CN108479823A - A kind of different crystalline phase bismuth phosphate photocatalysts and preparation method thereof containing phosphate radical defect - Google Patents
A kind of different crystalline phase bismuth phosphate photocatalysts and preparation method thereof containing phosphate radical defect Download PDFInfo
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- CN108479823A CN108479823A CN201810305386.5A CN201810305386A CN108479823A CN 108479823 A CN108479823 A CN 108479823A CN 201810305386 A CN201810305386 A CN 201810305386A CN 108479823 A CN108479823 A CN 108479823A
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- phosphate
- bismuth
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- defect
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- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 title claims abstract description 209
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 189
- 230000007547 defect Effects 0.000 title claims abstract description 159
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 150
- 239000010452 phosphate Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000013019 agitation Methods 0.000 claims abstract description 21
- 239000013049 sediment Substances 0.000 claims description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000001488 sodium phosphate Substances 0.000 claims description 28
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 28
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052797 bismuth Inorganic materials 0.000 claims description 21
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 21
- 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 21
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 206010001497 Agitation Diseases 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 203
- -1 phosphate radical Chemical class 0.000 description 138
- 235000021317 phosphate Nutrition 0.000 description 135
- 230000015556 catabolic process Effects 0.000 description 33
- 238000006731 degradation reaction Methods 0.000 description 33
- 238000002156 mixing Methods 0.000 description 22
- 238000011001 backwashing Methods 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 239000003643 water by type Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 244000144992 flock Species 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- LGUJZAHTSAGVMX-UHFFFAOYSA-N [Bi].P(O)(O)(O)=O Chemical compound [Bi].P(O)(O)(O)=O LGUJZAHTSAGVMX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/39—Particle morphology extending in three dimensions parallelepiped-like
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The different crystalline phase bismuth phosphate photocatalysts and preparation method thereof containing phosphate radical defect that this application discloses a kind of, the different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect are obtained by preparation processes such as precipitation, centrifuge washing, crystallization, magnetic agitations.The different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect prepared by preparation method shown in the application, pass through the structure of phosphate radical defect, a defect intermediate level is formd between the valence band and conduction band of photochemical catalyst, change the excitation transmission path of light induced electron, the Transport And Transformation of photogenerated charge is promoted, and then inhibits the compound of photo-generate electron-hole pair.Also visible light-responded range has been widened, the utilization rate of visible light is improved, the different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect of preparation is finally made to improve the removal rate to NO.In addition, the production economy of the different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect prepared by preparation method shown in the application is of low cost.
Description
Technical field
This application involves catalyst field more particularly to a kind of different crystalline phase bismuth phosphate photocatalysis containing phosphate radical defect
Agent and preparation method thereof.
Background technology
With the progress of mankind's science and technology civilization, industry has obtained developing on a large scale, and automobile is also more and more universal, largely
Discharged nitrous oxides enter in air.Nitrogen oxides as photochemical fog, acid rain, depletion of the ozone layer pollutant, nitrogen oxides
Have become countries in the world atmosphere pollution urgently to be resolved hurrily.It can be seen that the photocatalysis method of optical drive is as a kind of environmental-friendly
Green technology has all shown good application prospect in environmental pollution purification and solar energy conversion aspect.It can be seen that optical drive
Photocatalysis method nitrogen oxides can be made to occur oxidation reaction under photochemical catalyst effect, generate H2O, nitrate, nitrous acid etc.
And reach innoxious, to environment purification.
Bismuth series photocatalyst has good photocatalytic activity, and can effectively degrade nitrogen oxides.Most of bismuth system light
Catalyst can have visible light catalysis activity by excited by visible light.
But the light quantum transfer efficiency of the bismuth series photocatalyst of prior art preparation is relatively low, photoresponse narrow range, the sun
The presence for the problems such as energy (visible light) utilization rate is low hinders the application of photocatalysis technology.The bismuth system photocatalysis of prior art preparation
Agent cannot build a defect intermediate level between valence band and conduction band, can not change light induced electron and swash from valence band to conduction band transitions
Path is sent out, and then the raising of the transport efficiency of light induced electron can not be promoted.
Invention content
The different crystalline phase bismuth phosphate photocatalysts and preparation method thereof containing phosphate radical defect that this application provides a kind of are led to
It crosses the preparation method and prepares the different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect, due to the shape of phosphate radical defect
At can build a defect intermediate level between the valence band and conduction band of photochemical catalyst, change light induced electron from valence band to leading
Band transition excitation path enhances the purpose of its visible light catalysis activity to reach the light quantum transfer efficiency for improving photochemical catalyst.
First aspect shows that a kind of monocline crystalline phase bismuth phosphate light containing phosphate radical defect is urged according to an embodiment of the present application
The preparation method of agent, the method includes：
After S101 mixes bismuth nitrate with sodium phosphate, salpeter solution is added, obtains white mixture solution；
S102 takes out after the white mixture solution is carried out high temperature hydro-thermal reaction, staticly settles and is cooled to room temperature, obtains
To the first sediment；
The first sediment centrifuge washing is obtained the bismuth phosphate photocatalyst of pure monocline crystalline phase by S103, then by institute
The bismuth phosphate photocatalyst recrystallization for stating pure monocline crystalline phase, obtains recrystallized product；
The recrystallized product is dissolved in reducing agent solution by S104, is staticly settled after magnetic agitation, and the second precipitation is obtained
Object, by the second sediment centrifuge washing；
S105 recrystallizes second sediment after centrifuge washing again, obtains the monoclinic crystal containing phosphate radical defect
Phase bismuth phosphate photocatalyst.
