CN106824167A - Five vanadic acid tripotassium photochemical catalysts and pucherite/five vanadic acid tripotassium composite photo-catalyst and preparation method and application - Google Patents
Five vanadic acid tripotassium photochemical catalysts and pucherite/five vanadic acid tripotassium composite photo-catalyst and preparation method and application Download PDFInfo
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- CN106824167A CN106824167A CN201710041859.0A CN201710041859A CN106824167A CN 106824167 A CN106824167 A CN 106824167A CN 201710041859 A CN201710041859 A CN 201710041859A CN 106824167 A CN106824167 A CN 106824167A
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- bivo
- methylene blue
- vanadic acid
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 37
- 230000001699 photocatalysis Effects 0.000 claims abstract description 26
- 238000007146 photocatalysis Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 54
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 54
- 238000001354 calcination Methods 0.000 claims description 25
- 238000006731 degradation reaction Methods 0.000 claims description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- 238000005286 illumination Methods 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 19
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 10
- 238000000703 high-speed centrifugation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- B01J35/39—
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
Abstract
The present invention provides K3V5O14Photochemical catalyst and BiVO4/K3V5O14Composite photo-catalyst and preparation method and application.K3V5O14The preparation method of photochemical catalyst is：By K sources and V sources grinding compressing tablet, flaky mixture is obtained；Flaky mixture is calcined in air atmosphere, is fully ground after natural cooling, you can obtain K3V5O14Photochemical catalyst.BiVO4/K3V5O14Composite photo-catalyst is by by K3V5O14With BiVO4Natural cooling is obtained after being calcined in air atmosphere after mixing.The present invention is first by K3V5O14Apply in photocatalysis experiment, photocatalytic activity is preferable under visible light.Meanwhile, BiVO has been prepared first4/K3V5O14Optic catalytic composite material, preparation condition is gentle, it is adaptable to produce in enormous quantities, and has highlight catalytic active under visible light.
Description
Technical field
The present invention relates to inorganic catalysis material, more particularly to K3V5O14Photochemical catalyst and BiVO4/K3V5O14Complex light is urged
Agent and preparation method and application.
Background technology
Photocatalitic Technique of Semiconductor has room temperature deep reaction, can utilize Driven by Solar Energy reaction and non-secondary pollution etc.
Advantage, has been applied in the reparation of water pollution.In recent years, the oxysalt with semiconductor property is due to can absorb
Visible ray, photocatalytic activity in sunshine characteristic higher and environment-friendly, by the extensive concern of researcher.Research
Show, oxysalt conductor photocatalysis material overcomes conventional Ti O to a certain extent2Deng catalysis material band gap width
Greatly, electron-hole is easily combined and the low drawback of solar energy utilization ratio.The wherein research of vanadate is more ripe.Vanadate
The chemical general formula of based semiconductor compound is represented by AxVyOz, wherein A is alkali metal or transition metal.Vanadate based semiconductor
The energy gap of catalysis material is universal narrower, and Stability Analysis of Structures, thus can under visible light illumination show preferable light and urge
Change performance, with photocatalysis activity higher.Reporting in recent years more has pucherite (BiVO4), vanadic acid caesium (Cs2V4O11)
With silver vanadate (AgxVyOz) etc., it is the visible-light photocatalyst of high efficiency high activity.In order to preferably utilize solar energy, improve
Its photocatalytic activity is, it is necessary to use various methods to be modified monomer material to improve the photocatalysis of silver vanadate semi-conducting material
Performance.
The content of the invention
The present invention provides a kind of K of inexpensive, high catalytic activity to solve above-mentioned technical problem3V5O14Photochemical catalyst and
BiVO4/K3V5O14Composite photo-catalyst and preparation method and application.
The object of the invention is realized using following proposal：
K3V5O14Photochemical catalyst, it is prepared by following methods：
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs raw material K sources and V sources respectively；
Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture；
Above-mentioned flaky mixture is calcined in air atmosphere, calcining heat be 400~700 DEG C, calcination time be 12~
36h, is fully ground after natural cooling, you can obtain pure phase K3V5O14Photochemical catalyst.
In such scheme, the V sources are any one in vanadic anhydride and ammonium metavanadate or two kinds of mixtures.
In such scheme, the K sources are any one in potassium carbonate and potassium nitrate or two kinds of mixtures.
Described K3V5O14Application of the photochemical catalyst in photocatalysis removal methylene blue.
