kind of Bi2WO6/C3N4/BiPO4Composite photo-catalyst and its preparation side
Method and application.
Background technology
Bi2WO6Energy gap be about 3eV, be a kind of new visible light catalytic material with good visible light-responded
Material, the organic pollution that can be used in degraded industrial wastewater.Bi2WO6When by radiation of visible light, electronic energy is from valence band transition
To conduction band, room, light induced electron and hole and O are left in valence band2With surface OH-With reference to super oxygen of the formation with oxidisability is certainly
By base O2 -With hydroxyl radical free radical OH etc., the organic molecule in superoxide radical and hydroxyl radical free radical energy decomposition water reaches
The effect of degraded.C3N4It is also a kind of catalysis material of low energy gap, its energy gap is about 2.7eV, has to visible ray good
Response, and with laminar structured, there is certain absorption property.BiPO4Energy gap is about 4eV, is a kind of broad stopband
Semiconductor, has good response to ultraviolet light, but visible ray is not almost responded to.Bi2WO6And C3N4Energy gap it is smaller,
Electron-hole is susceptible to be combined, there is presently no by Bi2WO6、C3N4And BiPO4Combine preparation Bi2WO6/C3N4/
BiPO4The relevant report of composite photo-catalyst.
The content of the invention
It is an object of the invention to provide a kind of preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst, should
Method can prepare the Bi with good photocatalysis effect2WO6/C3N4/BiPO4Composite photo-catalyst, can be used for organic dirt
The aspect such as the degraded of dye thing and other photocatalysis.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst, comprises the following steps：
Step 1：It is in molar ratio 1:2 by Na2WO4With Bi (NO3)3It is dissolved in deionized water, stirs, is mixed
Solution A, mixed solution A is moved in hydrothermal reaction kettle after ultrasonic disperse and magnetic agitation successively, carries out microwave hydrothermal reaction, instead
By product stratification after should terminating, the sediment of lower floor is washed, is dried, obtained Bi2WO6Powder；
Step 2：In mass ratio it is 1:(1~1.5) adds in deionized water after being well mixed melamine and urea, obtains
To mixture, reaction is stirred to mixture, product is dried and ground by reaction after terminating, then is calcined in Muffle furnace, will
Calcined product is levigate, obtains C3N4Powder；
Step 3：It is in molar ratio 3:3:(4~5) are by Na3PO4、Bi(NO3)3It is dissolved in deionized water with nitric acid, stirring is equal
It is even, mixed solution B is obtained, mixed solution B is moved in hydrothermal reaction kettle after ultrasonic disperse and magnetic agitation successively, carries out microwave
Hydro-thermal reaction, reaction terminate after by product stratification, the sediment of lower floor is washed, is dried, obtain BiPO4Powder；
Step 4：By Bi obtained in step 12WO6C obtained in powder and step 23N4Powder in mass ratio for (1.2~
4.5):(5~6) are added in absolute methanol, and precursor aqueous solution A is formed after ultrasonic disperse, and magnetic agitation is carried out to precursor aqueous solution A,
Suspension A is obtained, by suspension A stratification, the sediment of lower floor is washed, is dried, obtain Bi2WO6/C3N4It is compound
Powder；
Step 5：By BiPO obtained in step 34Bi obtained in powder and step 42WO6/C3N4Composite granule is in mass ratio
(0.4~2.8):(9.6~7.2) are added in absolute methanol, and precursor aqueous solution B is formed after ultrasonic disperse, and precursor aqueous solution B is carried out
Magnetic agitation, obtains suspension B, by suspension B stratification, the sediment of lower floor is washed, is dried, and obtains wolframic acid
Bismuth/carbonitride/bismuth phosphate composite photo-catalyst.
The concentration of Bi elements is 0.133~0.15mol/L in mixed solution A in the step 1；
The concentration of melamine and urea is 0.25~0.333g/mL in mixture in the step 2；
The concentration of Bi elements is 0.067~0.084mol/L in mixed solution B in the step 3.
The time of ultrasonic disperse is 20~30min in the step 1 and step 3, and ultrasonic power is 400~500W；
The time of ultrasonic disperse is 2~3h in the step 4 and step 5, and ultrasonic power is 400~500W.
The time of magnetic agitation is 2~3h in the step 1 and step 3, and mixing speed is 200~300rad/min；
The time of stirring reaction is 3~4h in the step 2, and mixing speed is 200~300rad/min；
The time of magnetic agitation is 20~24h in the step 4 and step 5, and mixing speed is 200~300rad/min.
In the step 1 and step 3 microwave hydrothermal reaction be under the microwave power of 300W, it is micro- at 180~200 DEG C
0.5~1h of ripple hydro-thermal reaction；
Calcining heat in the step 2 is 500~550 DEG C, and calcination time is 3~4h.
