CN108970603A - A kind of three-dimensional grapheme load BiVO4Composite photo-catalyst and its preparation method and application - Google Patents
A kind of three-dimensional grapheme load BiVO4Composite photo-catalyst and its preparation method and application Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 94
- 239000002131 composite material Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 26
- 239000004098 Tetracycline Substances 0.000 claims abstract description 23
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 23
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229960002180 tetracycline Drugs 0.000 claims abstract description 18
- 229930101283 tetracycline Natural products 0.000 claims abstract description 18
- 238000013019 agitation Methods 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 13
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 13
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000002604 ultrasonography Methods 0.000 claims abstract description 13
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000006731 degradation reaction Methods 0.000 claims description 22
- 230000015556 catabolic process Effects 0.000 claims description 21
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
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- 230000036961 partial effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
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- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 10
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- 230000000593 degrading effect Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000005447 environmental material Substances 0.000 abstract description 2
- 230000003115 biocidal effect Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 229940040944 tetracyclines Drugs 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- 241000186046 Actinomyces Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to technical field of environmental material preparation, and in particular to a kind of three-dimensional grapheme load BiVO4Composite photo-catalyst and its preparation method and application.The present invention prepares three-dimensional grapheme and carries BiVO4The method of composite photo-catalyst specifically: by two-dimensional graphene, dissolution of ascorbic acid in deionized water, ultrasound, magnetic agitation, water-bath obtains three-dimensional grapheme；Five water bismuth nitrates are dissolved in deionized water, three-dimensional grapheme is added, ammonium metavanadate is added in ultrasound, stirring, and urea is added in magnetic agitation, and oil bath reaction obtains three-dimensional grapheme and carries BiVO4Composite photo-catalyst.It is of the invention that preparation method is simple, using in situ synthesis, nontoxic BiVO4In conjunction with three-dimensional grapheme, three-dimensional grapheme is prepared and carries BiVO4Composite photo-catalyst.The structure of three-dimensional grapheme three-dimensional porous of the invention possesses bigger specific surface area, and composite photo-catalyst reaction site can be made more, and excellent photocatalysis performance is shown to tetracycline, is suitable for tetracycline of degrading on a large scale.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to a kind of three-dimensional grapheme load BiVO4Complex light is urged
Agent and its preparation method and application.
Background technique
Antibiotic (Antibiotics) is also referred to as " antibacterial agent ", is a kind of for inhibiting bacterial growth or killing bacterium
Drug.It is to have to inhibit other quasi-microorganism growths, life caused by microorganism (including bacterium, fungi, actinomyces)
A kind of secondary metabolite deposited, and chemically synthesis or semi-synthetic similar compound.China's abuse of antibiotics is existing
As extremely serious, a large amount of antibiotic meeting contaminated soil and water source but will damage the health of the mankind.Therefore, environment is eliminated
In antibiotic have become vast researcher and urgently pay close attention to and urgent problem.
Graphene (Graphene) be one kind by carbon atom with sp2Hybridized orbit forms the plane that hexangle type is in honeycomb lattice
Film, the two-dimensional material of only one carbon atom thickness.Its electron mobility is more than 15000 cm under room temperature 2 / Vs, than receiving
Rice carbon pipe is high, resistivity about 10 -6Ω cm, it is lower than copper or silver, it is the current the smallest material of world resistivity.But two
The specific surface area for tieing up graphene is small, and the reaction site in conjunction with monomer photochemical catalyst is few.
In addition, BiVO4It is a kind of stable semiconductor material, band gap is only 2.4ev, has cubic, orthogonal, monocline three
Crystal form is planted, wherein the BiVO of monoclinic form4Photocatalytic activity is best, and light abstraction width can be extended to visible light region.Together
When BiVO4It is a kind of metal oxide of environmentally friendly low-carbon without the heavy metal element being harmful to the human body because its is cheap, nontoxic
Matter.But pure monomer pucherite there is also light induced electrons easily compound, the small problem of specific surface area, the degradation of monomer pucherite are living
Property is still to be improved this is because the poor transport efficiency of its electron-hole pair and weaker adsorption property, photoinduction
The Quick Casting of electrons and holes can lead to relatively low photocatalysis efficiency.
