CN107961785A - A kind of preparation method and applications of high activity bismuth chromate nano-photocatalyst - Google Patents
A kind of preparation method and applications of high activity bismuth chromate nano-photocatalyst Download PDFInfo
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- CN107961785A CN107961785A CN201711286334.XA CN201711286334A CN107961785A CN 107961785 A CN107961785 A CN 107961785A CN 201711286334 A CN201711286334 A CN 201711286334A CN 107961785 A CN107961785 A CN 107961785A
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- bismuth chromate
- photochemical catalyst
- bismuth
- mentioned steps
- chromate
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- DHMGMTYGCBZFST-UHFFFAOYSA-N dibismuth;dioxido(dioxo)chromium Chemical compound [Bi+3].[Bi+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O DHMGMTYGCBZFST-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 230000000694 effects Effects 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 11
- 235000010355 mannitol Nutrition 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 150000004690 nonahydrates Chemical class 0.000 claims abstract description 9
- 229940064457 osmitrol Drugs 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 77
- 239000010865 sewage Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229930195725 Mannitol Natural products 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000594 mannitol Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 3
- 238000011109 contamination Methods 0.000 claims description 3
- 244000178870 Lavandula angustifolia Species 0.000 claims 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 claims 1
- 239000001102 lavandula vera Substances 0.000 claims 1
- 235000018219 lavender Nutrition 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical group C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 description 2
- 241001104043 Syringa Species 0.000 description 2
- 235000004338 Syringa vulgaris Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical group [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/14—Chromates; Bichromates
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method and applications of high activity bismuth chromate nano-photocatalyst, belong to technical field of nano material.Five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate are dissolved in Osmitrol first；Saturated aqueous sodium carbonate is added dropwise into solution, and is uniformly mixing to obtain emulsion；Emulsion is transferred to hydro-thermal reaction in hydrothermal reaction kettle, after being cooled to room temperature, centrifuges, wash and dry to obtain precursor powder, precursor powder is calcined, obtains bismuth chromate nano-photocatalyst.Using a process for preparing bismuth chromate nano-photocatalyst, size is in 40~50nm scopes, light absorbs band edge can be extended to red light district, there is efficient photocatalysis contaminant degradation and production oxygen activity in visible region at the same time, the sub- efficiency of oxygen-producing amount at 600nm has reached 1.52%, also with extraordinary photostability.In the preparation method that this method provides, raw material is inexpensive, and technique is simple, is adapted to industrial mass production, has good application prospect.
Description
Technical field
The present invention relates to a kind of preparation method and applications of high activity bismuth chromate nano-photocatalyst, high activity bismuth chromate
Molecular formula be Bi7.38Cr0.62O12+x, belong to technical field of nano material.
Background technology
Since the discovery of Honda-rattan island effect, water is directly decomposed using semiconductor light-catalyst becomes solar energy
Utilize most one of desirable route with being converted into chemical energy.However, reach can the liberation of hydrogen speed of practical application usually require very
High overpotential, this is mainly due to the dynamic (dynamical) result of slow oxygen evolution reaction.Although the production oxygen catalysis of photocatalysis in recent years
Agent is quickly grown, such as pucherite, oxide, although the production oxygen performance of these catalyst increases, efficiency is still very
It is low, it is mainly due to the following aspects：(1) light abstraction width is narrow；(2) photo-generate electron-hole is to compound fast；(3) light is stablized
Property is poor.Therefore, from the perspective of practical application, exploitation is urged with the good light of broad absorption band, high-quantum efficiency and stability
Change production VPO catalysts to be very important in artificial photosynthesis.
The content of the invention
The purpose of the present invention is to propose to a kind of preparation method and applications of high activity bismuth chromate nano-photocatalyst, pass through
Simple Hydrothermal Synthesiss combination high-temperature calcination is handled, and prepares that particle size is small, light abstraction width is wide, the bismuth chromate light of high activity
Catalyst, using the visible optical property of the material, can be widely used in producing the technical fields such as oxygen, sewage disposal.