Selectable, the temperature of the high temperature hydro-thermal reaction is 160 DEG C~200 DEG C, and the reaction time is 12h~36h.
Selectable, the solution used in the centrifuge washing is ethyl alcohol and deionized water, and the centrifuge washing includes difference
Successively ethyl alcohol, deionized water respectively wash twice.
Selectable, the temperature of the recrystallization is 40 DEG C~80 DEG C, and recrystallization temperature is 30 DEG C~50 DEG C again.
Selectable, the reducing agent solution includes stabilizer and reducing agent, and the stabilizer is polyvinylpyrrolidone,
The reducing agent is sodium borohydride.
Selectable, the molar ratio that the bismuth nitrate, the sodium phosphate, the sodium borohydride are is 1:2:40.
The application second aspect shows a kind of monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect, described to contain
The monocline crystalline phase bismuth phosphate photocatalyst of phosphate radical defect under conditions of radiation of visible light to the removal rate of NO be 25%~
36%.
The embodiment of the present application third aspect shows a kind of hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect
Preparation method, the method includes：
After S201 mixes bismuth nitrate with sodium phosphate, salpeter solution is added, obtains white mixture solution, white is mixed
Object solution is ultrasonic at room temperature and staticly settles, and obtains the first sediment；
The first sediment centrifuge washing is obtained the bismuth phosphate photocatalyst of pure hexagonal phase by S202, will be described pure
The bismuth phosphate photocatalyst of hexagonal phase recrystallizes, and obtains recrystallized product；
The recrystallized product is dissolved in reducing agent solution by S203, is staticly settled after magnetic agitation, and the second precipitation is obtained
Object, by the second sediment centrifuge washing；
S204 recrystallizes second sediment after centrifuge washing again, obtains the hexagonal crystal containing phosphate radical defect
Phase bismuth phosphate photocatalyst.
Selectable, the molar ratio of the bismuth nitrate and the sodium phosphate is 1:2.
The application fourth aspect shows a kind of hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect, described to contain
The hexagonal phase bismuth phosphate photocatalyst of phosphate radical defect under conditions of radiation of visible light to the removal rate of NO be 38%~
51%.
By above technical scheme it is found that the embodiment of the present application provides a kind of different crystalline phase phosphoric acid containing phosphate radical defect
Bismuth photochemical catalyst and preparation method thereof is added salpeter solution, obtains white after mixing bismuth nitrate with sodium phosphate
Color contamination polymer solution, by white mixture solution at room temperature ultrasound and staticly settle, obtain the first sediment；By described first
Sediment centrifuge washing obtains monocline pure phase bismuth phosphate photocatalyst or six side's pure phase bismuth phosphate photocatalysts, by the monocline
The bismuth phosphate photocatalyst of pure phase or pure hexagonal phase recrystallizes, and obtains recrystallized product；The recrystallized product is dissolved in also
It in former agent solution, is staticly settled after magnetic agitation, obtains the second sediment, by the second sediment centrifuge washing；It will centrifugation
Second sediment after washing recrystallizes again, obtain the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect or
Hexagonal phase bismuth phosphate photocatalyst.Prepared by preparation method shown in the embodiment of the present application containing phosphate radical defect not
With crystalline phase bismuth phosphate photocatalyst one is formd between the valence band and conduction band of photochemical catalyst by the structure of phosphate radical defect
Defect intermediate level changes the excitation transmission path of light induced electron, promotes the Transport And Transformation of photogenerated charge, and then inhibits
Photo-generate electron-hole pair it is compound.Visible light-responded range has also been widened simultaneously, has improved the utilization rate of visible light, finally
The different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect of preparation are made to improve the removal rate to NO.In addition, the application
Implement the production warp of the different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect prepared by the preparation method exemplified
It helps of low cost.
Description of the drawings
In order to illustrate more clearly of the technical solution of the application, letter will be made to attached drawing needed in the embodiment below
Singly introduce, it should be apparent that, for those of ordinary skills, without having to pay creative labor,
Other drawings may also be obtained based on these drawings.
Fig. 1 is a kind of preparation method of the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect of the embodiment of the present application
Flow chart；
Fig. 2 is a kind of preparation method of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect of the embodiment of the present application
Flow chart；
Fig. 3 is the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and pure prepared by the embodiment of the present application 1,2
The XRD diagram of hexagonal phase bismuth phosphate photocatalyst, (XRD is the abbreviation of X-ray diffraction, i.e. X-ray diffraction)；
Fig. 4 is the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect and pure prepared by the embodiment of the present application 3,4
The XRD diagram of monocline crystalline phase bismuth phosphate photocatalyst；
Fig. 5 is the SEM of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 1
Figure, (SEM is the abbreviation of scanning electron microscope, i.e. scanning electron microscope)；
Fig. 6 is the SEM figures of pure hexagonal phase bismuth phosphate photocatalyst prepared by the embodiment of the present application 2；
Fig. 7 is the SEM of the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 3
Figure；
Fig. 8 is the SEM figures of pure monocline crystalline phase bismuth phosphate photocatalyst prepared by the embodiment of the present application 4；
Fig. 9 is the TEM of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 1
Figure, (TEM is the abbreviation of transmission electron microscope, i.e. transmission electron microscope)；
Figure 10 is monocline crystalline phase bismuth phosphate photocatalyst TEM figures prepared by the embodiment of the present application 3；
Figure 11 is the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 1
HRTEM schemes, and (HRTEM is the abbreviation of high resolution transmission electron microscope, i.e. high score
Resolution transmission electron microscope)；
Figure 12 is the HRTEM figures containing monocline crystalline phase bismuth phosphate photocatalyst prepared by the embodiment of the present application 3；
