CN107029770B - A kind of preparation method of metastable phase bismuth oxide and its application in photocatalysis degradation organic contaminant - Google Patents
A kind of preparation method of metastable phase bismuth oxide and its application in photocatalysis degradation organic contaminant Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 33
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 12
- 230000015556 catabolic process Effects 0.000 title abstract description 16
- 238000006731 degradation reaction Methods 0.000 title abstract description 16
- 238000007146 photocatalysis Methods 0.000 title abstract description 9
- 239000000356 contaminant Substances 0.000 title abstract description 6
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims abstract description 43
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 29
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 16
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- 239000011941 photocatalyst Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000011109 contamination Methods 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
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- 238000000034 method Methods 0.000 description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
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- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 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 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
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- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003911 water pollution Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000012360 testing method Methods 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
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- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [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 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 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 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical class O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910006362 δ-Bi2O3 Inorganic materials 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- B01J35/39—
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- B01J35/613—
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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
- C02F1/30—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a kind of preparation method of metastable phase bismuth oxide and its applications in photocatalysis degradation organic contaminant, preparation method is that the aqueous solution for containing bismuth and ammonium citrate, urea and cetyl trimethylammonium bromide is obtained bismuthyl carbonate micro flowery by hydro-thermal reaction, the bismuthyl carbonate micro flowery, which is placed in air environment, to be calcined, and metastable phase bismuth oxide β-Bi is obtained2O3/Bi2O2.33@Bi2O2CO3；The preparation method is easy to operate controllable, it is environmentally friendly, the metastable phase bismuth oxide of synthesis has visible light-responded, large specific surface area, the advantages such as catalytic activity height, fast and efficiently feature is shown during visible light photocatalytic degradation of organic pollutants, can be widely applied to organic pollutant processing technology field.
Description
Technical field
The present invention relates to a kind of preparation method of bismuth oxidation photocatalyst, in particular to a kind of bismuthyl carbonate micro flowery is certainly
The application of the method and metastable phase bismuth oxide of synthesis metastable phase bismuth oxide in photocatalysis degradation organic contaminant is sacrificed,
Belong to nano-photocatalyst material technical field.
Background technique
With industry, the development of heavy industry, environmental pollution is increasingly serious, especially waste water treatment outstanding problem.Chemical industry water
Pollution because its complicated component, toxicity is big, corrosivity is strong, refractory reason the characteristics of, the processing methods such as traditional sedimentation, filtering, absorption
It has been difficult to meet improvement demand, it is extremely urgent to find efficient, stable water pollution control method.
" photocatalysis " concept is proposed from Fujishima the and Honda professor of Tokyo Univ Japan in 1972, directly using too
Sun can degrade the organic pollutant in air or water be considered as 21 century water pollution control breach, cause numerous in the whole world
The concern of person expert's this inexhaustible new energy to solar energy.However, the semiconductor light-catalyst developed and used at present with
TiO2, for ZnO, generally existing forbidden bandwidth is wider with the limited problem of optical response range, is only capable of left using in solar energy 4%
Right ultraviolet light, seriously reduces the effective rate of utilization of solar energy.People do not take to the doping of traditional photochemical catalyst, modification
On the basis of obtaining breakthrough greatly, the visible light-responded novel photocatalyst of efficient stable is begun look for.
In recent years, bismuth based semiconductor photochemical catalyst is because of its special layer structure, low cost, high chemical stability and nontoxic
Free of contamination advantage is developing progressively as the research hotspot of nanometer new energy photocatalysis field.Sill é n bismuth system layer structure light
Catalyst Bi2O2CO3, n-type semiconductor, by [Bi2O2]2+Cationic layer and CO3 2-Anion layer along Z axis alternating orthogonal grow and
At, the electrostatic field formed between layers promotes the migration of photo-generate electron-hole pair, but its wider band gap reduces the sun
It can utilization rate.Current effective method is to be compounded to form hetero-junctions generation collaboration effect therewith by introducing narrow gap semiconductor
It answers, on the one hand widens optical response range, improve solar energy utilization ratio；On the other hand, it largely improves to organic pollutant
Visible light degradation property, have the advantages that at low cost, green and pollution-free.Chinese patent (CN106268895A) discloses
A kind of preparation method of di-iron trioxide-bismuthyl carbonate composite photo-catalyst, for the first time with iron-based gel (by six trichloride hydrates
Iron, dehydrated alcohol, deionized water and propylene oxide are prepared) it is presoma, three oxidations are introduced on the surface of bismuthyl carbonate
Two iron form composite photo-catalyst.The preparation method simple process is controllable, but the bismuthyl carbonate band gap about 3.5eV of its preparation, still
The unresolved problem lower to solar energy utilization ratio, and di-iron trioxide is introduced in the form of iron-based gel, change carbonic acid gas
The pattern of bismuth micro-flowers has very big deficiency.
