CN109647462A - A kind of preparation method and application of Bi base catalyst - Google Patents
A kind of preparation method and application of Bi base catalyst Download PDFInfo
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- CN109647462A CN109647462A CN201910046293.XA CN201910046293A CN109647462A CN 109647462 A CN109647462 A CN 109647462A CN 201910046293 A CN201910046293 A CN 201910046293A CN 109647462 A CN109647462 A CN 109647462A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 20
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 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 abstract description 10
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000005457 ice water Substances 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000006166 lysate Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 22
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 20
- 239000000975 dye Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 15
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 7
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 7
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 5
- 229940052223 basic fuchsin Drugs 0.000 description 5
- 239000013256 coordination polymer Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 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 description 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910001451 bismuth ion Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052695 Americium Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910052781 Neptunium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- LXQXZNRPTYVCNG-UHFFFAOYSA-N americium atom Chemical compound [Am] LXQXZNRPTYVCNG-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 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
- 230000002596 correlated effect Effects 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- LFNLGNPSGWYGGD-UHFFFAOYSA-N neptunium atom Chemical compound [Np] LFNLGNPSGWYGGD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- -1 reaction is simple Chemical compound 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method and applications of Bi base catalyst, this method comprises the following steps: polyphosphoric acids (1) being dissolved in the mixed liquor of water or ethyl alcohol or water and ethyl alcohol, poly phosphoric acid solution is made, in ice-water bath, Bi salt is added, stirring dissolves Bi salt;(2) inorganic acid solution is added in the lysate of step (1), is stirred evenly;(3) mixed liquor of step (2) is stood, precipitating, by washing, drying and grinds to obtain BiPO4, or the mixed liquor of step (2) is transferred in reaction kettle, it seals, carries out hydro-thermal process, wash, dry and grind up to BiPO4.Being completely dissolved for bismuth nitrate is realized using polyphosphoric acids ice-water bath, and no hydrolysis phenomena occurs, the BiPO being prepared4It, can a variety of different types of dyestuffs of high efficiency photocatalysis degradation and mixed dye pollutant with different pattern and crystal phase.
Description
Technical field
The present invention relates to micro Nano material preparation, in particular to a kind of preparation method and application of Bi base catalyst.
Background technique
Global industry metaplasia produces and also brings serious environmental pollution while rapid development.Especially water environment pollution is asked
The living environment that threaten the mankind increasingly severely is inscribed, society and economic progress are restrict.Therefore, it water pollution control and controls
Reason becomes the hot issue that the whole world is paid close attention to jointly.Printing and dyeing industry is one of the world's largest pollution sources and water resources consumption person.
There are about the waste water from dyestuff of 1.6 billion cubic meters to discharge into natural water every year in China according to investigations, causes the serious pollution of water body.But mesh
The method of preceding water process is big, highly concentrated pollutant mostly for discharge amount, having of being difficult to convert low for concentration in water body
There are no very effective methods for the purification of machine pollutant, and Photocatalyst developed in recent years is this problem
Solution provide preferable approach.
BiPO4It is a kind of important Bi based nano-material, it is not only stable, safe and non-toxic, and also being proved to be one kind can
With photocatalysis degradation organic contaminant, fluorescence radiation, catalysis organic synthesis, sensor and can be used for radioactive element (uranium, americium,
Plutonium, neptunium etc.) measurement and nuclear waste disposal multifunctional material.Currently, synthesis BiPO4Method be mainly liquid phase method: hydro-thermal
Method, solvent-thermal method, microwave method, ultrasonic method etc..The source Bi used is mostly Bi (NO3)3.However, Bi salt is extremely easy hydrolysis, cause
BiPO4Synthesis process be difficult to, the BiPO of preparation4Microstructure appearance is single.Existing literature is disclosed using organic solvent come molten
Bismuth nitrate is solved, but on the one hand organic solvent increases production cost, on the other hand serious pollution environment, instrument and equipment and damage
Operator's health.Also there is document to disclose using nitric acid the acid-base property for adjusting reaction solution simultaneously, but bismuth nitrate cannot
It is completely dissolved, and the phosphorus source used is single, such as sodium phosphate (Na3PO4) and phosphoric acid (H3PO4) etc., phosphate radical therein
(PO4 3-) directly with bismuth ion (Bi3+) reaction generation bismuth phosphate (BiPO4), reaction is simple, bismuth phosphate pattern is single.
