CN107126953A - This compound nano composite of viral and its preparation method and application in a kind of bismuth/non-stoichiometric is difficult to understand - Google Patents
This compound nano composite of viral and its preparation method and application in a kind of bismuth/non-stoichiometric is difficult to understand Download PDFInfo
- Publication number
- CN107126953A CN107126953A CN201710358220.5A CN201710358220A CN107126953A CN 107126953 A CN107126953 A CN 107126953A CN 201710358220 A CN201710358220 A CN 201710358220A CN 107126953 A CN107126953 A CN 107126953A
- Authority
- CN
- China
- Prior art keywords
- bismuth
- stoichiometric
- preparation
- viral
- nano composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 51
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 42
- 230000003612 virological effect Effects 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 9
- 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
- 235000015393 sodium molybdate Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 230000001699 photocatalysis Effects 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 239000000356 contaminant Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 45
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 229940106691 bisphenol a Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 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 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 235000016768 molybdenum Nutrition 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- -1 Bi2MoO6 Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- GTXSRWDSFFWONO-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi+3] GTXSRWDSFFWONO-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AQRDGTBNWBTFKJ-UHFFFAOYSA-N molybdenum;dihydrate Chemical compound O.O.[Mo] AQRDGTBNWBTFKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/16—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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/50—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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 invention discloses this compound nano composite of viral and its preparation method and application in a kind of bismuth/non-stoichiometric Austria.The composite includes Bi/Bi3.64Mo0.36O6.55And Bi/Bi3.84W0.16O6.24.The present invention regulates and controls the reproducibility of gained reaction system using sodium hydroxide first, by solvent-thermal method controlledly synthesis different composite than bismuth be combined Emission in Cubic it is non-metering than bismuth molybdate nano composite material, products therefrom pattern is homogeneous, particle diameter is smaller, it is to avoid nano particle pattern made from some methods is uneven or the problems such as larger particle diameter；Pass through alkali adjustment and control system reproducibility, it is not necessary to extra to add reducing substances and surfactant etc., it is to avoid the generation of secondary pollution, simplify synthesis technique, environmental protection effectively reduces production cost, the large-scale production of product can be achieved.
Description
Technical field
The invention belongs to chemical, functional material, technical field of nano material, and in particular to a kind of bismuth is combined non-chemical
Metering is than nano composite material of this compound of viral and its preparation method and application in Austria.
Background technology
Bismuth based material is widely used in electron ceramic material, electrolyte, photoelectricity material due to its special physicochemical property
In each field such as material, sensor, microelectronic element, high temperature superconducting materia, catalyst, ferroelectric material, while being additionally operable to fire proofing wood
The field such as material, high refractive index glass, nuclear engineering glass manufacture and nuclear reactor fuel.Viral this type oxidation in wherein a series of Austria
Thing gradually causes concern, and this kind of compound is by perovskite [An-1BnO3n+1] layer and fluorite layer be alternately arranged and form.In these Austria
This type oxide of viral has excellent PhotoelectrochemicalProperties Properties, thus is attracted wide attention as photochemical catalyst.This kind of catalysis
The light-catalyzed reaction of agent is main to be carried out in interlayer, and its activity changes also with the difference of interlayer ion；Such as Bi2MoO6、
Bi2WO6、BiVO4Deng.It need to be carried from the photocatalysis performance for having this type oxide of viral in document report, Austria at present
It is high.