Bismuth oxide (Bi2O3) there is a variety of phase structures, monocline α-Bi2O3, cubic β-Bi2O3, body-centered cubic γ-Bi2O3,
Face-centered cubic δ-Bi2O3With two non-stoichiometric phase Bi2O2.33And Bi2O2.75.Chinese patent (CN105271405A) is open
It is a kind of based on bismuthyl carbonate or to aoxidize the material and preparation method thereof of bismuth nanotube and containing using five water bismuth nitrates as raw material
CO2Atmosphere is free of CO2Stirred to get in atmosphere bismuthyl carbonate or oxidation bismuth nanotube, can be used for photocatalysis absorption, degrade it is organic
Pollutant etc., but preparation process is complicated, higher cost.
Summary of the invention
For the defect existing for bismuth based semiconductor photochemical catalyst and its synthetic method in the prior art, of the invention
One purpose is to be to provide a kind of side for synthesizing metastable phase bismuth oxidation photocatalyst from sacrifice based on bismuthyl carbonate micro flowery
Method, this method simple process, process control, the metastable phase bismuth oxide β-Bi of preparation2O3/Bi2O2.33@Bi2O2CO3Remain carbon
Sour oxygen bismuth micro-flowers Large ratio surface, feature of uniform morphology, and purity is high, energy bandgaps are narrow, have visible light-responded, catalysis work
The high advantage of property.
Second object of the present invention is to be that provide the metastable phase bismuth oxidation photocatalyst has in photocatalytic degradation
Application in machine pollutant shows visible light-responded, the high feature of degradation efficiency.
In order to achieve the above technical purposes, the present invention provides a kind of preparation method of metastable phase bismuth oxide, this method
It is that the aqueous solution containing bismuth and ammonium citrate, urea and cetyl trimethylammonium bromide by hydro-thermal reaction obtains bismuthyl carbonate micron
Flower；The bismuthyl carbonate micro flowery, which is placed in air environment, to be calcined, and metastable phase bismuth oxide β-Bi is obtained2O3/Bi2O2.33@
Bi2O2CO3。
In technical solution of the present invention, bismuth and ammonium citrate is used as bismuth source and carbon source simultaneously, and urea is carbon source, cetyl three
Methyl bromide ammonium is surfactant and template, and in hydrothermal reaction process, bismuth and ammonium citrate and urea reaction generate nanometer
Sheet bismuthyl carbonate, for nano-sheet bismuthyl carbonate under cetyl trimethylammonium bromide dispersion and template action, self assembly is raw
It is petal-shaped, micron order bismuthyl carbonate particle of uniform size at pattern, has high-ratio surface, the narrow feature of band gap；Herein
On the basis of, it is from sacrifice agent, by calcining in air, in a small amount of metastable phase of bismuthyl carbonate Surface Creation with bismuthyl carbonate powder
Bismuth oxide β-Bi2O3And Bi2O2.33, with Bi2O2CO3Three-phase coexistence constitutes β-Bi2O3/Bi2O2CO3And Bi2O2.33/
Bi2O2CO3Two kinds of p-n heterojunctions effectively promote quick separating and the migration of photo-generated carrier, greatly improve light and urge
Change the efficiency of degradable organic pollutant.Metastable phase bismuth oxide β-Bi2O3/Bi2O2.33@Bi2O2CO3Maintain bismuthyl carbonate micron
Colored shape characteristic has the characteristics of Large ratio surface, while metastable phase bismuth oxide band gap is narrow, have it is visible light-responded, to too
Positive energy utilization rate is high；On the one hand organic pollutant can be adsorbed using its high-ratio surface, promotes organic pollutant in catalyst
Activated centre is nearby enriched with, and is on the other hand degraded using its high activity center to organic pollutant, is substantially increased to having
The disposal efficiency of machine pollutant.
