CN106824207A - A kind of pn types CaFe2O4@a‑Fe2O3Heterojunction composite photocatalyst and its preparation method and application - Google Patents
A kind of pn types CaFe2O4@a‑Fe2O3Heterojunction composite photocatalyst and its preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910004333 CaFe2O4 Inorganic materials 0.000 title claims abstract description 29
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 241000186216 Corynebacterium Species 0.000 claims abstract description 5
- 239000001110 calcium chloride Substances 0.000 claims abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 abstract 1
- 229940039790 sodium oxalate Drugs 0.000 abstract 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of pn types CaFe2O4@a‑Fe2O3Heterojunction composite photocatalyst and its preparation method and application, iron chloride and calcium chloride are dissolved in deionized water first, sodium oxalate is added, mixed solution is uniformly mixing to obtain, moving into reactor after adjusting mixed solution pH value with alkaline solution carries out hydro-thermal reaction, after hydro-thermal reaction terminates, room temperature is cooled to, secondary precipitation is carried out, then mixed solution pH value is adjusted with alkaline solution again, finally by product centrifugation, washing, dry, grinding, then product is obtained final product through being heat-treated in short-term.Preparation process is simple of the present invention; with low cost, preparation process is pollution-free, and obtained catalyst has corynebacterium, graininess or stub/particle mixing microstructure; with good photocatalytic activity and regeneration cycle usability, organic dye pollutant in wastewater by photocatalysis can be efficiently applied to.
Description
Technical field
The invention belongs to photochemical catalyst preparing technical field, and in particular to a kind of pn types CaFe2O4@a-Fe2O3Hetero-junctions is answered
Closing light catalyst and its preparation method and application.
Background technology
Photocatalysis has energy-saving and environmental protection, efficient effect, is expected to turn into the mankind solution fossil fuel crisis and water pollution
Optimal path.Photochemical catalyst is the deciding factor of light-catalyzed reaction efficiency, to improve photocatalysis efficiency, constructs hetero-junctions and answers
Closing light catalysis material has turned into the research and development focus in the field at present to reduce the recombination rate of photo-generate electron-hole.Current research and development compared with
Based on nn type hetero-junctions, because p-type oxide semiconductor is less, pn types hetero-junctions is combined many hetero-junctions class composite photo-catalysts
The report of photochemical catalyst technology of preparing is also few.Compared to nn type hetero-junctions, pn type hetero-junctions has stronger light induced electron-sky
Cave separating power, therefore it is significant to develop the technology of preparing of new pn types heterojunction photocatalyst.
In numerous narrow band gap oxide semiconductors, Fe base oxides are wide because physicochemical properties stabilization, resource are easy to get
It is concerned.Wherein, CaFe2O4And a-Fe2O3Adhere to p-type and n-type semiconductor separately, optical band gap is respectively 1.9 and 2.1 eV（The sun
Spectrum utilization factor more than 40%）, may make up the hetero-junctions of wrong row's energy band（CaFe2O4Conduction band and valence band location compared to a-Fe2O3
About 0.5eV is moved to negative potential direction）, light induced electron/hole separative efficiency, the life-span of extension carrier are effectively lifted, because
This CaFe2O4@a-Fe2O3Hetero-junctions complex is the visible light catalytic material of great application prospect.So far, open source literature
In rarely seen relevant pn types CaFe2O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst and its report of photocatalytic applications.
The content of the invention
It is an object of the invention to provide a kind of good stability, visible light-responded wide ranges, photocatalytic activity pn types high
CaFe2O4@a-Fe2O3Heterojunction composite photocatalyst and its preparation method and application.
The purpose of the present invention is achieved through the following technical solutions：
A kind of pn types CaFe2O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst, comprises the following steps：
（1）By mol ratio 40 ~ 4:1 FeCl3And CaCl2Dissolve in deionized water, add solid Na2C2O4, stir, obtain
To the mixed solution of clarification；
（2）Use alkaline solution regulating step（1）The mixed solution pH value prepared stirs to 4 ~ 6, moves into autoclave
In carry out hydro-thermal reaction, then naturally cool to room temperature, obtain the solid-liquid system containing primary precipitation thing；
（3）Use alkaline solution regulating step（2）The solid-liquid system pH value for obtaining stirs to 8 ~ 10, stand, spend successively from
Sub- water and absolute ethanol washing, filtering, by drying precipitate, grinding, obtain predecessor；
（4）By step（3）The predecessor of preparation is heat-treated in air atmosphere, grinding, and pn types CaFe is obtained2O4@a-Fe2O3It is different
Matter knot composite photo-catalyst.