Summary of the invention
It is an object of the invention to overcome technological deficiency existing in the prior art, such as: the specific surface area of two-dimensional graphene
Small, the reaction site in conjunction with monomer photochemical catalyst is few；Pure monomer pucherite there is also light induced electrons easily compound, specific surface
The small problem etc. of product, the present invention provides a kind of three-dimensional graphemes to carry BiVO4The preparation method of composite photo-catalyst, the present invention with
Hydro-thermal method is technological means, prepares three-dimensional grapheme and carries BiVO4Composite photo-catalyst.
Specifically, the present invention is carried out by following technical scheme:
(1) three-dimensional grapheme is prepared:
It by two-dimensional graphene, dissolution of ascorbic acid in deionized water, is put into supersonic cleaning machine after ultrasound, then carries out magnetic force and stir
It mixes, after obtained mixed liquor is carried out water-bath, washing；Obtained reaction solution is freeze-dried, three-dimensional grapheme is obtained
(rGH)；
(2) it prepares three-dimensional grapheme and carries BiVO4Composite photo-catalyst:
Five water bismuth nitrates are dissolved in deionized water, three-dimensional grapheme is added later, after stirring, ammonium metavanadate, magnetic force is added in ultrasound
Urea is added in stirring, and oil bath reaction is centrifuged, washs, dry, obtains three-dimensional grapheme and carries BiVO4Composite photo-catalyst (rGH/
BiVO4).
In step (1), the mass ratio of the two-dimensional graphene and ascorbic acid is 1:15-20, and the ultrasonic time is 1-
2h, the time of the magnetic agitation are 0.5h, and the bath temperature is 90-99 DEG C, water-bath time 1.5-2h；
In step (2), the five water bismuth nitrate, three-dimensional grapheme mass ratio be 485:2.43-7.27；Five water bismuth nitrates and partially
The molar ratio of ammonium vanadate is 1:1；The mass ratio of three-dimensional grapheme and urea is 2.43-7.27:3000-5000；
In step (2), the time of the ultrasound is 0.5h；The time of the stirring is 2h；The time of the magnetic agitation is 1h；
The temperature of the oil bath reaction is 80-100 DEG C, and the oil bath reaction time is 24-36h.
BiVO is carried according to three-dimensional grapheme prepared by the above technical step4Composite photo-catalyst, wherein three-dimensional grapheme
Account for BiVO4Mass percent be 0.5%-1.5%.
The present invention also provides a kind of three-dimensional graphemes to carry BiVO4Composite photo-catalyst, BiVO4Particle is dispersed in three-dimensional stone
The surface of black alkene, wherein BiVO4Particle is spherical in shape, and partial size is between 50nm-200nm；Three-dimensional grapheme shows porous three-dimensional
Structure.
The present invention also provides a kind of three-dimensional graphemes to carry BiVO4The application of composite photo-catalyst, the composite photocatalyst
Agent is for tetracycline of degrading.
Compared with prior art compared with beneficial effects of the present invention embody as follows:
(1) preparation method is simple by the present invention, is raw material by the three-dimensional grapheme of five water bismuth nitrates, ammonium metavanadate, preparation, adopts
With in situ synthesis, nontoxic BiVO4In conjunction with three-dimensional grapheme, preparation generates three-dimensional grapheme and carries BiVO4Composite photocatalyst
Agent.Three-dimensional grapheme carries BiVO it can be seen from attached drawing 24The maximum absorption wavelength of composite photo-catalyst is relative to monomer BiVO4
It expands, and then expands the light abstraction width of catalyst, to improve the utilization rate of luminous energy.
(2) three-dimensional grapheme prepared by the present invention shows the structure of three-dimensional porous it can be seen from attached drawing 3, rather than
The laminated structure of conventional two-dimensional graphene.The structure of three-dimensional porous possesses bigger specific surface area, three-dimensional grapheme can be made to carry
BiVO4Composite photo-catalyst possesses more reaction sites, and light reaction can be made more abundant, improves light-catalysed efficiency.By
Attached drawing 4 is it can be seen that BiVO4Even particulate dispersion is inside three-dimensional grapheme.