The molar ratio of preferred scheme, the bismuth and ammonium citrate and urea is 1:0.8~1.2, most preferably 1:1.Urea
Additional amount is very few, then what is obtained is nano-sheet bismuthyl carbonate, and specific surface is small, band gap is wide；Urea additive amount is excessive, then is formed
Be the relatively compact bismuthyl carbonate of structure, specific surface area is small；The ratio of urea and bismuth and ammonium citrate in preferred range,
It is narrow that band gap can be obtained, pattern is good, the big bismuthyl carbonate micro flowery of specific surface.
The molar ratio of preferred scheme, the cetyl trimethylammonium bromide and bismuth and ammonium citrate is 0.2~1:1；Compared with
Preferably 0.6~0.8:1；Most preferably 0.8:1.Cetyl trimethylammonium bromide is as dispersing agent and template, by tight
Lattice control its additive amount can control the pattern of bismuthyl carbonate well.
Preferred scheme, during the aqueous solution pH containing bismuth and ammonium citrate, urea and cetyl trimethylammonium bromide is
Property.In hydrothermal reaction process, the preferably pH of adjusting solution system to neutrality.
Preferred scheme, the condition of the hydro-thermal reaction are as follows: temperature be 140 DEG C~200 DEG C, the time be 12~for 24 hours.It is more excellent
The scheme of choosing, the temperature of hydro-thermal reaction are 160 DEG C~180 DEG C, and the time is 16~20h.
Preferred scheme, the condition of the calcining are as follows: temperature is 290 DEG C~320 DEG C, and the time is 3~5h.In preferred temperature
It spends in range, can guarantee and generate tetragonal phase β-Bi in bismuthyl carbonate surface in situ2O3And Bi2O2.33, and be conducive in bismuthyl carbonate
Surface Creation β-Bi2O3/Bi2O2CO3And Bi2O2.33/Bi2O2CO3Two kinds of p-n heterojunctions, effectively promote photo-generated carrier
Quick separating and migration greatly improve the efficiency of photocatalysis degradation organic contaminant.
Bismuthyl carbonate micro flowery of the invention is about 2.5 micro- by being self-assembled into average grain diameter by nano-sheet bismuthyl carbonate
The flower-like structure of rice.
The present invention also provides application of the metastable phase bismuth oxide in photocatalysis degradation organic contaminant, as light
Catalyst is applied to Visible Light Induced Photocatalytic organic pollutant.
Metastable phase bismuth oxide β-Bi of the invention2O3/Bi2O2.33@Bi2O2CO3Preparation method include walk in detail below
It is rapid:
1) preparation of bismuthyl carbonate micro flowery:
A) weigh bismuth and ammonium citrate, urea is added to the water, be stirred well to be completely dissolved into white solution at room temperature；
B) a certain amount of cetyl trimethylammonium bromide (CTAB) is weighed to be added in above-mentioned solution；
C) after adjusting pH value to neutrality, it is stirred for 30min, is transferred in polytetrafluoroethyllining lining, in stainless steel cauldron
In, time and the temperature of reaction are controlled, to cooled to room temperature after reaction；
D) above-mentioned reaction product is collected, after being centrifuged 3 times with the speed of 13000 turns/min respectively with water and alcohol, in 60 DEG C
Lower drying obtains pure phase bismuthyl carbonate micro flowery grey powder；
2) preparation of metastable phase bismuth oxidation photocatalyst:
A) the bismuthyl carbonate micro flowery grey powder for weighing the preparation of 200mg preferred parameter is to fill in mortar from sacrifice agent
After dividing grinding, it is added in corundum Noah's ark；
B) Muffle furnace temperature program is set, target temperature is heated in air with the heating rate of 2.3 DEG C/min, is kept the temperature
After 4h, after furnace cooled to room temperature, powder is collected.