It is non-metering than compound, due to the presence of crystal defect so that it has special light, electricity, sound, magnetic, power, hot
Energy.Thus synthesize non-metering ratio it is difficult to understand in viral this type oxide there is important theory significance and real value.Such as Xie
(Journal of Alloys and Compounds,2010,503:159-162) report with five water bismuth nitrates and molybdate dihydrate
Sour sodium is reactant, using two-step method, bismuth source, molybdenum source is dispersed in salpeter solution under first normal temperature, then dried, then will mixing
Thing and nitrate mixed grinding, then calcine 2h by a certain percentage, prepare Bi3.64Mo0.36O6.55Nanosphere.This method and step is numerous
Multiple, complex operation is unfavorable for popularization and application.And Chinese patent (application publication number CN103418333A) discloses one kind
Bi3.64Mo0.36O6.55The preparation method of nano-particle, this method, by adjusting the pH value of solution, is obtained in aqueous phase
Bi3.64Mo0.36O6.55Nano-particle, but the Bi of pure phase3.64Mo0.36O6.55Due to the limitation of itself characteristic, photo-generated carrier
Utilization ratio is low, it is impossible to embody higher photocatalytic activity.Be conducive to lifting material by constructing composite nano material
Photoelectric properties, so as to lift the photocatalysis performance of material.Wherein by Metal Supported directional separation photo-generated carrier to lift material
Material photocatalysis performance method largely reported, but in alcohol phase system by NaOH regulation and control generate Bi be combined it is non-metering
Synthetic method than viral in Austria this type oxide composite is reported.
The content of the invention
It is an object of the invention to provide the nano combined material that a kind of bismuth is combined this compound of viral in non-stoichiometric Austria
Material, the material has stronger photocatalytic activity, and application is wider, and the preparation method being related to is simple, reaction condition gentle,
It is repeated strong, it is adaptable to the application field such as photocatalytic degradation organic matter.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of bismuth is combined the nano composite material of this compound of viral in non-stoichiometric Austria, and its chemical expression is
Bi/Bi3.64Mo0.36O6.55Or Bi/Bi3.84W0.16O6.24, it by non-stoichiometric Bi3.64Mo0.36O6.55Or
Bi3.84W0.16O6.24Particle surface deposited metal Bi is formed, and its pattern is homogeneous nano particle, and average grain diameter is 20~30nm.
A kind of above-mentioned bismuth is combined the preparation method of the nano composite material of this compound of viral in non-stoichiometric Austria, bag
Include following steps：Bismuth nitrate and the dissolving of sodium molybdate or sodium tungstate are scattered in ethylene glycol (EG) and are well mixed to obtain mixed liquor I,
Then add in ethanol and alkali lye, stir into gained mixed liquor I, then gained reaction solution is subjected to hydro-thermal reaction, so
Centrifuge washing removes residual impurity afterwards, then through drying, cooling, produces the bismuth and be combined this chemical combination of viral in non-stoichiometric Austria
The nano composite material of thing.
In such scheme, the mol ratio of the bismuth nitrate and sodium molybdate or bismuth nitrate and sodium tungstate is 2:1.
In such scheme, the concentration of bismuth nitrate is 0.1~0.5mol/L in the mixed liquor I.
In such scheme, the volume ratio of the ethylene glycol and ethanol is (2~1):1.
In such scheme, the alkali lye is sodium hydroxide or potassium hydroxide solution, and sodium hydroxide or potassium hydroxide are in reaction
Concentration is 0.35~0.65mol/L in solution.
In such scheme, the hydrothermal temperature is 140~200 DEG C, and the time is 10~16h.
It is synthesized present invention also offers the application in the composite under visible light degradable organic pollutant field
Bismuth be combined non-stoichiometric it is difficult to understand in viral this compound nano composite material, because its small size and bismuth with elementary are to electronics
Orientation transfer, further increases the utilization ratio of photo-generated carrier, so as to show excellent photocatalysis performance.