(3) conductor photocatalysis material three-dimensional grapheme prepared by the present invention carries BiVO4Composite photo-catalyst is through illumination
After penetrating, by the interfacial interaction with contaminant molecule, the very strong free radical group of oxidisability is produced, so that it may effective
Degradation of contaminant is a kind of environmentally protective technology；Three-dimensional grapheme prepared by the present invention carries BiVO4Composite photo-catalyst pair
The degradation rate of 10mg/L tetracycline can reach 95%, can reach 73% to the degradation rate of 20mg/L tetracycline, shows excellent light
Catalytic performance.Therefore, the present invention is successfully realized three-dimensional grapheme and carries BiVO4The purpose of composite photocatalyst for degrading waste water.
Detailed description of the invention
Fig. 1 is that three-dimensional grapheme prepared by the present invention carries BiVO4The XRD diagram of composite photo-catalyst；
Fig. 2 is that three-dimensional grapheme prepared by the present invention carries BiVO4The UV-vis of composite photo-catalyst schemes；
Fig. 3 is the SEM figure of two-dimensional graphene (a) and three-dimensional grapheme (b) prepared by the present invention；
Fig. 4 is that three-dimensional grapheme prepared by the present invention carries BiVO4The TEM of composite photo-catalyst schemes.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described.
Five water bismuth nitrate used in the present invention, ammonium metavanadate, urea are that analysis is pure, and it is limited to be purchased from traditional Chinese medicines chemical reagent
Company.Tetracycline is mark product, is purchased from Shanghai along vigorous bioengineering Co., Ltd.The use of deionized water in technical solution of the present invention
Amount is that solid can be made to be completely dissolved.
Photocatalytic activity assessment: carrying out in DW-01 type photochemical reactor (being purchased from Educational Instrument Factory of Yangzhou University), can
100ml tetracycline simulated wastewater is added in reactor and measures initial absorbance by light-exposed light irradiation, and complex light is then added and urges
Agent, magnetic agitation, and air pump blowing air into solution is opened, so that catalyst is in uniform suspended state in the solution, to
After reaching adsorption equilibrium, light source is opened, every 10min sampling is analyzed later.In spectrophotometer λ after centrifugation acquisition supernatant
Measure absorbance at max=360nm, and pass through formula: DR=[(A0-Ai)/A0] × 100% calculates degradation rate, and wherein A0 is to reach
The absorbance of tetracycline when adsorption equilibrium, Ai are the absorbance of the tetracycline of timing sampling measurement.
Embodiment 1:
(1) preparation of three-dimensional grapheme:
It takes 100mg two-dimensional graphene to be put into 250mL beaker, adds 1.5g ascorbic acid, take 100mL deionization water-soluble later
Solution, is put into ultrasound 1h in supersonic cleaning machine, later magnetic agitation 0.5h again；Obtained mixed liquor is put into water in 90 DEG C of water-baths
It after bathing 1.5h, washes 5 times, obtained reaction solution is put into drying 2 days in freeze drier, sample is collected, obtains three-dimensional stone
Black alkene (rGH).
(2) three-dimensional grapheme carries BiVO4The preparation of composite photo-catalyst:
The beaker for taking a 250mL weighs five water bismuth nitrate of 1mmol (0.485 g) and is dissolved in deionized water, 2.43mg is added later
Three-dimensional grapheme, ultrasonic 0.5h, is vigorously stirred 2h, is then slowly added into 1mmol ammonium metavanadate (0.117 g), magnetic agitation 1h
Afterwards, 3g urea is added, reacts for 24 hours, is centrifuged in 80 DEG C of oil baths, wash, it is dry, sample is collected, three-dimensional grapheme load is obtained
BiVO4Composite photo-catalyst (rGH/BiVO4), wherein three-dimensional grapheme accounts for BiVO4Mass percent be 0.5%.