Summary of the invention
Goal of the invention: it is an object of the present invention to provide a kind of preparation methods of Bi base catalyst, utilize polyphosphoric acids ice-water bath
Realize being completely dissolved for bismuth nitrate, no hydrolysis phenomena occurs, the BiPO being prepared4With different pattern and crystal phase.
It is a further object of the present invention to provide a kind of application of Bi base catalyst, which can high efficiency photocatalysis drop
Solve a variety of different types of dyestuffs and mixed dye pollutant.
Technical solution: the present invention provides a kind of preparation method of Bi base catalyst, includes the following steps:
(1) polyphosphoric acids is dissolved in the mixed liquor of water or ethyl alcohol or water and ethyl alcohol, poly phosphoric acid solution is made, in ice-water bath
In, Bi salt is added, stirring dissolves Bi salt;
(2) inorganic acid solution is added in the lysate of step (1), is stirred evenly;
(3) mixed liquor of step (2) is stood, precipitating, by washing, drying and grinds to obtain BiPO4, or by step (2)
Mixed liquor be transferred in reaction kettle, seal, carry out hydro-thermal process, wash, dry and grind up to BiPO4。
Further, the Bi salt of the step (1) is bismuth nitrate.
Further, step (2) inorganic acid is phosphoric acid, sulfuric acid, nitric acid or hydrochloric acid.
Further, the concentration of step (2) inorganic acid solution is 1.2~9mol/L.
Further, the concentration of step (1) poly phosphoric acid solution is 0.06~1g/mL.
Further, the quality that bismuth nitrate is added in the step (1) is less than the quality of polyphosphoric acids.
Bismuth phosphate BiPO4Synthesis be substantially and use bismuth nitrate as bismuth source, however bismuth source, especially bismuth nitrate easily water
Solution cannot be dissolved in water and form uniform solution, further affect bismuth ion and participate in reaction, cause BiPO4Synthesis process it is difficult
With regulation, the BiPO of preparation4Microstructure appearance is single.Polyphosphoric acids, can be under water environment due to its unique paradigmatic structure
Bismuth nitrate is completely dissolved to form uniform clear solution, provides condition for subsequent correlated response.Then pass through control reaction
Acid environment (sulfuric acid, nitric acid, hydrochloric acid etc. the is added) crystal phase of Lai Shixian bismuth phosphate of liquid and the regulation of pattern.
The structural formula of polyphosphoric acids is as follows:
The Bi base catalyst is applied to the degradation of organic pollutant in environment water.Pass through the organic mould of photocatalytic degradation
Quasi- pollutant has investigated the photocatalysis performance of bismuth phosphate prepared by the present invention, finds it not only and can effectively degrade and is a variety of not of the same race
The organic dye pollutant of class, and the mixed liquor for a variety of organic dye pollutants that can degrade simultaneously, it is shown that bismuth phosphate exists
Potential application in terms of environmental improvement.
The utility model has the advantages that the BiPO with different-shape and crystal phase is prepared by the method for the invention4Material, such as China's folding
Fan is fan-shaped, with rugby shape amphitrichous, hexagonal prism etc..This method simple process, reaction condition are mild, can be to avoid Bi salt water
Solution, reaction is controllable, while raw materials used cheap and easy to get, effectively reduces cost.BiPO of the invention4Applied to environment water
The photocatalytic degradation of middle Some Organic Pollutants, the high advantage of active stability, can effectively protect environment.
Detailed description of the invention
Fig. 1 be embodiment 1 (BIP-PP), embodiment 2 (BIP-SP), embodiment 3 (BIP-NP), embodiment 4 (BIP-CP),
BiPO obtained by embodiment 5 (BIP-PH), embodiment 6 (BIP-NH) and embodiment 7 (BIP-CH)4XRD diagram;
Fig. 2 is 1 gained BiPO of embodiment4SEM figure;
Fig. 3 is 2 gained BiPO of embodiment4SEM figure (upper right corner illustration for its amplification SEM figure);
Fig. 4 is 3 gained BiPO of embodiment4SEM figure;
Fig. 5 is 4 gained BiPO of embodiment4SEM figure;
Fig. 6 is 5 gained BiPO of embodiment4SEM figure;
Fig. 7 is 6 gained BiPO of embodiment4SEM figure;
Fig. 8 is 7 gained BiPO of embodiment4SEM figure;
Fig. 9 is 5 gained BiPO of embodiment4Photocatalysis degradation organic contaminant curve graph;
Figure 10 is 5 gained BiPO of embodiment4Photocatalytic degradation xylenol orange, the isometric mixed liquor of Congo red and bromocresol green
The Line Chart of (elecrtonegativity dyestuff mixed liquor);
Figure 11 is 5 gained BiPO of embodiment4Photocatalytic degradation brilliant cresyl blue, basic fuchsin and methyl orange mix in equal volume
The Line Chart of liquid (electropositive dyestuff mixed liquor);
Figure 12 is 5 gained BiPO of embodiment4Photocatalytic degradation brilliant cresyl blue, xylenol orange and Congo red isometric mixing
The Line Chart of liquid (positive elecrtonegativity dyestuff mixed liquor);
Figure 13 is 5 gained BiPO of embodiment4Reuse 15 minutes degradation rates of photocatalytic degradation xylenol orange and catalysis
The degradation rate comparison diagram that agent is degraded xylenol orange 15 minutes after placing 4 years.
