CN106732327A - A kind of mesoporous BiOCl/Bi2O3Composite granule and its preparation method and application - Google Patents
A kind of mesoporous BiOCl/Bi2O3Composite granule and its preparation method and application Download PDFInfo
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- CN106732327A CN106732327A CN201611059937.1A CN201611059937A CN106732327A CN 106732327 A CN106732327 A CN 106732327A CN 201611059937 A CN201611059937 A CN 201611059937A CN 106732327 A CN106732327 A CN 106732327A
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000008187 granular material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002131 composite material Substances 0.000 claims abstract description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 25
- 150000001621 bismuth Chemical class 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 230000001788 irregular Effects 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000013335 mesoporous material Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000001802 infusion Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000011017 operating method Methods 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 description 12
- 239000003643 water by type Substances 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 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 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
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Abstract
The invention provides a kind of mesoporous BiOCl/Bi2O3Composite granule and its preparation method and application, Bi is prepared first with hydro-thermal method2O3Crystallite, then to obtained Bi2O3Middle addition HCl carries out ultrasonic reaction, realizes BiOCl and Bi2O3It is compound.The present invention combines hydro-thermal method, hydrochloric acid infusion method and ultrasonic and mesoporous BiOCl/Bi has been obtained2O3Composite granule, the method has that the reaction time is short, flow is few, operating procedure is simple, reaction condition is gentle, cost is relatively low, advantages of environment protection, is a kind of succinct, green BiOCl/Bi2O3Raw powder's production technology.Obtained mesoporous BiOCl/Bi of the invention2O3The overall pattern of composite granule, with the characterization of adsorption to organic pollution higher, can effectively improve pure phase Bi in mesoporous spherical2O3The photocatalysis effect of powder, with good researching value and application prospect.
Description
Technical field
The invention belongs to field of functional materials, it is related to a kind of mesoporous BiOCl/Bi2O3Composite granule and preparation method thereof and should
With.
Background technology
Deepened continuously with industrialized, growing environmental problem has gradually threatened the sustainable development of human society
Exhibition.Conductor photocatalysis are a kind of extraordinary selections for solving these environmental problems, as it means that can be using one kind
The mode of green directly utilizes sunshine degradation of contaminant.Play main in view of the photo-generated carrier in photocatalytic process
Effect, an activity photochemical catalyst high should possess relatively wide spectral absorption scope and quantum yield very high.By two
Planting can be combined with the narrow gap semiconductor of matching, and transfer of the photo-generated carrier between two kinds of compound semiconductors will the amount of raising
Sub- yield.
BiOCl and Bi2O3It is the very popular narrow gap semiconductor photochemical catalyst of mesh first two research.Bi2O3Because of band-gap energy
Adjustability, high-performance oxonium ion conductance and it is widely used in optical thin film, photovoltaic cell, combustion with characteristics such as various crystal formations
The fields such as material battery, chemical sensor and catalysis.Bi2O3As a kind of important functional material, because narrower with energy gap
(2.8eV or so), the advantages of Lacking oxygen is more, photoconductive property is good, it is set to have utilization rate higher, oxidability to sunshine
By force, it is a kind of with visible light-responded conductor photocatalysis material.BiOCl is a kind of new photochemical catalyst, and it is oxyhalogen
Simplest a member is constituted in Hua Bi families, crystal is by [Bi2O2] and [Cl] construction unit composition, with layer structure.It is this
Layer structure contributes to the transfer of the photo-generated carrier in photocatalytic process, improves the quantum efficiency of photochemical catalyst.Just because of
BiOCl layer structures and suitable energy gap, preferable photocatalytic activity becomes a kind of very potential light and urges
Change material.
So far, BiOCl and Emission in Cubic Bi is realized using hydrochloric acid infusion method combination ultrasonic method2O3Compound work is not yet
Appear in the newspapers, also no patent and document report are crossed and prepare mesoporous BiOCl/Bi2O3The method of composite granule.