(3) light-catalyzed reaction:
The three-dimensional grapheme in step (2) is taken to carry BiVO4Composite photocatalyst sample carries out photocatalysis in photochemical reactor
Degradation experiment measures 0.05g photochemical catalyst and reaches 87% in 1h to the degradation rate of 10 mg/L antibiotic tetracyclines；To 20mg/L
The degradation rate of antibiotic tetracycline reaches 65% in 1h.
Embodiment 2:
(1) preparation of three-dimensional grapheme:
It takes 100mg two-dimensional graphene to be put into 250mL beaker, adds 1.7g ascorbic acid, take 100mL deionization water-soluble later
Solution, is put into ultrasound 1.5h in supersonic cleaning machine, later magnetic agitation 0.5h again；Obtained mixed liquor is put into 95 DEG C of water-baths
It is washed 5 times after water-bath 1.6h, obtained reaction solution is put into drying 2 days in freeze drier, sample is collected, obtains three-dimensional stone
Black alkene (rGH).
(2) three-dimensional grapheme carries BiVO4The preparation of composite photo-catalyst:
The beaker for taking a 250mL weighs five water bismuth nitrate (0.485g) of 1mmol and is dissolved in deionized water, 3.64mg is added later
Three-dimensional grapheme, ultrasonic 0.5h, is vigorously stirred 2h, is then slowly added into 1mmol ammonium metavanadate (0.117g), magnetic agitation 1h,
4g urea is added, reacts 30h in 90 DEG C of oil baths, is centrifuged, washs, it is dry, sample is collected, three-dimensional grapheme is obtained and carries BiVO4
Composite photo-catalyst (rGH/BiVO4), wherein three-dimensional grapheme accounts for BiVO4Mass percent be 0.75%.
(3) light-catalyzed reaction:
The three-dimensional grapheme in step (2) is taken to carry BiVO4Composite photocatalyst sample carries out photocatalysis in photochemical reactor
Degradation experiment measures the 0.05g photochemical catalyst and reaches 92% in 1h to the degradation rate of 10 mg/L antibiotic tetracyclines；It is right
The degradation rate of 20mg/L antibiotic tetracycline reaches 68% in 1h.
Embodiment 3:
(1) preparation of three-dimensional grapheme:
It takes 100mg two-dimensional graphene to be put into 250mL beaker, adds 2g ascorbic acid, take 100mL deionization water-soluble later
Solution, is put into ultrasound 2h in supersonic cleaning machine, later magnetic agitation 0.5h again；Obtained mixed liquor is put into water in 99 DEG C of water-baths
It bathes 2h to wash 5 times later, obtained reaction solution is put into drying 2 days in freeze drier, sample is collected, obtains three-dimensional grapheme
(rGH).
(2) three-dimensional grapheme carries BiVO4The preparation of composite photo-catalyst:
The beaker for taking a 250mL weighs five water bismuth nitrate (0.485g) of 1mmol and is dissolved in deionized water, 4.85mg is added later
Three-dimensional grapheme, ultrasonic 0.5h, is vigorously stirred 2h, is then slowly added into 1mmol ammonium metavanadate (0.117g), magnetic agitation 1h,
5g urea is added, reacts 36h in 100 DEG C of oil baths, is centrifuged, washs, it is dry, sample is collected, three-dimensional grapheme is obtained and carries BiVO4
Composite photo-catalyst (rGH/BiVO4), wherein three-dimensional grapheme accounts for BiVO4Mass percent be 1%.
(3) light-catalyzed reaction:
The three-dimensional grapheme in step (2) is taken to carry BiVO4Composite photocatalyst sample carries out photocatalysis in photochemical reactor
Degradation experiment measures the 0.05g photochemical catalyst and reaches 95% in 1h to the degradation rate of 10 mg/L antibiotic tetracyclines；It is right
The degradation rate of 20mg/L antibiotic tetracycline reaches 73% in 1h.