The present invention synthesis mechanism be：The present invention uses mol ratio for 2:1 bismuth source and molybdenum source (or tungsten source), in preparation
Appropriate sodium hydroxide is added in ethanol/glycol system, the dissociation of alcohol is regulated and controled by changing concentration hydroxy in solvent so that
Bi in system3+Polymerization forms high polymer [BinOn]n+；Then under hydrothermal reaction condition, molybdenum (or tungsten) acid ion in solution
([Bi is reacted with bismuth oxonium ionnOn]n+With MoO4 -Or WO4 -Reaction), many molybdenums of bismuth (or tungsten) are few, and then generate non-stoichiometric
Bismuth molybdate (Bi3.64Mo0.36O6.55) or bismuth tungstate (Bi3.84W0.16O6.24)；In addition, with solution amount of sodium hydroxide increase,
The reproducibility of ethylene glycol gradually strengthens, and the bismuth oxonium ion in solution is reduced and is deposited on the molybdic acid for the non-stoichiometric to be formed
Bismuth (bismuth tungstate) particle surface, that is, obtain described Bi/Bi3.64Mo0.36O6.55Or Bi/Bi3.84W0.16O6.24Nano particle.
The present invention beneficial outcomes be：
1) this patent proposes and synthesized to obtain Bi/Bi first3.64Mo0.36O6.55And Bi/Bi3.84W0.16O6.24Both nanometers
Composite, its pattern is homogeneous, particle diameter is smaller, it is to avoid nano particle pattern obtained by existing method is uneven or particle diameter distribution
Wider the shortcomings of.
2) this patent uses solvent structure technique, using alcohol as solvent and reducing agent, the reactant as obtained by regulating and controlling alkali
The reproducibility of system, it is not necessary to extra to add reducing substances and surfactant etc., it is to avoid the generation of secondary pollution, is simplified
Synthesis technique, effectively reduces production cost, and environmental protection, and the large-scale production of product can be achieved.
Brief description of the drawings
Fig. 1 is the XRD that the gained bismuth of embodiment 1 is combined the nano composite material of this compound of viral in non-stoichiometric Austria
Collection of illustrative plates.
Fig. 2 is the SEM that the gained bismuth of embodiment 1 is combined the nano composite material of this compound of viral in non-stoichiometric Austria
Figure.
Fig. 3 is the TEM that the gained bismuth of embodiment 1 is combined the nano composite material of this compound of viral in non-stoichiometric Austria
Figure.
Fig. 4 is the XRD that the gained bismuth of embodiment 2 is combined the nano composite material of this compound of viral in non-stoichiometric Austria
Collection of illustrative plates.
Fig. 5 be the gained bismuth of embodiment 2 be combined non-stoichiometric it is difficult to understand in the nano composite material of viral this compound consolidate
Body UV-Vis DRS collection of illustrative plates.
Fig. 6 is the XRD that the gained bismuth of embodiment 5 is combined the nano composite material of this compound of viral in non-stoichiometric Austria
Collection of illustrative plates.
Fig. 7 is the SEM that the gained bismuth of embodiment 5 is combined the nano composite material of this compound of viral in non-stoichiometric Austria
Figure.
Fig. 8 is the nano composite material and list that the gained bismuth of embodiment 2 is combined this compound of viral in non-stoichiometric Austria
The performance comparison figure of the photocatalytic degradation bisphenol-A of component non-stoichiometric bismuth molybdate.
Embodiment
The present invention is described further with reference to embodiment and accompanying drawing, the scope of protection of present invention is not limited to
The scope stated in embodiment.
Embodiment 1
This compound nano composite of viral in a kind of bismuth/non-stoichiometric is difficult to understand, its preparation method includes following step
Suddenly：
The water bismuth nitrates of 4mmol five, 2mmol sodium molybdates are dissolved in 20mL ethylene glycol (EG), ultrasonic disperse is uniform, then will
Resulting solution is placed on agitator, while stirring the addition 20mL ethanol in mixed solution, 10mL sodium hydroxide (2mol/L),
Stir 30min to be well mixed, then gained reaction solution be placed in reactor, reacted at 160 DEG C after 12h, be cooled to room temperature,
Products therefrom removes residual impurity by centrifuge washing, and dries 12h at 60 DEG C, and bismuth/non-stoichiometric is produced after cooling
Bismuth molybdate (Bi/Bi3.64Mo0.36O6.55) nano composite material.