Further, the step（1）Middle Na2C2O4With FeCl3And CaCl2Molal quantity and the ratio between be 1.02 ~ 2.0：
1。
Further, the step（1）~（3）Middle speed of agitator is all 300 ~ 500 rpm, and mixing time is all 20 ~ 60
min。
Further, the step（2）In autoclave be polytetrafluoroethyllining lining stainless steel autoclave, water
Thermal response temperature is 150 ~ 200 DEG C, and the reaction time is 5 ~ 10 h.
Further, the step（2）~（3）Neutral and alkali solution is NaOH solution, KOH solution or ammoniacal liquor.
Further, the step（3）Middle time of repose is 5 ~ 10 h.
Further, the step（3）Middle drying temperature is 70 ~ 90 DEG C, the h of drying time 10 ~ 20.
Further, the step（4）Middle heat treatment temperature is 800 ~ 1000 DEG C, and the time is 20 ~ 40 min.
Pn types CaFe prepared by described preparation method2O4@a-Fe2O3Heterojunction composite photocatalyst have corynebacterium,
Granular or stub/particle mixing microstructure, has strong light absorbs in visible region.
Pn types CaFe prepared by described preparation method2O4@a-Fe2O3Heterojunction composite photocatalyst is applied to be had in degraded
In machine waste water from dyestuff.
Beneficial effects of the present invention：
（1）The pn types CaFe that the present invention is prepared by " hydro-thermal-room temperature secondary precipitation-be heat-treated in short-term " method2O4@a-Fe2O3It is different
Matter knot composite photo-catalyst, product better crystallinity degree（Be can be seen that in the XRD spectrum of accompanying drawing 1, two kinds of things phases in compound
See sharp characteristic diffraction peak）, catalyst recycling is good, can substantially reduce the usage amount of catalyst, cost-effective.
（2）Pn types CaFe of the present invention2O4@a-Fe2O3Composite photo-catalyst, with visible light-responded scope, stability wide
Good and photocatalytic activity high, it is adaptable to the field such as Solar use, environmental improvement, such as has engine dyeing containing methylene blue
Expect the degraded of Industry Waste organic pollutants.
（3）Preparation method of the invention is raw materials used cheap and easy to get, and preparation method is simple, low production cost, preparation process
Non-pollution discharge.
Brief description of the drawings
Fig. 1 is pn types CaFe prepared by the embodiment of the present invention 12O4@a-Fe2O3The XRD of heterojunction composite photocatalyst
Spectrum.
Fig. 2 is pn types CaFe prepared by the embodiment of the present invention 1,2,32O4@a-Fe2O3The SEM of heterojunction composite photocatalyst
Photo.
Fig. 3 is pn types CaFe prepared by the present invention2O4@a-Fe2O3Heterojunction composite photocatalyst is useless to methylene blue simulation
The degradation effect of water.
Fig. 4 is pn types CaFe prepared by the present invention2O4@a-Fe2O3Heterojunction composite photocatalyst is useless to methylene blue simulation
The circulation photocatalysis effect of water.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
（1）Take the FeCl of 0.4mol/L3With the CaCl of 0.1mol/L2Each 10mL mixing of solution, adds the Na of 0.69 g2C2O4, mix
Close stirring 30min, the mixed solution clarified.
（2）Under stirring, with the NaOH solution regulating step of 1mol/L（1）The pH value of matched somebody with somebody mixed solution is used to 5
Solution is settled to 50mL by deionized water, and moves into polytetrafluoroethylene (PTFE) stainless steel high-pressure hydrothermal reaction kettle, anti-in 160 DEG C of hydro-thermals
8h is answered, room temperature is naturally cooled to, the solid-liquid system containing primary precipitation thing is obtained.
（3）With the NaOH solution regulating step of 1mol/L（2）The pH of the solid-liquid system that hydro-thermal reaction is obtained to 8.5, stirring
8h is stood after 30min, successively with respectively washing 3 times of deionized water and ethanol, by sediment in 12h is dried at 80 DEG C, is ground, obtained
Predecessor.