The preparation method of high activity bismuth chromate nano-photocatalyst proposed by the present invention, includes the following steps：
(1) at room temperature, five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate are dissolved in Osmitrol, obtained pale purple
Color clear solution, wherein, the concentration of five nitric hydrate bismuths is 0.02~0.08mol/L, five nitric hydrate bismuths and nine nitric hydrates
The molar ratio of chromium is 12:1, the concentration of mannitol solution is 0.5~5mol/L；
(2) aqueous sodium carbonate of 1~5ml saturations is added dropwise into the solution of above-mentioned steps (1), continuously stirs to obtain
Lilac emulsion；
(3) emulsion of above-mentioned steps (2) is transferred in hydrothermal reaction kettle, under the conditions of 130~180 DEG C react 6~
12h, after natural cooling, obtains the precipitation of celadon；
(4) precipitation of above-mentioned steps (3) is filtered, collects solid, solid is fully washed with deionized water, and will be solid
Body is dried in vacuo, and vacuum drying temperature is 60~80 DEG C, and drying time is 6~12h, obtains celadon powder；
(5) powder of above-mentioned steps (4) is placed in Muffle furnace 5~10min of calcining under the conditions of 500~580 DEG C, existed side by side
Quick cooling is taken out, obtains orange-red bismuth chromate photochemical catalyst.
Above-mentioned high activity bismuth chromate photochemical catalyst proposed by the present invention, bismuth chromate photocatalyst applications are produced in photocatalysis
Oxygen, comprises the following steps：
(1) bismuth chromate photochemical catalyst is added in water, and the mass volume ratio of bismuth chromate photochemical catalyst and water is 0.05~2g/
L；
(2) silver nitrate is added in the reaction system of above-mentioned steps (1) as sacrifice agent, the addition of silver nitrate is chromic acid
The 10 of bismuth photochemical catalyst2~105Times；
(3) reaction system of above-mentioned steps (2), output oxygen are irradiated with the light source that wavelength is 300~850nm.
The application of high activity bismuth chromate photochemical catalyst proposed by the present invention, bismuth chromate photocatalyst applications are dirty in photocatalysis
Water process, application process comprise the following steps：
(1) bismuth chromate photochemical catalyst, the addition quality of bismuth chromate photochemical catalyst are added in the sewage that organic contamination produces
Volume ratio is 0.5~5g/L；
(2) it is sufficiently stirred, bismuth chromate photochemical catalyst is uniformly dispersed in sewage；
(3) sewage of above-mentioned steps (2) is irradiated with the light source that wavelength is 300~850nm, irradiation time reaches row for sewage
Put standard.
The preparation method and applications of high activity bismuth chromate nano-photocatalyst proposed by the present invention, its advantage are：
1st, bismuth chromate photochemical catalyst prepared by the method for the present invention, compared to commercialized titanium dioxide (P25) photochemical catalyst,
Bismuth chromate photochemical catalyst has the light abstraction width of non-constant width, can will absorb band edge and extend to 610nm, therefore with very high
Photocatalysis quantum efficiency；Meanwhile its suitable position of energy band so that hydroxyl radical free radical can as main active specy, because
This bismuth chromate photochemical catalyst has very strong mineralization ability to organic pollution.
2nd, the method for the present invention is handled by simple hydro-thermal reaction combination high-temperature calcination, is prepared for the bismuth chromate light of high activity
Catalyst, and preparation method is easy to operate, is easy to repeat, and provides good technical foundation for commercial applications and material is protected
Card.
3rd, the bismuth chromate photochemical catalyst for preparing of the present invention, under visible light being capable of effectively catalytic degradation organic pollution
Thing, therefore there is self-care effect for environmental pollution；Under visible light illumination, water decomposition precipitated oxygen can be catalyzed, therefore can
For producing clean energy resource.
Brief description of the drawings
Fig. 1 is the powder x-ray diffraction spectrum of the bismuth chromate photochemical catalyst prepared in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the bismuth chromate photochemical catalyst prepared in embodiment 1.
Fig. 3 is the transmission electron microscope picture of the bismuth chromate photochemical catalyst prepared in embodiment 1.
Fig. 4 is the high power transmission electron microscope picture of the bismuth chromate photochemical catalyst prepared in embodiment 1.
Fig. 5 is the electronic energy spectrum of the bismuth chromate photochemical catalyst prepared in embodiment 1.
Fig. 6 is the UV-Vis DRS spectrum of the bismuth chromate photochemical catalyst prepared in embodiment 1.
Fig. 7 is the surface photovoltaic spectroscopy of the bismuth chromate photochemical catalyst prepared in embodiment 1.
Fig. 8 is the scanning electron microscope (SEM) photograph of the bismuth chromate photochemical catalyst prepared in embodiment 2.
Fig. 9 is the transmission electron microscope picture of the bismuth chromate photochemical catalyst prepared in embodiment 2.
Figure 10 is the Photocatalytic Degradation of Phenol sewage of bismuth chromate photochemical catalyst in embodiment 3.