The present embodiment products therefrom is carried out into X-ray using Bruker axs D8 type X-ray diffraction analysis instrument (XRD) to spread out
Analysis is penetrated, Fig. 1 is as a result seen.Reference standard card PDF#85-1330 (Bi) and PDF#43-446 (Bi3.64Mo0.36O6.55), from figure
Spectrum is as can be seen that the products therefrom of embodiment 1 is Bi/Bi3.64Mo0.36O6.55Nano composite material；And go out without other impurity peaks
It is existing, illustrate the Bi/Bi that products obtained therefrom is high-purity3.64Mo0.36O6.55Nano composite material.
Fig. 2 is to use the present embodiment products therefrom observed by Hitachi S4800 types SEM (SEM)
SEM figure.As seen from Figure 2, Bi/Bi3.64Mo0.36O6.55Nano composite material is nanometer little particle, and synthesized material
Pattern is homogeneous, and average grain diameter is 20nm or so.
Fig. 3 is to use the present embodiment gained observed by Philips TecnaiG2 types transmission electron microscopes (TEM)
The TEM figures of product, as can be seen that synthesized material is that size is homogeneous, the preferable nano particle of decentralization in Fig. 3 (a), and
Particle diameter is in 20nm or so.Synthesized non-stoichiometric molybdenum is can be seen that from the electronics selected diffraction figure in Fig. 3 (b)
Sour bismuth is polycrystalline structure, is therefrom clear that the crystal boundary contact of bismuth with elementary and non-stoichiometric bismuth molybdate.
Embodiment 2
This compound nano composite of viral in a kind of bismuth/non-stoichiometric is difficult to understand, its preparation method includes following step
Suddenly：
The water bismuth nitrates of 4mmol five, 2mmol sodium molybdates are dissolved in 20mL ethylene glycol (EG), ultrasonic disperse is uniform, then will
Resulting solution is placed on agitator, while stirring the addition 10mL ethanol in mixed solution, 8mL sodium hydroxide (2mol/L),
Stir 30min to be well mixed, then gained reaction solution be placed in reactor, reacted at 160 DEG C after 14h, be cooled to room temperature,
Products therefrom removes residual impurity by centrifuge washing, and dries 12h at 60 DEG C, and bismuth/non-stoichiometric is produced after cooling
Bismuth molybdate (Bi/Bi3.64Mo0.36O6.55) nano composite material.
Fig. 4 is the XRD that the present embodiment products therefrom is tested using Bruker axs D8 type X-ray diffraction analysis instrument (XRD)
Collection of illustrative plates.From collection of illustrative plates as can be seen that the present embodiment products therefrom is Bi/Bi3.64Mo0.36O6.55Nano composite material.And it is other
Impurity peaks occur, and illustrate the Bi/Bi that products obtained therefrom is high-purity3.64Mo0.36O6.55Nano composite material.
Fig. 5 is the solid UV-Vis DRS collection of illustrative plates of the present embodiment products therefrom.As illustrated, the Bi/ of gained
Bi3.64Mo0.36O6.55Relative to Bi3.64Mo0.36O6.55Absorption region significantly widened.
Embodiment 3
This compound nano composite of viral in a kind of bismuth/non-stoichiometric is difficult to understand, its preparation method includes following step
Suddenly：
The water bismuth nitrates of 2mmol five, 1mmol sodium molybdates are dissolved in 10mL ethylene glycol (EG), ultrasonic disperse is uniform, then will
Resulting solution is placed on agitator, adds 10mL ethanol, 2mL potassium hydroxide (4mol/L) in mixed solution while stirring,
Stir 30min to be well mixed, then gained reaction solution be placed in reactor, reacted at 140 DEG C after 16h, be cooled to room temperature,
Products therefrom removes residual impurity by centrifuge washing, and dries 12h at 60 DEG C, and bismuth/non-stoichiometric is produced after cooling
Bismuth molybdate (Bi/Bi3.64Mo0.36O6.55) nano composite material.