（4）By step（3）The predecessor of preparation is heat-treated 20 minutes in 950 DEG C of air atmospheres, and different component ratio is obtained
Pn types CaFe2O4@a-Fe2O3Heterojunction composite photocatalyst, detects, CaFe in product through XRF and XRD2O4:a-Fe2O3Mole
Than 1: 1.
Fig. 1 is the pn types CaFe of preparation in embodiment 12O4/a-Fe2O3The XRD spectrum of heterojunction composite photocatalyst, can
See prepared pn types CaFe2O4@a-Fe2O3Sample is by CaFe2O4And a-Fe2O3Two kinds are mutually composited, its diffraction maximum with
CaFe2O4Standard card PCPDF#74-2136, a-Fe2O3Standard card PCPDF#79-1741 is completely the same, and is not detected by it
Its impurity peaks, illustrates that purer pn types CaFe has been obtained2O4@a-Fe2O3Heterojunction composite photocatalyst.
Fig. 2 (a) is the pn types CaFe of preparation in embodiment 12O4@a-Fe2O3The SEM photograph of heterojunction composite photocatalyst,
Illustrate CaFe2O4:a-Fe2O3Mol ratio is 1:1 pn types CaFe2O4@a-Fe2O3The microcosmic shape of heterojunction composite photocatalyst
Looks are in corynebacterium substantially.
Embodiment 2
（1）Take the FeCl of 0.6mol/L3With the CaCl of 0.1mol/L2Solution 10mL mixes, and adds the Na of 0.97 g2C2O4, mix
Close stirring 40min, the mixed solution clarified.
（2）Under stirring, with the KOH solution regulating step of 0.8mol/L（1）The pH value of matched somebody with somebody mixed solution is extremely
4.5, solution is settled to 70mL with deionized water, and move into polytetrafluoroethylene (PTFE) stainless steel high-pressure hydrothermal reaction kettle, in 180 DEG C
Hydro-thermal reaction 6h, naturally cools to room temperature, obtains the solid-liquid system containing primary precipitation thing.
（3）With the KOH solution regulating step of 0.8mol/L（2）The pH of the solid-liquid system that hydro-thermal reaction is obtained to 9, stirring
7h is stood after 40min, successively with respectively washing 3 times of deionized water and ethanol, by sediment in 20h is dried at 70 DEG C, is ground, obtained
Predecessor.
（4）By step（3）The predecessor of preparation is heat-treated 30 minutes in 850 DEG C of air atmospheres, and different component ratio is obtained
Pn types CaFe2O4@a-Fe2O3Heterojunction composite photocatalyst, detects, CaFe in product through XRF and XRD2O4:a-Fe2O3Mole
Than 1: 2.
Fig. 2 (b) is the pn types CaFe of preparation in embodiment 22O4@a-Fe2O3The SEM photograph of heterojunction composite photocatalyst,
Illustrate CaFe2O4:a-Fe2O3Mol ratio is 1:2 pn types CaFe2O4@a-Fe2O3Microcosmic group of heterojunction composite photocatalyst
Knit and be made up of corynebacterium and granular substance.
Pn types CaFe obtained in the present embodiment 22O4@a-Fe2O3The XRD spectrum of heterojunction composite photocatalyst and Fig. 1 phases
Seemingly, but CaFe2O4Characteristic peak relative intensity is slightly weak.
Embodiment 3
（1）Take the FeCl of 1mol/L3With the CaCl of 0.1mol/L2Each 10mL mixing of solution, and add the Na of 1.5 g2C2O4, mix
Close stirring 50min, the mixed solution clarified.
（2）Under stirring, with the ammoniacal liquor regulating step of 0.5mol/L（1）The pH value of matched somebody with somebody mixed solution is used to 5.5
Solution is settled to 100mL by deionized water, and moves into polytetrafluoroethylene (PTFE) stainless steel high-pressure hydrothermal reaction kettle, in 170 DEG C of hydro-thermals
Reaction 7h, naturally cools to room temperature, obtains the solid-liquid system containing primary precipitation thing.
（3）With the ammoniacal liquor regulating step of 0.5mol/L（2）The pH of the solid-liquid system that hydro-thermal reaction is obtained to 9.5, stirring
6h is stood after 50min, successively with respectively washing 3 times of deionized water and ethanol, by sediment in 10h is dried at 90 DEG C, is ground, obtained
Predecessor.