Embodiment 4:
(1) preparation of three-dimensional grapheme:
It takes 100mg two-dimensional graphene to be put into 250mL beaker, adds 1.5g ascorbic acid, take 100mL deionization water-soluble later
Solution, is put into ultrasound 2h in supersonic cleaning machine, later magnetic agitation 0.5h again；Obtained mixed liquor is put into water in 95 DEG C of water-baths
1.5h is bathed to wash 5 times later.It is put into drying 2 days in freeze drier later, collects sample and obtains three-dimensional grapheme (rGH).
(2) three-dimensional grapheme carries BiVO4The preparation of composite photo-catalyst:
The beaker for taking a 250mL weighs five water bismuth nitrate (0.485g) of 1mmol and is dissolved in deionized water, 6.06mg is added later
Three-dimensional grapheme, ultrasonic 0.5h, is vigorously stirred 2h, is then slowly added into 1mmol ammonium metavanadate (0.117g), magnetic agitation 1h,
3g urea is added, is reacted for 24 hours in 80 DEG C of oil baths.Centrifugation is washed, dry, collects sample, is obtained three-dimensional grapheme and is carried BiVO4
Composite photo-catalyst (rGH/BiVO4), wherein three-dimensional grapheme accounts for BiVO4Mass percent be 1.25%.
(3) light-catalyzed reaction
The three-dimensional grapheme in step (2) is taken to carry BiVO4Composite photocatalyst sample carries out photocatalysis in photochemical reactor
Degradation experiment measures the 0.05g photochemical catalyst and reaches 93% in 1h to the degradation rate of 10 mg/L antibiotic tetracyclines；It is right
The degradation rate of 20mg/L antibiotic tetracycline reaches 70% in 1h.
Embodiment 5:
(1) preparation of three-dimensional grapheme:
It takes 100mg two-dimensional graphene to be put into 250mL beaker, adds 1.5g ascorbic acid, take 100mL deionization water-soluble later
Solution, is put into ultrasound 2h in supersonic cleaning machine, later magnetic agitation 0.5h again；Obtained mixed liquor is put into water in 95 DEG C of water-baths
1.5h is bathed to wash 5 times later.It is put into drying 2 days in freeze drier later, collects sample, obtains three-dimensional grapheme (rGH).
(2) three-dimensional grapheme carries BiVO4The preparation of composite photo-catalyst:
The beaker for taking a 250mL weighs five water bismuth nitrate (0.485g) of 1mmol and is dissolved in deionized water, 7.27mg is added later
Three-dimensional grapheme, ultrasonic 0.5h, is vigorously stirred 2h, is then slowly added into 1mmol ammonium metavanadate (0.117g), magnetic agitation 1h,
3g urea is added, is reacted for 24 hours in 80 DEG C of oil baths.Centrifugation is washed, dry, collects sample, is obtained three-dimensional grapheme and is carried BiVO4
Composite photo-catalyst (rGH/BiVO4), wherein three-dimensional grapheme accounts for BiVO4Mass percent be 1.5%.
(3) light-catalyzed reaction:
The three-dimensional grapheme in step (2) is taken to carry BiVO4Composite photocatalyst sample carries out photocatalysis in photochemical reactor
Degradation experiment measures the 0.05g photochemical catalyst and reaches 90% in 1h to the degradation rate of 10 mg/L antibiotic tetracyclines；It is right
The degradation rate of 20mg/L antibiotic tetracycline reaches 69% in 1h.
The effect of ascorbic acid is added in the present invention are as follows: the laminated structure of two-dimensional graphene is peeled away, is formed porous vertical
Body structure, obtains three-dimensional grapheme.The excessive very few three-dimensional grapheme porous three dimensional structure of being unfavorable for of ascorbic acid addition
It is formed, is found by experimental exploring, when the mass ratio of two-dimensional graphene of the invention and ascorbic acid is 1:15-20, prepared
Three-dimensional grapheme be in porous three dimensional structure.