Embodiment 4
This compound nano composite of viral in a kind of bismuth/non-stoichiometric is difficult to understand, its preparation method includes following step
Suddenly：
The water bismuth nitrates of 2mmol five, 1mmol sodium molybdates are dissolved in 20mL ethylene glycol (EG), ultrasonic disperse is uniform, then will
Resulting solution is placed on agitator, adds 20mL ethanol, 13mL potassium hydroxide (2mol/L) in mixed solution while stirring,
Stir 30min to be well mixed, then gained reaction solution be placed in reactor, reacted at 200 DEG C after 10h, be cooled to room temperature,
Products therefrom removes residual impurity by centrifuge washing, and dries 12h at 60 DEG C, and bismuth/non-stoichiometric is produced after cooling
Bismuth molybdate (Bi/Bi3.64Mo0.36O6.55) nano composite material.
Embodiment 5
This compound nano composite of viral in a kind of bismuth/non-stoichiometric is difficult to understand, its preparation method includes following step
Suddenly：
The water bismuth nitrates of 4mmol five, 2mmol sodium tungstates are dissolved in 20mL ethylene glycol (EG), ultrasonic disperse is uniform, then will
Resulting solution is placed on agitator, adds 10mL ethanol, 8mL sodium hydroxide (2mol/L) in mixed solution while stirring,
Stir 30min to be well mixed, then gained reaction solution be placed in reactor, reacted at 160 DEG C after 12h, be cooled to room temperature,
Products therefrom removes residual impurity by centrifuge washing, and dries 12h at 60 DEG C, and bismuth/non-stoichiometric is produced after cooling
Bismuth tungstate (Bi/Bi3.84W0.16O6.24) nano composite material.
Fig. 6 is the XRD that this implementation products therefrom is tested using Bruker axs D8 type X-ray diffraction analysis instrument (XRD)
Spectrum.Reference standard card PDF#85-1330 (Bi) and PDF#43-447 (Bi3.84W0.16O6.24), from collection of illustrative plates as can be seen that this reality
Products therefrom is applied for Bi/Bi3.84W0.16O6.24Nano composite material, and occur without other impurity peaks, it is height to illustrate products obtained therefrom
The bismuth oxide of purity.
Fig. 7 is using this implementation products therefrom observed by Hitachi S4800 types SEM (SEM)
SEM schemes.It can be seen from figure 7 that Bi/Bi3.64Mo0.36O6.55Nano composite material is nanometer little particle, and synthesized material
Pattern is homogeneous, and average grain diameter is 20nm or so.
Embodiment 6
This compound nano composite of viral in a kind of bismuth/non-stoichiometric is difficult to understand, its preparation method includes following step
Suddenly：
The water bismuth nitrates of 2mmol five, 1mmol sodium tungstates are dissolved in 10mL ethylene glycol (EG), then ultrasonic disperse uniformly will
Resulting solution is placed on agitator, adds 10mL ethanol, 6mL sodium hydroxide (2mol/L) in mixed solution while stirring,
Stir 30min to be well mixed, then gained reaction solution be placed in reactor, reacted at 180 DEG C after 14h, be cooled to room temperature,
Products therefrom removes residual impurity by centrifuge washing, and dries 12h at 60 DEG C, and bismuth/non-stoichiometric is produced after cooling
Bismuth tungstate (Bi/Bi3.84W0.16O6.24) nano composite material.
