CN106824247B - A kind of bismuth tungstate/carbon nitride/bismuth phosphate composite photocatalyst and its preparation method and application - Google Patents
A kind of bismuth tungstate/carbon nitride/bismuth phosphate composite photocatalyst and its preparation method and application Download PDFInfo
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- CN106824247B CN106824247B CN201710115037.2A CN201710115037A CN106824247B CN 106824247 B CN106824247 B CN 106824247B CN 201710115037 A CN201710115037 A CN 201710115037A CN 106824247 B CN106824247 B CN 106824247B
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 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 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 79
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000015556 catabolic process Effects 0.000 claims abstract description 19
- 238000006731 degradation reaction Methods 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000007146 photocatalysis Methods 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000356 contaminant Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 53
- 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
- 239000002243 precursor Substances 0.000 claims description 42
- 239000000725 suspension Substances 0.000 claims description 37
- 238000013019 agitation Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 238000013517 stratification Methods 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 10
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000012535 impurity Substances 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
- 238000005406 washing Methods 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 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 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
- 230000001376 precipitating effect Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 230000000593 degrading effect Effects 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
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 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
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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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Abstract
The invention discloses a kind of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalysts and its preparation method and application, with the Bi of microwave attenuation materials2WO6Powder and BiPO4Powder and the C obtained by melamine and urea cofiring3N4Powder is raw material, and methanol is solvent, synthesizes Bi with two step of ultrasonic method paddling process2WO6/BiPO4/C3N4Composite photo-catalyst, composite granule crystallinity prepared by this method is high, forms heterojunction structure between component, recombination process carries out at room temperature, reaction condition is mild, 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, are related to a kind of Bi2WO6/C3N4/BiPO4Composite photo-catalyst and its preparation side
Method and application.
Background technique
Bi2WO6Forbidden bandwidth be about 3eV, have good visible light-responded, be a kind of novel visible light catalytic material
Expect, the organic pollutant in the industrial wastewater that can be used for degrading.Bi2WO6When by radiation of visible light, electronics can be from valence band transition
To conduction band, vacancy, light induced electron and hole and O are left in valence band2With surface OH-In conjunction with formation has the super oxygen of oxidisability certainly
By base O2 -With hydroxyl radical free radical OH etc., superoxide radical and hydroxyl radical free radical can decompose the organic molecule in water, reach
The effect of degradation.C3N4It is also a kind of catalysis material of low energy gap, forbidden bandwidth is about 2.7eV, is had to visible light good
Response, and have it is laminar structured, have certain absorption property.BiPO4Forbidden bandwidth is about 4eV, is a kind of broad stopband
Semiconductor has good response to ultraviolet light, but to visible light almost without response.Bi2WO6And C3N4Forbidden bandwidth it is smaller,
Electron-hole is easy to happen compound, and there is presently no by Bi2WO6、C3N4And BiPO4Combine preparation Bi2WO6/C3N4/
BiPO4The relevant report of composite photo-catalyst.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods 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
Contaminate object degradation and other photocatalysis etc..
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst, comprising the following steps:
Step 1: being in molar ratio 1:2 by Na2WO4With Bi (NO3)3It is dissolved in deionized water, stirs evenly, mixed
Solution A, mixed solution A are successively moved back through ultrasonic disperse and magnetic agitation into hydrothermal reaction kettle, carry out microwave hydrothermal reaction, instead
By product stratification after answering, the sediment of lower layer is washed, is dried, Bi is obtained2WO6Powder；
Step 2: being in mass ratio 1:(1 ~ 1.5 melamine and urea are added in deionized water after mixing), obtained
To mixture, mixture is stirred to react, product is dried and ground after reaction, then is calcined in Muffle furnace, it will
Calcined product is levigate, obtains C3N4Powder；
Step 3: being in molar ratio 3:3:(4 ~ 5) 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 successively moved back through ultrasonic disperse and magnetic agitation into hydrothermal reaction kettle, carries out microwave
Hydro-thermal reaction is washed the sediment of lower layer, is dried, obtain BiPO after reaction by product stratification4Powder；
Step 4: by Bi made from step 12WO6C made from powder and step 23N4Powder is (1.2 ~ 4.5) in mass ratio:
(5 ~ 6) are added in anhydrous methanol, and precursor solution A is formed after ultrasonic disperse, are carried out magnetic agitation to precursor solution A, are hanged
Suspension A stratification washs the sediment of lower layer, is dried, obtain Bi by turbid A2WO6/C3N4Composite granule；
Step 5: by BiPO made from step 34Bi made from powder and step 42WO6/C3N4Composite granule is in mass ratio
(0.4 ~ 2.8): (9.6 ~ 7.2) are added in anhydrous methanol, and precursor solution B is formed after ultrasonic disperse, carry out magnetic to precursor solution B
Power stirring, obtain suspension B, by suspension B stratification, the sediment of lower layer washed, is dried, obtain bismuth tungstate/
Carbonitride/bismuth phosphate composite photo-catalyst.