In such scheme, the application includes configuration methylene blue solution at room temperature and adds the K3V5O14Photocatalysis
Agent, opens magnetic agitation, and catalytic degradation reaction is carried out under visible light illumination.
BiVO4/K3V5O14Composite photo-catalyst, it includes BiVO4And K3V5O14, the BiVO4Mass fraction be 5%-
20%, the K3V5O14Mass fraction be 80%-95%.
Described BiVO4/K3V5O14The preparation method of composite photo-catalyst, comprises the following steps：
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs raw material K sources and V sources respectively；
Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture；
Above-mentioned flaky mixture is calcined in air atmosphere, calcining heat be 400~700 DEG C, calcination time be 12~
36h, is fully ground after natural cooling, you can obtain pure phase K3V5O14Photochemical catalyst；
By K3V5O14With BiVO obtained in hydro-thermal method4Mix in ethanol, using ultrasonic disperse；
Said mixture is calcined in air atmosphere, calcining heat is 200-300 DEG C, and calcination time is 1-3h, it is natural
The BiVO is obtained after cooling4/K3V5O14Composite photo-catalyst.
Described composite photo-catalyst is in H2O2Application in the lower photocatalysis removal methylene blue of collaboration.
In such scheme, the application includes configuration methylene blue solution at room temperature and adds the composite photocatalyst
Agent, adjusts solution initial pH value, while H is added dropwise2O2, magnetic agitation is opened, catalytic degradation reaction is carried out under visible light illumination.
In such scheme, solution initial pH value is 3~11, and catalyst charge is 0.25g/L, H2O2Addition accounts for solution
Percent by volume be 0.5~1.5%, the catalytic degradation reaction time be 60~180min.
Beneficial effects of the present invention are：
1. the present invention is first by K3V5O14Apply in photocatalysis experiment, and to it under visible light to dyestuff methylene blue
Photocatalytic Degradation Property and absorption property be analyzed；
2. the present invention has prepared BiVO first4/K3V5O14Optic catalytic composite material, its mechanism of action is degraded-absorption association
Same-action；
3. the present invention takes solid phase method that pure phase K is obtained3V5O14, reaction carried out in Muffle furnace, can temperature programmed control, heat up,
Constant temperature and temperature-fall period are relatively stable；
4. preparation process of the present invention is easily operated, and preparation method is simple, and mild condition is nontoxic, relatively safety, for large quantities of
Amount production；
5. the composite photocatalyst material yield that the present invention is finally obtained is higher, and purity is higher, and photocatalysis under visible light
It is active preferable.
Brief description of the drawings
Fig. 1 is the obtained pure phase BiVO of the present invention4The X-ray powder diffraction figure of sample；
Fig. 2 is the pure phase BiVO obtained by the embodiment of the present invention 14SEM (SEM) photo of sample；
Fig. 3 is obtained pure phase K for the embodiment of the present invention 23V5O14The X-ray powder diffraction figure of sample；
Fig. 4 is obtained pure phase K for the embodiment of the present invention 23V5O14The SEM photograph of sample；
Fig. 5 is obtained pure phase K for the embodiment of the present invention 23V5O14TEM (transmission electron microscope) photo of sample；
Fig. 6 is that the embodiment of the present invention 2~4 is obtained pure phase K3V5O14Removing, adsorption curve of the sample to methylene blue；
Fig. 7 is BiVO obtained in the embodiment of the present invention 7~94/K3V5O14The x-ray powder of composite photo-catalyst sample
Diffraction pattern；
Fig. 8 is BiVO obtained in the embodiment of the present invention 7~94/K3V5O14Composite photo-catalyst sample to methylene
Blue removal efficiency curve and pure phase BiVO4The comparison diagram of degradation curve；
Fig. 9 is BiVO of the invention4/K3V5O14Composite photocatalyst material described in embodiment 10~13 under the conditions of to Asia
The photocatalysis removal efficiency curve and adsorption rate curve of methyl blue；
Figure 10 is BiVO of the invention4/K3V5O14Composite photocatalyst material described in embodiment 14~16 under the conditions of to Asia
The photocatalytic degradation curve of methyl blue.
Specific embodiment
To make present disclosure, technical scheme and advantage become more apparent, below in conjunction with specific embodiments and the drawings
The present invention is expanded on further, these embodiments are merely to illustrate the present invention, and the present invention is not limited only to following examples.