Figure 13 is the XPS of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 1
SURVERY figure, (XPS figures are the abbreviation of X-ray photoelectron spectroscop, i.e., x-ray photoelectron spectroscopy divide
Analysis)；
Figure 14 is the XPS containing phosphate radical defect monocline crystalline phase bismuth phosphate photocatalyst prepared by the embodiment of the present application 3
SURVERY schemes；
Figure 15 is that the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 1 passes through argon
After ion surface sputters 20nm depth, the high-resolution XPS figures of the Bi 4f of respective crystalline phase；
Figure 16 is that the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 3 passes through argon
After ion surface sputters 20nm depth, the high-resolution XPS figures of the Bi 4f of respective crystalline phase；
Figure 17 is the different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect prepared by the embodiment of the present application 1,2,3,4
Respectively accordingly the PL of the bismuth phosphate photocatalyst of pure crystalline phase schemes, and (PL is the abbreviation of Photoluminescence, i.e. fluorescence
Spectrum)；
Figure 18 is the different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect prepared by the embodiment of the present application 1,2,3,4
Respectively accordingly the UV-Vis DRS of the bismuth phosphate photocatalyst of pure crystalline phase scheme, and (UV-Vis DRS are UV-Visible
Diffuse-reflection spectra, i.e. UV-vis DRS)；
Figure 19 is the different crystalline phase bismuth phosphate photocatalysis containing phosphate radical defect prepared by the embodiment of the present application 1,2,3,4,5
The bismuth phosphate photocatalyst of agent and respective accordingly pure crystalline phase is under visible light conditions to the degradation efficiency comparison chart of NO degradations；
Figure 20 is the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and pure prepared by the embodiment of the present application 1,2
Hexagonal phase bismuth phosphate photocatalyst detects figure under visible light conditions to the living radical of NO degradations；
Figure 21 is the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect and pure prepared by the embodiment of the present application 3,4
Monocline crystalline phase bismuth phosphate photocatalyst detects figure under visible light conditions to the living radical of NO degradations；
Figure 22 is the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and pure prepared by the embodiment of the present application 1,2
Hexagonal phase bismuth phosphate photocatalyst detects figure under visible light conditions to the living radical of NO degradations；
Figure 23 is the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect and pure prepared by the embodiment of the present application 3,4
Monocline crystalline phase bismuth phosphate photocatalyst detects figure under visible light conditions to the living radical of NO degradations；
Figure 24 is the DOS of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 1
Figure, (DOS is Density of states, the i.e. density of states)；
Figure 25 is the DOS of the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 3
Figure；
Figure 26 is the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and pure prepared by the embodiment of the present application 1,2
The solid phase ESR figures of hexagonal phase bismuth phosphate photocatalyst；
Figure 27 is the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect and pure prepared by the embodiment of the present application 3,4
The solid phase ESR figures of monocline crystalline phase bismuth phosphate photocatalyst；
Figure 28 is the original position of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 1
Infrared figure；
Figure 29 is the original position of the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application 3
Infrared figure.
Wherein, H-BPO-50 is the hexagonal phase phosphorus containing phosphate radical defect prepared by the preparation method shown in embodiment 1
Sour bismuth photochemical catalyst；H-BPO is pure hexagonal phase bismuth phosphate photocatalyst prepared by the preparation method shown in embodiment 2；M-
BPO-50 is the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the preparation method shown in embodiment 3；M-
BPO is pure monocline crystalline phase bismuth phosphate photocatalyst prepared by the preparation method shown in embodiment 4；H-BPO-30 is that embodiment 5 is shown
Hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the preparation method gone out；H-BPO-10 is that embodiment 6 is shown
Hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the preparation method gone out；M-BPO-30 is that embodiment 7 is shown
Monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the preparation method gone out；M-BPO-10 is that embodiment 8 is shown
Monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the preparation method gone out.
Specific implementation mode
With reference to the attached drawing in the application, technical solutions in the embodiments of the present application is clearly and completely described,
Obviously, described embodiment is only a part of the embodiment of the application, instead of all the embodiments.Based in the application
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts,
It shall fall within the protection scope of the present invention.
Many details are elaborated in the following description in order to fully understand the application, but the application can be with
It is different from the other modes that describe again using other to implement, those skilled in the art can be without prejudice to the application intension
In the case of do similar popularization, therefore the application is not limited by following public specific embodiment.
Fig. 1 is a kind of system of monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect shown in the embodiment of the present application
Preparation Method, the method includes：
After S101 mixes bismuth nitrate with sodium phosphate, salpeter solution is added, obtains white mixture solution；
S102 takes out after the white mixture solution is carried out high temperature hydro-thermal reaction, staticly settles and is cooled to room temperature, obtains
To the first sediment；
The first sediment centrifuge washing is obtained the bismuth phosphate photocatalyst of pure monocline crystalline phase by S103, then by institute
The bismuth phosphate photocatalyst recrystallization for stating pure monocline crystalline phase, obtains recrystallized product；
The recrystallized product is dissolved in reducing agent solution by S104, is staticly settled after magnetic agitation, and the second precipitation is obtained
Object, by the second sediment centrifuge washing；
S105 recrystallizes second sediment after centrifuge washing again, obtains the monoclinic crystal containing phosphate radical defect
Phase bismuth phosphate photocatalyst.