The concentration of Bi element 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 element 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 being stirred to react in the step 2 is 3 ~ 4h, and mixing speed is 200 ~ 300rad/min；
In the step 4 and step 5 time of magnetic agitation be 20 ~ for 24 hours, mixing speed be 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 wave hydro-thermal reaction；
Calcination temperature 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 dehydrated alcohol and to go sediment respectively
Ionized water cleaning removes impurity, then dry 15 ~ 20h 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 solution A in the step 42WO6And C3N4Total concentration be 0.1 ~ 0.15g/mL；
BiPO in precursor solution B in the step 54And Bi2WO6/C3N4Total concentration be 0.1 ~ 0.15g/mL.
Bismuth tungstate/carbonitride made from bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst preparation method/
Bismuth phosphate composite photo-catalyst, the object of bismuth tungstate is mutually orthorhombic phase Bi in the composite photo-catalyst2WO6, space group Pca21
(29), the object of bismuth phosphate is mutually monoclinic phase BiPO4, space group is P21/n (14), and carbonitride is nonwoven fabric from filaments；In 300W xenon lamp
Under simulated solar irradiation irradiation condition, photocatalytic activity is Bi2WO61.75 ~ 2.17 times of powder, are C3N4The 1.91 of powder ~
2.36 again.
Under the simulated solar irradiation irradiation condition of 300W xenon lamp, the degradation rate to rhodamine B is 0.021 ~ 0.026
min-1。
Bismuth tungstate/the carbonitride/bismuth phosphate composite photo-catalyst answering in terms of photocatalysis degradation organic contaminant
With.
Compared with the prior art, the invention has the following advantages:
1. ultrasonic agitation method is applied to Bi for the first time by the present invention2WO6/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 cofiring are obtained into C3N4Powder, then stirred with mild ultrasound
Mix process prepares Bi in two steps2WO6/C3N4/BiPO4Composite photo-catalyst, simple process, recombination process carry out at room temperature, reaction
Mild condition, Bi in recombination process2WO6、C3N4And BiPO4Three kinds of respective objects of powder mutually remain unchanged, prepared by the present invention
Composite granule crystallinity is high, forms heterojunction structure between component.
2. 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 compound, obtain one kind
Novel photocatalytic semiconductor, i.e. Bi2WO6/C3N4/BiPO4Composite photo-catalyst, the Bi2WO6/C3N4/BiPO4Composite photocatalyst
Agent had both had good absorption property, and all had photoresponse in visible light and ultraviolet light wave band, simultaneously as Bi2WO6、C3N4
And BiPO4The valence band conduction band positions of these three semiconductors are different, can move in conduction band, valence band after light induced electron, hole separation
It moves, improves separative efficiency, and then promote Bi2WO6/C3N4/BiPO4The photocatalysis efficiency of composite photo-catalyst.
3. 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 simulated solar irradiation irradiation condition of 300W xenon lamp, 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 sides
Face has wide practical use.
Detailed description of the invention
Fig. 1 is Bi prepared by the present invention2WO6/C3N4/BiPO4The XRD diagram of composite photo-catalyst；
Fig. 2 is Bi prepared by the present invention2WO6/C3N4/BiPO4The FT-IR of composite photo-catalyst schemes；
Fig. 3 is Bi prepared by the present invention2WO6/C3N4/BiPO4The SEM of composite photo-catalyst schemes, wherein (a) is Bi2WO6Powder
Body (b) is BiPO4Powder (c) is C3N4Powder (d) is Bi2WO6/C3N4Composite granule, (e), (f) be 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 the present invention preferably embodiment with reference to the accompanying drawing.
