CN109647486A - Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method and application - Google Patents
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method and application Download PDFInfo
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- CN109647486A CN109647486A CN201910077846.8A CN201910077846A CN109647486A CN 109647486 A CN109647486 A CN 109647486A CN 201910077846 A CN201910077846 A CN 201910077846A CN 109647486 A CN109647486 A CN 109647486A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 230000005496 eutectics Effects 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 13
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 229960003178 choline chloride Drugs 0.000 claims abstract description 13
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 8
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 14
- 230000001699 photocatalysis Effects 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910052603 melanterite Inorganic materials 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 abstract description 12
- 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 abstract description 6
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000004088 simulation Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- 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
- C02F2101/38—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to visible-light photocatalyst technical fields, are related to a kind of preparation method and application of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, first heat graphite-like carbon nitride precursor and graphite-like carbonitride is made；Choline chloride, urea and deionized water are mixed again, 20~40min of reaction obtains deep eutectic solvent at 35~65 DEG C；Then will graphite-like carbonitride, ferrous salt, inorganic base and deep eutectic solvent mix after react, transfer to reaction kettle, 100~130 DEG C of 3~5h of reaction, product is cleaned after natural cooling, after crushing to obtain the final product.Preparation process condition of the present invention is simple, by the modification to conventional graphite class carbonitride, can not only efficient fast degradation organic pollutant, and the photochemical catalyst after reacting can fast implement separation of solid and liquid under conditions of externally-applied magnetic field.Waste water of the removal containing methylene blue is simulated by experiment, the results showed that, 95% is greater than to the photocatalytic degradation efficiency of methylene blue, provides reliable theoretical and reality support for practical application.
Description
Technical field
The invention belongs to visible-light photocatalyst technical fields, are related to the preparation of graphite-like carbon nitride photocatalyst, especially
It is related to a kind of preparation method and application of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
Background technique
Currently, the environmental problem that the mankind face becomes increasingly severeer, energy shortage receives numerous researchers in recent years
Extensive concern, in this context, the research for photocatalyst technology receives the favor of researcher.Graphite-like nitridation
Carbon is novel visible-light photocatalyst, and synthetic method is simple, material properties is stable, and presoma is cheap, can be used for
Organic pollutant in hydrogen producing and catalytic degradation water body.
However, photocatalytic activity is low, is difficult to realize be separated by solid-liquid separation, limits graphite-like carbonitride and be widely used in work
Industry.It is because solid state quantum yield is only 5% that photocatalytic activity is low, while its specific surface area is lower than 10m2/ g cannot urge for light
Change reaction and more active sites are provided；Secondly, the forbidden bandwidth of graphite-like carbonitride is 2.7eV, limit to visible light
Absorption region, in summary two o'clock, it is believed that the photocatalytic activity of pure graphite-like carbonitride is very low.Due to graphite-like carbonitride
It is usually powdered, after completion of the reaction, it is difficult to photochemical catalyst be extracted from solution, cannot realize solid-liquid point well
From secondary pollution may be caused to environment.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is disclose a kind of ferroso-ferric oxide-graphite-like
The preparation method of carbonitride composite magnetic photochemical catalyst.
Technical solution:
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor is placed in Muffle furnace, 500~600 DEG C of 2~3.5h of heating, preferably 520 DEG C add
Hot 3.0h, heating rate are 2.5~3.5 DEG C of min-1, cooled to room temperature is crushed into powder, and obtains graphite-like carbonitride；
It b) is the mixing of 1~2g:1g:5~20ml ratio according to choline chloride, urea and deionized water solid-to-liquid ratio, preferably
Solid-to-liquid ratio is 1.2g:1g:10mL, reacts 20~40min at 35~65 DEG C, it is molten to obtain deep eutectic by preferably 50 DEG C reaction 30min
Agent；
It c) is 1g:0.05~1g:0.018 by solid-to-liquid ratio by graphite-like carbonitride, ferrous salt, inorganic base and deep eutectic solvent
The ratio of~0.072g:10mL mixes, preferably 1g:0.1g:0.036g:10mL, and 20~40min, stirring are reacted at 30~60 DEG C
Rate is 500~700rmin-1, obtain mixed solution；
D) ratio for being 0.0126~0.0504g:1g according to the mass ratio of inorganic base and graphite-like carbonitride, continuously adds
Inorganic base reacts 20~40min into above-mentioned mixed solution at 70~90 DEG C, be then transferred to reaction kettle, and 100~130 DEG C anti-
Answer 3~5h, preferably 110 DEG C reaction 4h, cooled to room temperature；
E) it is successively rinsed well with water, ethyl alcohol, is dried at 80~100 DEG C, be milled to powder, obtain ferroso-ferric oxide-stone
Black class carbonitride composite magnetic photochemical catalyst.