Washing, drying in the step 1, step 3, step 4 and step 5 are with absolute ethyl alcohol and to remove sediment respectively
The removal of impurity is gone in ionized water cleaning, and 15~20h is then dried at 70~80 DEG C；
Drying temperature in the step 2 is 70~80 DEG C, and drying time is 15~20h.
Bi in precursor aqueous solution A in the step 42WO6And C3N4Total concentration be 0.1~0.15g/mL；
BiPO in precursor aqueous solution B in the step 54And Bi2WO6/C3N4Total concentration be 0.1~0.15g/mL.
Bismuth tungstate/carbonitride obtained in the preparation method of described bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst/
Bismuth phosphate composite photo-catalyst, the thing of bismuth tungstate is mutually orthorhombic phase Bi in the composite photo-catalyst2WO6, space group is Pca21
(29), the thing of bismuth phosphate is mutually monoclinic phase BiPO4, space group is P21/n (14), and carbonitride is nonwoven fabric from filaments；In 300W xenon lamps
Under the conditions of simulated solar light irradiation, its photocatalytic activity is Bi2WO61.75~2.17 times of powder, are C3N4The 1.91 of powder~
2.36 times.
Under the conditions of the simulated solar light irradiation of 300W xenon lamps, its degradation rate to rhodamine B be 0.021~
0.026min-1。
Described bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst answering in terms of photocatalysis degradation organic contaminant
With.
Relative to existing technology, the invention has the advantages that：
1. ultrasonic agitation method is applied to Bi by the present invention first2WO6/C3N4/BiPO4The preparation of composite photo-catalyst.This hair
The Bi of bright offer2WO6/C3N4/BiPO4Composite photo-catalyst preparation method, first prepares two kinds of crystallization degrees with microwave-hydrothermal method
Good Bi2WO6Powder and BiPO4Powder, then melamine and urea are burnt into acquisition C altogether3N4Powder, then stirred with gentle ultrasound
Mix process prepares Bi in two steps2WO6/C3N4/BiPO4Composite photo-catalyst, process is simple, recombination process is carried out at room temperature, reaction
Mild condition, Bi in recombination process2WO6、C3N4And BiPO4Three kinds of respective things of powder mutually keep constant, prepared by the present invention
Composite granule crystallinity is high, and heterojunction structure is formed between component.
2. the Bi prepared by the present invention2WO6/C3N4/BiPO4Composite photo-catalyst has good photocatalysis performance, can use
In photocatalysis degradation organic contaminant.The present invention is by Bi2WO6、C3N4And BiPO4These three semiconductors are mutually combined, and obtain one kind
New photocatalytic semiconductor, i.e. Bi2WO6/C3N4/BiPO4Composite photo-catalyst, the Bi2WO6/C3N4/BiPO4Composite photocatalyst
Agent both has good absorption property, and all has photoresponse in visible ray and ultraviolet light wave band, simultaneously as Bi2WO6、C3N4
And BiPO4The valence band conduction band positions of these three semiconductors are different, and light induced electron, hole can move after separating in conduction band, valence band
Move, improve separative efficiency, and then lift Bi2WO6/C3N4/BiPO4The photocatalysis efficiency of composite photo-catalyst.
3. the Bi prepared by the present invention2WO6/C3N4/BiPO4Composite photo-catalyst is with respect to Bi2WO6And C3N4Photochemical catalyst
Photocatalysis performance is obviously improved, and under the conditions of the simulated solar light irradiation of 300W xenon lamps, its photocatalytic activity is Bi2WO6Powder
1.75~2.17 times, be C3N41.91~2.36 times of powder, in terms of photocatalysis degradation organic contaminant and other photocatalysis
Aspect has wide practical use.
Brief description of the drawings
Fig. 1 is Bi prepared by the present invention2WO6/C3N4/BiPO4The XRD of composite photo-catalyst；
Fig. 2 is Bi prepared by the present invention2WO6/C3N4/BiPO4The FT-IR figures of composite photo-catalyst；
Fig. 3 is Bi prepared by the present invention2WO6/C3N4/BiPO4The SEM figures of composite photo-catalyst, wherein (a) is Bi2WO6Powder
Body, (b) is BiPO4Powder, (c) is C3N4Powder, (d) is Bi2WO6/C3N4Composite granule, (e), (f) are Bi2WO6/C3N4/
BiPO4Composite photo-catalyst.
Fig. 4 is Bi prepared by the present invention2WO6/C3N4/BiPO4The degradation curve figure of composite photo-catalyst.
Specific embodiment
The present invention is described in further details with preferably embodiment of the invention below in conjunction with the accompanying drawings.