Embodiment 1
Step 1: by raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is vigorously stirred 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi element be 0.133mol/L, by mixed solution in Ultrasound Instrument with
The power ultrasonic disperse 30min of 400W, then hydro-thermal is transferred to finally with the revolving speed magnetic agitation 2h of 300rad/min at normal temperature
In reaction kettle, microwave power 300W, microwave hydrothermal reacts 1h at 180 DEG C, obtains white mixed solution, and mixed solution is quiet
Layering is set, supernatant is removed, precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, dry 15h, obtains at 80 DEG C
White Bi2WO6Powder；
Step 2: weighing melamine and urea respectively in mass ratio for 1:1, be added in deionized water, obtain after mixing
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, obtains yellow C3N4Powder；
Step 3: by 3mmol Na3PO4、3mmol Bi(NO3)3It is dissolved in deionized water with 5mL 1mol/L nitric acid solution,
White mixed solution is obtained after stirring, the concentration of Bi element is 0.067mol/L in mixed solution, by mixed solution in Ultrasound Instrument
In with the power ultrasonic disperse 30min of 400W, then be finally transferred to the revolving speed magnetic agitation 2h of 300rad/min at normal temperature
In hydrothermal reaction kettle, microwave power 300W, microwave hydrothermal reacts 1h at 200 DEG C, obtains white suspension, and suspension is quiet
Layering is set, supernatant is removed, precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, dry 15h, obtains at 80 DEG C
White BiPO4Powder；
Step 4: by gained Bi in step 12WO6Gained C in powder and step 23N4Powder is added with the mass ratio of 3.6:6
Into anhydrous methanol, with the power ultrasonic disperse 3h of 400W, precursor solution, Bi in precursor solution are formed2WO6And C3N4It is total dense
Degree be 0.15g/mL, with the revolving speed of 300rad/min to precursor solution magnetic agitation for 24 hours, yellow suspension is obtained, by suspension
Stratification removes supernatant, and gained yellow mercury oxide dehydrated alcohol and deionized water are respectively washed three times, dry 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 is added in anhydrous methanol by the mass ratio of 0.4:9.6, with the power ultrasonic disperse 3h of 400W, forms precursor solution, forerunner
Bi in solution2WO6/C3N4And BiPO4Total concentration be 0.15g/mL, with the revolving speed of 300rad/min to precursor solution magnetic agitation
For 24 hours, yellow suspension is obtained, suspension is stood into a period of time, supernatant is removed, gained yellow mercury oxide dehydrated alcohol and goes
Ionized water respectively washs three times, and dry 15h, obtains Bi at 80 DEG C2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 2
Step 1: by raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is vigorously stirred 20min,
White mixed solution is obtained, the concentration of Bi element is 0.14mol/L in mixed solution, by mixed solution with 500W in Ultrasound Instrument
Power ultrasonic disperse 20min, then hydro-thermal reaction is transferred to finally with the revolving speed magnetic agitation 3h of 200rad/min at normal temperature
In kettle, microwave power 300W, microwave hydrothermal reacts 0.5h at 200 DEG C, obtains white mixed solution, mixed solution is stood
Layering removes supernatant, and precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, and dry 16h, obtains white at 70 DEG C
Color Bi2WO6Powder；
Step 2: melamine and urea are weighed respectively for 1:1.1 in mass ratio, are added in deionized water after mixing,
Mixture is obtained, the concentration of melamine and urea is 0.25g/mL in mixture, is stirred with the revolving speed of 200rad/min
Object 3.5h, then dries 16h in 70 DEG C of baking oven, and dry powder is taken out and is fully ground, and finally calcines in 500 DEG C of Muffle furnace
3.8h obtains yellow block, 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 nitric acid solution,
White mixed solution is obtained after stirring, the concentration of Bi element is 0.07mol/L in mixed solution, by mixed solution in Ultrasound Instrument
With the power ultrasonic disperse 20min of 500W, then water is transferred to finally with the revolving speed magnetic agitation 3h of 200rad/min at normal temperature
In thermal response kettle, microwave power 300W, microwave hydrothermal reacts 0.6h at 190 DEG C, obtains white suspension, and suspension is quiet