In the more excellent disclosed example of the present invention, graphite-like carbon nitride precursor described in step a) be melamine, dicyandiamide or
Any one of thiocarbamide.
In the more excellent disclosed example of the present invention, ferrous salt described in step c) is FeSO4·7H2O or FeCl2·4H2O；The nothing
Machine alkali is KOH or NaOH.
A further object of the invention is to urge obtained ferroso-ferric oxide-graphite-like carbonitride composite magnetic light
Agent is applied to waste water of the Photocatalytic Activity for Degradation containing organic dyestuff.
Experiment simulation photocatalytic degradation contains the waste water of engine dyeing material
Using methylene blue as organic dyestuff, using 500W xenon lamp as visible light source, filtered with the optical filter of 400nm
Fall ultraviolet light.0.5h is stirred before light-catalyzed reaction in the dark, to reach absorption-desorption balance, experimentation urges the light of 20mg
Agent is added separately in 50ml dye solution containing machine, and the concentration of dyestuff is 10mg/L, carries out one every 10min in experimentation
Sub-sampling measures the concentration of Methylene Blue in Solution at 631nm, urges to acquire light after 0.22 micron of filter filtering
Change degradation rate.
Blank assay is added without ferrous salt and graphite-like carbon nitride photocatalyst is made, to Asia according to above-mentioned preparation step
The degradation rate of methyl blue is 27.6%.
The invention has the characteristics that
(1) present invention prepares graphite-like carbonitride using simple thermal polycondensation process, and preparation process is simple, and will not to environment
Generate harm.
(2) present invention synthesizes ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst using oxidation and coprecipitation method,
Reaction carries out in deep eutectic solvent, prepares that required reaction temperature is low, and simultaneously synthesizing rate is fast, can be accorded with energy saving
Close Eco-power synthetic method.
(3) ferroso-ferric oxide provided by the invention-graphite-like carbonitride composite magnetic photochemical catalyst, the advantage is that preparation
Process is simple, can not only promote photochemical catalyst efficiency, and may be implemented quickly to be separated by solid-liquid separation, before wide application
Scape.
Beneficial effect
The present invention discloses a kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst and answers
With.Preparation process experiment condition is simple, can not only the efficiently organic dirt of fast degradation by the modification to conventional graphite class carbonitride
Object is contaminated, and the photochemical catalyst after reaction can fast implement separation of solid and liquid under conditions of externally-applied magnetic field.It is gone by testing simulation
Except the waste water containing methylene blue, the results showed that, 95% is greater than to the photocatalytic degradation efficiency of methylene blue, is provided for practical application
Reliable theoretical and reality support.
Detailed description of the invention
The scanning electron microscopic picture of photochemical catalyst obtained by Fig. 1.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited to following embodiments.
Unless otherwise defined, term (including scientific and technical terminology) used herein above should be construed as having as belonging to the present invention
The identical meaning that those skilled in the art are commonly understood by.It will also be understood that term used herein above should be explained
To have the meaning consistent with their meanings in the content of this specification and the relevant technologies, and should not be with idealization
Or excessive form is explained, unless expressly so limiting here.
Embodiment 1
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor dicyandiamide is placed in Muffle furnace, air atmosphere is in 500 DEG C of heating 2.0h, heating
Rate is 2.5 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 1:1, and are dissolved in the deionized water of 5ml,
Solution is placed at 35 DEG C after mixing and reacts 20min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeSO that will be prepared in step a)4·7H2O and NaOH is 1:0.05 according to mass ratio:
0.018 ratio mixing, and be added in the deep eutectic solvent prepared in step b), 20min, stirring rate are reacted at 30 DEG C
For 500rmin-1；
D) NaOH of 0.0126g is added in the mixed solution prepared in step c), reacts 20min at 70 DEG C, turned
It moves on in reaction kettle, reacts 3.0h at 100 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 80 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity of experiment simulation removal organic dyestuff is 95.17%.