Embodiment 1
Step 1：By raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is stirred vigorously 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi elements be 0.133mol/L, by mixed solution in Ultrasound Instrument with
The power ultrasonic dispersion 30min of 400W, then hydro-thermal is finally transferred to the rotating speed magnetic agitation 2h of 300rad/min at normal temperatures
In reactor, microwave power is 300W, and microwave hydrothermal reaction 1h, obtains white mixed solution at 180 DEG C, and mixed solution is quiet
Layering is put, supernatant is removed, precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, 15h is dried at 80 DEG C, obtained
White Bi2WO6Powder；
Step 2：In mass ratio it is 1:1 weighs melamine and urea respectively, is added after being well mixed in deionized water, obtains
To mixture, the concentration of melamine and urea is 0.333g/mL in mixture, with the rotary speed stirring mixture of 250rad/min
4h, then dries 15h in 80 DEG C of baking oven, and dry powder is taken out and is fully ground, and finally calcines 4h in 550 DEG C of Muffle furnace,
Yellow block is obtained, block is fully ground, obtain yellow C3N4Powder；
Step 3：By 3mmol Na3PO4、3mmol Bi(NO3)3It is dissolved in deionized water with 5mL 1mol/L salpeter solutions,
White mixed solution is obtained after stirring, the concentration of Bi elements is 0.067mol/L in mixed solution, by mixed solution in Ultrasound Instrument
In 30min is disperseed with the power ultrasonic of 400W, then be finally transferred to the rotating speed magnetic agitation 2h of 300rad/min at normal temperatures
In hydrothermal reaction kettle, microwave power is 300W, and microwave hydrothermal reaction 1h, obtains white suspension at 200 DEG C, and suspension is quiet
Layering is put, supernatant is removed, precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, 15h is dried at 80 DEG C, obtained
White BiPO4Powder；
Step 4：By gained Bi in step 12WO6Gained C in powder and step 23N4Powder is with 3.6:6 mass ratio is added
To in absolute methanol, 3h is disperseed with the power ultrasonic of 400W, form precursor aqueous solution, Bi in precursor aqueous solution2WO6And C3N4It is total dense
It is 0.15g/mL to spend, and with the rotating speed of 300rad/min to precursor aqueous solution magnetic agitation 24h, yellow suspension is obtained, by suspension
Stratification, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and deionized water respectively washing three times, is dried at 80 DEG C
15h, obtains Bi2WO6/C3N4Composite granule.
Step 5：By the BiPO of microwave attenuation materials in step 34The Bi synthesized in powder and step 42WO6/C3N4Composite powder
Body presses 0.4:9.6 mass ratio is added in absolute methanol, and 3h is disperseed with the power ultrasonic of 400W, forms precursor aqueous solution, forerunner
Bi in solution2WO6/C3N4And BiPO4Total concentration be 0.15g/mL, with the rotating speed of 300rad/min to precursor aqueous solution magnetic agitation
24h, obtains yellow suspension, and suspension is stood into a period of time, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and goes
Ionized water respectively washing three times, 15h is dried at 80 DEG C, obtains Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 2
Step 1：By raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is stirred vigorously 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi elements be 0.14mol/L, by mixed solution in Ultrasound Instrument with 500W
Power ultrasonic dispersion 20min, then hydro-thermal reaction is finally transferred to the rotating speed magnetic agitation 3h of 200rad/min at normal temperatures
In kettle, microwave power is 300W, and microwave hydrothermal reaction 0.5h, obtains white mixed solution at 200 DEG C, and mixed solution is stood
Layering, removes supernatant, and precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, and 16h is dried at 70 DEG C, obtains white
Color Bi2WO6Powder；
Step 2：In mass ratio it is 1:1.1 weigh melamine and urea respectively, after being well mixed in addition deionized water,
Mixture is obtained, the concentration of melamine and urea is 0.25g/mL in mixture, and mixing is stirred with the rotating speed of 200rad/min
Thing 3.5h, then dries 16h in 70 DEG C of baking oven, and dry powder is taken out and is fully ground, and is finally calcined in 500 DEG C of Muffle furnace
3.8h, obtains yellow block, and block is fully ground, and obtains yellow C3N4Powder；
Step 3：By 3mmol Na3PO4、3mmol Bi(NO3)3It is dissolved in deionized water with 4mL 1mol/L salpeter solutions,
White mixed solution is obtained after stirring, the concentration of Bi elements is 0.07mol/L in mixed solution, by mixed solution in Ultrasound Instrument
20min is disperseed with the power ultrasonic of 500W, then water is finally transferred to the rotating speed magnetic agitation 3h of 200rad/min at normal temperatures
In thermal response kettle, microwave power is 300W, and microwave hydrothermal reaction 0.6h, obtains white suspension at 190 DEG C, and suspension is quiet
Layering is put, supernatant is removed, precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, 16h is dried at 70 DEG C, obtained
White BiPO4Powder；
Step 4：By gained Bi in step 12WO6Gained C in powder and step 23N4Powder is with 2.8:6 mass ratio is added
To in absolute methanol, 2h is disperseed with the power ultrasonic of 500W, form precursor aqueous solution, Bi in precursor aqueous solution2WO6And C3N4It is total dense
It is 0.1g/mL to spend, and with the rotating speed of 200rad/min to precursor aqueous solution magnetic agitation 23h, obtains yellow suspension, and suspension is quiet
Layering is put, supernatant, gained yellow mercury oxide absolute ethyl alcohol and deionized water respectively washing three times are removed, 16h is dried at 70 DEG C,
Obtain Bi2WO6/C3N4Composite granule.