Layering is set, supernatant is removed, precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, dry 16h, obtains at 70 DEG C
White BiPO4Powder；
Step 4: by gained Bi in step 12WO6Gained C in powder and step 23N4Powder is added with the mass ratio of 2.8:6
Into anhydrous methanol, with the power ultrasonic disperse 2h of 500W, precursor solution, Bi in precursor solution are formed2WO6And C3N4It is total dense
Degree obtains yellow suspension with the revolving speed of 200rad/min to precursor solution magnetic agitation 23h for 0.1g/mL, and suspension is quiet
Layering to be set, supernatant is removed, gained yellow mercury oxide dehydrated alcohol and deionized water are respectively washed three times, the dry 16h 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 is added in anhydrous methanol by the mass ratio of 1.2:8.8, with the power ultrasonic disperse 2h of 500W, forms precursor solution, forerunner
Bi in solution2WO6/C3N4And BiPO4Total concentration be 0.1g/mL, with the revolving speed of 200rad/min to precursor solution magnetic agitation
23h obtains yellow suspension, and suspension is stood a period of time, supernatant is removed, gained yellow mercury oxide dehydrated alcohol and goes
Ionized water respectively washs three times, and dry 16h, obtains Bi at 70 DEG C2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 3
Step 1: by raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is vigorously stirred 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi element be 0.145mol/L, by mixed solution in Ultrasound Instrument with
The power ultrasonic disperse 25min of 450W, then water is transferred to finally with the revolving speed magnetic agitation 2.5h of 250rad/min at normal temperature
In thermal response kettle, microwave power 300W, microwave hydrothermal reacts 0.6h at 190 DEG C, obtains white mixed solution, will mix molten
Liquid stratification removes supernatant, and precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, the dry 17h at 75 DEG C,
Obtain white Bi2WO6Powder；
Step 2: melamine and urea are weighed respectively for 1:1.2 in mass ratio, are added in deionized water after mixing,
Mixture is obtained, the concentration of melamine and urea is 0.28g/mL in mixture, is stirred with the revolving speed of 300rad/min
Object 3h, then dries 17h in 75 DEG C of baking oven, and dry powder is taken out and is fully ground, and finally calcines in 510 DEG C of Muffle furnace
3.6h obtains yellow block, 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 nitric acid solution
In, white mixed solution is obtained after stirring, the concentration of Bi element is 0.075mol/L in mixed solution, by mixed solution in ultrasound
With the power ultrasonic disperse 25min of 450W in instrument, then finally turned with the revolving speed magnetic agitation 2.5h of 250rad/min at normal temperature
It moves in hydrothermal reaction kettle, microwave power 300W, microwave hydrothermal reacts 0.7h at 180 DEG C, obtains white suspension, will hang
Turbid stratification removes supernatant, and precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, dry at 75 DEG C
17h obtains white BiPO4Powder；
Step 4: by gained Bi in step 12WO6Gained C in powder and step 23N4Powder is added to the mass ratio of 2:6
In anhydrous methanol, with the power ultrasonic disperse 2.5h of 450W, precursor solution, Bi in precursor solution are formed2WO6And C3N4It is total dense
Degree obtains yellow suspension with the revolving speed of 250rad/min to precursor solution magnetic agitation 22h for 0.11g/mL, by suspension
Stratification removes supernatant, and gained yellow mercury oxide dehydrated alcohol and deionized water are respectively washed three times, dry 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 is added in anhydrous methanol by the mass ratio of 2:8, with the power ultrasonic disperse 2.5h of 450W, forms precursor solution, Qian Qurong
Bi in liquid2WO6/C3N4And BiPO4Total concentration be 0.11g/mL, with the revolving speed of 250rad/min to precursor solution magnetic agitation
22h obtains yellow suspension, and suspension is stood a period of time, supernatant is removed, gained yellow mercury oxide dehydrated alcohol and goes
Ionized water respectively washs three times, and dry 17h, obtains Bi at 75 DEG C2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 4
Step 1: by raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is vigorously stirred 20min,