The content of the invention
It is an object of the invention to provide a kind of mesoporous BiOCl/Bi2O3Composite granule and its preparation method and application, the party
The method reaction time is short, and technological process is simple, obtained BiOCl/Bi2O3Composite granule is special with absorption higher in mesoporous spherical
Property, can effectively improve pure phase Bi2O3The photocatalysis effect of powder, with good researching value and application prospect.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of mesoporous BiOCl/Bi2O3The preparation method of composite granule, comprises the following steps：
Step 1, by Bi (NO3)3·5H2O is dissolved in deionized water, is stirred, and obtains bismuth salt solution；By NH4VO3It is dissolved in
In ionized water, stir, obtain vanadic salts solution；
Step 2, by bismuth salt solution and vanadic salts solution according to Bi:V=1:1 mol ratio mixing, stirs, and is mixed
Close liquid；
Step 3, to B mL NaOH solutions are added in A mL mixed liquors, stirring reaction and releases ammonia, before obtaining at room temperature
Drive liquid, wherein A:B=20:(10~20)；
Step 4, precursor liquid is poured into hydrothermal reaction kettle, 6~12h of hydro-thermal reaction at 180~220 DEG C, after having reacted
Room temperature is naturally cooled to, by product washing, is dried, obtain Emission in Cubic Bi2O3Crystallite；
Step 5, Emission in Cubic Bi is added by hydrochloric acid2O3In crystallite, carry out ultrasonic reaction at room temperature, the wherein HCl in hydrochloric acid with
Bi2O3Mol ratio be (3.8~4.2):1, product is washed, dried by reaction after terminating, and obtains mesoporous BiOCl/Bi2O3It is compound
Powder.
The concentration of bismuth salt solution and vanadic salts solution is 0.1~0.15mol/L in the step 1.
The concentration of NaOH solution is 3.5~4.5mol/L in the step 3.
The time of stirring reaction is 25~35min in the step 3.
Before the step 4 is carried out, first to deionized water is added in C mL precursor liquids, the volume constant volume for making precursor liquid is D
ML, wherein C:D=(30~40):45.
Precursor liquid is poured into hydrothermal reaction kettle in the step 4, the filling rate of hydrothermal reaction kettle is 75~80%.
Absolute ethyl alcohol and deionized water washing reaction product are used in the step 4 and step 5；Drying in the step 4
Condition is that 10~12h is dried at 70~80 DEG C, and the drying condition in the step 5 is that 8~10h is dried at 80~85 DEG C.
The concentration of hydrochloric acid is 0.45~0.55mol/L in the step 5, and the time of ultrasonic reaction is 50~60min.
Described mesoporous BiOCl/Bi2O3Mesoporous BiOCl/Bi obtained in the preparation method of composite granule2O3Composite granule,
The composite granule is Tetragonal BiOCl and Emission in Cubic Bi2O3Two-phase coexistent structure, and BiOCl and Bi2O3Both form hetero-junctions
Structure；The pattern of the composite granule is the Bi of irregular spherical structure2O3Plane of crystal has the BiOCl crystal of sheet；The composite powder
Body is mesoporous material, and mesoporous pore size is 20~80nm.
Described mesoporous BiOCl/Bi2O3Composite granule as adsorbent adsorb organic pollution in terms of and processing environment
Application in terms of sewage.
Compared with prior art, the invention has the advantages that：
The mesoporous BiOCl/Bi that the present invention is provided2O3The preparation method of composite granule, first with Bi (NO3)3·5H2O and
NH4VO3For raw material prepares precursor liquid, Emission in Cubic Bi is prepared using hydro-thermal method2O3Crystallite.Again to obtained Bi2O3Add in crystallite
Entering HCl carries out ultrasonic reaction, finally realizes BiOCl and Bi2O3It is compound.The present invention combines traditional hydro-thermal method, hydrochloric acid infusion method
And ultrasonic has been obtained mesoporous BiOCl/Bi2O3Composite granule, the method has that the reaction time is short, flow is few, operative employee
Skill is simple, reaction condition is gentle, cost is relatively low, advantages of environment protection, is a kind of succinct, green BiOCl/Bi2O3Composite powder
The preparation method of body.