Compared with prior art, technical solution of the present invention has the advantages that
1) preparation process of metastable phase bismuth oxide of the invention is by first carbonate synthesis oxygen bismuth micro-flowers, then by carbonic acid
The calcining of oxygen bismuth micro-flowers generates metastable phase bismuth oxide.The bismuthyl carbonate micro flowery average diameter of preparation is 2.5 μm, and size is equal
Even, stable structure has biggish specific surface area (12.64m2·g-1), it is preferable to the adsorptivity of organic pollutant；Band gap width
It significantly reduces (2.93eV), visible light can be absorbed and utilized, improve the utilization rate to visible light, degradation property is significantly higher than carbon
Sour oxygen bismuth nanometer sheet；It on this basis, is that the oxidation of metastable phase bismuth is prepared by calcination method from sacrifice agent with bismuthyl carbonate micro flowery
Object, the metastable phase bismuth oxide of preparation remain the pattern of bismuthyl carbonate micro flowery substantially, have Large ratio surface (12.11m2·g-1) the characteristics of, organic pollutant can be adsorbed；β-Bi is generated simultaneously2O3/Bi2O2CO3And Bi2O2.33/Bi2O2CO3Two kinds of p-n
Hetero-junctions effectively promotes quick separating and the migration of photo-generated carrier, and band gap is narrow, have the characteristics that it is visible light-responded,
Substantially increase the efficiency of photocatalysis degradation organic contaminant；Preparation metastable phase bismuth oxidation is calcined by bismuthyl carbonate micro flowery
Object does not introduce impurity, purity is high；
2) metastable phase bismuth oxide of the invention shows visible light-responded and high catalytic activity, realizes to organic pollutant
Rapidly and efficiently visible light photocatalytic degradation, in 45min or so, degradation efficiency reaches 90% or more, in terms of chemical industry water pollution control
It has broad application prospects.
3) metastable phase bismuth oxide preparation method of the invention is simply controllable, at low cost, meets demand of industrial production.
Detailed description of the invention
[Fig. 1] is scanning electron microscope (SEM) image of 1 gained sample 1 of embodiment；
[Fig. 2] is scanning electron microscope (SEM) image of 2 gained sample 2 of embodiment；
[Fig. 3] is scanning electron microscope (SEM) image of 3 gained sample 3 of embodiment；
[Fig. 4] is scanning electron microscope (SEM) image of 4 gained sample 4 of embodiment；
[Fig. 5] is scanning electron microscope (SEM) image of 5 gained sample 5 of embodiment；
[Fig. 6] is the XRD powder diagram of sample prepared by embodiment 1-5；
[Fig. 7] is the DRS UV-vis DRS spectrum of embodiment 2, sample prepared by embodiment 4 and embodiment 5；
[Fig. 8] is the Visible Light Induced Photocatalytic figure of embodiment 2, sample prepared by embodiment 4 and embodiment 5；
Specific embodiment
Implement to be intended to further illustrate the content of present invention below, rather than limits the protection scope of the claims in the present invention.
Embodiment 1 (control experiment group)
1. weighing 113.04mg bismuth and ammonium citrate, 9mg urea is added in 25ml water, it is stirred well at room temperature completely
It is dissolved into white solution；
2. weighing 72.89mg cetyl trimethylammonium bromide (CTAB) to be added in above-mentioned solution；
3. being stirred for 30min after adjusting pH=7, it is transferred in polytetrafluoroethyllining lining, 180 DEG C in stainless steel cauldron
18h is kept the temperature, to cooled to room temperature after reaction；
4. above-mentioned reaction product is collected, after being centrifuged 3 times with the speed of 13000 turns/min respectively with water and alcohol, in 60 DEG C
Lower drying marks sample 1, saves to subsequent detection.