Application examples
By the gained bismuth of embodiment 2/non-stoichiometric bismuth molybdate (Bi/Bi3.64Mo0.36O6.55) nano composite material progress
Photocatalytic degradation bisphenol-A performance test, is comprised the following steps that：
Weigh the products therefrom of 0.02g embodiments 2 to be distributed in 40mg/L bisphenol-A solution, be placed in dark place magnetic agitation half
Hour reaches adsorption/desorption balance.Then 300W xenon lamp (below 400nm ultraviolet light is filtered with optical filter) is opened,
At regular intervals 2 milliliters of suspension is taken out with dropper.Supernatant is taken after centrifuging in quartz colorimetric utensil, it is ultraviolet-can
See in spectrophotometer and analyze the absorbance change of bisphenol-A, so as to characterize its degradation effect.The calculation formula of degradation rate is (A0-
A)/A0× 100% (A0- original absorbance；Absorbance after A- degradeds).Fig. 8 is the compound non-chemical meter of the gained bismuth of embodiment 2
Amount is than bismuth molybdate (Bi/Bi3.64Mo0.36O6.55) the visible ray light of non-stoichiometric bismuth molybdate of nano material and one-component urges
Change the performance comparison figure of degraded bisphenol-A, it can be seen that the compound non-stoichiometric molybdic acid of the bismuth of the gained of embodiment 2
Bismuth (Bi/Bi3.64Mo0.36O6.55) nano material in 4h can by bisphenol-A degrade 80%, one-component non-stoichiometric bismuth molybdate
To the degradation rate of bisphenol-A less than 20% in 4h.It can illustrate from Fig. 8, it is non-chemical that the bismuth that the inventive method is obtained is combined
Metering is than bismuth molybdate (Bi/Bi3.64Mo0.36O6.55) degradation efficiency of nano composite material photocatalytic degradation bisphenol-A is substantially better than list
Component non-stoichiometric bismuth molybdate.
What deserves to be explained is, organic pollution of the present invention is not limited to bisphenol-A.
The preparation method of the non-stoichiometric bismuth molybdate of one-component described above comprises the following steps：By the water of 2mmol five
Bismuth nitrate, 1mmol sodium molybdates are dissolved in 20mL ethylene glycol (EG), and ultrasonic disperse is uniform, and resulting solution then is placed in into agitator
On, 20mL ethanol, 6mL sodium hydroxide (2mol/L) are added in mixed solution while stirring, stirring 30min is well mixed,
Gained reaction solution is placed in reactor again, is reacted at 160 DEG C after 12h, is cooled to room temperature, products therefrom is washed by centrifugation
Removal residual impurity is washed, and 12h is dried at 60 DEG C, non-stoichiometric bismuth molybdate (Bi is produced after cooling3.64Mo0.36O6.55)。
It should be noted that above preferred embodiments are merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment invention is described in detail, it is to be understood by those skilled in the art that can be in shape
Various changes are made in formula and details to it, without departing from claims of the present invention limited range.
Claims (8)
- This compound nano composite of viral in 1. a kind of bismuth/non-stoichiometric is difficult to understand, its chemical expression is Bi/ Bi3.64Mo0.36O6.55Or Bi/Bi3.84W0.16O6.24, it by non-stoichiometric Bi3.64Mo0.36O6.55Or Bi3.84W0.16O6.24 Particle surface deposited metal Bi is formed, and its pattern is homogeneous nano particle, and average grain diameter is 20~30nm.
- The preparation method of this compound nano composite of viral in 2. bismuth described in claim 1/non-stoichiometric is difficult to understand, it is special Levy and be, comprise the following steps：Bismuth nitrate and the dissolving of sodium molybdate or sodium tungstate are scattered in and is well mixed and must mix in ethylene glycol Liquid I is closed, then adds in ethanol and alkali lye, stirs into gained mixed liquor I, then gained reaction solution progress hydro-thermal is anti- Should, then through centrifuge washing, drying, cooling, produce this compound nano composite of viral in bismuth/non-stoichiometric Austria.
- 3. preparation method according to claim 1, it is characterised in that the bismuth nitrate and sodium molybdate or bismuth nitrate and wolframic acid The mol ratio of sodium is 2:1.