White mixed solution is obtained, the concentration of Bi element is 0.15mol/L in mixed solution, by mixed solution with 420W in Ultrasound Instrument
Power ultrasonic disperse 28min, then it is anti-to be finally transferred to the revolving speed magnetic agitation 2.8h of 220rad/min for hydro-thermal at normal temperature
It answers in kettle, microwave power 300W, microwave hydrothermal reacts 0.7h at 195 DEG C, obtains white mixed solution, and mixed solution is quiet
Layering is set, supernatant is removed, precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, dry 18h, obtains at 72 DEG C
White Bi2WO6Powder；
Step 2: melamine and urea are weighed respectively for 1:1.3 in mass ratio, are added in deionized water after mixing,
Mixture is obtained, the concentration of melamine and urea is 0.30g/mL in mixture, is stirred with the revolving speed of 220rad/min
Object 3.2h, then dries 18h in 72 DEG C of baking oven, and dry powder is taken out and is fully ground, and finally calcines in 520 DEG C of Muffle furnace
3.2h obtains yellow block, 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 nitric acid solution
In, white mixed solution is obtained after stirring, the concentration of Bi element is 0.08mol/L in mixed solution, by mixed solution in ultrasound
With the power ultrasonic disperse 28min of 420W in instrument, then finally turned with the revolving speed magnetic agitation 2.8h of 220rad/min at normal temperature
It moves in hydrothermal reaction kettle, microwave power 300W, microwave hydrothermal reacts 0.8h at 185 DEG C, obtains white suspension, will hang
Turbid stratification removes supernatant, and precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, dry at 72 DEG C
18h obtains white BiPO4Powder；
Step 4: by gained Bi in step 12WO6Gained C in powder and step 23N4Powder is added with the mass ratio of 1.2:6
Into anhydrous methanol, with the power ultrasonic disperse 2.8h of 420W, precursor solution, Bi in precursor solution are formed2WO6And C3N4It is total
Concentration is 0.12g/mL, with the revolving speed of 220rad/min to precursor solution magnetic agitation for 24 hours, obtain yellow suspension, will be suspended
Liquid stratification removes supernatant, and gained yellow mercury oxide dehydrated alcohol and deionized water are respectively washed three times, dry 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 is added in anhydrous methanol by the mass ratio of 2.8:7.2, with the power ultrasonic disperse 2.8h of 420W, forms precursor solution, preceding
Drive Bi in solution2WO6/C3N4And BiPO4Total concentration be 0.12g/mL, precursor solution magnetic force is stirred with the revolving speed of 220rad/min
22.5h is mixed, yellow suspension is obtained, suspension is stood into a period of time, removes supernatant, gained yellow mercury oxide dehydrated alcohol
It is respectively washed with deionized water three times, dry 18h, obtains Bi at 72 DEG C2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 5
Step 1: by raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is vigorously stirred 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi element be 0.137mol/L, by mixed solution in Ultrasound Instrument with
The power ultrasonic disperse 22min of 480W, then water is transferred to finally with the revolving speed magnetic agitation 2.2h of 280rad/min at normal temperature
In thermal response kettle, microwave power 300W, microwave hydrothermal reacts 0.8h at 185 DEG C, obtains white mixed solution, will mix molten
Liquid stratification removes supernatant, and precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, the dry 19h at 78 DEG C,
Obtain white Bi2WO6Powder；
Step 2: melamine and urea are weighed respectively for 1:1.4 in mass ratio, are added in deionized water after mixing,
Mixture is obtained, the concentration of melamine and urea is 0.31g/mL in mixture, is stirred with the revolving speed of 280rad/min
Object 3.8h, then dries 19h in 78 DEG C of baking oven, and dry powder is taken out and is fully ground, and finally calcines in 530 DEG C of Muffle furnace
3.5h obtains yellow block, 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 nitric acid solution
In, white mixed solution is obtained after stirring, the concentration of Bi element is 0.078mol/L in mixed solution, by mixed solution in ultrasound
With the power ultrasonic disperse 22min of 480W in instrument, then finally turned with the revolving speed magnetic agitation 2.2h of 280rad/min at normal temperature