Step 5：By the BiPO of microwave attenuation materials in step 34The Bi synthesized in powder and step 42WO6/C3N4Composite powder
Body presses 1.2:8.8 mass ratio is added in absolute methanol, and 2h is disperseed with the power ultrasonic of 500W, forms precursor aqueous solution, forerunner
Bi in solution2WO6/C3N4And BiPO4Total concentration be 0.1g/mL, with the rotating speed of 200rad/min to precursor aqueous solution magnetic agitation
23h, obtains yellow suspension, and suspension is stood into a period of time, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and goes
Ionized water respectively washing three times, 16h is dried at 70 DEG C, obtains Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 3
Step 1：By raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is stirred vigorously 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi elements be 0.145mol/L, by mixed solution in Ultrasound Instrument with
The power ultrasonic dispersion 25min of 450W, then water is finally transferred to the rotating speed magnetic agitation 2.5h of 250rad/min at normal temperatures
In thermal response kettle, microwave power is 300W, and microwave hydrothermal reaction 0.6h, obtains white mixed solution at 190 DEG C, will mix molten
Liquid stratification, removes supernatant, and precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, and 17h is dried at 75 DEG C,
Obtain white Bi2WO6Powder；
Step 2：In mass ratio it is 1:1.2 weigh melamine and urea respectively, after being well mixed in addition deionized water,
Mixture is obtained, the concentration of melamine and urea is 0.28g/mL in mixture, and mixing is stirred with the rotating speed of 300rad/min
Thing 3h, then dries 17h in 75 DEG C of baking oven, and dry powder is taken out and is fully ground, and is finally calcined in 510 DEG C of Muffle furnace
3.6h, obtains yellow block, and block is fully ground, and obtains yellow C3N4Powder；
Step 3：By 3mmol Na3PO4、3mmol Bi(NO3)3Deionized water is dissolved in 4.5mL 1mol/L salpeter solutions
In, white mixed solution is obtained after stirring, the concentration of Bi elements is 0.075mol/L in mixed solution, by mixed solution in ultrasound
25min is disperseed with the power ultrasonic of 450W in instrument, then is finally turned with the rotating speed magnetic agitation 2.5h of 250rad/min at normal temperatures
Move in hydrothermal reaction kettle, microwave power is 300W, microwave hydrothermal reaction 0.7h, obtains white suspension at 180 DEG C, will be outstanding
Turbid liquid stratification, removes supernatant, and precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, is dried at 75 DEG C
17h, obtains white BiPO4Powder；
Step 4：By gained Bi in step 12WO6Gained C in powder and step 23N4Powder is with 2:6 mass ratio is added to
In absolute methanol, 2.5h is disperseed with the power ultrasonic of 450W, form precursor aqueous solution, Bi in precursor aqueous solution2WO6And C3N4It is total dense
It is 0.11g/mL to spend, and with the rotating speed of 250rad/min to precursor aqueous solution magnetic agitation 22h, yellow suspension is obtained, by suspension
Stratification, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and deionized water respectively washing three times, is dried at 75 DEG C
17h, obtains Bi2WO6/C3N4Composite granule.