Specific embodiment
Bi salt in following embodiment is only with Bi (NO3)3·5H2O, other Bi salt with effects equivalent are similarly suitable
It answers.
Embodiment 1: reference examples
The present embodiment prepares BiPO as follows4(BIP-PP):
Step 1, the phosphoric acid of 6.66mL is dissolved in 13.33mL water;
Step 2, by the Bi (NO of 0.967g3)3·5H2Above-mentioned solution is added in O, makes it dissolve;
Step 3, above-mentioned mixed liquor is stood 2 days to its precipitating, by washing, drying and ground up to BiPO4。
The powder x-ray diffraction analysis (XRD) of BIP-PP sample prepared by the present embodiment is as shown in Figure 1, can by figure
Know, all diffraction maximums of BIP-PP are and BiPO4Standard hexagonal phase (JCPDS:15-0766) it is consistent, illustrate that the method obtains
Arrive be pure phase hexagonal phase BiPO4.Fig. 2 is scanning electron microscope (SEM) figure of BIP-PP, and as seen from the figure, BIP-PP is by wadding a quilt with cotton
Shape nano particle or dispersion or composition of reuniting.
Embodiment 2
The present embodiment prepares BiPO as follows4(BIP-SP):
Step 1, the polyphosphoric acids of 1.014g is dissolved in 13.33mL ethyl alcohol;
Step 2, by the Bi (N0 of 0.967g3)3·5H2Above-mentioned solution is added in O, makes it dissolve, solution clarification;
Step 3, above-mentioned solution is added in the sulfuric acid of 6.66mL, stirred evenly;
Step 4, above-mentioned mixed liquor is stood 2 days to its precipitating, by washing, drying and ground up to BiPO4。
The XRD of BIP-SP sample prepared by the present embodiment is as shown in Figure 1, from the figure 3, it may be seen that all diffraction maximums of BIP-SP
Also and BiPO4Standard hexagonal phase (JCPDS:15-0766) it is consistent, illustrating that the method obtains is the hexagonal phase of pure phase
BiPO4.Schemed by Fig. 3 SEM it is found that BIP-SP is made of uniform hexagonal prism.
Embodiment 3
The present embodiment preparation BiPO same as Example 24(BIP-NP), the difference is that being the water of 16mL in step 1;
It is the nitric acid of 4mL in step 3.
The XRD of BIP-NP sample prepared by the present embodiment is as shown in Figure 1, as shown in Figure 4, all diffraction maximums of BIP-NP
Also and BiPO4Standard hexagonal phase (JCPDS:45-1370) it is consistent, illustrating that the method obtains is another hexagonal phase
BiPO4.Schemed by Fig. 4 SEM it is found that the pattern of BIP-NP is fan-shaped for Chinese folding fan.
Embodiment 4
The present embodiment preparation BiPO same as Example 24(BIP-CP), the difference is that for 18.2mL's in step 1
Water;It is the hydrochloric acid of 1.82mL in step 3.
The XRD of BIP-CP sample prepared by the present embodiment is as shown in Figure 1, as shown in Figure 5, BIP-CP is identical by two kinds
The material composition of content: the BiPO of hexagonal phase4(JCPDS:15-0766) and the BiOCl of tetragonal phase (JCPDS:06-0249).It says
Bright the method can be used for step preparation BiOCl/BiPO4Nanocomposite.Schemed by Fig. 5 SEM it is found that the pattern of BIP-CP is band
Rugby shape amphitrichous.