Figure 11 is the total organic Carbon removal of Pyrogentisinic Acid's sewage of bismuth chromate photochemical catalyst in embodiment 3.
Figure 12 is the Photocatalytic Degradation of Phenol sewage under the different wave length of bismuth chromate photochemical catalyst in embodiment 3.
Figure 13 is the photocatalysis Decomposition aquatic products oxygen of bismuth chromate photochemical catalyst in embodiment 4.
Figure 14 is the sub- efficiency of photochemical catalyzing oxygen-producing amount of bismuth chromate photochemical catalyst in embodiment 4.
Figure 15 is the circulation photocatalysis Decomposition aquatic products oxygen of bismuth chromate photochemical catalyst in embodiment 4.
Embodiment
The preparation method of high activity bismuth chromate nano-photocatalyst proposed by the present invention, includes the following steps：
(1) at room temperature, five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate are dissolved in Osmitrol, obtained pale purple
Color clear solution, wherein, the concentration of five nitric hydrate bismuths is 0.02~0.08mol/L, five nitric hydrate bismuths and nine nitric hydrates
The molar ratio of chromium is 12:1, the concentration of mannitol solution is 0.5~5mol/L；
(2) aqueous sodium carbonate of 1~5ml saturations is added dropwise into the solution of above-mentioned steps (1), continuously stirs to obtain
Lilac emulsion；
(3) emulsion of above-mentioned steps (2) is transferred in hydrothermal reaction kettle, under the conditions of 130~180 DEG C react 6~
12h, after natural cooling, obtains the precipitation of celadon；
(4) precipitation of above-mentioned steps (3) is filtered, collects solid, solid is fully washed with deionized water, and will be solid
Body is dried in vacuo, and vacuum drying temperature is 60~80 DEG C, and drying time is 6~12h, obtains celadon powder；
(5) powder of above-mentioned steps (4) is placed in Muffle furnace 5~10min of calcining under the conditions of 500~580 DEG C, existed side by side
Quick cooling is taken out, obtains orange-red bismuth chromate photochemical catalyst.
Above-mentioned high activity bismuth chromate photochemical catalyst proposed by the present invention, bismuth chromate photocatalyst applications are produced in photocatalysis
Oxygen, comprises the following steps：
(1) bismuth chromate photochemical catalyst is added in water, and the mass volume ratio of bismuth chromate photochemical catalyst and water is 0.05~2g/
L；
(2) silver nitrate is added in the reaction system of above-mentioned steps (1) as sacrifice agent, the addition of silver nitrate is chromic acid
The 10 of bismuth photochemical catalyst2~105Times, can be depending on the output demand of oxygen；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, output oxygen.
The application of high activity bismuth chromate photochemical catalyst proposed by the present invention, bismuth chromate photocatalyst applications are dirty in photocatalysis
Water process, application process comprise the following steps：
(1) bismuth chromate photochemical catalyst, the addition quality of bismuth chromate photochemical catalyst are added in the sewage that organic contamination produces
Volume ratio is 0.5~5g/L；
(2) it is sufficiently stirred, bismuth chromate photochemical catalyst is uniformly dispersed in sewage；
(3) sewage of above-mentioned steps (2) is irradiated with the light source that wavelength is 300~850nm, which can be monochromatic
Light source or ordinary light source, irradiation time reach discharge standard for sewage.
The embodiment of the present invention introduced below, material, reagent used in following embodiments etc., can be from business way
Footpath obtains.
Embodiment 1, prepare bismuth chromate photochemical catalyst
(1) at room temperature, five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate are dissolved in Osmitrol, obtained pale purple
Color clear solution, wherein, (five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate rub for 0.04mol/L for the concentration of five nitric hydrate bismuths
You are than being 12:1), the concentration of mannitol solution is 0.15mol/L；
(2) aqueous sodium carbonate of 5ml saturations is added dropwise into the solution of above-mentioned steps (1), continuously stirs to obtain light
The emulsion of purple；
(3) emulsion of above-mentioned steps (2) is transferred in hydrothermal reaction kettle, 12h is reacted under the conditions of 150 DEG C, it is natural
After cooling, the precipitation of celadon is obtained；
(4) precipitation of above-mentioned steps (3) is filtered, collects solid, solid is fully washed with deionized water, and will be solid
Body is dried in vacuo, and vacuum drying temperature is 80 DEG C, and drying time 6h, obtains celadon powder；
(5) powder of above-mentioned steps (4) is placed in Muffle furnace under the conditions of 520 DEG C and calcines 10min, and taken out immediately fast
Quickly cooling but, obtains orange-red bismuth chromate photochemical catalyst.