It moves in hydrothermal reaction kettle, microwave power 300W, microwave hydrothermal reacts 0.9h at 195 DEG C, obtains white suspension, will hang
Turbid stratification removes supernatant, and precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, dry at 78 DEG C
19h obtains white BiPO4Powder；
Step 4: by gained Bi in step 12WO6Gained C in powder and step 23N4Powder is added with the mass ratio of 4.5:5
Into anhydrous methanol, with the power ultrasonic disperse 2.2h of 480W, precursor solution, Bi in precursor solution are formed2WO6And C3N4It is total
Concentration is 0.13g/mL, with the revolving speed of 280rad/min to precursor solution magnetic agitation 20h, obtains yellow suspension, will be suspended
Liquid stratification removes supernatant, and gained yellow mercury oxide dehydrated alcohol and deionized water are respectively washed three times, dry 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 is added in anhydrous methanol by the mass ratio of 0.5:9.5, with the power ultrasonic disperse 2.2h of 480W, forms precursor solution, preceding
Drive Bi in solution2WO6/C3N4And BiPO4Total concentration be 0.13g/mL, precursor solution magnetic force is stirred with the revolving speed of 280rad/min
Mix 20h, obtain yellow suspension, by suspension stand a period of time, remove supernatant, gained yellow mercury oxide dehydrated alcohol and
Deionized water is respectively washed three times, and dry 19h, obtains Bi at 78 DEG C2WO6/C3N4/BiPO4Composite photo-catalyst.
Embodiment 6
Step 1: by raw material 3mmol Na2WO4With 6mmol Bi (NO3)3It is dissolved in deionized water, is vigorously stirred 20min,
Obtain white mixed solution, in mixed solution the concentration of Bi element be 0.135mol/L, by mixed solution in Ultrasound Instrument with
The power ultrasonic disperse 26min of 460W, then water is transferred to finally with the revolving speed magnetic agitation 2.4h of 260rad/min at normal temperature
In thermal response kettle, microwave power 300W, microwave hydrothermal reacts 0.9h at 180 DEG C, obtains white mixed solution, will mix molten
Liquid stratification removes supernatant, and precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, the dry 20h at 80 DEG C,
Obtain white Bi2WO6Powder；
Step 2: melamine and urea are weighed respectively for 1:1.5 in mass ratio, are added in deionized water after mixing,
Mixture is obtained, the concentration of melamine and urea is 0.32g/mL in mixture, is stirred with the revolving speed of 260rad/min
Object 3.6h, then dries 20h in 80 DEG C of baking oven, and dry powder is taken out and is fully ground, and finally calcines in 540 DEG C of Muffle furnace
3h obtains yellow block, 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 nitric acid solution
In, white mixed solution is obtained after stirring, the concentration of Bi element is 0.084mol/L in mixed solution, by mixed solution in ultrasound
With the power ultrasonic disperse 26min of 460W in instrument, then finally turned with the revolving speed magnetic agitation 2.4h of 260rad/min at normal temperature
It moves in hydrothermal reaction kettle, microwave power 300W, microwave hydrothermal reacts 0.5h at 200 DEG C, obtains white suspension, will hang
Turbid stratification removes supernatant, and precipitating is cleaned 3 times with dehydrated alcohol and deionized water respectively, dry at 80 DEG C
20h obtains white BiPO4Powder；
Step 4: by gained Bi in step 12WO6Gained C in powder and step 23N4Powder is added to the mass ratio of 4:5
In anhydrous methanol, with the power ultrasonic disperse 2.4h of 460W, precursor solution, Bi in precursor solution are formed2WO6And C3N4It is total dense
Degree obtains yellow suspension with the revolving speed of 260rad/min to precursor solution magnetic agitation 21h for 0.14g/mL, by suspension
Stratification removes supernatant, and gained yellow mercury oxide dehydrated alcohol and deionized water are respectively washed three times, dry 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 is added in anhydrous methanol by the mass ratio of 1:9, with the power ultrasonic disperse 2.4h of 460W, forms precursor solution, Qian Qurong
Bi in liquid2WO6/C3N4And BiPO4Total concentration be 0.14g/mL, with the revolving speed of 260rad/min to precursor solution magnetic agitation
21h obtains yellow suspension, and suspension is stood a period of time, supernatant is removed, gained yellow mercury oxide dehydrated alcohol and goes
Ionized water respectively washs three times, and dry 20h, obtains Bi at 80 DEG C2WO6/C3N4/BiPO4Composite photo-catalyst.