- 4. preparation method according to claim 1, it is characterised in that in the mixed liquor I concentration of bismuth nitrate be 0.1~ 0.5mol/L。
- 5. preparation method according to claim 1, it is characterised in that the volume ratio of the ethylene glycol and ethanol for (2~ 1):1。
- 6. preparation method according to claim 1, it is characterised in that the alkali lye is that sodium hydroxide or potassium hydroxide are molten Liquid, its concentration in reaction solution is 0.35~0.65mol/L.
- 7. preparation method according to claim 1, it is characterised in that the hydrothermal temperature is 140~200 DEG C, when Between be 10~16h.
- Viral in 8. bismuth/non-stoichiometric made from the preparation method of any one of claim 1 or claim 2~7 is difficult to understand This application of compound nano composite in photocatalysis degradation organic contaminant field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710358220.5A CN107126953B (en) | 2017-05-19 | 2017-05-19 | Bismuth/non-stoichiometric ratio Oriviris compound nano composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710358220.5A CN107126953B (en) | 2017-05-19 | 2017-05-19 | Bismuth/non-stoichiometric ratio Oriviris compound nano composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107126953A true CN107126953A (en) | 2017-09-05 |
| CN107126953B CN107126953B (en) | 2020-05-22 |
Family
ID=59732516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710358220.5A Active CN107126953B (en) | 2017-05-19 | 2017-05-19 | Bismuth/non-stoichiometric ratio Oriviris compound nano composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107126953B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107626297A (en) * | 2017-09-29 | 2018-01-26 | 中南大学 | A kind of tiny balloon shape bismuth/composite bismuth vanadium photocatalyst and its preparation method and application |
| CN108970605A (en) * | 2017-05-30 | 2018-12-11 | 镇江杜微人才咨询有限公司 | A kind of preparation method of bismuth molybdate photochemical catalyst |
| CN113797918A (en) * | 2020-06-16 | 2021-12-17 | 中国科学院化学研究所 | Defect-containing sandwich type perovskite catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418333A (en) * | 2013-07-30 | 2013-12-04 | 安徽师范大学 | Preparation method of Bi<3.64>Mo<0.36>O<6.55> nanometer particles and nanometer material made of Bi<3.64>Mo<0.36>O<6.55> nanometer particles |
| CN104525186A (en) * | 2014-12-17 | 2015-04-22 | 武汉工程大学 | Spherical bismuth molybdate nanocomposite having heterostructure as well as preparation method and application of nanocomposite |
| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
-
2017
- 2017-05-19 CN CN201710358220.5A patent/CN107126953B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418333A (en) * | 2013-07-30 | 2013-12-04 | 安徽师范大学 | Preparation method of Bi<3.64>Mo<0.36>O<6.55> nanometer particles and nanometer material made of Bi<3.64>Mo<0.36>O<6.55> nanometer particles |
| CN104525186A (en) * | 2014-12-17 | 2015-04-22 | 武汉工程大学 | Spherical bismuth molybdate nanocomposite having heterostructure as well as preparation method and application of nanocomposite |
| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
Non-Patent Citations (2)
| Title |
|---|
| CHUNYING WANG等: ""Characterization of photocatalyst Bi3.84W0.16O6.24 and its photodegradation on bisphenol A under simulated solar light irradiation"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| JIA REN等: ""Heterostructured Bismuth Molybdate Composite: Preparation and Improved Photocatalytic Activity under Visible-Light Irradiation"", 《ACS APPL. MATER. INTERFACES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108970605A (en) * | 2017-05-30 | 2018-12-11 | 镇江杜微人才咨询有限公司 | A kind of preparation method of bismuth molybdate photochemical catalyst |
| CN107626297A (en) * | 2017-09-29 | 2018-01-26 | 中南大学 | A kind of tiny balloon shape bismuth/composite bismuth vanadium photocatalyst and its preparation method and application |