X-ray diffraction identifies that final product is bismuthyl carbonate, but since urea content is low, the pattern of bismuthyl carbonate is shown as
Nano flake is not self-assembled into micro-flowers.(see figure attached 1 and 6)
Embodiment 2
1. weighing 113.04mg bismuth and ammonium citrate, 15mg urea is added in 25ml water, it has been stirred well at room temperature
Fully dissolved is at white solution；
2. weighing 72.89mg cetyl trimethylammonium bromide (CTAB) to be added in above-mentioned solution；
3. being stirred for 30min after adjusting pH=7, it is transferred in polytetrafluoroethyllining lining, 180 DEG C in stainless steel cauldron
18h is kept the temperature, to cooled to room temperature after reaction；
4. above-mentioned reaction product is collected, after being centrifuged 3 times with the speed of 13000 turns/min respectively with water and alcohol, in 60 DEG C
Lower drying marks sample 2, saves to subsequent detection.
Preparation bismuthyl carbonate micro flowery visible light degradation property test it is as follows: in the reactor be added 10mg sample with
The rhodamine B solution (10mg/L) of 15mL is shone after dark field stirring 60min reaches adsorption equilibrium at visible light source (300W xenon lamp)
It penetrates, is sampled from reaction system every 15min, supernatant is taken to measure absorbance after being centrifuged at a high speed.
X-ray diffraction identifies that final product is bismuthyl carbonate, and pattern shows as the micron being self-assembled by nano flake
Flower, about 2.5 μm of diameter, micro-flowers are uniform in size, have large specific surface area (12.64m2·g-1)；Its optical response range is about
420nm, forbidden bandwidth is significantly reduced compared with document report, and bismuthyl carbonate micro flowery photochemical catalyst can drop under visible light illumination
Solve rhodamine B.(see figure attached 2,6,7,8 and table 1)
Embodiment 3 (control experiment group)
The preparation method of bismuthyl carbonate micro flowery of the invention, comprising the following steps:
1. weighing 113.04mg bismuth and ammonium citrate, 45mg urea is added in 25ml water, it has been stirred well at room temperature
Fully dissolved is at white solution；
2. weighing 72.89mg cetyl trimethylammonium bromide (CTAB) to be added in above-mentioned solution；
3. being stirred for 30min after adjusting pH=7, it is transferred in polytetrafluoroethyllining lining, 180 DEG C in stainless steel cauldron
18h is kept the temperature, to cooled to room temperature after reaction；
4. above-mentioned reaction product is collected, after being centrifuged 3 times with the speed of 13000 turns/min respectively with water and alcohol, in 60 DEG C
Lower drying marks sample 3, saves to subsequent detection.
X-ray diffraction identifies that final product is bismuthyl carbonate, and pattern also shows as being assembled into micro-flowers by nanometer sheet, but
The carbon source that may be provided due to urea is excessive, causes self assembly excessive, micro-flowers " blade " are dense, it is clear that drop specific surface area
It is low, it is unfavorable for the quick separating of photo-generated carrier and migration in Photocatalytic Degradation Process.(see figure attached 3 and 6)
Embodiment 4
Metastable phase bismuth oxide β-Bi of the invention2O3/Bi2O2.33@Bi2O2CO3Preparation method, comprising the following steps:
1. weighing 200mg bismuthyl carbonate micro flowery grey powder (sample 2) is to be fully ground in mortar from sacrifice agent
Afterwards, it is added in corundum Noah's ark；
2. Muffle furnace temperature program is arranged, it is heated to 300 DEG C in air with the heating rate of 2.3 DEG C/min, keeps the temperature 4h
Afterwards, it after with furnace cooled to room temperature, collects powder and marks sample 4, save to subsequent detection.
The metastable phase bismuth oxide β-Bi of preparation2O3/Bi2O2.33@Bi2O2CO3Visible light degradation property test it is as follows:
The rhodamine B solution (10mg/L) of 10mg sample and 15mL is added in reactor, after dark field stirring 60min reaches adsorption equilibrium,
It is irradiated at visible light source (300W xenon lamp), is sampled from reaction system every 15min, take supernatant to survey after being centrifuged at a high speed
Determine absorbance.