Fig. 2 is a kind of system of hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect shown in the embodiment of the present application
Preparation Method, the method includes：
After S201 mixes bismuth nitrate with sodium phosphate, salpeter solution is added, obtains white mixture solution, white is mixed
Object solution is ultrasonic at room temperature and staticly settles, and obtains the first sediment；
The first sediment centrifuge washing is obtained the bismuth phosphate photocatalyst of pure hexagonal phase by S202, will be described pure
The bismuth phosphate photocatalyst of hexagonal phase recrystallizes, and obtains recrystallized product；
The recrystallized product is dissolved in reducing agent solution by S203, is staticly settled after magnetic agitation, and the second precipitation is obtained
Object, by the second sediment centrifuge washing；
S204 recrystallizes second sediment after centrifuge washing again, obtains the hexagonal crystal containing phosphate radical defect
Phase bismuth phosphate photocatalyst.
Experiment is it is found that the hexagonal phase bismuth phosphate containing phosphate radical defect prepared by above-mentioned preparation method by analysis
Photochemical catalyst and monocline crystalline phase bismuth phosphate photocatalyst its catalytic activity containing phosphate radical defect are higher than respective pure phase phosphoric acid
The catalytic activity of bismuth, and preparation method is simple, is conducive to actual application.
By to prepared by the embodiment of the present application the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and contain
There is the monocline crystalline phase bismuth phosphate photocatalyst of phosphate radical defect to be characterized, it can be seen that the hexagonal phase phosphorus containing phosphate radical defect
Sour bismuth photochemical catalyst and monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect have following characteristic：
(1) to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and the monocline crystalline phase containing phosphate radical defect
Bismuth phosphate photocatalyst carries out XRD analysis (as shown in Figure 3,4), it was demonstrated that has prepared the phosphorus of hexagonal phase and monocline crystalline phase respectively
Sour bismuth photochemical catalyst.
(2) to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect, pure hexagonal phase bismuth phosphate photocatalyst,
Monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect, pure monocline crystalline phase bismuth phosphate photocatalyst carry out sem analysis (such as
Shown in Fig. 5,6,7,8), it was demonstrated that the hexagonal phase containing phosphate radical defect prepared by the preparation method shown in the embodiment of the present application 1
Bismuth phosphate photocatalyst is made of the nanometer sheet and some circular granulars of stratiform；And the preparation method shown in the embodiment of the present application 3
The monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect prepared is made of bar-shaped nanostructure and some circular granulars；
Monocline crystalline phase bismuth phosphate light to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and containing phosphate radical defect is urged
Agent carries out tem analysis (as shown in Figures 9 and 10), can further confirm containing for the preparation of the preparation method shown in the embodiment of the present application
There are the hexagonal phase bismuth phosphate photocatalyst of phosphate radical defect and the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect
Laminar nano piece appearance structure.
(3) to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and the monocline crystalline phase containing phosphate radical defect
Bismuth phosphate photocatalyst carries out HRTEM analyses (as shown in Figure 11,12), and clearly lattice fringe can be observed.
(4) to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and the monocline crystalline phase containing phosphate radical defect
Bismuth phosphate photocatalyst carries out XPS analysis (as shown in Figure 13,14), it was demonstrated that the hexagonal phase bismuth phosphate light containing phosphate radical defect
There is Bi, P, O, C element in catalyst and monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect.
(5) to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and the monocline crystalline phase containing phosphate radical defect
Bismuth phosphate photocatalyst, after argon ion surface sputters 20nm depth, the high-resolution XPS figures of the Bi 4f of respective crystalline phase carry out
It analyzes (as shown in Figure 15,16), there is the peak position of zeroth order bismuth element to be formed after sputtering can be observed, it was confirmed that have the generation of bismuth simple substance
In bismuth phosphate photocatalyst.
(6) to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and the monocline crystalline phase containing phosphate radical defect
Bismuth phosphate photocatalyst carries out PL test analysis (as shown in figure 17), it was demonstrated that the hexagonal phase bismuth phosphate light containing phosphate radical defect
Catalyst and monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect make PL strength reductions, promote light induced electron and
The separation in hole.
(7) to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect, the monocline crystalline phase containing phosphate radical defect
Bismuth phosphate photocatalyst, pure hexagonal phase bismuth phosphate photocatalyst and pure monocline crystalline phase bismuth phosphate photocatalyst carry out UV-Vis
DRS analyzes (as shown in figure 18), it was demonstrated that the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect and scarce containing phosphate radical
Sunken monocline crystalline phase bismuth phosphate photocatalyst can increase the absorbability of light in ultraviolet-visible-infrared region, widen light suction
Range is received, while Red Shift Phenomena has occurred.
The application is to the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect, the monoclinic crystal containing phosphate radical defect
Phase bismuth phosphate photocatalyst, pure hexagonal phase bismuth phosphate photocatalyst and pure monocline crystalline phase bismuth phosphate photocatalyst performance are surveyed
Examination.Test process is as follows：
(1) by 0.2 gram of embodiment prepare the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect, contain phosphoric acid
Monocline crystalline phase bismuth phosphate photocatalyst, pure hexagonal phase bismuth phosphate photocatalyst and the pure monocline crystalline phase bismuth phosphate light of root defect are urged
Agent is placed in NO continuous flows in reactor.
(2) under dark condition, when NO concentration reaches balance, it is the halogen tungsten lamp of 150W as visible light to use power
Source, and with the edge filter filtering ultraviolet light of 420nm, when NO concentration reaches balance to six sides containing phosphate radical defect
Crystalline phase bismuth phosphate photocatalyst, the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect, pure hexagonal phase bismuth phosphate light
Catalyst and pure monocline crystalline phase bismuth phosphate photocatalyst are irradiated.
The condition of above-mentioned catalytic performance test process is：Relative humidity 60%, oxygen content 21%, the flow of NO air-flows
Initial concentration for 2.4L/min, NO is 500ppb.