| CN107626297B (en) * | 2017-09-29 | 2019-09-17 | 中南大学 | A kind of tiny balloon shape bismuth/composite bismuth vanadium photocatalyst and its preparation method and application |
| CN113797918A (en) * | 2020-06-16 | 2021-12-17 | 中国科学院化学研究所 | Defect-containing sandwich type perovskite catalyst and preparation method and application thereof |
| CN113797918B (en) * | 2020-06-16 | 2022-11-22 | 中国科学院化学研究所 | Defect-containing sandwich type perovskite catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107126953B (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shang et al. | Photocorrosion inhibition and high-efficiency photoactivity of porous g-C3N4/Ag2CrO4 composites by simple microemulsion-assisted co-precipitation method | |
| Li et al. | A facile route to the synthesis of magnetically separable BiOBr/NiFe2O4 composites with enhanced photocatalytic performance | |
| Ma et al. | Self-assembled three-dimensional hierarchical umbilicate Bi2WO6 microspheres from nanoplates: controlled synthesis, photocatalytic activities, and wettability | |
| CN106824246B (en) | A kind of TiO2/g-C3N4The preparation method of composite visible light catalyst | |
| CN105289693B (en) | A kind of Zn0.5Co0.5Fe2O4/g‑C3N4The preparation method of composite photo-catalyst | |
| Liu et al. | Ionic liquid-assisted hydrothermal preparation of BiOI/BiOCl heterojunctions with enhanced separation efficiency of photo-generated charge pairs and photocatalytic performance | |
| CN104801328B (en) | Method for preparing TiO2/g-C3N4 composite photocatalyst at low temperature | |
| Wang et al. | Doping induced grain size reduction and photocatalytic performance enhancement of SrMoO4: Bi3+ | |
| Wang et al. | A recyclable molten-salt synthesis of B and K co-doped g-C3N4 for photocatalysis of overall water vapor splitting | |
| Li et al. | A facile approach assembled magnetic CoFe2O4/AgBr composite for dye degradation under visible light | |
| Zhang et al. | Microwave-assisted synthesis of ZnNiAl-layered double hydroxides with calcination treatment for enhanced PNP photo-degradation under visible-light irradiation | |
| Hu et al. | Engineering 2D compressed layered g-C3N4 nanosheets by the intercalation of BiVO4-Bi2WO6 composites for boosting photocatalytic activities | |
| CN107282077A (en) | A kind of preparation method and applications of photocatalysis fixed nitrogen catalyst | |
| CN105819498B (en) | A kind of nano SnO2Hollow microsphere and its preparation method and application | |
| Li et al. | Effects of muscovite matrix on photocatalytic degradation in TiO2/muscovite nanocomposites | |
| Liu et al. | Low temperature synthesis of Bi2WO6 and its photocatalytic activities | |
| CN107126953A (en) | This compound nano composite of viral and its preparation method and application in a kind of bismuth/non-stoichiometric is difficult to understand | |
| CN102380367A (en) | Control synthetic method of high-visible-light-activity mixed crystal type BiVO4 photocatalysts | |
| Bi et al. | Room temperature synthesis of ultrathin iodine-doped BiOCl nanosheets | |
| CN109529872A (en) | Amorphous nano titanium dioxide visible light catalyzer compound and preparation method thereof | |
| Dong et al. | Sulfur nanoparticles in situ growth on TiO 2 mesoporous single crystals with enhanced solar light photocatalytic performance | |
| CN109529892A (en) | A kind of nano strip MOA composite photo-catalyst preparation method | |
| CN109012669A (en) | A kind of room temperature preparing process by ion exchange of wolframic acid silver photochemical catalyst | |
| CN106362768B (en) | A kind of honeycomb ceramic plate loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP | |
| CN103657628B (en) | A kind of SnO 2-TiO 2the preparation method of compound nanometer photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |