CN106861724A - A kind of preparation method of square cavernous structure Bi3O4Br nanometer monocrystallines ring catalysis material - Google Patents
A kind of preparation method of square cavernous structure Bi3O4Br nanometer monocrystallines ring catalysis material Download PDFInfo
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- cavernous structure
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001621 bismuth Chemical class 0.000 claims abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 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 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- -1 bismuth salt Chemical class 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 abstract description 12
- 229940012189 methyl orange Drugs 0.000 abstract description 11
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000002474 experimental method Methods 0.000 abstract description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 6
- 229960004889 salicylic acid Drugs 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 3
- 238000000034 method Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000001000 micrograph Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000002063 nanoring Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 240000000203 Salix gracilistyla Species 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- ANERHPOLUMFRDC-UHFFFAOYSA-K bismuth citrate Chemical class [Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ANERHPOLUMFRDC-UHFFFAOYSA-K 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
Abstract
The invention discloses a kind of square cavernous structure Bi3O4The preparation method of Br nanometer monocrystalline ring catalysis materials.It is primary raw material using soluble bismuth salt and bromine-containing compound, by two kinds of regulation and control of surfactant, square cavernous structure Bi is prepared with solvent-thermal method3O4Br nanometer monocrystalline ring catalysis materials.The square cavernous structure Bi of scanning electron microscope image display synthesis3O4The microstructure of Br nanometer monocrystalline rings is one kind by multilayer Bi3O4The square cavernous structure structure of the comparison rule that Br pieces are piled up and formed.Square cavernous structure Bi obtained by the present invention3O4Br nanometer monocrystalline ring catalysis materials can preferably absorb visible ray, and photocatalytic activity high is shown in simulated visible light produces oxygen, degraded salicylic acid, the experiment of methyl orange.The square cavernous structure Bi of present invention synthesis3O4The method of Br nanometer monocrystalline ring catalysis materials is simple, synthesis condition is gentle, be conducive to large-scale industrial production.
Description
Technical field
The present invention relates to nano material and solar energy photocatalytic field, and in particular to a kind of square cavernous structure Bi3O4Br is mono-
The preparation method of brilliant nano-rings catalysis material.
Background technology
Bi3O4Br nano materials due to its unique optics, electrical properties etc., by as a kind of new semiconductor material
Material, is widely used in photocatalysis field.
However, rare on Bi in recent years3O4The research report of Br nanostructure growths.The main bag reported
Include one-dimensional nanobelt, nanometer sheet and nanometer plate of two dimension etc..Wherein, Li Yadong seminar makees bromine with Surfactant CTAB
Source, the Bi of nano strip has been synthesized using hydro-thermal method by the pH value and reaction temperature of control system24O31Br10、Bi3O4Br、
Bi12O17Br2[Yadong Li et al.Chem.Eur.J.2005,11,6519-6524]；Zhang Lizhi et al. also makees bromine with CTAB
Source, be synthesized Bi in the basic conditions3O4Br single crystal nanoplates [Lizhi Zhang et al.Appl.Catal.B:
Environ.2013,136-137,112-121]；Chiing-Chang Chen seminar BiBr3Make bismuth source and bromine source, pass through
Change temperature and time and synthesize Bi3O4Br nanometer plates [Chiing-Chang Chen et
Al.J.Taiwan.Inst.Chem.E2014,45,2688-2697] etc..The Bi of these structures3O4Br materials are under visible light
All there is preferable photocatalytic activity, can effectively degradation of dye, organic pollution and other environmentally hazardous substances, in improvement
Or effect well is played in terms of repairing ecological environment.
Research has shown that, Bi3O4Br nano materials are a kind of ideal and up-and-coming catalysis materials.However, tool
There is the square cavernous structure Bi of high light catalysis activity3O4Br nanometer monocrystalline ring materials, have not yet to see report both at home and abroad so far.
The content of the invention
For the deficiencies in the prior art, present invention aim at being prepared there is provided a kind of new synthetic method
Square poroid Bi3O4Br nanometer monocrystalline ring catalysis materials, and this nanometer of ring structure is by Bi3O4Br nanometer sheet heaps
Come.
A kind of square cavernous structure Bi3O4The preparation method of Br nanometer monocrystalline ring catalysis materials, its step is：
1) soluble bismuth salt is dissolved in small-molecular-weight carboxylic acid, soluble bismuth salt is (1- with small-molecular-weight carboxylic acid ratio
2)mmol：(7-10) ml, is stirred continuously to bismuth salt and is completely dissolved to obtain solution A；
The soluble bismuth salt is the arbitrary proportion mixing of the one kind or 2-3 kinds in bismuth nitrate, bismuth citrate and bismuth sulfate
Thing, preferably bismuth nitrate；
The small-molecular-weight carboxylic acid is formic acid and/or acetic acid, preferably acetic acid；
2) above-mentioned solution A is added in small-molecular-weight alcohol, and adds bromine-containing compound and surfactant, containing solubility
Bismuth salt, bromine compounds, surfactant and small-molecular-weight alcohol ratio are (1-2) mmol：(1-2)mmol：(0.6-0.8)g：(30-
60) ml, obtains mixed solution B after stirring；
The small-molecular-weight alcohol is methyl alcohol and/or ethanol, preferably methyl alcohol；
The bromine-containing compound is the one kind in CTAB (cetyl trimethylammonium bromide), sodium bromide NaBr and benzyl bromine；
The surfactant be polyvinylpyrrolidone PVP, polyacrylic acid PAA, polyethyleneimine PEI in one kind or
The arbitrary proportion mixture of 2-3 kinds；
3) above-mentioned mixed solution B is transferred in the reactor of polytetrafluoroethyllining lining, the constant temperature under the conditions of 100-200 DEG C
Reaction 2-10h；
4) precipitation that reaction will be obtained after terminating respectively is washed 3-4 times with deionized water and absolute ethyl alcohol successively, then will be produced
Thing is dried in being placed on 60 DEG C of baking ovens, you can square poroid Bi is obtained3O4Br nanometer monocrystalline ring catalysis materials.
Compared with prior art, the advantages of the present invention are as follows：
1st, a kind of square poroid Bi has successfully been prepared3O4Br nanometer monocrystalline ring materials；
2nd, this square poroid Bi3O4Br monocrystal nano-materials have typical square poroid nano-rings structure；
3rd, with high light catalysis activity, can effective photodissociation aquatic products oxygen, while degrade methyl orange, bigcatkin willow can also be used for
The pollutants such as acid, effect well can be played at the aspect such as energy conversion and ecological environment treatment.
Brief description of the drawings
Fig. 1 is the square poroid Bi prepared by embodiment 13O4The XRD spectrum of Br nanometer monocrystalline ring catalysis materials；Figure
Bi obtained in middle display3O4Br crystallinity is preferable, the basic presence without miscellaneous peak.
Fig. 2 is the square poroid Bi prepared by embodiment 13O4The SEM image of Br nanometer monocrystalline ring catalysis materials；In figure
Low power SEM image shows obtained Bi3O4Br nanometer monocrystalline rings microscopic appearance is highly uniform, and high power SEM image can substantially be seen
It is by sheet Bi to these nano-rings3O4Br piles up what is formed, the external diameter 150-200nm of nano-rings, internal diameter 50-100nm, thickness
30-40nm。
Fig. 3 is the square poroid Bi prepared by embodiment 13O4The UV, visible light solid of Br nanometer monocrystalline ring catalysis materials
Diffusing reflection collection of illustrative plates；The poroid Bi of collection of illustrative plates display hexagon3O4The absorbing wavelength of Br nanometer monocrystalline ring catalysis materials in 460nm or so,
Visible ray can preferably be absorbed.
Fig. 4 is the square poroid Bi prepared by embodiment 13O4Br nanometer monocrystalline ring catalysis materials produce oxygen under visible light
Curve；It can be seen that square poroid Bi under visible light illumination3O4It is 72.54 μm of ol that Br nanometer monocrystallines ring produces oxygen speed
h-1。
Fig. 5 is the square poroid Bi prepared by embodiment 13O4Br nanometer monocrystalline ring catalysis materials are degraded under visible light
The degradation curve of salicylic acid SA；It can be seen that square poroid Bi under visible light illumination3O4Br nanometer monocrystalline ring bigcatkin willows
Acid degradation speed is 0.48042min-1.
The square poroid Bi prepared with embodiment 2,3,4,53O4The degraded salicylic acid SA of Br nanometer monocrystalline ring catalysis materials
Effect is essentially identical with embodiment 1, and degradation rate is respectively 93.4%, 94.7%, 92.9%, 91.2% during 5h.
Fig. 6 is the square poroid Bi prepared by embodiment 13O4Br nanometer monocrystalline ring catalysis materials are degraded under visible light
The degradation curve of methyl orange MO；It can be seen that square poroid Bi under visible light illumination3O4Br nanometer monocrystalline cyclohexyl methyls
Orange degradation rate is 0.0886min-1。
The square poroid Bi prepared with embodiment 2,3,4,53O4The degraded methyl orange MO of Br nanometer monocrystalline ring catalysis materials
Effect is essentially identical with embodiment 1, and degradation rate is respectively 98.4%, 97.7%, 97.9%, 97.2% during 28min.
Fig. 7 is the square poroid Bi prepared by embodiment 23O4The XRD spectrum of Br nanometer monocrystalline ring catalysis materials；
Fig. 8 is the square poroid Bi prepared by embodiment 23O4The SEM image of Br nanometer monocrystalline ring catalysis materials；
Fig. 9 is the square poroid Bi prepared by embodiment 33O4The XRD spectrum of Br nanometer monocrystalline ring catalysis materials；
Figure 10 is the square poroid Bi prepared by embodiment 33O4The SEM image of Br nanometer monocrystalline ring catalysis materials；
Figure 11 is the square poroid Bi prepared by embodiment 43O4The XRD spectrum of Br nanometer monocrystalline ring catalysis materials；
Figure 12 is the square poroid Bi prepared by embodiment 43O4The SEM image of Br nanometer monocrystalline ring catalysis materials；
Figure 13 is the square poroid Bi prepared by embodiment 53O4The XRD spectrum of Br nanometer monocrystalline ring catalysis materials；
Figure 14 is the square poroid Bi prepared by embodiment 53O4The SEM image of Br nanometer monocrystalline ring catalysis materials.
Specific embodiment
In order that those skilled in the art are better understood from technical scheme, below in conjunction with accompanying drawing to the present invention
It is described in further details.
Raw material sources in following examples：Polyvinylpyrrolidone PVP (production code member P110607, CAS 9003-39-
8, Chemical Reagent Co., Ltd., Sinopharm Group), polyacrylic acid PAA (production code member P104272, CAS 9003-01-4, traditional Chinese medicines collection
Chemical reagent Co., Ltd of group), polyethyleneimine PEI (production code member E107079, CAS 9002-98-6, Chinese medicines group chemistry
Reagent Co., Ltd).
Embodiment 1：
A kind of square cavernous structure Bi3O4The preparation method of Br nanometer monocrystalline ring catalysis materials, step is as follows：
1) the water bismuth nitrate (Bi (NO of 1.5mmol five are weighed3)3·5H2O) it is dissolved in 7.5mL acetic acid, is stirred continuously to nitre
Sour bismuth obtains solution A after being completely dissolved；
2) above-mentioned solution A is added in 60mL methyl alcohol, and adds 1.5mmol NaBr and 0.6g PEI, obtain molten after stirring
Liquid B；
3) above-mentioned solution B is transferred in the reactor of polytetrafluoroethyllining lining, the isothermal reaction 2h under the conditions of 100 DEG C；
4) precipitation that reaction will be obtained after terminating respectively is washed 3-4 times with deionized water and absolute ethyl alcohol successively, then will be produced
Thing is dried in being placed on 60 DEG C of baking ovens, you can square poroid Bi is obtained3O4Br nanometer monocrystalline ring catalysis materials, XRD spectrum such as Fig. 1
Shown, SEM image is as shown in Fig. 2 UV, visible light solid diffusing reflection collection of illustrative plates is as shown in Figure 3.
Embodiment 2：
A kind of square cavernous structure Bi3O4The preparation method of Br nanometer monocrystalline ring catalysis materials, step is as follows：
1) 1mmol bismuth citrates (Bi (C are weighed5H7O5COO)3) be dissolved in 7mL formic acid, it is stirred continuously to bismuth citrate
Solution A is obtained after being completely dissolved；
2) above-mentioned solution A is added in 60mL methyl alcohol, and adds 1mmol CTAB and 0.6g PVP, solution is obtained after stirring
B；
3) above-mentioned solution B is transferred in the reactor of polytetrafluoroethyllining lining, the isothermal reaction 5h under the conditions of 180 DEG C；
4) precipitation that reaction will be obtained after terminating respectively is washed 3-4 times with deionized water and absolute ethyl alcohol successively, then will be produced
Thing is dried in being placed on 60 DEG C of baking ovens, you can square poroid Bi is obtained3O4Br nanometer monocrystalline ring catalysis materials.XRD spectrum such as Fig. 7
It is shown, SEM image as shown in figure 8, crystallinity preferably, the basic presence without miscellaneous peak, microscopic appearance is highly uniform.
Embodiment 3：
A kind of square cavernous structure Bi3O4The preparation method of Br nanometer monocrystalline ring catalysis materials, step is as follows：
1) 1.3mmol bismuth sulfates (Bi is weighed2(SO4)3) be dissolved in 7.5mL acetic acid, it is stirred continuously completely molten to bismuth sulfate
Solution A is obtained after solution；
2) above-mentioned solution A is added in 45mL absolute ethyl alcohols, and adds 1.3mmol NaBr and 0.6g PVP, after stirring
Obtain solution B；
3) above-mentioned solution B is transferred in the reactor of polytetrafluoroethyllining lining, the isothermal reaction 5h under the conditions of 150 DEG C；
4) precipitation that reaction will be obtained after terminating respectively is washed 3-4 times with deionized water and absolute ethyl alcohol successively, then will be produced
Thing is dried in being placed on 60 DEG C of baking ovens, you can square poroid Bi is obtained3O4Br nanometer monocrystalline ring catalysis materials.XRD spectrum such as Fig. 9
Shown, as shown in Figure 10, preferably, the basic presence without miscellaneous peak, microscopic appearance is highly uniform for crystallinity for SEM image.
Embodiment 4：
A kind of square cavernous structure Bi3O4The preparation method of Br nanometer monocrystalline ring catalysis materials, step is as follows：
1) 1mmol bismuth citrates (Bi (C are weighed5H7O5COO)3) and the water bismuth nitrate (Bi (NO of 0.8mmol five3)3·5H2O)
It is dissolved in 8mL acetic acid, is stirred continuously to after being completely dissolved to obtain solution A；
2) above-mentioned solution A is added in 45mL absolute ethyl alcohols, and adds 1.8mmol benzyls bromine and 0.7985g PAA, stirred
Solution B is obtained afterwards；
3) above-mentioned solution B is transferred in the reactor of polytetrafluoroethyllining lining, the isothermal reaction 8h under the conditions of 180 DEG C；
4) precipitation that reaction will be obtained after terminating respectively is washed 3-4 times with deionized water and absolute ethyl alcohol successively, then will be produced
Thing is dried in being placed on 60 DEG C of baking ovens, you can square poroid Bi is obtained3O4Br nanometer monocrystalline ring catalysis materials.XRD spectrum such as Figure 11
Shown, as shown in figure 12, preferably, the basic presence without miscellaneous peak, microscopic appearance is highly uniform for crystallinity for SEM image.
Embodiment 5：
A kind of square cavernous structure Bi3O4The preparation method of Br nanometer monocrystalline ring catalysis materials, step is as follows：
1) 1mmol bismuth sulfates (Bi is weighed2(SO4)3) and the water bismuth nitrate (Bi (NO of 1mmol five3)3·5H2O) it is dissolved in 10mL
In acetic acid, solution A is stirred continuously to after being completely dissolved to obtain；
2) above-mentioned solution A is added in 30mL methyl alcohol, and adds 2mmol CTAB and 0.7g PAA, solution is obtained after stirring
B；
3) above-mentioned solution B is transferred in the reactor of polytetrafluoroethyllining lining, the isothermal reaction 10h under the conditions of 200 DEG C；
4) precipitation that reaction will be obtained after terminating respectively is washed 3-4 times with deionized water and absolute ethyl alcohol successively, then will be produced
Thing is dried in being placed on 60 DEG C of baking ovens, you can square poroid Bi is obtained3O4Br nanometer monocrystalline ring catalysis materials.XRD spectrum such as Figure 13
Shown, as shown in figure 14, preferably, the basic presence without miscellaneous peak, microscopic appearance is highly uniform for crystallinity for SEM image.
Embodiment 6：
A kind of square poroid Bi3O4The application of Br nanometer monocrystalline ring catalysis materials, oxygen is produced for being catalyzed water decomposition.
The accurate square poroid Bi weighed prepared by 50mg embodiments 13O4Br nanometer monocrystalline ring catalysis materials are added to
50mL contains 0.01mol Ag (NO3)3The aqueous solution in, after ultrasonic 10min lead to half an hour N2To remove the O in water2, so
Radiation of visible light is simulated after being filtered through 420nm optical filters with 350W xenon lamps, photocatalytic water splitting is carried out and is produced oxygen experiment.When 1h
Between interval in gas sampler sample 40 μ L, then sample introduction detected in the gas chromatograph equipped with 5A molecular sieves.Take peak face
Product value substitute into corrected in standard curve, measure oxygen-producing amount now.The speed of photocatalytic water splitting product oxygen=(during t
Oxygen content in the oxygen content-initial water at quarter) × 100%/produce oxygen time t.
Result is shown in Fig. 4, it can be seen that square poroid Bi under visible light illumination3O4Br nanometer monocrystallines ring produces oxygen speed
Rate is 72.54 μm of ol h-1。
Embodiment 7：
A kind of square poroid Bi3O4The application of Br nanometer monocrystalline ring photocatalysis materials, for photocatalytic degradation salicylic acid：
The square poroid Bi prepared by 50mg embodiments 1-5 is accurately weighed respectively3O4Br nanometer monocrystalline ring catalysis materials
It is added in the salicylic aqueous solution that 50mL concentration is 20mol/L, lucifuge stirring 1h after ultrasonic 10min, so that salicylic acid exists
Square poroid Bi3O4The surface of Br nanometer monocrystalline ring catalysis materials reaches adsorption-desorption balance, is then passed through with 350W xenon lamps
420nm optical filters simulate radiation of visible light after filtering, and carry out photocatalytic degradation experiment, and 4mL, centrifugation are sampled every 1h time intervals
Supernatant liquor is obtained after isolating catalyst, the concentration of supernatant liquor is analyzed with ultraviolet-uisible spectrophotometer.Photocatalysis
Salicylic degradation rate=(the initial salicylic salicylic concentration of concentration-residual) × 100%/initial water in degradation experiment
The concentration of poplar acid.
Result is shown in Fig. 5, under visible light illumination the square poroid Bi of embodiment 13O4Br nanometer monocrystalline ring salicylate degradation speed
It is 0.48042min-1, degradation rate is 97.4% during 5h
The square poroid Bi prepared with embodiment 2,3,4,53O4The degraded salicylic acid SA of Br nanometer monocrystalline ring catalysis materials
Effect is essentially identical with embodiment 1, and degradation rate is respectively 93.4%, 94.7%, 92.9%, 91.2% during 5h.
Embodiment 8：
A kind of square poroid Bi3O4The application of Br nanometer monocrystalline ring photocatalysis materials, for photo-catalytic degradation of methyl-orange：
The square poroid Bi prepared by 50mg embodiments 1-5 is accurately weighed respectively3O4Br nanometer monocrystalline ring catalysis materials
It is added in the aqueous solution of the methyl orange that 50mL concentration is 20mg/L, lucifuge stirring 1h after ultrasonic 10min, so that methyl orange is in side
The poroid Bi of shape3O4The surface of Br nanometer monocrystalline ring catalysis materials reaches adsorption-desorption balance, then with 350W xenon lamps through 420nm
Optical filter simulates radiation of visible light after filtering, and carries out photocatalytic degradation experiment, and 4mL, centrifugation point are sampled every 4min time intervals
Supernatant liquor is obtained after separating out catalyst, the concentration of supernatant liquor is analyzed with ultraviolet-uisible spectrophotometer.Photocatalysis is dropped
The degradation rate of methyl orange=(concentration of the concentration-residual methyl orange of initial orange) × 100%/initial in solution experiment
The concentration of orange.