The present invention is successfully prepared mesoporous BiOCl/Bi2O3Composite granule, obtained mesoporous BiOCl/Bi2O3Composite granule
It is Tetragonal BiOCl and Emission in Cubic Bi2O3Two-phase coexistent structure, and BiOCl and Bi2O3Both form heterojunction structure；The present invention
Obtained mesoporous BiOCl/Bi2O3The overall pattern of composite granule is in mesoporous spherical, specially irregular mesoporous sphere structure
Bi2O3Plane of crystal has the BiOCl crystal of sheet.Obtained mesoporous BiOCl/Bi of the invention2O3Composite granule has higher right
The characterization of adsorption of organic pollution, can effectively improve pure phase Bi2O3The photocatalysis effect of powder, can exist as adsorbent
The aspect such as absorption organic pollution aspect and processing environment sewage is applied, with good researching value and application prospect.
Brief description of the drawings
Fig. 1 is mesoporous BiOCl/Bi prepared by the present invention2O3The XRD diffracting spectrums of composite granule；
Fig. 2 is mesoporous BiOCl/Bi prepared by the present invention2O3The SEM figures of composite granule, wherein b possesses enlarged drawing for a's；
Fig. 3 is mesoporous BiOCl/Bi prepared by the present invention2O3The N of composite granule2Adsorption-desorption isothermal curve, illustration is hole
Footpath distribution curve；
Fig. 4 is mesoporous BiOCl/Bi prepared by the present invention2O3Degradation rate-the time graph of composite granule rhodamine B degradation.
Specific embodiment
The present invention is described further with currently preferred specific embodiment below in conjunction with the accompanying drawings, raw material is analysis
It is pure.
Embodiment 1：
Step 1, by Bi (NO3)3·5H2O is dissolved in 10mL deionized waters, is stirred, and obtains concentration for 0.13mol/L
Bismuth salt solution；By NH4VO3It is dissolved in 10mL deionized waters, stirs, obtains the vanadic salts solution that concentration is 0.13mol/L；
Step 2, by bismuth salt solution and vanadic salts solution according to Bi:V=1:1 mol ratio mixing (bismuth salt solution and vanadic salts
Each 10mL of solution), stir, obtain 20mL mixed liquors；
Step 3, to adding 10mL concentration to be NaOH, the stirring reaction 30min of 4mol/L in 20mL mixed liquors, releases ammonia
Gas, obtains 30mL precursor liquids；
Step 4, to 15mL distilled water is added in 30mL precursor liquids, the volume constant volume for making precursor liquid is 45mL；
Step 5, the precursor liquid after constant volume is put into hydrothermal reaction kettle, it is ensured that the filling rate of hydrothermal reaction kettle is 80%,
The hydro-thermal reaction 12h at 180 DEG C.Room temperature is naturally cooled to after having reacted, is reacted with deionized water and washes of absolute alcohol respectively
Product, until the supernatant after washing is in neutrality, then dries 12h by the product after washing at 70 DEG C, obtains Emission in Cubic
Bi2O3Crystallite.
Step 6, by concentration for the hydrochloric acid of 0.5mol/L is added to obtained Emission in Cubic Bi2O3In crystallite, ultrasonic reaction is carried out
HCl and Bi in 60min, wherein hydrochloric acid2O3Mol ratio be 3.96:1, reaction uses deionized water and anhydrous second respectively after terminating
Alcohol cleans product, until the supernatant after washing is in neutrality, then the product after washing is dried into 10h at 80 DEG C,
Obtain mesoporous BiOCl/Bi2O3Composite granule.