Hexagonal phase bismuth phosphate photocatalyst provided by the embodiments of the present application containing phosphate radical defect contains phosphate radical
The degradation that the monocline crystalline phase bismuth phosphate photocatalyst of defect degrades to NO is as follows：
(1) the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect or the monocline crystalline phase phosphorus containing phosphate radical defect
Sour bismuth photochemical catalyst is 36%-51% (as shown in figure 19) to the degradation rate of NO, to be apparently higher than pure phase bismuth phosphate photocatalyst
To the degradation rate of NO, the calculation formula of degradation rate is η (%)=(1-C/C0) × 100%, C0For initial NO concentration, C is illumination
The instantaneous concentration of NO after 30min.
(2) superoxide anion (O2 -) and hydroxyl radical free radical (OH) be the hexagonal phase bismuth phosphate containing phosphate radical defect
Photochemical catalyst or monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect are degraded the main drop of NO under visible light conditions
Solve free radical (as shown in Figure 20,21,22,23).
(3) compared to pure monocline crystalline phase bismuth phosphate photocatalyst, pure hexagonal crystal it can be seen from Density function theory
Phase bismuth phosphate photocatalyst, the bismuth phosphate photocatalyst after reducing agent is further processed, phosphate radical defect is in its respective valence
Defect intermediate level is formd between band and conduction band.This changes light induced electron from valence band to conduction band transitions excitation path, by original
Electronics becomes the migration pattern of valence band → defect intermediate level → conduction band from the migration path of valence band → conduction band.Effectively increase light
The transport efficiency of raw electronics, inhibits the compound of photo-generate electron-hole pair to a certain extent, improves catalyst well can
The light-exposed lower degradation rate to NO (as shown in Figure 24,25).
(4) the monocline crystalline phase after reducing agent is further processed, the bismuth phosphate photocatalyst of hexagonal phase, compared to it
The respectively bismuth phosphate photocatalyst background that is not further processed, the signal peak enhanced in figure are regarded as the letter of phosphate radical defect
Number.This also illustrates that phosphate radical defect is successfully built in bismuth phosphate photocatalyst (as shown in Figure 26,27).
(5) compared to the bismuth phosphate photocatalyst of pure phase, the original position of the bismuth phosphate photocatalyst containing phosphate radical defect is red
Occurs intermediate product NO in outer collection of illustrative plates+, it was demonstrated that the conversion pathway for affecting NO degradations of phosphate radical defect promotes photoproduction load
The Transport And Transformation of son is flowed, while being conducive to the absorption and conversion of NO, promotes photochemical catalyst to the removal performance of NO pollutants (as schemed
28, shown in 29).
Embodiment 1：
1) bismuth nitrate, sodium phosphate and 1ml nitric acid (4mol/l) are added in the 100ml beakers containing 46mL deionized waters,
Bismuth nitrate, sodium phosphate molar ratio be 1:2, ultrasonic disperse mixing 30 minutes, staticly settle and detach and obtain with solution at room temperature
To white flock precipitate, with ethyl alcohol and deionized water, front and back washing is each twice respectively, obtains the first sediment；
2) the first sediment is recrystallized under the conditions of 60 DEG C in an oven, obtains the bismuth phosphate light of pure hexagonal phase
Catalyst；
3) bismuth phosphate photocatalyst of 0.25 gram of pure hexagonal phase is weighed, 0.25 gram of polyvinylpyrrolidone addition is equipped with
In the 100ml beakers of 50ml deionized waters, magnetic agitation mixing, obtains white mixture solution, is then added dropwise dropwise at room temperature
For sodium borohydride (50mmol) solution of 15ml in white mixture solution, it is heavy to be stood after magnetic agitation mixing again at room temperature
It forms sediment, obtains the second sediment.
4) after the second sediment being used to ethyl alcohol and deionized water again front and back washing being each twice respectively, in 40 DEG C of conditions of baking oven
Under recrystallized, finally obtain the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect.
To the embodiment of the present application prepare the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect by XRD,
SEM, TEM, HRTEM, XPS, PL, UV-Vis DRS, ESR, In-situ Infrared are characterized.
Hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect prepared by the embodiment of the present application degrades to NO
With its determining photocatalytic activity, detailed process is：It is in the flow of relative humidity 60%, oxygen content 21%, NO air-flows
Under conditions of the initial concentration of 2.4L/min, NO are 500ppb, six sides containing phosphate radical defect prepared by 0.2g embodiments
It is the halogen tungsten lamp of 150W as visible light source that crystalline phase bismuth phosphate photocatalyst, which is placed in NO continuous flows and in reactor, uses power,
And with the edge filter filtering ultraviolet light of 420nm, when NO concentration reaches balance to described containing phosphate radical defect six
Prismatic crystal phase bismuth phosphate photocatalyst is irradiated, and the hexagonal crystal containing phosphate radical defect of the embodiment of the present application preparation is calculated
Phase bismuth phosphate photocatalyst photochemical catalyst is 51% to the degradation rate of NO.
Embodiment 2：
1) bismuth nitrate, sodium phosphate, 1ml nitric acid (4mol/l), nitre are added in the 100ml beakers containing 46mL deionized waters
Sour bismuth, sodium phosphate molar ratio be 1:2, ultrasonic disperse mixing 30 minutes, staticly settle and detach and obtain with solution at room temperature
White flock precipitate, with ethyl alcohol and deionized water, front and back washing is each twice respectively, obtains the first sediment；
2) the first sediment is recrystallized under the conditions of 60 DEG C in an oven, obtains pure hexagonal phase bismuth phosphate light and urges
Agent.