Using XRD determining Bi2WO6/C3N4/BiPO4The object phase composition structure of composite photo-catalyst preparation method；Use Fourier
The functional group's type and locating chemical environment of infrared spectrum characterization photochemical catalyst are characterized；Surface topography is by S-4800 type field
Transmitting scanning electron microscope is characterized；The degradation experiment of rhodamine B, characterization are carried out in XPA-7 type light-catalyzed reaction instrument
The photocatalysis performance of photochemical catalyst.
Fig. 1 is Bi prepared by the present invention2WO6/C3N4/BiPO4The XRD diagram 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/BiPO4Composite photo-catalyst is in 2 θ=28.34 °, and 32.94 °, 47.18 °, 55.96 ° or so go out
Corresponding existing diffraction maximum is orthorhombic phase Bi2WO6(131), (002), (202), (133) of (PDF No.79-2381) are brilliant
Face, corresponding diffraction maximum at 2 θ=19.06 °, 21.40 °, 27.20 °, 29.14 °, 31.24 ° is monoclinic phase BiPO4
(011) of (PDF NO.15-0767), (- 111), (200), (120), (012) crystal face.Because of C3N4For flaky material, in XRD diagram
In can not measure.Illustrate that the present invention successfully synthesizes Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Fig. 2 is Bi2WO6/C3N4/BiPO4The FT-IR of composite photo-catalyst schemes, in 730cm-1Locate corresponding to be Bi2WO6's
W-O stretches shock absorption peak, 1073cm-1To 921cm-1Corresponding is the stretching vibration absworption peak of (PO4), 600cm-1It arrives
554cm-1Corresponding is the bending vibration absorption peak of (PO4), 1414 ~ 1640cm-1The corresponding absorption peak at place is in carbon azacyclo-
The stretching vibration peak of C-N and C=N, 3500 ~ 4000cm-1The absorption peak at place belongs to g-C3N4The N- not decomposed completely in synthesis process
The H of H and adsorption2The absorption peak of O, further explanation form Bi2WO6/C3N4/BiPO4Composite photo-catalyst.
Fig. 3 is Bi2WO6/C3N4/BiPO4The SEM of composite photo-catalyst schemes, Bi2WO6In flower-shaped, petal edge is in sawtooth
Shape, particle size are 2 μm (Fig. 3 a), BiPO4Pattern be the smooth rectangular rod-shpaed particle in surface, size is at 2 ~ 0.2 μm or so, directly
Diameter is at 0.4 ~ 0.15 μm (Fig. 3 b), pure phase C3N4For porous blocks (Fig. 3 c), the C of compound rear photochemical catalyst3N4Size reduces, attached
In 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 lamp), 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 0.023 min to the degradation rate constant k of RhB-1、0.026
min-1、0.025 min-1With 0.021 min-1, Bi2WO6Powder is 0.012 min to the degradation rate constant k of powder RhB-1,
C3N4Powder is 0.011 min to the degradation rate constant k of RhB-1, Bi2WO6/C3N4/BiPO4Composite photo-catalyst is light-catalysed
Degradation rate constant is Bi2WO61.75 ~ 2.17 times of degradation rate constant, are C3N41.91 ~ 2.36 times of degradation rate constant,
Bi2WO6/C3N4/BiPO4The photocatalysis performance of composite photo-catalyst, which has, to be obviously improved.
Above said content is that a further detailed description of the present invention in conjunction with specific preferred embodiments, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention to technical solution of the present invention
Any equivalent transformation taken, all are covered by the claims of the invention.