Embodiment 1：Pure phase BiVO4Preparation
Weigh the Bi (NO of 2.5mmol3)3·5H2The NH of O and 2.5mmol4VO3, magnetic in the distilled water of 7mL is dissolved in respectively
Power stirs 30min, by NH4VO3Suspension is added dropwise over Bi (NO3)3·5H2In O, pH=9 is adjusted with NaOH, continue magnetic agitation
30min.Mixing suspension is transferred in water heating kettle inner bag, and it is 80% to add appropriate distilled water to compactedness, at 160 DEG C
Heating 12h, will react the yellow solid distilled water and alcohol flushing of generation for several times to neutral, in 60 DEG C of oven for drying 6h, obtain
To pure phase BiVO4Photochemical catalyst, its X-ray powder diffraction figure (XRD) is shown in Fig. 1.Pure phase BiVO prepared by the present embodiment4Sample
Stereoscan photograph (SEM) referring to Fig. 2.Take BiVO4Sample dosage is 0.25g/L, and methylene blue solution initial concentration is
20mg/L, first lucifuge absorption 30min, then opens light source before photocatalysis performance test starts.5mL is sampled every 15min, it is high
Supernatant is taken after speed centrifugation and test its absorbance, and calculate its degradation rate, referring to Fig. 8.
Embodiment 2：Pure phase K3V5O14Preparation
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs the raw material of certain mol proportion, K sources respectively
It is one or two mixtures in potassium carbonate and potassium nitrate, V sources are one or two in vanadic anhydride and ammonium metavanadate
Mixture.Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture.By sheet above
Shape mixture is calcined in air atmosphere, and calcining heat is 500 DEG C, and calcination time is 12h, is fully ground after natural cooling, is obtained
To pure phase K3V5O14Photochemical catalyst, its X-ray powder diffraction figure (XRD) is shown in Fig. 3.Pure phase K prepared by the present embodiment3V5O14Sample
Layer structure is visible as under the stereoscan photograph (SEM) and transmission electron microscope photo (TEM) of product, respectively referring to Fig. 4 and Fig. 5.
K3V5O14Sample visible obvious layer structure at 500 DEG C, thus it is speculated that its excellent absorption property is primarily due to its layer structure
Presence.Increase when reaction temperature rising, reaction time, its layer structure is possible to destroyed, reduces its absorption property, so that
Have impact on the removal efficiency to methylene blue.
K3V5O14The removing curve and adsorption curve of sample photocatalytic degradation methylene blue under visible light illumination are referring to figure
6.Photocatalysis performance is tested and absorption property test takes catalyst concn for 0.25g/L, is owned in photocatalysis performance test
Equal lucifuge adsorbs 30min to sample before the test begins.5mL is sampled every 15min, supernatant is taken after high speed centrifugation and is tested its extinction
Degree, and calculate its removal efficiency and adsorption rate.Be can see in Fig. 6, methylene blue 90.15%, and conductor have been removed in 75min
Material is mainly derived from its absorption to methylene blue molecule to the removing ability of methylene blue.
Embodiment 3：Pure phase K3V5O14Preparation
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs the raw material of certain mol proportion, K sources respectively
It is one or two mixtures in potassium carbonate and potassium nitrate, V sources are one or two in vanadic anhydride and ammonium metavanadate
Mixture.Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture.By sheet above
Shape mixture is calcined in air atmosphere, and calcining heat is 500 DEG C, and calcination time is 24h, is fully ground after natural cooling, is obtained
To pure phase K3V5O14Photochemical catalyst.Photocatalysis result shows, be can see in Fig. 6, in 75min to the clearance of methylene blue
Can reach 88.47%.
Embodiment 4：Pure phase K3V5O14Preparation
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs the raw material of certain mol proportion, K sources respectively
It is one or two mixtures in potassium carbonate and potassium nitrate, V sources are one or two in vanadic anhydride and ammonium metavanadate
Mixture.Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture.By sheet above
Shape mixture is calcined in air atmosphere, and calcining heat is 500 DEG C, and calcination time is 36h, is fully ground after natural cooling, is obtained
To pure phase K3V5O14Photochemical catalyst.Be can see in Fig. 6, photocatalysis result shows, in 75min to the clearance of methylene blue
Can reach 86.55%.
Embodiment 5：Pure phase K3V5O14Preparation
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs the raw material of certain mol proportion, K sources respectively
It is one or two mixtures in potassium carbonate and potassium nitrate, V sources are one or two in vanadic anhydride and ammonium metavanadate
Mixture.Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture.By sheet above
Shape mixture is calcined in air atmosphere, and calcining heat is 600 DEG C, and calcination time is 24h, is fully ground after natural cooling, is obtained
To pure phase K3V5O14Photochemical catalyst.Using method of testing same as Example 2, its photocatalysis result shows, in 75min pair
The clearance of methylene blue can reach 87.08%.
Embodiment 6：Pure phase K3V5O14Preparation
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs the raw material of certain mol proportion, K sources respectively
It is one or two mixtures in potassium carbonate and potassium nitrate, V sources are one or two in vanadic anhydride and ammonium metavanadate
Mixture.Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture.By sheet above
Shape mixture is calcined in air atmosphere, and calcining heat is 700 DEG C, and calcination time is 24h, is fully ground after natural cooling, is obtained
To pure phase K3V5O14Photochemical catalyst.Using method of testing same as Example 2, its photocatalysis result shows, in 75min pair
The clearance of methylene blue can reach 84.22%.
Embodiment 7：BiVO4/K3V5O14The preparation of composite photo-catalyst
It is chosen at the K that at 500 DEG C prepared by constant temperature 12h3V5O14With pure phase BiVO4It is combined.Take BiVO4Mass fraction is
5% mixes in ethanol, using ultrasonic disperse；Said mixture is calcined in air atmosphere, calcining heat is 300 DEG C, is forged
The burning time be 2h, a kind of new optic catalytic composite material is obtained after natural cooling, its X-ray powder diffraction figure (XRD) referring to
Fig. 7.Photocatalysis performance test process is that configuration concentration is the methylene blue solution 100mL of 20mg/L at room temperature, and adds this reality
Apply obtained composite photo-catalyst 25mg in example, open magnetic agitation, under visible light illumination, every 15min take supernatant 3~
5mL, tests its absorbance, and calculate its Visible Light Induced Photocatalytic rate after high speed centrifugation.Photocatalysis result shows, in 75min to Asia
The clearance of methyl blue can reach 89.61%, and its degradation curve to methylene blue is referring to Fig. 8.
Embodiment 8：BiVO4/K3V5O14The preparation of composite photo-catalyst
It is chosen at the K that at 500 DEG C prepared by constant temperature 12h3V5O14With pure phase BiVO4It is combined.Take BiVO4Mass fraction is
10% mixes in ethanol, using ultrasonic disperse；Said mixture is calcined in air atmosphere, calcining heat is 300 DEG C, is forged
The burning time be 2h, a kind of new optic catalytic composite material is obtained after natural cooling, its X-ray powder diffraction figure (XRD) referring to
Fig. 7.Using the identical method of same embodiment 7, photocatalysis result shows that the clearance in 75min to methylene blue can reach
87.73%.
When compositely proportional is 5% and 10%, BiVO4It is covered in K3V5O14Surface, has blocked its lamellar spacing, makes it to methylene
The blue adsorption rate of base has declined, and less amount of BiVO4There is not obvious contribution to Photocatalytic Degradation Property, so its
Removal efficiency has gradually declined.When compositely proportional reaches 20%, BiVO4Although to K3V5O14It has been blocked that, but it is more
BiVO4Its Photocatalytic Degradation Property is increased, therefore also improve the removal efficiency to methylene blue.
Embodiment 9：BiVO4/K3V5O14The preparation of composite photo-catalyst
It is chosen at the K that at 500 DEG C prepared by constant temperature 12h3V5O14With pure phase BiVO4It is combined.Take BiVO4Mass fraction is
20% mixes in ethanol, using ultrasonic disperse；Said mixture is calcined in air atmosphere, calcining heat is 300 DEG C, is forged
The burning time be 2h, a kind of new optic catalytic composite material is obtained after natural cooling, its X-ray powder diffraction figure (XRD) referring to
Fig. 7.Using the identical method of same embodiment 7, photocatalysis result shows that the clearance in 75min to methylene blue can reach
91.72%.
Embodiment 10：Regulation solution ph carries out photocatalytic degradation methylene blue
Configuration concentration is the methylene blue solution 100mL of 20mg/L at room temperature, and adds BiVO4Mass fraction is 20%
Composite photo-catalyst 25mg, adjusts solution ph and is equal to 3 with HCl, magnetic agitation is opened, under visible light illumination, every one section
Time takes 3~5mL of supernatant, high speed centrifugation post analysis.Under visible light to the degradation curve of methylene blue referring to Fig. 9.By Fig. 9
Understand, the clearance in 75min to methylene blue is 75.40%.