The precipitation that urea is conducive to pucherite crystal is added in the present invention, makes BiVO4Particle is dispersed in three-dimensional grapheme
Surface forms three-dimensional grapheme and carries BiVO4Composite photo-catalyst.Found by experimental exploring, three-dimensional grapheme of the invention with
When the mass ratio of urea is 2.43-7.27:3000-5000, the three-dimensional grapheme of preparation carries BiVO4In composite photo-catalyst,
BiVO4Even particulate dispersion is on the surface of three-dimensional grapheme, the preferable photocatalytic activity that obtains the composite photo-catalyst.
The present invention prepares three-dimensional grapheme and carries BiVO4Composite photo-catalyst obtains reaction principle are as follows: in situ synthesis is utilized, it will
Five water bismuth nitrates are dissolved to arrive Bi3+In solution, three-dimensional grapheme is added later, after being sufficiently stirred, makes Bi3+Sufficiently it is adsorbed on
The surface of three-dimensional grapheme；The inclined alum acid ammonium solid with five water bismuth nitrate equimolar amounts, Bi are added later3+With VO4 3-In three-dimensional stone
Reaction generates BiVO on black alkene4, so that obtaining three-dimensional grapheme carries BiVO4Composite photo-catalyst.
Fig. 1 is that three-dimensional grapheme prepared by the present invention carries BiVO4The XRD diagram of composite photo-catalyst will be apparent that from figure
Find out the corresponding monoclinic phase BiVO at x=18.669,28.94,35.224(110), (121), (002) crystal face characteristic peak,
Show that the present invention has been successfully prepared the BiVO of monoclinic phase4；In addition, monoclinic phase BiVO4It is the best BiVO of catalytic activity4Crystal form.
Fig. 2 is that three-dimensional grapheme prepared by the present invention carries BiVO4The UV-vis of composite photo-catalyst schemes；It can be seen that in figure
Three-dimensional grapheme carries BiVO4The maximum absorption wavelength of composite photo-catalyst is greater than monomer BiVO4, it means that three-dimensional grapheme
Carry BiVO4Composite photo-catalyst possesses broader visible absorption range, promotes optical response range, improves the benefit to luminous energy
With rate, to enhance the photocatalytic activity of composite catalyst.
Fig. 3 is the SEM figure of two-dimensional graphene (a) and three-dimensional grapheme (b) prepared by the present invention；It can be seen by Fig. 3 (a)
It arrives, two-dimensional graphene structure in the form of sheets.From Fig. 3 (b), it can be seen that, three-dimensional grapheme then shows the structure of porous three-dimensional, and
It is not the sheet-like morphology of conventional two-dimensional graphene；The specific surface area of three-dimensional grapheme is larger, and bigger specific surface area means more
More reaction sites, can making light degradation reaction carry out more abundant, raising is to the utilization rate of luminous energy.
Fig. 4 is that three-dimensional grapheme prepared by the present invention carries BiVO4The TEM of composite photo-catalyst schemes, can be clear in figure
See BiVO4Even particulate dispersion is on the surface of three-dimensional grapheme, wherein BiVO4Particle is spherical in shape, and partial size is in 50nm-200nm
Between；Three-dimensional grapheme shows the structure of porous three-dimensional.When photochemical reaction occurs for the composite photo-catalyst and tetracycline,
BiVO4Particle can be contacted preferably with pollutant, carry out reaction abundant thorough.In addition BiVO4It is dispersed in three-dimensional grapheme
In, when photochemical reaction occurs, light induced electron can be transferred on three-dimensional grapheme, to inhibit light induced electron and light indirectly
The compound of hole is given birth to, to improve photocatalysis efficiency.
It can be obtained by the experimental result of embodiment 1-5, three-dimensional grapheme prepared by embodiment 3 carries BiVO4Composite photo-catalyst
Middle three-dimensional grapheme accounts for BiVO4Mass percent be 1% when, the composite photo-catalyst activity preferably, the three-dimensional stone of 0.05g
Black alkene carries BiVO4Composite photo-catalyst reaches 95% to the Effective degradability of the tetracycline of 10mg/L in 1h, to 20mg/L
The Effective degradability of tetracycline reach 73%.The three-dimensional grapheme of Examples 1 and 2 preparation carries BiVO4Composite photo-catalyst
Middle three-dimensional grapheme accounts for BiVO4Mass percent be respectively 0.5%, 0.75%, three-dimensional grapheme carry BiVO4Composite photo-catalyst
Activity it is slightly worse, it may be possible to since the amount of three-dimensional grapheme is less, as the amount of three-dimensional grapheme in embodiment 3 gradually increases,
Light induced electron is able to preferably by BiVO4It is transferred on three-dimensional grapheme, to inhibit the compound of light induced electron and photohole.