Embodiment 2：
Step 1, by Bi (NO3)3·5H2O is dissolved in 10mL deionized waters, is stirred, and obtains concentration for 0.15mol/L
Bismuth salt solution；By NH4VO3It is dissolved in 10mL deionized waters, stirs, obtains the vanadic salts solution that concentration is 0.15mol/L；
Step 2, by bismuth salt solution and vanadic salts solution according to Bi:V=1:1 mol ratio mixing (bismuth salt solution and vanadic salts
Each 10mL of solution), stir, obtain 20mL mixed liquors；
Step 3, to adding 15mL concentration to be NaOH, the stirring reaction 25min of 3.8mol/L in 20mL mixed liquors, releases ammonia
Gas, obtains 35mL precursor liquids；
Step 4, to the distilled water that 10mL is added in 35mL precursor liquids, the volume constant volume for making precursor liquid is 45mL；
Step 5, the precursor liquid after constant volume is put into hydrothermal reaction kettle, it is ensured that the filling rate of hydrothermal reaction kettle is 75%,
The hydro-thermal reaction 10h at 190 DEG C.Room temperature is naturally cooled to after having reacted, is reacted with deionized water and washes of absolute alcohol respectively
Product, until the supernatant after washing is in neutrality, then dries 11h by product at 75 DEG C, obtains Emission in Cubic Bi2O3Crystallite.
Step 6, by concentration for the hydrochloric acid of 0.45mol/L is added to obtained Emission in Cubic Bi2O3In crystallite, carry out ultrasonic anti-
Answer 52min, HCl and Bi wherein in hydrochloric acid2O3Mol ratio be 3.8:1, reaction uses deionized water and anhydrous second respectively after terminating
Alcohol cleans product, until the supernatant after washing is in neutrality, then the product after washing is dried into 10h at 84 DEG C,
Obtain mesoporous BiOCl/Bi2O3Composite granule.
Embodiment 3：
Step 1, by Bi (NO3)3·5H2O is dissolved in 10mL deionized waters, is stirred, and obtains concentration for 0.12mol/L
Bismuth salt solution；By NH4VO3It is dissolved in 10mL deionized waters, stirs, obtains the vanadic salts solution that concentration is 0.12mol/L；
Step 2, by bismuth salt solution and vanadic salts solution according to Bi:V=1:1 mol ratio mixing (bismuth salt solution and vanadic salts
Each 10mL of solution), stir, obtain 20mL mixed liquors；
Step 3, to adding 20mL concentration to be NaOH, the stirring reaction 35min of 3.5mol/L in 20mL mixed liquors, releases ammonia
Gas, obtains 40mL precursor liquids；
Step 4, to the distilled water that 5mL is added in 40mL precursor liquids, the volume constant volume for making precursor liquid is 45mL；
Step 5, the precursor liquid after constant volume is put into hydrothermal reaction kettle, it is ensured that the filling rate of hydrothermal reaction kettle is 78%,
The hydro-thermal reaction 8h at 200 DEG C.Room temperature is naturally cooled to after having reacted, is reacted with deionized water and washes of absolute alcohol produce respectively
Thing, until the supernatant after washing is in neutrality, then dries 10h by product at 80 DEG C, obtains Emission in Cubic Bi2O3Crystallite.
Step 6, by concentration for the hydrochloric acid of 0.55mol/L is added to obtained Emission in Cubic Bi2O3In crystallite, carry out ultrasonic anti-
Answer 55min, HCl and Bi wherein in hydrochloric acid2O3Mol ratio be 4.12:1, reaction terminate after respectively with deionized water and anhydrous
Ethanol cleans product, until the supernatant after washing is in neutrality, then the product after washing is dried into 9h at 82 DEG C,
Obtain mesoporous BiOCl/Bi2O3Composite granule.