（4）By step（3）The predecessor of preparation is heat-treated 40 minutes in 800 DEG C of air atmospheres, and different component ratio is obtained
Pn types CaFe2O4@a-Fe2O3Heterojunction composite photocatalyst, detects, CaFe in product through XRF and XRD2O4:a-Fe2O3Mole
Than 1: 4.
Fig. 2 (c) is the pn types CaFe of preparation in embodiment 32O4@a-Fe2O3The SEM photograph of heterojunction composite photocatalyst,
Illustrate CaFe2O4:a-Fe2O3Mol ratio is 1:4 pn types CaFe2O4@a-Fe2O3The microcosmic shape of heterojunction composite photocatalyst
Looks are in granular form.
Pn types CaFe obtained in the present embodiment 32O4@a-Fe2O3The XRD spectrum of heterojunction composite photocatalyst and Fig. 1 phases
Seemingly, but CaFe2O4Characteristic peak relative intensity tends to become weak.
Application Example 1
The pn types CaFe for being prepared using embodiment 1,2 and 3 respectively2O4@a-Fe2O3Heterojunction composite photocatalyst, with 10mg/L's
Methylene blue solution dye wastewater, carries out photocatalytic degradation reaction under simulated solar light irradiation, and specific implementation step is such as
Under：
Take pn types CaFe obtained in 30mg2O4@a-Fe2O3 composite catalysts, are distributed to the methylene blue that concentration is 10mg/L molten
In liquid 100mL, concussion 5min obtains suspension under the supersonic frequency of 20 kHz；By suspension in darkroom stir 30min with
Adsorption-desorption balance is reached, the 30%H of 2mL is added dropwise2O2, photocatalytic degradation reaction, light source and liquid level are carried out under simulated solar irradiation
Apart from 10cm.2mL is sampled every 30min, 5min is centrifuged in 9000r/min, take supernatant liquid in UV-vis spectroscopy light
The absorbance at 664nm is detected on degree meter.
Accompanying drawing 3 is pn types CaFe prepared by embodiment 1,2 and 32O4@a-Fe2O3Heterojunction composite photocatalyst is being simulated too
The concentration-time change curve of the lower degradation of methylene blue of sunlight irradiation.From Fig. 3 comparative test results, in 180min,
Obtained pure a-Fe under comparable conditions2O3Degradation rate to methylene blue is 48%, and pn types prepared by embodiment 1,2 and 3
CaFe2O4@a-Fe2O3Heterojunction composite photocatalyst is respectively 91%, 96%, 96% to the degradation rate of methylene blue.Pure a-Fe2O3
Photocatalytic activity it is relatively low the reason for be its photo-generate electron-hole easily be combined, pn types CaFe2O4@a-Fe2O3Hetero-junctions
The hetero-junctions of composite photo-catalyst efficiently separates photo-generate electron-hole, suppresses its compound effect, so as to improve catalyst
Photocatalytic activity.Therefore, the pn types CaFe that prepared by the present invention2O4@a-Fe2O3Heterojunction composite photocatalyst can be answered effectively
For the organic dye pollutant in Visible Light Induced Photocatalytic waste water.
Application Example 2
Pn types CaFe prepared by the present invention2O4@a-Fe2O3The regeneration of heterojunction composite photocatalyst, repeat performance test
（By taking the photochemical catalyst prepared by embodiment 2 as an example, degraded object is methylene blue）, comprise the following steps that：
Weigh the pn types CaFe prepared by embodiment 22O4@a-Fe2O3Heterojunction composite photocatalyst 40mg, being distributed to concentration is
In the methylene blue solution 150mL of 10mg/L, remaining step and Application Example 1 are identical.Treat first time degradation reaction 180min
After end, suspension is stood into 3h, remove supernatant liquor, successively each 2 times with deionized water and ethanol washing catalyst, to remove
The dyestuff of catalyst surface, 10h is dried then at 70 DEG C, and the catalyst for being regenerated carries out degradation experiment next time.
Accompanying drawing 4 is 5 results of circulation degradation experiment, it is seen then that sample is through 4 regeneration and reuses, 5 each 180min
Degradation rate is respectively 95.5%, 94%, 91.5%, 89%, 88%, composite photocatalytic activity stabilization, it was demonstrated that manufactured in the present embodiment
Pn types CaFe2O4@a-Fe2O3Heterojunction composite photocatalyst has preferable stability.