But as the amount of three-dimensional grapheme in embodiment 4 and 5 further increases, BiVO4Amount relative reduction, excessive three-dimensional graphite
Alkene will appear light absorptive, so that three-dimensional grapheme be made to carry BiVO4Composite photo-catalyst reduces the utilization rate of luminous energy, makes photocatalysis
Activity decline.
Claims (10)
1. a kind of three-dimensional grapheme carries BiVO4The preparation method of composite photo-catalyst, which comprises the following steps:
(1) three-dimensional grapheme is prepared:
It by two-dimensional graphene, dissolution of ascorbic acid in deionized water, is put into supersonic cleaning machine after ultrasound, then carries out magnetic force and stir
It mixes, after obtained mixed liquor is carried out water-bath, washing；Obtained reaction solution is freeze-dried, three-dimensional grapheme is obtained；
(2) it prepares three-dimensional grapheme and carries BiVO4Composite photo-catalyst:
Five water bismuth nitrates are dissolved in deionized water, three-dimensional grapheme is added later, after stirring, ammonium metavanadate, magnetic force is added in ultrasound
Urea is added in stirring, and oil bath reaction is centrifuged, washs, dry, obtains three-dimensional grapheme and carries BiVO4Composite photo-catalyst.
2. three-dimensional grapheme according to claim 1 carries BiVO4The preparation method of composite photo-catalyst, which is characterized in that step
Suddenly in (1), the mass ratio of the two-dimensional graphene and ascorbic acid is 1:15-20.
3. three-dimensional grapheme according to claim 1 carries BiVO4The preparation method of composite photo-catalyst, which is characterized in that step
Suddenly in (1), the ultrasonic time is 1-2h, and the time of the magnetic agitation is 0.5h；The bath temperature is 90-99 DEG C, institute
Stating water-bath time is 1.5-2h.
4. three-dimensional grapheme according to claim 1 carries BiVO4The preparation method of composite photo-catalyst, which is characterized in that step
Suddenly in (2), the five water bismuth nitrate, three-dimensional grapheme mass ratio be 485:2.43-7.27.
5. three-dimensional grapheme according to claim 1 carries BiVO4The preparation method of composite photo-catalyst, which is characterized in that step
Suddenly in (2), the molar ratio of five water bismuth nitrates and ammonium metavanadate is 1:1.
6. three-dimensional grapheme according to claim 1 carries BiVO4The preparation method of composite photo-catalyst, which is characterized in that step
Suddenly in (2), the mass ratio of three-dimensional grapheme and urea is 2.43-7.27:3000.
7. three-dimensional grapheme according to claim 1 carries BiVO4The preparation method of composite photo-catalyst, which is characterized in that step
Suddenly in (2), the time of the ultrasound is 0.5h；The time of the stirring is 2h；The time of the magnetic agitation is 1h.
8. three-dimensional grapheme according to claim 1 carries BiVO4The preparation method of composite photo-catalyst, which is characterized in that step
Suddenly in (2), the temperature of the oil bath reaction is 80-100 DEG C, and the oil bath reaction time is 24-36h.
9. three-dimensional grapheme prepared by the method as described in claim 1-8 any one carries BiVO4Composite photo-catalyst, it is special
Sign is, BiVO4Particle is dispersed in the surface of three-dimensional grapheme, wherein BiVO4Particle is spherical in shape, partial size 50nm-200nm it
Between；Three-dimensional grapheme shows the structure of porous three-dimensional.
10. three-dimensional grapheme prepared by the method as described in claim 1-8 any one carries BiVO4Composite photo-catalyst is used for
Degradation tetracycline.
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