Embodiment 4：
Step 1, by Bi (NO3)3·5H2O is dissolved in 10mL deionized waters, is stirred, and obtains concentration for 0.14mol/L
Bismuth salt solution；By NH4VO3It is dissolved in 10mL deionized waters, stirs, obtains the vanadic salts solution that concentration is 0.14mol/L；
Step 2, by bismuth salt solution and vanadic salts solution according to Bi:V=1:1 mol ratio mixing (bismuth salt solution and vanadic salts
Each 10mL of solution), stir, obtain 20mL mixed liquors；
Step 3, to adding 12mL concentration to be NaOH, the stirring reaction 32min of 4.5mol/L in 20mL mixed liquors, releases ammonia
Gas, obtains 32mL precursor liquids；
Step 4, to the distilled water that 13mL is added in 32mL precursor liquids, the volume constant volume for making precursor liquid is 45mL；
Step 5, the precursor liquid after constant volume is put into hydrothermal reaction kettle, it is ensured that the filling rate of hydrothermal reaction kettle is 80%,
The hydro-thermal reaction 7h at 210 DEG C.Room temperature is naturally cooled to after having reacted, is reacted with deionized water and washes of absolute alcohol produce respectively
Thing, until the supernatant after washing is in neutrality, then dries 11.5h by product at 72 DEG C, obtains Emission in Cubic Bi2O3Crystallite.
Step 6, by concentration for the hydrochloric acid of 0.48mol/L is added to obtained Emission in Cubic Bi2O3In crystallite, carry out ultrasonic anti-
Answer 58min, HCl and Bi wherein in hydrochloric acid2O3Mol ratio be 4:1, reaction uses deionized water and absolute ethyl alcohol respectively after terminating
Cleaning product, until the supernatant after washing is in neutrality, then dries 8.5h by the product after washing at 81 DEG C, obtains
To mesoporous BiOCl/Bi2O3Composite granule.
Embodiment 5
Step 1, by Bi (NO3)3·5H2O is dissolved in 10mL deionized waters, is stirred, and obtains concentration for 0.11mol/L
Bismuth salt solution；By NH4VO3It is dissolved in 10mL deionized waters, stirs, obtains the vanadic salts solution that concentration is 0.11mol/L；
Step 2, by bismuth salt solution and vanadic salts solution according to Bi:V=1:1 mol ratio mixing (bismuth salt solution and vanadic salts
Each 10mL of solution), stir, obtain 20mL mixed liquors；
Step 3, to adding 18mL concentration to be NaOH, the stirring reaction 28min of 4mol/L in 20mL mixed liquors, releases ammonia
Gas, obtains 38mL precursor liquids；
Step 4, to the distilled water that 7mL is added in 38mL precursor liquids, the volume constant volume for making precursor liquid is 45mL；
Step 5, the precursor liquid after constant volume is put into hydrothermal reaction kettle, it is ensured that the filling rate of hydrothermal reaction kettle is 80%,
The hydro-thermal reaction 6h at 220 DEG C.Room temperature is naturally cooled to after having reacted, is reacted with deionized water and washes of absolute alcohol produce respectively
Thing, until the supernatant after washing is in neutrality, then dries 10.5h by product at 78 DEG C, obtains Emission in Cubic Bi2O3Crystallite.
Step 6, by concentration for the hydrochloric acid of 0.52mol/L is added to obtained Emission in Cubic Bi2O3In crystallite, carry out ultrasonic anti-
Answer 50min, HCl and Bi wherein in hydrochloric acid2O3Mol ratio be 4.05:1, reaction terminate after respectively with deionized water and anhydrous
Ethanol cleans product, until the supernatant after washing is in neutrality, then the product after washing is dried into 8h at 85 DEG C,
Obtain mesoporous BiOCl/Bi2O3Composite granule.