To the embodiment of the present application prepare pure hexagonal phase bismuth phosphate photocatalyst characterization and the degradation of NO was tested
Journey is the same as embodiment 1.The bismuth phosphate photocatalyst photochemical catalyst of the pure hexagonal phase of the embodiment of the present application preparation is calculated to NO
Degradation rate be 2%.
Embodiment 3：
1) bismuth nitrate, sodium phosphate, 1ml nitric acid (4mol/l), nitre are added in the 100ml beakers containing 46mL deionized waters
Sour bismuth, sodium phosphate molar ratio be 1:2, ultrasonic disperse mixing 30 minutes at room temperature are transferred to 100ml water heating kettles, at 180 DEG C
Hydro-thermal reaction is for 24 hours；It is cooled to room temperature after reaction, with ethyl alcohol and deionized water, front and back washing is each twice respectively, obtains first
Sediment；
2) the first sediment is recrystallized under the conditions of 60 DEG C in an oven, obtains the bismuth phosphate light of pure monocline crystalline phase
Catalyst；
3) bismuth phosphate photocatalyst of 0.25 gram of pure monocline crystalline phase is weighed, 0.25 gram of polyvinylpyrrolidone addition is equipped with
In the 100ml beakers of 50ml deionized waters, magnetic agitation mixing, obtains white mixture solution at room temperature；Then it is added dropwise dropwise
For sodium borohydride (50mmol) solution of 15ml in white mixture solution, it is heavy to be stood after magnetic agitation mixing again at room temperature
It forms sediment, obtains the second sediment；
4) after the second sediment being used to ethyl alcohol and deionized water again front and back washing being each twice respectively, in 40 DEG C of conditions of baking oven
Under recrystallized, finally obtain the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect.
The characterization of the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect that prepared to the embodiment of the present application and right
The degradation test process of NO is the same as embodiment 1.The monocline crystalline phase containing phosphate radical defect of the embodiment of the present application preparation is calculated
Bismuth phosphate photocatalyst is 36% to the degradation rate of NO.
Embodiment 4：
1) bismuth nitrate, sodium phosphate, 1ml nitric acid (4mol/l), nitre are added in the 100ml beakers containing 46mL deionized waters
Sour bismuth, sodium phosphate molar ratio be 1:2, ultrasonic disperse mixing 30 minutes at room temperature are transferred to 100ml water heating kettles, at 180 DEG C
Hydro-thermal reaction for 24 hours, is cooled to room temperature after reaction, and with ethyl alcohol and deionized water, front and back washing is each twice respectively, obtains first
Sediment.
2) the first sediment is recrystallized under the conditions of 60 DEG C in an oven, obtains pure monocline crystalline phase bismuth phosphate light and urges
Agent.
To the embodiment of the present application 4 prepare pure monocline crystalline phase bismuth phosphate photocatalyst characterization and the degradation of NO was tested
Cheng Tong
Embodiment 1.Pure monocline crystalline phase photochemical catalyst prepared by the embodiment of the present application is calculated is to the degradation rate of NO
2%.
Embodiment 5：
1) bismuth nitrate, sodium phosphate, 1ml nitric acid (4mol/l), nitre are added in the 100ml beakers containing 46mL deionized waters
Sour bismuth, sodium phosphate molar ratio be 1:2, ultrasonic disperse mixing 30 minutes, staticly settle and detach and obtain with solution at room temperature
White flock precipitate, with ethyl alcohol and deionized water, front and back washing is each twice respectively, obtains the first sediment；
2) the first sediment is recrystallized under the conditions of 60 DEG C in an oven, obtains the bismuth phosphate light of pure hexagonal phase
Catalyst；
3) bismuth phosphate photocatalyst of 0.25 gram of pure hexagonal phase is weighed, 0.25 gram of polyvinylpyrrolidone addition is equipped with
In the 100ml beakers of 50ml deionized waters, magnetic agitation mixing, obtains white mixture solution, is then added dropwise dropwise at room temperature
For sodium borohydride (30mmol) solution of 15ml in white mixture solution, it is heavy to be stood after magnetic agitation mixing again at room temperature
It forms sediment, obtains the second sediment；
4) after the second sediment being used to ethyl alcohol and deionized water again front and back washing being each twice respectively, in 40 DEG C of conditions of baking oven
Under recrystallized, finally obtain the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect.
The characterization of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect that prepared to the embodiment of the present application and right
The degradation test process of NO is the same as embodiment 1.The hexagonal phase containing phosphate radical defect of the embodiment of the present application preparation is calculated
Bismuth phosphate photocatalyst is 38% to the degradation rate of NO.
Embodiment 6：
1) bismuth nitrate, sodium phosphate, 1ml nitric acid (4mol/l), nitre are added in the 100ml beakers containing 46mL deionized waters
Sour bismuth, sodium phosphate molar ratio be 1:2, ultrasonic disperse mixing 30 minutes, staticly settle and detach and obtain with solution at room temperature
White flock precipitate, with ethyl alcohol and deionized water, front and back washing is each twice respectively, obtains the first sediment；
2) the first sediment is recrystallized under the conditions of 60 DEG C in an oven, obtains the bismuth phosphate light of pure hexagonal phase
Catalyst；
3) bismuth phosphate photocatalyst of 0.25 gram of pure hexagonal phase is weighed, 0.25 gram of polyvinylpyrrolidone addition is equipped with
In the 100ml beakers of 50ml deionized waters, magnetic agitation mixing, obtains white mixture solution at room temperature；Then it is added dropwise dropwise
For sodium borohydride (10mmol) solution of 15ml in white mixture solution, it is heavy to be stood after magnetic agitation mixing again at room temperature
It forms sediment, obtains the second sediment；
4) after the second sediment being used to ethyl alcohol and deionized water again front and back washing being each twice respectively, in 40 DEG C of conditions of baking oven
Under recrystallized, finally obtain the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect.