Step 5：By the BiPO of microwave attenuation materials in step 34The Bi synthesized in powder and step 42WO6/C3N4Composite powder
Body presses 2:8 mass ratio is added in absolute methanol, and 2.5h is disperseed with the power ultrasonic of 450W, forms precursor aqueous solution, Qian Qurong
Bi in liquid2WO6/C3N4And BiPO4Total concentration be 0.11g/mL, with the rotating speed of 250rad/min to precursor aqueous solution magnetic agitation
22h, obtains yellow suspension, and suspension is stood into a period of time, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and goes
Ionized water respectively washing three times, 17h is dried at 75 DEG C, obtains Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 4
Step 1：By raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is stirred vigorously 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi elements be 0.15mol/L, by mixed solution in Ultrasound Instrument with 420W
Power ultrasonic dispersion 28min, then hydro-thermal is finally transferred to anti-with the rotating speed magnetic agitation 2.8h of 220rad/min at normal temperatures
Answer in kettle, microwave power is 300W, microwave hydrothermal reaction 0.7h, obtains white mixed solution at 195 DEG C, and mixed solution is quiet
Layering is put, supernatant is removed, precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, 18h is dried at 72 DEG C, obtained
White Bi2WO6Powder；
Step 2：In mass ratio it is 1:1.3 weigh melamine and urea respectively, after being well mixed in addition deionized water,
Mixture is obtained, the concentration of melamine and urea is 0.30g/mL in mixture, and mixing is stirred with the rotating speed of 220rad/min
Thing 3.2h, then dries 18h in 72 DEG C of baking oven, and dry powder is taken out and is fully ground, and is finally calcined in 520 DEG C of Muffle furnace
3.2h, obtains yellow block, and block is fully ground, and obtains yellow C3N4Powder；
Step 3：By 3mmol Na3PO4、3mmol Bi(NO3)3Deionized water is dissolved in 4.2mL 1mol/L salpeter solutions
In, white mixed solution is obtained after stirring, the concentration of Bi elements is 0.08mol/L in mixed solution, by mixed solution in ultrasound
28min is disperseed with the power ultrasonic of 420W in instrument, then is finally turned with the rotating speed magnetic agitation 2.8h of 220rad/min at normal temperatures
Move in hydrothermal reaction kettle, microwave power is 300W, microwave hydrothermal reaction 0.8h, obtains white suspension at 185 DEG C, will be outstanding
Turbid liquid stratification, removes supernatant, and precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, is dried at 72 DEG C
18h, obtains white BiPO4Powder；
Step 4：By gained Bi in step 12WO6Gained C in powder and step 23N4Powder is with 1.2:6 mass ratio is added
To in absolute methanol, 2.8h is disperseed with the power ultrasonic of 420W, form precursor aqueous solution, Bi in precursor aqueous solution2WO6And C3N4It is total
Concentration is 0.12g/mL, with the rotating speed of 220rad/min to precursor aqueous solution magnetic agitation 24h, obtains yellow suspension, will be suspended
Liquid stratification, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and deionized water respectively washing three times, is dried at 72 DEG C
18h, obtains Bi2WO6/C3N4Composite granule.
Step 5：By the BiPO of microwave attenuation materials in step 34The Bi synthesized in powder and step 42WO6/C3N4Composite powder
Body presses 2.8:7.2 mass ratio is added in absolute methanol, and 2.8h is disperseed with the power ultrasonic of 420W, forms precursor aqueous solution, preceding
Drive Bi in solution2WO6/C3N4And BiPO4Total concentration be 0.12g/mL, precursor aqueous solution magnetic force is stirred with the rotating speed of 220rad/min
22.5h is mixed, yellow suspension is obtained, suspension is stood into a period of time, remove supernatant, gained yellow mercury oxide absolute ethyl alcohol
Respectively washed with deionized water three times, 18h is dried at 72 DEG C, obtain Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 5
Step 1：By raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is stirred vigorously 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi elements be 0.137mol/L, by mixed solution in Ultrasound Instrument with
The power ultrasonic dispersion 22min of 480W, then water is finally transferred to the rotating speed magnetic agitation 2.2h of 280rad/min at normal temperatures
In thermal response kettle, microwave power is 300W, and microwave hydrothermal reaction 0.8h, obtains white mixed solution at 185 DEG C, will mix molten
Liquid stratification, removes supernatant, and precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, and 19h is dried at 78 DEG C,
Obtain white Bi2WO6Powder；
Step 2：In mass ratio it is 1:1.4 weigh melamine and urea respectively, after being well mixed in addition deionized water,
Mixture is obtained, the concentration of melamine and urea is 0.31g/mL in mixture, and mixing is stirred with the rotating speed of 280rad/min
Thing 3.8h, then dries 19h in 78 DEG C of baking oven, and dry powder is taken out and is fully ground, and is finally calcined in 530 DEG C of Muffle furnace
3.5h, obtains yellow block, and block is fully ground, and obtains yellow C3N4Powder；
Step 3：By 3mmol Na3PO4、3mmol Bi(NO3)3Deionized water is dissolved in 4.8mL 1mol/L salpeter solutions
In, white mixed solution is obtained after stirring, the concentration of Bi elements is 0.078mol/L in mixed solution, by mixed solution in ultrasound
22min is disperseed with the power ultrasonic of 480W in instrument, then is finally turned with the rotating speed magnetic agitation 2.2h of 280rad/min at normal temperatures
Move in hydrothermal reaction kettle, microwave power is 300W, microwave hydrothermal reaction 0.9h, obtains white suspension at 195 DEG C, will be outstanding
Turbid liquid stratification, removes supernatant, and precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, is dried at 78 DEG C
19h, obtains white BiPO4Powder；
Step 4：By gained Bi in step 12WO6Gained C in powder and step 23N4Powder is with 4.5:5 mass ratio is added
To in absolute methanol, 2.2h is disperseed with the power ultrasonic of 480W, form precursor aqueous solution, Bi in precursor aqueous solution2WO6And C3N4It is total
Concentration is 0.13g/mL, with the rotating speed of 280rad/min to precursor aqueous solution magnetic agitation 20h, obtains yellow suspension, will be suspended
Liquid stratification, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and deionized water respectively washing three times, is dried at 78 DEG C
19h, obtains Bi2WO6/C3N4Composite granule.