Claims (10)
1. a kind of pn types CaFe2O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst, it is characterised in that including following step
Suddenly：
（1）By mol ratio 40 ~ 4:1 FeCl3And CaCl2Dissolve in deionized water, add solid Na2C2O4, stir, obtain
The mixed solution of clarification；
（2）Use alkaline solution regulating step（1）The mixed solution pH value prepared stirs to 4 ~ 6, moves into autoclave
In carry out hydro-thermal reaction, then naturally cool to room temperature, obtain the solid-liquid system containing primary precipitation thing；
（3）Use alkaline solution regulating step（2）The solid-liquid system pH value for obtaining stirs to 8 ~ 10, stand, spend successively from
Sub- water and absolute ethanol washing, filtering, by drying precipitate, grinding, obtain predecessor；
（4）By step（3）The predecessor of preparation is heat-treated in air atmosphere, grinding, and pn types CaFe is obtained2O4@a-Fe2O3It is heterogeneous
Knot composite photo-catalyst.
2. a kind of pn types CaFe according to claim 12O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst, its
It is characterised by, the step（1）Middle Na2C2O4With FeCl3And CaCl2Molal quantity and the ratio between be 1.02 ~ 2.0：1.
3. a kind of pn types CaFe according to claim 12O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst, its
It is characterised by, the step（1）~（3）Middle speed of agitator is all 300 ~ 500 rpm, and mixing time is all 20 ~ 60 min.
4. a kind of pn types CaFe according to claim 12O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst, its
It is characterised by, the step（2）In autoclave be polytetrafluoroethyllining lining stainless steel autoclave, hydro-thermal reaction temperature
It is 150 ~ 200 DEG C to spend, and the reaction time is 5 ~ 10 h.
5. a kind of pn types CaFe according to claim 12O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst, its
It is characterised by, the step（2）~（3）Neutral and alkali solution is NaOH solution, KOH solution or ammoniacal liquor.
6. a kind of pn types CaFe according to claim 12O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst, its
It is characterised by, the step（3）Middle time of repose is 5 ~ 10 h.
7. pn types CaFe according to claim 12O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst, its feature
It is, the step（3）Middle drying temperature is 70 ~ 90 DEG C, the h of drying time 10 ~ 20.
8. a kind of pn types CaFe according to claim 12O4@a-Fe2O3The preparation method of heterojunction composite photocatalyst,
Characterized in that, the step（4）Middle heat treatment temperature is 800 ~ 1000 DEG C, and the time is 20 ~ 40 min.
9. the pn types CaFe that prepared by a kind of preparation method according to claim 1-8 is any2O4@a-Fe2O3Hetero-junctions is combined
Photochemical catalyst, it is characterised in that the pn types CaFe2O4@a-Fe2O3It is micro- with corynebacterium, graininess or stub/particle mixing
Tissue is seen, there are strong light absorbs in visible region.
10. a kind of pn types CaFe according to claim 92O4@a-Fe2O3Heterojunction composite photocatalyst has engine dyeing in degraded
Application in material waste water.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112811472A (en) * | 2021-01-11 | 2021-05-18 | 重庆工商大学 | Calcium ferrite gas sensing material, preparation method and application |
| CN114797871A (en) * | 2022-04-12 | 2022-07-29 | 湘潭大学 | Preparation of calcium-iron composite catalyst for degrading pollutants in electroplating wastewater |
| CN115738999A (en) * | 2022-12-08 | 2023-03-07 | 中国科学院合肥物质科学研究院 | Calcium ferrate nanosphere material as well as preparation method and application thereof |
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- 2017-01-22 CN CN201710046966.2A patent/CN106824207A/en active Pending
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112811472A (en) * | 2021-01-11 | 2021-05-18 | 重庆工商大学 | Calcium ferrite gas sensing material, preparation method and application |
| CN112811472B (en) * | 2021-01-11 | 2022-11-18 | 重庆工商大学 | Calcium ferrite gas sensing material, preparation method and application |
| CN114797871A (en) * | 2022-04-12 | 2022-07-29 | 湘潭大学 | Preparation of calcium-iron composite catalyst for degrading pollutants in electroplating wastewater |
| CN115738999A (en) * | 2022-12-08 | 2023-03-07 | 中国科学院合肥物质科学研究院 | Calcium ferrate nanosphere material as well as preparation method and application thereof |
| CN115738999B (en) * | 2022-12-08 | 2024-03-22 | 中国科学院合肥物质科学研究院 | Calcium ferrate nanosphere material and preparation method and application thereof |
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