The characterization of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect that prepared to the embodiment of the present application and right
The degradation test process of NO is the same as embodiment 1.The hexagonal phase containing phosphate radical defect of the embodiment of the present application preparation is calculated
Bismuth phosphate photocatalyst is 45% to the degradation rate of NO.
Embodiment 7：
1) bismuth nitrate, sodium phosphate, 1ml nitric acid (4mol/l), nitre are added in the 100ml beakers containing 46mL deionized waters
Sour bismuth, sodium phosphate molar ratio be 1:2, ultrasonic disperse mixing 30 minutes at room temperature are transferred to 100ml water heating kettles, at 180 DEG C
Hydro-thermal reaction for 24 hours, is cooled to room temperature after reaction, and with ethyl alcohol and deionized water, front and back washing is each twice respectively, obtains first
Sediment；
2) the first sediment is recrystallized under the conditions of 60 DEG C in an oven, obtains the bismuth phosphate light of pure monocline crystalline phase
Catalyst；
3) bismuth phosphate photocatalyst of 0.25 gram of pure monocline crystalline phase is weighed, 0.25 gram of polyvinylpyrrolidone addition is equipped with
In the 100ml beakers of 50ml deionized waters, magnetic agitation mixing, obtains white mixture solution, is then added dropwise dropwise at room temperature
For sodium borohydride (30mmol) solution of 15ml in white mixture solution, it is heavy to be stood after magnetic agitation mixing again at room temperature
It forms sediment, obtains the second sediment；
4) after the second sediment being used to ethyl alcohol and deionized water again front and back washing being each twice respectively, in 40 DEG C of conditions of baking oven
Under recrystallized, finally obtain the monocline crystalline phase phosphate radical photochemical catalyst containing phosphate radical defect.
The characterization of the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect that prepared to the embodiment of the present application and right
The degradation test process of NO is the same as embodiment 1.The monocline crystalline phase containing phosphate radical defect of the embodiment of the present application preparation is calculated
Bismuth phosphate photocatalyst is 30% to the degradation rate of NO.
Embodiment 8：
1) bismuth nitrate, sodium phosphate, 1ml nitric acid (4mol/l), nitre are added in the 100ml beakers containing 46mL deionized waters
Sour bismuth, sodium phosphate molar ratio be 1:2, ultrasonic disperse mixing 30 minutes at room temperature are transferred to 100ml water heating kettles, at 180 DEG C
Hydro-thermal reaction for 24 hours, is cooled to room temperature after reaction, and with ethyl alcohol and deionized water, front and back washing is each twice respectively, obtains first
Sediment；
2) the first sediment is recrystallized under the conditions of 60 DEG C in an oven, obtains the bismuth phosphate light of pure monocline crystalline phase
Catalyst；
3) bismuth phosphate photocatalyst of 0.25 gram of pure monocline crystalline phase is weighed, 0.25 gram of polyvinylpyrrolidone addition is equipped with
In the 100ml beakers of 50ml deionized waters, magnetic agitation mixing, obtains white mixture solution, is then added dropwise dropwise at room temperature
For sodium borohydride (10mmol) solution of 15ml in white mixture solution, it is heavy to be stood after magnetic agitation mixing again at room temperature
It forms sediment, obtains the second sediment；
4) after the second sediment being used to ethyl alcohol and deionized water again front and back washing being each twice respectively, in 40 DEG C of conditions of baking oven
Under recrystallized, finally obtain the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect.
The characterization of the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect that prepared to the embodiment of the present application and right
The degradation test process of NO is the same as embodiment 1.The monocline crystalline phase containing phosphate radical defect of the embodiment of the present application preparation is calculated
Bismuth phosphate photocatalyst is 25% to the degradation rate of NO.
Table 1 is the degradation rate that each photochemical catalyst degrades to NO in above-described embodiment 1-8：
As it can be seen from table 1 by building that phosphate radical defect prepares on photochemical catalyst containing phosphate radical defect
Hexagonal phase bismuth phosphate photocatalyst and the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect are opposite to the degradation of NO
In pure hexagonal phase bismuth phosphate photocatalyst, pure monocline crystalline phase bismuth phosphate for the degradation of NO, the former degradation effect is apparent
It improves.As soon as this is because phosphate radical defect forms a defect intermediate level between photochemical catalyst valence band and conduction band, this also changes
Become light induced electron from valence band to conduction band transitions excitation path, becomes valence band from original electronics from the migration path of valence band → conduction band
The migration pattern of → defect intermediate level → conduction band.The transport efficiency for effectively increasing light induced electron, inhibits to a certain extent
Photo-generate electron-hole pair it is compound, improve catalyst well under visible light to the degradation rate of NO.Side provided by the present application
Method economic cost is cheap, and operation is simple.Generated simultaneously using bismuth simple substance improve on photochemical catalyst photochemical catalyst can
Light-exposed absorption region enhances the performance of photochemical catalyst.
It should be noted that the hexagonal phase bismuth phosphate photocatalyst provided by the embodiments of the present application containing phosphate radical defect
With the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect to the nitrogen oxygen of sulfide, volatile organic compounds, non-NO
The catalytic mechanism of other air pollutants such as compound is identical as the catalytic mechanism to nitrogen oxides, therefore in the embodiment of the present application
It is representative by testing the degradation of NO.
It is apparent to those skilled in the art although describing the application in a manner of specific embodiment
, in the case where not departing from spirit and scope defined by the appended claims, can to the application into
Row variations and modifications, these change and modification are also included in scope of the present application.