Embodiment 11：Regulation solution ph carries out photocatalytic degradation methylene blue
Configuration concentration is the methylene blue solution 100mL of 20mg/L at room temperature, and adds BiVO4Mass fraction is 20%
Composite photo-catalyst 25mg, it is neutral to adjust pH value of solution with HCl and NaOH, opens magnetic agitation, under visible light illumination, every
A period of time takes 3~5mL of supernatant, high speed centrifugation post analysis.Under visible light to the degradation curve of methylene blue referring to Fig. 9.
As shown in Figure 9, the clearance in 75min to methylene blue is 88.74%.
Embodiment 12：Regulation solution ph carries out photocatalytic degradation methylene blue
Configuration concentration is the methylene blue solution 100mL of 20mg/L at room temperature, and adds BiVO4Mass fraction is 20%
Composite photo-catalyst 25mg, adjusts solution ph and is equal to 9 with NaOH, magnetic agitation is opened, under visible light illumination, every one section
Time takes 3~5mL of supernatant, high speed centrifugation post analysis.Under visible light to the degradation curve of methylene blue referring to Fig. 9.By Fig. 9
Understand, the clearance in 75min to methylene blue is 87.60%.
Embodiment 13：Photocatalytic degradation methylene blue
Configuration concentration is the methylene blue solution 100mL of 20mg/L at room temperature, and adds BiVO4Mass fraction is 20%
Composite photo-catalyst 25mg, adjusts solution ph and is equal to 11 with NaOH, opens magnetic agitation, under visible light illumination, Mei Geyi
The section time takes 3~5mL of supernatant, high speed centrifugation post analysis.Under visible light to the degradation curve of methylene blue referring to Fig. 9.By
Fig. 9 understands that the clearance in 75min to methylene blue is 93.85%.
Embodiment 14：H2O2Cooperate with and adjust and carry out photocatalytic degradation methylene blue under the conditions of pH
Configuration concentration is the methylene blue solution 100mL of 20mg/L at room temperature, and adds BiVO4Mass fraction is 20%
Composite photo-catalyst 25mg, adjusts solution ph and is equal to 11 with NaOH, and the H that 0.5mL mass fractions are 30% is added dropwise2O2, open magnetic
Power is stirred, and under visible light illumination, 3~5mL of supernatant, high speed centrifugation post analysis is taken at regular intervals.It is to methylene blue
Referring to Figure 10, as shown in Figure 10, the clearance in 75min to methylene blue can reach degradation curve under visible light
93.98%.
Embodiment 15：H2O2Cooperate with and adjust and carry out photocatalytic degradation methylene blue under the conditions of pH
Configuration concentration is the methylene blue solution 100mL of 20mg/L at room temperature, and adds BiVO4Mass fraction is 20%
Composite photo-catalyst 25mg, adjusts solution ph and is equal to 11 with NaOH, and the H that 1mL mass fractions are 30% is added dropwise2O2, open magnetic force
Stirring, under visible light illumination, takes 3~5mL of supernatant, high speed centrifugation post analysis at regular intervals.It exists to methylene blue
Referring to Figure 10, as shown in Figure 10, the clearance in 75min to methylene blue can reach degradation curve under visible ray
96.71%.
Embodiment 16：H2O2Cooperate with and adjust and carry out photocatalytic degradation methylene blue under the conditions of pH
Configuration concentration is the methylene blue solution 100mL of 20mg/L at room temperature, and adds BiVO4Mass fraction is 20%
Composite photo-catalyst 25mg, adjusts solution ph and is equal to 11, and the H that mass fraction is 30% is added dropwise with NaOH2O2Make its volume integral
Number reaches 1.5%, i.e. 1.5mL, opens magnetic agitation, under visible light illumination, 3~5mL of supernatant is taken at regular intervals, high
Speed centrifugation post analysis.It, referring to Figure 10, as shown in Figure 10, works as light-catalyzed reaction to methylene blue degradation curve under visible light
During for 75min, methylene blue has been removed 98%.
Claims (10)
1. five vanadic acid tripotassium photochemical catalyst, it is characterised in that it is prepared by following methods：
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs raw material K sources and V sources respectively；
Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture；
Above-mentioned flaky mixture is calcined in air atmosphere, calcining heat is 400~700 DEG C, calcination time is 12~36h,
It is fully ground after natural cooling, you can obtain pure phase K3V5O14Photochemical catalyst.
2. five vanadic acid tripotassium photochemical catalyst as claimed in claim 1, it is characterised in that the V sources are vanadic anhydride and partially
Any one in ammonium vanadate or two kinds of mixtures.