Claims (10)
1. a kind of preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst, which comprises the following steps:
Step 1: being in molar ratio 1:2 by Na2WO4With Bi (NO3)3It is dissolved in deionized water, stirs evenly, obtain mixed solution A,
Mixed solution A is successively moved back through ultrasonic disperse and magnetic agitation into hydrothermal reaction kettle, carries out microwave hydrothermal reaction, and reaction terminates
Afterwards by product stratification, the sediment of lower layer is washed, is dried, Bi is obtained2WO6Powder；
Step 2: being in mass ratio 1:(1~1.5 melamine and urea are added in deionized water after mixing), mixed
Object is closed, mixture is stirred to react, product is dried and ground after reaction, then is calcined in Muffle furnace, will be calcined
Product is levigate, obtains C3N4Powder；
Step 3: being in molar ratio 3:3:(4~5) by Na3PO4、Bi(NO3)3It is dissolved in deionized water, stirs evenly with nitric acid, obtain
It is successively moved back to mixed solution B, mixed solution B through ultrasonic disperse and magnetic agitation into hydrothermal reaction kettle, carries out microwave hydrothermal
Reaction, after reaction by product stratification, washs the sediment of lower layer, is dried, obtain BiPO4Powder；
Step 4: by Bi made from step 12WO6C made from powder and step 23N4Powder is (1.2~4.5) in mass ratio: (5~
6) it is added in anhydrous methanol, forms precursor solution A after ultrasonic disperse, magnetic agitation is carried out to precursor solution A, obtains suspension
Suspension A stratification washs the sediment of lower layer, is dried, obtain Bi by A2WO6/C3N4Composite granule；
Step 5: by BiPO made from step 34Bi made from powder and step 42WO6/C3N4Composite granule is (0.4 in mass ratio
~2.8): (9.6~7.2) are added in anhydrous methanol, and precursor solution B is formed after ultrasonic disperse, carry out magnetic force to precursor solution B
Stirring, obtains suspension B, by suspension B stratification, is washed, dried to the sediment of lower layer, obtain 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, feature exist
In the concentration of Bi element 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 element 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, feature exist
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, feature exist
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 being stirred to react in the step 2 is 3~4h, and mixing speed is 200~300rad/min；
In the step 4 and step 5 time of magnetic agitation be 20~for 24 hours, mixing speed be 200~300rad/min.
5. the preparation method of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 1, feature exist
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；
Calcination temperature 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, feature exist
In washing, drying in the step 1, step 3, step 4 and step 5 are that sediment is used dehydrated alcohol and deionization respectively
Water cleaning removes impurity, then dry 15~20h 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, feature exist
In Bi in precursor solution A in the step 42WO6And C3N4Total concentration be 0.1~0.15g/mL；
BiPO in precursor solution B in the step 54And Bi2WO6/C3N4Total concentration be 0.1~0.15g/mL.
8. bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst preparation method system described in any one of claim 1-7
Bismuth tungstate/carbonitride/bismuth phosphate the composite photo-catalyst obtained, which is characterized in that the object phase of bismuth tungstate in the composite photo-catalyst
For orthorhombic phase Bi2WO6, space group is Pca21 (29), and the object of bismuth phosphate is mutually monoclinic phase BiPO4, space group is P21/n (14),
Carbonitride is nonwoven fabric from filaments；Under the simulated solar irradiation irradiation condition of 300W xenon lamp, light-catalysed degradation rate constant is Bi2WO6
1.75~2.17 times of powder, are C3N41.91~2.36 times of powder.
9. bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst according to claim 8, which is characterized in that in 300W xenon
Under the simulated solar irradiation irradiation condition of lamp, the degradation rate constant to rhodamine B is 0.021~0.026min-1。
10. bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst described in claim 1 is in photocatalysis degradation organic contaminant
The application of aspect.
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| CN113457710A (en) * | 2021-07-02 | 2021-10-01 | 南京师范大学 | PDI/g-C3N4/Bi2WO6Composite photocatalyst and preparation method and application thereof |
| CN116020508A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | A kind of composite photocatalytic material and its preparation method and application |
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