Embodiment 6
Step 1, by Bi (NO3)3·5H2O is dissolved in 10mL deionized waters, is stirred, and it is 0.1mol/L's to obtain concentration
Bismuth salt solution；By NH4VO3It is dissolved in 10mL deionized waters, stirs, obtains the vanadic salts solution that concentration is 0.1mol/L；
Step 2, by bismuth salt solution and vanadic salts solution according to Bi:V=1:1 mol ratio mixing (bismuth salt solution and vanadic salts
Each 10mL of solution), stir, obtain 20mL mixed liquors；
Step 3, to adding 16mL concentration to be NaOH, the stirring reaction 30min of 4.2mol/L in 20mL mixed liquors, releases ammonia
Gas, obtains 36mL precursor liquids；
Step 4, to the distilled water that 9mL is added in 36mL precursor liquids, the volume constant volume for making precursor liquid is 45mL；
Step 5, the precursor liquid after constant volume is put into hydrothermal reaction kettle, it is ensured that the filling rate of hydrothermal reaction kettle is 80%,
The hydro-thermal reaction 11h at 185 DEG C.Room temperature is naturally cooled to after having reacted, is reacted with deionized water and washes of absolute alcohol respectively
Product, until the supernatant after washing is in neutrality, then dries 12h by product at 70 DEG C, obtains Emission in Cubic Bi2O3Crystallite.
Step 6, by concentration for the hydrochloric acid of 0.5mol/L is added to obtained Emission in Cubic Bi2O3In crystallite, ultrasonic reaction is carried out
HCl and Bi in 60min, wherein hydrochloric acid2O3Mol ratio be 4.2:1, reaction uses deionized water and absolute ethyl alcohol respectively after terminating
Cleaning product, until the supernatant after washing is in neutrality, then dries 9.5h by the product after washing at 83 DEG C, obtains
To mesoporous BiOCl/Bi2O3Composite granule.
Fig. 1 is mesoporous BiOCl/Bi obtained in the present invention2O3The XRD of composite granule, it can be seen that 2 θ be 27 ° and 31 °
Place have two less diffraction maximums respectively with pure phase Bi2O3(310) and (222) crystallographic plane diffraction peak match, illustrate composite granule
In contain Bi2O3.It is also seen that having many diffraction maximums and pure phase BiOCl kissings between being 24 ° or so and 32 °~50 ° in 2 θ
Close, illustrate that the content of BiOCl in the powder after being combined is more.There is no the presence for finding other diffraction maximums in whole collection of illustrative plates.It is logical
Analysis XRD results are crossed, to be may certify that and be successfully realized BiOCl and Bi by hydrochloric acid infusion method2O3It is compound.
Fig. 2 is mesoporous BiOCl/Bi obtained in the present invention2O3The SEM figures of composite granule, it can be seen that composite granule is not advise
Then spherical structure (Fig. 2 a), irregular spherical structure Bi2O3There is (Fig. 2 b) in the BiOCl that there is sheet on surface, illustrates by salt acidleach
Bubble method, BiOCl and Bi2O3Complete compound.
Fig. 3 is mesoporous BiOCl/Bi prepared by the present invention2O3The N of composite granule2Adsorption-desorption isothermal curve, illustration is hole
Footpath distribution curve；It can be seen that mesoporous BiOCl/Bi2O3The N of composite granule2Adsorption-desorption isothermal belongs to IUPAC regulations
Typical IV type adsorption isotherms, are 0.48-1.00 (P/P in relative pressure0) in the range of there is obvious hysteresis loop, it was demonstrated that
Obtained mesoporous BiOCl/Bi of the invention2O3Composite granule mesoporous pore size is distributed in 20-80nm scopes, with typical mesoporous
Design feature, illustrates the mesoporous BiOCl/Bi of present invention preparation2O3Composite granule belongs to mesoporous material.
Fig. 4 is mesoporous BiOCl/Bi prepared by the present invention2O3Degradation rate-the time graph of composite granule rhodamine B degradation,
It can be seen that mesoporous BiOCl/Bi2O3The suction-operated of composite granule is protruded, after the dark suction-operateds of 30min, the absorption to RhB
Reach 56.22%, hence it is evident that better than pure Bi2O3And BiOCl.
One embodiment of the present invention is the foregoing is only, is not all of or unique implementation method, this area is common
Any equivalent conversion that technical staff is taken technical solution of the present invention by reading description of the invention, is the present invention
Claim covered.