3. five vanadic acid tripotassium photochemical catalyst as claimed in claim 1, it is characterised in that the K sources are potassium carbonate and potassium nitrate
In any one or two kinds of mixtures.
4. application of the five vanadic acid tripotassium photochemical catalyst as claimed in claim 1 in photocatalysis removal methylene blue.
5. application as claimed in claim 4, it is characterised in that the application includes that configuration methylene blue solution is simultaneously at room temperature
The five vanadic acid tripotassium photochemical catalyst photochemical catalyst is added, magnetic agitation is opened, catalytic degradation is carried out under visible light illumination anti-
Should.
6. pucherite/five vanadic acid tripotassium composite photo-catalyst, it is characterised in that it includes BiVO4And K3V5O14, the BiVO4's
Mass fraction is 5%-20%, the K3V5O14Mass fraction be 80%-95%.
7. the preparation method of pucherite/five vanadic acid tripotassium composite photo-catalyst as claimed in claim 6, it is characterised in that bag
Include following steps：
By chemical formula K3V5O14The stoichiometric proportion of middle element K and element V, weighs raw material K sources and V sources respectively；
Two kinds of reactant ground and mixeds are uniform, and powder compressing machine compressing tablet is utilized, obtain flaky mixture；
Above-mentioned flaky mixture is calcined in air atmosphere, calcining heat is 400~700 DEG C, calcination time is 12~36h,
It is fully ground after natural cooling, you can obtain pure phase K3V5O14Photochemical catalyst；
By K3V5O14With BiVO obtained in hydro-thermal method4Mix in ethanol, using ultrasonic disperse；
Said mixture is calcined in air atmosphere, calcining heat is 200-300 DEG C, and calcination time is 1-3h, natural cooling
After obtain the BiVO4/K3V5O14Composite photo-catalyst.
8. composite photo-catalyst as claimed in claim 7 is in H2O2Application in the lower photocatalysis removal methylene blue of collaboration.
9. application as claimed in claim 8, it is characterised in that the application includes that configuration methylene blue solution is simultaneously at room temperature
The composite photo-catalyst is added, solution initial pH value is adjusted, while H is added dropwise2O2, magnetic agitation is opened, under visible light illumination
Carry out catalytic degradation reaction.
10. application as claimed in claim 9, it is characterised in that solution initial pH value is 3~11, and catalyst charge is
0.25g/L, H2O2The percent by volume that addition accounts for solution is 0.5~1.5%, and the catalytic degradation reaction time is 60~180min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876820A (en) * | 2019-03-13 | 2019-06-14 | 重庆师范大学 | A kind of 17 water two protonation hydration boron vanadic acid nickel potassium and its preparation with photocatalysis performance |
| CN113219123A (en) * | 2021-02-09 | 2021-08-06 | 重庆交通大学 | Light-storage-assisted photocatalytic composite material catalytic effect detection method and screening method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238761A (en) * | 1991-07-29 | 1993-08-24 | The United States Of America As Represented By The Secretary Of The Air Force | Cathode material for electrochemical cells |
| CN1611641A (en) * | 2003-10-30 | 2005-05-04 | 中国科学院福建物质结构研究所 | Birefraction functional material potassium pentavanadate crystal |
| CN101089241A (en) * | 2006-06-13 | 2007-12-19 | 中国科学院福建物质结构研究所 | Growing method of potassium vanadate non-linear optical crystal |
| US20150252490A1 (en) * | 2011-11-04 | 2015-09-10 | University Of Houston System | System and Method for Monolithic Crystal Growth |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5238761A (en) * | 1991-07-29 | 1993-08-24 | The United States Of America As Represented By The Secretary Of The Air Force | Cathode material for electrochemical cells |
| CN1611641A (en) * | 2003-10-30 | 2005-05-04 | 中国科学院福建物质结构研究所 | Birefraction functional material potassium pentavanadate crystal |
| CN101089241A (en) * | 2006-06-13 | 2007-12-19 | 中国科学院福建物质结构研究所 | Growing method of potassium vanadate non-linear optical crystal |
| US20150252490A1 (en) * | 2011-11-04 | 2015-09-10 | University Of Houston System | System and Method for Monolithic Crystal Growth |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876820A (en) * | 2019-03-13 | 2019-06-14 | 重庆师范大学 | A kind of 17 water two protonation hydration boron vanadic acid nickel potassium and its preparation with photocatalysis performance |
| CN113219123A (en) * | 2021-02-09 | 2021-08-06 | 重庆交通大学 | Light-storage-assisted photocatalytic composite material catalytic effect detection method and screening method |
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