By above technical scheme it is found that the embodiment of the present application provides a kind of different crystalline phase phosphoric acid containing phosphate radical defect
Bismuth photochemical catalyst and preparation method thereof is added salpeter solution, obtains white after mixing bismuth nitrate with sodium phosphate
Color contamination polymer solution, by white mixture solution at room temperature ultrasound and staticly settle, obtain the first sediment；By described first
Sediment centrifuge washing obtains monocline pure phase bismuth phosphate photocatalyst or six side's pure phase bismuth phosphate photocatalysts, by the monocline
The bismuth phosphate photocatalyst of pure phase or pure hexagonal phase recrystallizes, and obtains recrystallized product；The recrystallized product is dissolved in also
It in former agent solution, is staticly settled after magnetic agitation, obtains the second sediment, by the second sediment centrifuge washing；It will be described
Second sediment recrystallizes again, obtains the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect or hexagonal phase phosphoric acid
Bismuth photochemical catalyst.The different crystalline phase bismuth phosphates containing phosphate radical defect prepared by preparation method shown in the embodiment of the present application
Photochemical catalyst forms a defect intermediate level by the structure of phosphate radical defect between the valence band and conduction band of photochemical catalyst,
The excitation transmission path for changing light induced electron, promotes the Transport And Transformation of photogenerated charge, and then inhibits photo-generate electron-hole
To it is compound.Visible light-responded range has also been widened simultaneously, has improved the utilization rate of visible light, finally make preparation contains phosphorus
The different crystalline phase bismuth phosphate photocatalysts of acid group defect improve the removal rate to NO.In addition, the system shown in the embodiment of the present application
The production economy of the different crystalline phase bismuth phosphate photocatalysts containing phosphate radical defect prepared by Preparation Method is of low cost.
It the above is only the specific implementation mode of the application, it is noted that those skilled in the art are come
It says, under the premise of not departing from the application principle, several improvements and modifications can also be made, these improvements and modifications also should be regarded as
The protection domain of the application.
Claims (10)
1. a kind of preparation method of the monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect, which is characterized in that the side
Method includes：
After S101 mixes bismuth nitrate with sodium phosphate, salpeter solution is added, obtains white mixture solution；
S102 will the white mixture solution carry out high temperature hydro-thermal reaction after take out, staticly settle and be cooled to room temperature, obtain the
One sediment；
The first sediment centrifuge washing is obtained the bismuth phosphate photocatalyst of pure monocline crystalline phase by S103, then will be described pure
The bismuth phosphate photocatalyst of monocline crystalline phase recrystallizes, and obtains recrystallized product；
The recrystallized product is dissolved in reducing agent solution by S104, is staticly settled after magnetic agitation, and the second sediment is obtained, will
The second sediment centrifuge washing；
S105 recrystallizes second sediment after centrifuge washing again, obtains the monocline crystalline phase phosphorus containing phosphate radical defect
Sour bismuth photochemical catalyst.
2. preparation method as described in claim 1, which is characterized in that the temperature of the high temperature hydro-thermal reaction is 160 DEG C~200
DEG C, the reaction time is 12h~36h.
3. preparation method as described in claim 1, which is characterized in that solution used in the centrifuge washing be ethyl alcohol and go from
Sub- water, the centrifuge washing include being taken up in order of priority respectively to be washed twice with ethyl alcohol, deionized water.
4. preparation method as described in claim 1, which is characterized in that the temperature of the recrystallization is 40 DEG C~80 DEG C, again
Recrystallization temperature is 30 DEG C~50 DEG C.
5. preparation method as described in claim 1, which is characterized in that the reducing agent solution includes stabilizer and reducing agent,
The stabilizer is polyvinylpyrrolidone, and the reducing agent is sodium borohydride.
6. preparation method as claimed in claim 5, which is characterized in that the bismuth nitrate, the sodium phosphate, the sodium borohydride
For molar ratio be 1:2:40.
7. a kind of monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect, which is characterized in that the bismuth phosphate photocatalysis
Agent is prepared by the preparation method described in claim 1-6 any one；
The monocline crystalline phase bismuth phosphate photocatalyst containing phosphate radical defect is under conditions of radiation of visible light to the removal of NO
Rate is 25%~36%.
8. a kind of preparation method of the hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect, which is characterized in that the side
Method includes：
After S201 mixes bismuth nitrate with sodium phosphate, salpeter solution is added, obtains white mixture solution, white mixture is molten
Liquid is ultrasonic at room temperature and staticly settles, and obtains the first sediment；
The first sediment centrifuge washing is obtained the bismuth phosphate photocatalyst of pure hexagonal phase by S202, by pure six side
The bismuth phosphate photocatalyst of crystalline phase recrystallizes, and obtains recrystallized product；
The recrystallized product is dissolved in reducing agent solution by S203, is staticly settled after magnetic agitation, and the second sediment is obtained, will
The second sediment centrifuge washing；
S204 recrystallizes second sediment after centrifuge washing again, obtains the hexagonal phase phosphorus containing phosphate radical defect
Sour bismuth photochemical catalyst.
9. preparation method as claimed in claim 8, which is characterized in that the molar ratio of the bismuth nitrate and the sodium phosphate is 1:
2。
10. a kind of hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect, which is characterized in that the bismuth phosphate photocatalysis
Agent is prepared by the preparation method described in claim 8 or 9；
The hexagonal phase bismuth phosphate photocatalyst containing phosphate radical defect is under conditions of radiation of visible light to the removal of NO
Rate is 38%~51%.
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| CN113385210A (en) * | 2021-06-08 | 2021-09-14 | 太原理工大学 | Photocatalytic hydrogen production catalyst and preparation method and application thereof |
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| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
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