X-ray diffraction identifies that final product is β-Bi2O3/Bi2O2.33@Bi2O2CO3, pattern be able to maintain that micro-flowers and
Big specific surface area (12.11m2·g-1)；Bi after calcining2O2CO3In there is metastable phase bismuth oxide β-Bi2O3/Bi2O2.33It widens
The optical response range of photochemical catalyst illustrates the β-Bi of this method preparation2O3/Bi2O2.33@Bi2O2CO3It can be improved Solar use
Rate, and degradation property is optimal, can after radiation of visible light 45min degradable rhodamine B.(see figure attached 4,6,7,8 and table 1)
Embodiment 5
Metastable phase bismuth oxide β-Bi of the invention2O3/Bi2O2.33@Bi2O2CO3Preparation method, comprising the following steps:
1. weighing 200mg bismuthyl carbonate micro flowery grey powder (sample 2) is to be fully ground in mortar from sacrifice agent
Afterwards, it is added in corundum Noah's ark；
2. Muffle furnace temperature program is arranged, it is heated to 310 DEG C in air with the heating rate of 2.3 DEG C/min, keeps the temperature 4h
Afterwards, it after with furnace cooled to room temperature, collects powder and marks sample 5, save to subsequent detection.
The metastable phase bismuth oxide β-Bi of preparation2O3/Bi2O2.33@Bi2O2CO3Visible light degradation property test it is as follows:
The rhodamine B solution (10mg/L) of 10mg sample and 15mL is added in reactor, after dark field stirring 60min reaches adsorption equilibrium,
It is irradiated at visible light source (300W xenon lamp), is sampled from reaction system every 15min, take supernatant to survey after being centrifuged at a high speed
Determine absorbance.
X-ray diffraction identifies that final product is β-Bi2O3/Bi2O2.33@Bi2O2CO3, pattern can maintain micron substantially
Colored and specific surface area (12.08m2·g-1), Bi after calcining2O2CO3In there is metastable phase bismuth oxide β-Bi2O3/Bi2O2.33Significantly
The optical response range for widening photochemical catalyst illustrates the β-Bi of this method preparation2O3/Bi2O2.33@Bi2O2CO3It can be improved solar energy
Utilization rate, and degradation property is preferable, it is seen that light irradiates after 45min to rhodamine B degradation rate up to 90%.(see figure attached 5,6,7,8 Hes
Table 1)
Table 1 is the specific surface area of embodiment 2, sample prepared by embodiment 4 and embodiment 5
Claims (4)
1. a kind of preparation method of metastable phase bismuth oxide, it is characterised in that: contain bismuth and ammonium citrate, urea and cetyl front three
The aqueous solution of base ammonium bromide obtains bismuthyl carbonate micro flowery by hydro-thermal reaction；The bismuthyl carbonate micro flowery is placed in air environment
Middle calcining obtains metastable phase bismuth oxide β-Bi2O3/Bi2O2.33@Bi2O2CO3；
The molar ratio of the bismuth and ammonium citrate and urea is 1:0.8~1.2；
The molar ratio of the cetyl trimethylammonium bromide and bismuth and ammonium citrate is 0.6~0.8:1；
The condition of the calcining are as follows: temperature is 290 DEG C~320 DEG C, and the time is 3~5h；
The aqueous solution pH containing bismuth and ammonium citrate, urea and cetyl trimethylammonium bromide is neutrality.
2. the preparation method of metastable phase bismuth oxide according to claim 1, it is characterised in that: the condition of the hydro-thermal reaction
Are as follows: temperature be 140 DEG C~200 DEG C, the time be 12~for 24 hours.
3. the preparation method of metastable phase bismuth oxide according to claim 2, it is characterised in that: the condition of the hydro-thermal reaction
Are as follows: temperature is 160 DEG C~180 DEG C, and the time is 16~20h.
4. the metastable phase bismuth oxide of any one of claims 1 to 3 preparation method preparation is in photocatalytic degradation organic contamination
Application in object, it is characterised in that: as photocatalyst applications in Visible Light Induced Photocatalytic organic pollutant.
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| CN108993474B (en) * | 2018-06-26 | 2020-12-15 | 陕西科技大学 | BiO (bismuth oxide)2-x/Bi2O2.75/Zn2SnO4Composite photocatalyst and preparation method and application thereof |
| CN109317174A (en) * | 2018-10-19 | 2019-02-12 | 岭南师范学院 | A kind of titanium wire network loads three-dimensional bismuthyl carbonate bouquet and its preparation method and application |
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| CN112774706B (en) * | 2021-01-31 | 2023-10-24 | 湖南科技大学 | Bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof |
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