Embodiment 5
The present embodiment preparation BiPO same as Example 14(BIP-PH), the difference is that reagent amount used is all amplified
4 times;It is transferred to reaction kettle in step 3, seals, hydrothermal temperature and time are 160 DEG C and 12 hours, to its natural cooling, are passed through
It washs, dry and grinds up to BiPO4。
The XRD of BIP-PH sample prepared by the present embodiment is as shown in Figure 1, it will be appreciated from fig. 6 that BIP-PH is the monocline of pure phase
Phase BiPO4(JCPDS:15-0767).Schemed by Fig. 6 SEM it is found that BIP-PH is made of nanometer rods and polyhedron.By with implementation
Example 1 is compared, it can be found that can regulate and control BiPO by improving synthesis temperature4The transformation of crystal phase and pattern.
BiPO obtained by the present embodiment4Photocatalytic degradation brilliant cresyl blue, basic fuchsin and the isometric mixed liquor of methyl orange are (just
Electrical dyestuff mixed liquor) Line Chart see Figure 11;BiPO obtained by the present embodiment4Photocatalytic degradation brilliant cresyl blue, xylenol orange
Figure 12 is seen with the Line Chart of Congo red isometric mixed liquor (positive elecrtonegativity dyestuff mixed liquor);BiPO obtained by the present embodiment4It repeats
Degradation xylenol orange degradation in 15 minutes after being placed 4 years using 15 minutes degradation rates of photocatalytic degradation xylenol orange and catalyst
Rate comparison diagram is shown in Figure 13.
Embodiment 6
The present embodiment preparation BiPO same as Example 34(BIP-NH), the difference is that reagent amount used is all amplified
4 times;It is transferred to reaction kettle in step 4, seals, hydrothermal temperature and time are 160 DEG C and 12 hours, to its natural cooling, are passed through
It washs, dry and grinds up to BiPO4。
The XRD of BIP-NH sample prepared by the present embodiment is as shown in Figure 1, as shown in Figure 7, BIP-NH is the monocline of pure phase
Phase BiPO4(JCPDS:15-0767).Schemed by Fig. 7 SEM it is found that BIP-NH is made of micron polyhedron.By with embodiment 3
It compares, it can be found that BiPO can be regulated and controled by improving synthesis temperature4The transformation of crystal phase and pattern.
Embodiment 7
The present embodiment preparation BiPO same as Example 44(BIP-CH), the difference is that reagent amount used is all amplified
4 times;It is transferred to reaction kettle in step 4, seals, hydrothermal temperature and time are 160 DEG C and 12 hours, to its natural cooling, are passed through
It washs, dry and grinds up to BiPO4。
The XRD of BIP-CH sample prepared by the present embodiment is as shown in Figure 1, as shown in Figure 8, BIP-CH is six sides of pure phase
Phase BiPO4(JCPDS:15-0766).Schemed by Fig. 8 SEM it is found that BIP-CH pattern is atrichous rugby shape.By with implementation
Example 4 is compared, it can be found that BiOCl can be promoted as BiPO by improving synthesis temperature4The transformation of crystal phase modulation and pattern.
Performance test
By the BiPO of the embodiment of the present invention 54(BIP-PH) sample be used for photocatalysis degradation organic contaminant, detailed process and
Steps are as follows:
Brilliant cresyl blue, basic fuchsin, the xylenol orange, Congo red, bromocresol green, methylene blue of 10ppm are prepared respectively
And methyl orange aqueous solution.By the BIP-PH sample degradation organic pollutant solution of embodiment 5, as a result as shown in figure 9, magnificent cresols
Blue, xylenol orange and bromocresol green can be completely degraded after illumination 15 minutes;Congo red and methylene blue is in illumination 20
It is completely degraded after minute;Basic fuchsin and methyl orange also can realize that 100% is degraded after 25 minutes.Photocatalytic degradation experiment
Show BiPO4Nano material all has extraordinary photocatalytic degradation to different types of organic pollutant under ultraviolet light
Effect.