Step 5：By the BiPO of microwave attenuation materials in step 34The Bi synthesized in powder and step 42WO6/C3N4Composite powder
Body presses 0.5:9.5 mass ratio is added in absolute methanol, and 2.2h is disperseed with the power ultrasonic of 480W, forms precursor aqueous solution, preceding
Drive Bi in solution2WO6/C3N4And BiPO4Total concentration be 0.13g/mL, precursor aqueous solution magnetic force is stirred with the rotating speed of 280rad/min
Mix 20h, obtain yellow suspension, by suspension stand a period of time, remove supernatant, gained yellow mercury oxide absolute ethyl alcohol and
Deionized water respectively washing three times, 19h is dried at 78 DEG C, obtains Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 6
Step 1：By raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is stirred vigorously 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi elements be 0.135mol/L, by mixed solution in Ultrasound Instrument with
The power ultrasonic dispersion 26min of 460W, then water is finally transferred to the rotating speed magnetic agitation 2.4h of 260rad/min at normal temperatures
In thermal response kettle, microwave power is 300W, and microwave hydrothermal reaction 0.9h, obtains white mixed solution at 180 DEG C, will mix molten
Liquid stratification, removes supernatant, and precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, and 20h is dried at 80 DEG C,
Obtain white Bi2WO6Powder；
Step 2：In mass ratio it is 1:1.5 weigh melamine and urea respectively, after being well mixed in addition deionized water,
Mixture is obtained, the concentration of melamine and urea is 0.32g/mL in mixture, and mixing is stirred with the rotating speed of 260rad/min
Thing 3.6h, then dries 20h in 80 DEG C of baking oven, and dry powder is taken out and is fully ground, and is finally calcined in 540 DEG C of Muffle furnace
3h, obtains yellow block, and block is fully ground, and obtains yellow C3N4Powder；
Step 3：By 3mmol Na3PO4、3mmol Bi(NO3)3Deionized water is dissolved in 4.6mL 1mol/L salpeter solutions
In, white mixed solution is obtained after stirring, the concentration of Bi elements is 0.084mol/L in mixed solution, by mixed solution in ultrasound
26min is disperseed with the power ultrasonic of 460W in instrument, then is finally turned with the rotating speed magnetic agitation 2.4h of 260rad/min at normal temperatures
Move in hydrothermal reaction kettle, microwave power is 300W, microwave hydrothermal reaction 0.5h, obtains white suspension at 200 DEG C, will be outstanding
Turbid liquid stratification, removes supernatant, and precipitation is cleaned 3 times with absolute ethyl alcohol and deionized water respectively, is dried at 80 DEG C
20h, obtains white BiPO4Powder；
Step 4：By gained Bi in step 12WO6Gained C in powder and step 23N4Powder is with 4:5 mass ratio is added to
In absolute methanol, 2.4h is disperseed with the power ultrasonic of 460W, form precursor aqueous solution, Bi in precursor aqueous solution2WO6And C3N4It is total dense
It is 0.14g/mL to spend, and with the rotating speed of 260rad/min to precursor aqueous solution magnetic agitation 21h, yellow suspension is obtained, by suspension
Stratification, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and deionized water respectively washing three times, is dried at 80 DEG C
20h, obtains Bi2WO6/C3N4Composite granule.
Step 5：By the BiPO of microwave attenuation materials in step 34The Bi synthesized in powder and step 42WO6/C3N4Composite powder
Body presses 1:9 mass ratio is added in absolute methanol, and 2.4h is disperseed with the power ultrasonic of 460W, forms precursor aqueous solution, Qian Qurong
Bi in liquid2WO6/C3N4And BiPO4Total concentration be 0.14g/mL, with the rotating speed of 260rad/min to precursor aqueous solution magnetic agitation
21h, obtains yellow suspension, and suspension is stood into a period of time, removes supernatant, gained yellow mercury oxide absolute ethyl alcohol and goes
Ionized water respectively washing three times, 20h is dried at 80 DEG C, obtains Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Using XRD determining Bi2WO6/C3N4/BiPO4The thing phase composition structure of composite photo-catalyst preparation method；Use Fourier
Functional group's species and residing chemical environment of infrared spectrum characterization photochemical catalyst are characterized；Surface topography is by S-4800 types
Transmitting SEM is characterized；The degradation experiment of rhodamine B is carried out in XPA-7 type light-catalyzed reaction instrument, is characterized
The photocatalysis performance of photochemical catalyst.