Composed from the powder x-ray diffraction of Fig. 1, the sample of preparation belongs to tetragonal structure (JCPDS No.50-0373)
Bismuth chromate (Bi7.38Cr0.62O12+x).It can see from the surface sweeping electron microscope and transmission electron microscope picture of Fig. 2 and Fig. 3, the chromic acid of synthesis
Bismuth photochemical catalyst sample is in flaky nanometer structure, and particle size is in 40~50nm scopes.Can by the electron spectroscopy data of Fig. 4
Know, the constituent of bismuth chromate photochemical catalyst is mainly comprising three kinds of bismuth, chromium, oxygen elements, ratio 12.1:1.0:19.5, this with
Its stoichiometric ratio is very close.In the high power transmission electron microscope picture of Fig. 5, the clear orderly lattice fringe of bismuth chromate photochemical catalyst
Disclose its highly crystalline feature.It can be seen that, bismuth chromate photochemical catalyst is can from the UV-Vis DRS spectrum of Fig. 6
Jian Guang areas have shown the absorption region of non-constant width, can will absorb band edge and expand to red light district, utilize Kubelka-Munk functions
It is 2.03eV to obtain its energy gap.The energy gap meets the thermodynamics energy criteria of water decomposition reaction, this causes bismuth chromate
Photochemical catalyst becomes a kind of very potential catalysis material.In the surface photovoltaic spectroscopy of Fig. 7, with its absorption spectrum one
Cause, the photovoltage response range of bismuth chromate photochemical catalyst also can be extended to red light district, and show very strong photovoltage
Signal, illustrates that bismuth chromate photochemical catalyst has the separative efficiency of very efficient photo-generate electron-hole pair.Moreover, its positive photoelectricity
Pressure response demonstrates the N-type semiconductor characteristic of bismuth chromate, also indicates that its photohole is shifted to surface, this is conducive to its light and urges
Change oxidation susceptibility.
Embodiment 2, prepare bismuth chromate photochemical catalyst
(1) at room temperature, five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate are dissolved in Osmitrol, obtained pale purple
Color clear solution, wherein, (five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate rub for 0.08mol/L for the concentration of five nitric hydrate bismuths
You are than being 12:1), the concentration of mannitol solution is 0.2mol/L；
(2) aqueous sodium carbonate of 2ml saturations is added dropwise into the solution of above-mentioned steps (1), continuously stirs to obtain light
The emulsion of purple；
(3) emulsion of above-mentioned steps (2) is transferred in hydrothermal reaction kettle, 6h is reacted under the conditions of 180 DEG C, it is naturally cold
But after, the precipitation of celadon is obtained；
(4) precipitation of above-mentioned steps (3) is filtered, collects solid, solid is fully washed with deionized water, and will be solid
Body is dried in vacuo, and vacuum drying temperature is 60 DEG C, and drying time 12h, obtains celadon powder；
(5) powder of above-mentioned steps (4) is placed in Muffle furnace under the conditions of 560 DEG C and calcines 5min, and taken out immediately fast
Quickly cooling but, obtains orange-red bismuth chromate photochemical catalyst.
It is observed that the bismuth chromate photochemical catalyst prepared is in from the transmission electron microscope picture of the scanning electron microscope (SEM) photograph of Fig. 8 and Fig. 9
Flaky nanometer structure, particle size is in 40~50nm scopes.
The Photocatalytic Degradation of Phenol sewage of embodiment 3, bismuth chromate photochemical catalyst
(1) in 50mL, 25mg tetracarboxylic phenyl porphyrin supermolecule photochemical catalysts are added in the sewage that phenol concentration is 5ppm；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst；
(3) sewage of above-mentioned steps (2) is irradiated with the light source that wavelength is 300~850nm, irradiation time reaches row for sewage
The standard of putting is limited.
It can see from the phenol degrading curve and corresponding total organic Carbon removal (shown in Figure 11) of Figure 10, bismuth chromate
Photochemical catalyst has shown efficient catalytic degradation activity and strong mineralization ability under visible light, the degradation rate of Pyrogentisinic Acid in 6h
75% and 60% are respectively reached with total organic Carbon removal, its degradation rate constant is silver orthophosphate, carbonitride and wolframic acid respectively
2.2,19.6 and 20.2 times of bismuth photochemical catalyst, and its mineralization ability is catalyzed apparently higher than the visible light activity reported at present
Agent.Meanwhile in the phenol degrading data under the different wave length of Figure 12, the rate of photocatalytic oxidation of bismuth chromate photochemical catalyst with
The variation tendency of wavelength is consistent with its UV-Vis DRS curvilinear motion, or even Pyrogentisinic Acid's progress is remained able at 600nm
Effectively mineralising.
The photocatalytic water splitting production oxygen of embodiment 4, bismuth chromate photochemical catalyst
(1) bismuth chromate photochemical catalyst is added in 100ml water, the addition quality of bismuth chromate photochemical catalyst is 50mg, ultrasound
It is scattered to obtain aaerosol solution；
(2) silver nitrate is added into the aaerosol solution of above-mentioned steps (1), the dosage of silver nitrate is 10ml, and concentration is
0.05mol/L；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength.
As can see from Figure 13, bismuth chromate photochemical catalyst has shown efficient photocatalytic water splitting production oxygen activity,
Its production oxygen speed has reached 1540.4 μm of olg under visible ray-1·h-1, it is silver orthophosphate and the 11.7 of carbonitride and 23.0 respectively
Times, its sub- efficiency of oxygen-producing amount at 600nm has reached 1.52% (Figure 14), although the pucherite and tungsten oxide reported in recent years
There is the sub- efficiency of very high oxygen-producing amount Deng visible light catalyst, but the optical wavelength that they work is in below 530nm.This
Outside, the stability of photochemical catalyst is also to weigh an important indicator of its performance quality.Can be with from the production oxygen cycle figure of Figure 15
See, bismuth chromate still can keep efficiently producing very much oxygen activity, illustrate chromic acid in oxygen test process is produced in continuous photocatalysis
Bismuth photochemical catalyst has extraordinary photostability.
Claims (3)
1. a kind of preparation method of high activity bismuth chromate nano-photocatalyst, it is characterised in that this method comprises the following steps：
(1) at room temperature, five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate are dissolved in Osmitrol, it is saturating obtains lavender
Bright solution, wherein, the concentration of five nitric hydrate bismuths is 0.02~0.08mol/L, five nitric hydrate bismuths and Chromium nitrate (Cr(NO3)3),nonahydrate
Molar ratio is 12:1, the concentration of mannitol solution is 0.5~5mol/L；
(2) aqueous sodium carbonate of 1~5ml saturations is added dropwise into the solution of above-mentioned steps (1), continuously stirs to obtain pale purple
The emulsion of color；
(3) emulsion of above-mentioned steps (2) is transferred in hydrothermal reaction kettle, 6~12h is reacted under the conditions of 130~180 DEG C,
After natural cooling, the precipitation of celadon is obtained；
(4) precipitation of above-mentioned steps (3) is filtered, collects solid, solid is fully washed with deionized water, and by solid into
Row vacuum drying, vacuum drying temperature are 60~80 DEG C, and drying time 6-12h, obtains celadon powder；
(5) powder of above-mentioned steps (4) is placed in Muffle furnace 5~10min of calcining under the conditions of 500~580 DEG C, and taken immediately
Go out quick cooling, obtain orange-red bismuth chromate photochemical catalyst.
2. a kind of application of high activity bismuth chromate photochemical catalyst as claimed in claim 1, it is characterised in that urge bismuth chromate light
Agent is applied to photocatalysis production oxygen, comprises the following steps：
(1) bismuth chromate photochemical catalyst is added in water, and the mass volume ratio of bismuth chromate photochemical catalyst and water is 0.05~2g/L；
(2) silver nitrate is added in the reaction system of above-mentioned steps (1) as sacrifice agent, the addition of silver nitrate is bismuth chromate light
The 10 of catalyst2~105Times；
(3) reaction system of above-mentioned steps (2), output oxygen are irradiated with the light source that wavelength is 300~850nm.
3. a kind of application of high activity bismuth chromate photochemical catalyst as claimed in claim 1, it is characterised in that urge bismuth chromate light
Agent comprises the following steps applied to photocatalysis sewage processing, application process：
(1) bismuth chromate photochemical catalyst, the addition quality volume of bismuth chromate photochemical catalyst are added in the sewage that organic contamination produces
Than for 0.5~5g/L；
(2) it is sufficiently stirred, bismuth chromate photochemical catalyst is uniformly dispersed in sewage；
(3) sewage of above-mentioned steps (2) is irradiated with the light source that wavelength is 300~850nm, irradiation time reaches discharge mark for sewage
It is accurate.
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