A variety of different dye molecules are usually contained in actual dying, in order to further investigate it to simulating pollution
The degradation capability of object is mixed according to the electrical property of dye molecule and is made into different types of simulating pollution object aqueous solution: the first
Elecrtonegativity dyestuff mixed liquor: xylenol orange, Congo red and bromocresol green are mixed be made into equal volume;Second of electropositive dyestuff is mixed
It closes liquid: brilliant cresyl blue, basic fuchsin and methyl orange being mixed in equal volume and are made into;The third positive elecrtonegativity dyestuff mixed liquor: will
Brilliant cresyl blue, xylenol orange and Congo red isometric mixing are made into.Practical degradation effect is respectively such as Figure 10, Figure 11 and Figure 12 institute
Show.As seen from the figure, BiPO prepared by the present invention4Elecrtonegativity mixed dye, electropositive mixed dye and positive elecrtonegativity are mixed and contaminated
Material waste water simulating pollution object all shows excellent degradation effect.
In addition to the high efficiency of catalyst, the stability of catalyst is also the important parameter of the practical application of catalyst.In order to
Investigate catalyst activity stability, by catalyst circulation use 5 degradation xylenol orange, by Figure 13 it can be seen that, BiPO4Again
After being recycled five times, 100% is still maintained to the degradation rate of xylenol orange, photocatalytic activity does not reduce, explanation
Prepared BiPO4There is good activity stability.On the other hand, practical application of the stability of catalyst to catalyst
BiPO critically important, that on December 10th, 2014 is synthesized4, it is stored in plastic tube with cover, tests it on December 29th, 2018
The performance of degradation xylenol orange, as seen from Figure 13, sample after it placed 4 years, still protect by the degradation rate of degradation xylenol orange
Hold 99.9%, it is shown that good stability.
Claims (7)
1. a kind of preparation method of Bi base catalyst, characterized by the following steps:
(1) polyphosphoric acids is dissolved in the mixed liquor of water or ethyl alcohol or water and ethyl alcohol, poly phosphoric acid solution is made, in ice-water bath,
Bi salt is added, stirring dissolves Bi salt;
(2) inorganic acid solution is added in the lysate of step (1), is stirred evenly;
(3) mixed liquor of step (2) is stood, precipitating, by washing, drying and grinds to obtain BiPO4, or by the mixing of step (2)
Liquid is transferred in reaction kettle, and sealing carries out hydro-thermal process, is washed, dries and is ground up to BiPO4。
2. the preparation method of Bi base catalyst according to claim 1, it is characterised in that: the Bi salt of the step (1) is
Bismuth nitrate.
3. the preparation method of Bi base catalyst according to claim 1, it is characterised in that: step (2) inorganic acid is
Phosphoric acid, sulfuric acid, nitric acid or hydrochloric acid.
4. the preparation method of Bi base catalyst according to claim 1, it is characterised in that: step (2) inorganic acid is molten
The concentration of liquid is 1.2~9mol/L.
5. the preparation method of Bi base catalyst according to claim 1, it is characterised in that: step (1) polyphosphoric acids
The concentration of solution is 0.06~1g/mL.
6. the preparation method of Bi base catalyst according to claim 1, it is characterised in that: Bi salt adds in the step (1)
Enter the amount that amount is less than polyphosphoric acids.
7. a kind of application of Bi base catalyst, it is characterised in that: the described in any item Bi base catalyst applications of claim 1~6
The degradation of organic pollutant in environment water.
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Cited By (2)
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CN113893840A (en) * | 2021-08-31 | 2022-01-07 | 浙江树人学院(浙江树人大学) | Composite photocatalyst, preparation method and application in dye wastewater |
CN115155629A (en) * | 2022-06-29 | 2022-10-11 | 衢州学院 | Bi/BiPO 4 Preparation method and application of/BiOCl nanosheet composite material |
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CN108134090A (en) * | 2017-12-19 | 2018-06-08 | 中南大学 | A kind of nanometer of bismuth/carbon composite and preparation method thereof |
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EP0366544A1 (en) * | 1988-10-28 | 1990-05-02 | Boehringer Ingelheim France | Method for the preparation of a bismuth phosphate gel |
CN1506157A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Solid phosphoric acid catalyst and its prepn process |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113893840A (en) * | 2021-08-31 | 2022-01-07 | 浙江树人学院(浙江树人大学) | Composite photocatalyst, preparation method and application in dye wastewater |
CN115155629A (en) * | 2022-06-29 | 2022-10-11 | 衢州学院 | Bi/BiPO 4 Preparation method and application of/BiOCl nanosheet composite material |
CN115155629B (en) * | 2022-06-29 | 2023-05-02 | 衢州学院 | Bi/BiPO 4 Preparation method and application of BiOCl nano-sheet composite material |
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