Fig. 1 is Bi prepared by the present invention2WO6/C3N4/BiPO4The XRD of composite photo-catalyst, is followed successively by from top to bottom
Bi2WO6、C3N4And BiPO4Mass ratio be 2.8:6:1.2、2:6:2 and 1.2:6:2.8 Bi2WO6/C3N4/BiPO4Complex light
Catalyst.Wherein Bi2WO6/C3N4/BiPO4In 2 θ=28.34 °, 32.94 °, 47.18 °, 55.96 ° or so go out composite photo-catalyst
It is orthorhombic phase Bi that existing diffraction maximum is corresponding respectively2WO6(131), (002), (202), (133) of (PDF No.79-2381) are brilliant
Face, in 2 θ=19.06 °, 21.40 °, 27.20 °, 29.14 °, it is monoclinic phase BiPO that diffraction maximum at 31.24 ° is corresponding respectively4
(PDFNO.15-0767) (011), (- 111), (200), (120), (012) crystal face.Because of C3N4It is flaky material, in XRD
Cannot measure.Illustrate that the present invention successfully synthesizes Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Fig. 2 is Bi2WO6/C3N4/BiPO4The FT-IR figures of composite photo-catalyst, in 730cm-1It is Bi that place is corresponding2WO6's
W-O stretches shock absorption peak, 1073cm-1To 921cm-1Corresponding is the stretching vibration absworption peak of (PO4), 600cm-1Arrive
554cm-1Corresponding is the flexural vibrations absworption peak of (PO4), 1414~1640cm-1It is carbon azacyclo- that the absworption peak at place is corresponding
The stretching vibration peak of middle C-N and C=N, 3500~4000cm-1The absworption peak at place belongs to g-C3N4Do not decomposed completely in building-up process
N-H and adsorption H2The absworption peak of O, further illustrates to form Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Fig. 3 is Bi2WO6/C3N4/BiPO4The SEM figures of composite photo-catalyst, Bi2WO6In flower-shaped, petal edge is in sawtooth
Shape, particle size is 2 μm (Fig. 3 a), BiPO4Pattern be the smooth square rod-shpaed particle in surface, size at 2~0.2 μm or so,
Diameter is in 0.4~0.15 μm (Fig. 3 b), pure phase C3N4It is porous blocks (Fig. 3 c), the C of photochemical catalyst after being combined3N4Size reduces,
It is attached to Bi2WO6Surface (Fig. 3 d), BiPO4Particle intercalation is in Bi2WO6/C3N4Upper (Fig. 3 e, f).
Fig. 4 is Bi prepared by the present invention2WO6/C3N4/BiPO4The degradation curve figure of composite photo-catalyst, in simulated solar irradiation
(300W xenon lamps), Bi under irradiation2WO6、C3N4And BiPO4Mass ratio be 3.6:6:0.4、2.8:6:1.2、2:6:2 and 1.2:6:
2.8 Bi2WO6/C3N4/BiPO4Composite photo-catalyst is followed successively by 0.023cm to the degradation rate k of RhB-1、0.026cm-1、
0.025cm-1And 0.021cm-1, Bi2WO6Powder is 0.012cm to the degradation rate k of powder RhB-1, C3N4Drop of the powder to RhB
Solution speed k is 0.011cm-1, Bi2WO6/C3N4/BiPO4Composite photo-catalyst photocatalytic activity is Bi2WO6The 1.75 of degradation rate
~2.17 times, be C3N41.91~2.36 times of reaction rate, Bi2WO6/C3N4/BiPO4The photocatalysis performance of composite photo-catalyst
Have and be obviously improved.
Above said content is to combine specific preferred embodiment further description made for the present invention, is not
All or unique implementation method, those of ordinary skill in the art by read description of the invention and to technical solution of the present invention
Any equivalent conversion taken, is claim of the invention and is covered.