Claims (10)
1. a kind of mesoporous BiOCl/Bi2O3The preparation method of composite granule, it is characterised in that comprise the following steps：
Step 1, by Bi (NO3)3·5H2O is dissolved in deionized water, is stirred, and obtains bismuth salt solution；By NH4VO3It is dissolved in deionization
In water, stir, obtain vanadic salts solution；
Step 2, by bismuth salt solution and vanadic salts solution according to Bi:V=1:1 mol ratio mixing, stirs, and is mixed
Liquid；
Step 3, to B mL NaOH solutions are added in A mL mixed liquors, stirring reaction and releases ammonia at room temperature, obtains forerunner
Liquid, wherein A:B=20:(10~20)；
Step 4, precursor liquid is poured into hydrothermal reaction kettle, 6~12h of hydro-thermal reaction at 180~220 DEG C, natural after having reacted
Room temperature is cooled to, by product washing, is dried, obtain Emission in Cubic Bi2O3Crystallite；
Step 5, Emission in Cubic Bi is added by hydrochloric acid2O3In crystallite, ultrasonic reaction, HCl and Bi wherein in hydrochloric acid are carried out at room temperature2O3
Mol ratio be (3.8~4.2):1, product is washed, dried by reaction after terminating, and obtains mesoporous BiOCl/Bi2O3Composite granule.
2. mesoporous BiOCl/Bi according to claim 12O3The preparation method of composite granule, it is characterised in that：The step
The concentration of bismuth salt solution and vanadic salts solution is 0.1~0.15mol/L in 1.
3. mesoporous BiOCl/Bi according to claim 12O3The preparation method of composite granule, it is characterised in that：The step
The concentration of NaOH solution is 3.5~4.5mol/L in 3.
4. mesoporous BiOCl/Bi according to claim 12O3The preparation method of composite granule, it is characterised in that：The step
The time of stirring reaction is 25~35min in 3.
5. mesoporous BiOCl/Bi according to claim 12O3The preparation method of composite granule, it is characterised in that：The step
Before 4 are carried out, first to deionized water is added in C mL precursor liquids, the volume constant volume for making precursor liquid is D mL, wherein C:D=(30~
40):45。
6. mesoporous BiOCl/Bi according to claim 12O3The preparation method of composite granule, it is characterised in that：The step
Precursor liquid is poured into hydrothermal reaction kettle in 4, the filling rate of hydrothermal reaction kettle is 75~80%.
7. mesoporous BiOCl/Bi according to claim 12O3The preparation method of composite granule, it is characterised in that：The step
4 and step 5 in use absolute ethyl alcohol and deionized water washing reaction product；Drying condition in the step 4 is at 70~80 DEG C
10~12h of lower drying, the drying condition in the step 5 is that 8~10h is dried at 80~85 DEG C.
8. mesoporous BiOCl/Bi according to claim 12O3The preparation method of composite granule, it is characterised in that：The step
The concentration of hydrochloric acid is 0.45~0.55mol/L in 5, and the time of ultrasonic reaction is 50~60min.
9. the mesoporous BiOCl/Bi according to any one in claim 1-82O3The preparation method of composite granule is obtained to be situated between
Hole BiOCl/Bi2O3Composite granule, it is characterised in that：The composite granule is Tetragonal BiOCl and Emission in Cubic Bi2O3Two-phase coexistent
Structure, and BiOCl and Bi2O3Both form heterojunction structure；The pattern of the composite granule is the Bi of irregular spherical structure2O3
Plane of crystal has the BiOCl crystal of sheet；The composite granule is mesoporous material, and mesoporous pore size is 20~80nm.
10. the mesoporous BiOCl/Bi described in claim 92O3Composite granule as adsorbent adsorb organic pollution in terms of and
Application in terms of processing environment sewage.
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| CN108187699A (en) * | 2018-01-31 | 2018-06-22 | 安徽师范大学 | BiOX-Bi4O5X2Hetero-junctions and its preparation method and application |
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