Result is shown in Fig. 6, under visible light illumination the square poroid Bi of embodiment 13O4Br nanometer monocrystallines cyclohexyl methyl orange degradation rate
It is 0.0886min-1, degradation rate is 99.6% during 28min
The square poroid Bi prepared with embodiment 2,3,4,53O4The degraded methyl orange MO of Br nanometer monocrystalline ring catalysis materials
Effect is essentially identical with embodiment 1, and degradation rate is respectively 98.4%, 97.7%, 97.9%, 97.2% during 28min.
Claims (7)
1. a kind of square cavernous structure Bi3O4The preparation method of Br nanometer monocrystalline ring catalysis materials, its step is：
1) soluble bismuth salt is dissolved in small-molecular-weight carboxylic acid, soluble bismuth salt/small-molecular-weight carboxylic acid ratio is (1-2)
mmol：(7-10) ml, is stirred continuously to bismuth salt and is completely dissolved to obtain solution A；
2) above-mentioned solution A is added in small-molecular-weight alcohol, and adds bromine-containing compound and surfactant, make soluble bismuth
Salt/bromine-containing compound/surfactant/small-molecular-weight alcohol ratio is (1-2) mmol：(1-2)mmol：(0.6-0.8)g：(30-
60) ml, obtains solution B after stirring；
The bromine-containing compound is the one kind in cetyl trimethylammonium bromide, sodium bromide or benzyl bromine；
Described surfactant be polyvinylpyrrolidone, polyacrylic acid and polyethyleneimine in one kind or 2-3 kinds appoint
Meaning scalemic thereof；
3) above-mentioned mixed solution B is transferred in the reactor of polytetrafluoroethyllining lining, 2- is reacted under the conditions of 100-200 °C
10 h；
4) then product is placed on 60 °C by the precipitation that reaction will be obtained after terminating successively with deionized water and absolute ethanol washing
Dried in baking oven, that is, square cavernous structure Bi is obtained3O4Br nanometer monocrystalline ring catalysis materials.
2. square cavernous structure Bi as claimed in claim 13O4The preparation method of Br nanometer monocrystalline ring catalysis materials, it is special
Levy and be, described soluble bismuth salt is the arbitrary proportion mixing of the one kind in bismuth nitrate, bismuth citrate and bismuth sulfate or 2-3 kinds
Thing.
3. square cavernous structure Bi according to claim 23O4The preparation method of Br nanometer monocrystalline ring catalysis materials, its
It is characterised by：The soluble bismuth salt is bismuth nitrate.
4. square cavernous structure Bi as claimed in claim 13O4The preparation method of Br nanometer monocrystalline ring catalysis materials, it is special
Levy and be, described small-molecular-weight carboxylic acid is the one kind or this two kinds arbitrary proportion mixture in formic acid, acetic acid.
5. square cavernous structure Bi according to claim 43O4The preparation method of Br nanometer monocrystalline ring catalysis materials, its
It is characterised by：The small-molecular-weight carboxylic acid is acetic acid.
6. square cavernous structure Bi as claimed in claim 13O4The preparation method of Br nanometer monocrystalline ring catalysis materials, it is special
Levy and be, described small-molecular-weight alcohol is the one kind or the arbitrary proportion mixture of both in methyl alcohol, ethanol.
7. square cavernous structure Bi according to claim 63O4The preparation method of Br nanometer monocrystalline ring catalysis materials, its
It is characterised by：The small-molecular-weight alcohol is methyl alcohol.
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| CN111908417A (en) * | 2019-05-10 | 2020-11-10 | 中国科学院化学研究所 | Perovskite single crystal nanoring and preparation method and application thereof |
| CN113275023A (en) * | 2021-05-28 | 2021-08-20 | 南开大学 | Bi3O4Br/CuBi2O4Preparation method and application of bimetallic heterojunction catalyst |
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| CN113275023A (en) * | 2021-05-28 | 2021-08-20 | 南开大学 | Bi3O4Br/CuBi2O4Preparation method and application of bimetallic heterojunction catalyst |
| CN115337941A (en) * | 2022-08-09 | 2022-11-15 | 河南科技大学 | Photocatalytic fresh-keeping material and preparation method and application thereof |
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