Claims (10)
1. a kind of preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst, it is characterised in that comprise the following steps：
Step 1：It is in molar ratio 1:2 by Na2WO4With Bi (NO3)3It is dissolved in deionized water, stirs, obtains mixed solution A,
Mixed solution A is moved in hydrothermal reaction kettle after ultrasonic disperse and magnetic agitation successively, carries out microwave hydrothermal reaction, and reaction terminates
Afterwards by product stratification, the sediment of lower floor is washed, is dried, obtained Bi2WO6Powder；
Step 2：In mass ratio it is 1:(1~1.5) adds in deionized water after being well mixed melamine and urea, is mixed
Compound, reaction is stirred to mixture, and product is dried and ground by reaction after terminating, then is calcined in Muffle furnace, will be calcined
Product is levigate, obtains C3N4Powder；
Step 3：It is in molar ratio 3:3:(4~5) are by Na3PO4、Bi(NO3)3It is dissolved in deionized water with nitric acid, is stirred, is obtained
To mixed solution B, mixed solution B is moved in hydrothermal reaction kettle after ultrasonic disperse and magnetic agitation successively, carries out microwave hydrothermal
Reaction, reaction terminate after by product stratification, the sediment of lower floor is washed, is dried, obtain BiPO4Powder；
Step 4：By Bi obtained in step 12WO6C obtained in powder and step 23N4Powder is (1.2~4.5) in mass ratio:(5~
6) it is added in absolute methanol, precursor aqueous solution A is formed after ultrasonic disperse, magnetic agitation is carried out to precursor aqueous solution A, obtains suspension
A, by suspension A stratification, is washed to the sediment of lower floor, is dried, and obtains Bi2WO6/C3N4Composite granule；
Step 5：By BiPO obtained in step 34Bi obtained in powder and step 42WO6/C3N4Composite granule is (0.4 in mass ratio
~2.8):(9.6~7.2) are added in absolute methanol, and precursor aqueous solution B is formed after ultrasonic disperse, and magnetic force is carried out to precursor aqueous solution B
Stirring, obtains suspension B, by suspension B stratification, the sediment of lower floor is washed, is dried, and obtains bismuth tungstate/nitrogen
Change carbon/bismuth phosphate composite photo-catalyst.
2. the preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 1, its feature exists
In the concentration of Bi elements is 0.133~0.15mol/L in mixed solution A in the step 1；
The concentration of melamine and urea is 0.25~0.333g/mL in mixture in the step 2；
The concentration of Bi elements is 0.067~0.084mol/L in mixed solution B in the step 3.
3. the preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 1, its feature exists
In the time of ultrasonic disperse is 20~30min in the step 1 and step 3, and ultrasonic power is 400~500W；
The time of ultrasonic disperse is 2~3h in the step 4 and step 5, and ultrasonic power is 400~500W.
4. the preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 1, its feature exists
In the time of magnetic agitation is 2~3h in the step 1 and step 3, and mixing speed is 200~300rad/min；
The time of stirring reaction is 3~4h in the step 2, and mixing speed is 200~300rad/min；
The time of magnetic agitation is 20~24h in the step 4 and step 5, and mixing speed is 200~300rad/min.
5. the preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 1, its feature exists
In the microwave hydrothermal reaction in the step 1 and step 3 is the Microwave Water at 180~200 DEG C under the microwave power of 300W
0.5~1h of thermal response；
Calcining heat in the step 2 is 500~550 DEG C, and calcination time is 3~4h.
6. the preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 1, its feature exists
In washing, drying in the step 1, step 3, step 4 and step 5 are that sediment is used into absolute ethyl alcohol and deionization respectively
The removal of impurity is gone in water cleaning, and 15~20h is then dried at 70~80 DEG C；
Drying temperature in the step 2 is 70~80 DEG C, and drying time is 15~20h.
7. the preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 1, its feature exists
In Bi in precursor aqueous solution A in the step 42WO6And C3N4Total concentration be 0.1~0.15g/mL；
BiPO in precursor aqueous solution B in the step 54And Bi2WO6/C3N4Total concentration be 0.1~0.15g/mL.
8. the preparation method system of the bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst in claim 1-7 described in any one
Bismuth tungstate/carbonitride/bismuth phosphate the composite photo-catalyst for obtaining, it is characterised in that the thing phase of bismuth tungstate in the composite photo-catalyst
It is orthorhombic phase Bi2WO6, space group is Pca21 (29), and the thing of bismuth phosphate is mutually monoclinic phase BiPO4, space group is P21/n (14),
Carbonitride is nonwoven fabric from filaments；Under the conditions of the simulated solar light irradiation of 300W xenon lamps, its photocatalytic activity is Bi2WO6The 1.75 of powder
~2.17 times, be C3N41.91~2.36 times of powder.
9. bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 8, it is characterised in that in 300W xenons
Under the conditions of the simulated solar light irradiation of lamp, its degradation rate to rhodamine B is 0.021~0.026min-1。
10. bismuth tungstate/carbonitride/bismuth phosphate the composite photo-catalyst described in claim 1 is in photocatalysis degradation organic contaminant
The application of aspect.
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