Embodiment 2
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor melamine is placed in Muffle furnace, air atmosphere rises in 520 DEG C of heating 2.5h
Warm rate is 3.0 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 1.2:1, and is dissolved in the deionized water of 10ml
In, solution is placed at 50 DEG C after mixing and reacts 30min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeSO that will be prepared in step a)4·7H2O and KOH is 1:0.1:0.036 according to mass ratio
Ratio mixing, and be added in the deep eutectic solvent prepared in step b), 30min reacted at 50 DEG C, stirring rate is
600r·min-1；
D) KOH of 0.0252g is added in the mixed solution prepared in step c), 30min is reacted at 80 DEG C, shifted
Into reaction kettle, 4.0h is reacted at 110 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 90 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity of experiment simulation removal organic dyestuff is 97.38%.
Embodiment 3
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor thiocarbamide is placed in Muffle furnace, air atmosphere is in 550 DEG C of heating 3.0h, heating speed
Rate is 3.5 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 1.5:1, and is dissolved in the deionized water of 15ml
In, solution is placed at 65 DEG C after mixing and reacts 40min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeCl that will be prepared in step a)2·4H2O and KOH is 1:0.2:0.072 according to mass ratio
Ratio mixing, and be added in the deep eutectic solvent prepared in step b), 40min reacted at 40 DEG C, stirring rate is
700r·min-1；
D) KOH of 0.0504g is added in the mixed solution prepared in step c), 40min is reacted at 90 DEG C, shifted
Into reaction kettle, 4.0h is reacted at 120 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 90 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity 95.62% of experiment simulation removal organic dyestuff.
Embodiment 4
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor dicyandiamide is placed in Muffle furnace, air atmosphere is in 600 DEG C of heating 3.5h, heating
Rate is 3.0 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 2:1, and are dissolved in the deionized water of 20ml,
Solution is placed at 35 DEG C after mixing and reacts 30min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeCl that will be prepared in step a)2·4H2O and KOH is 1:0.2:0.072 according to mass ratio
Ratio mixing, and be added in the deep eutectic solvent prepared in step b), 30min reacted at 60 DEG C, stirring rate is
600r·min-1；
D) KOH of 0.0504g is added in the mixed solution prepared in step c), 30min is reacted at 80 DEG C, shifted
Into reaction kettle, 3h is reacted at 130 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 100 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity of experiment simulation removal organic dyestuff is 95.08%.
Embodiment 5
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor melamine is placed in Muffle furnace, air atmosphere rises in 520 DEG C of heating 3.0h
Warm rate is 2.5 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 1.2:1, and is dissolved in the deionized water of 10ml
In, solution is placed at 50 DEG C after mixing and reacts 20min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeCl that will be prepared in step a)2·4H2O and NaOH is 1:0.1 according to mass ratio:
0.036 ratio mixing, and be added in the deep eutectic solvent prepared in step b), 40min, stirring rate are reacted at 50 DEG C
For 500rmin-1；
D) NaOH of 0.0252g is added in the mixed solution prepared in step c), reacts 40min at 90 DEG C, turned
It moves on in reaction kettle, reacts 5h at 110 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 80 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity of experiment simulation removal organic dyestuff is 96.11%.
Embodiment 6
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor thiocarbamide is placed in Muffle furnace, air atmosphere is in 500 DEG C of heating 2.0h, heating speed
Rate is 3.5 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 1.5:1, and is dissolved in the deionized water of 15ml
In, solution is placed at 65 DEG C after mixing and reacts 40min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeSO that will be prepared in step a)4·7H2O and NaOH is 1:0.05 according to mass ratio:
0.018 ratio mixing, and be added in the deep eutectic solvent prepared in step b), 20min, stirring rate are reacted at 30 DEG C
For 700rmin-1；
D) NaOH of 0.0126g is added in the mixed solution prepared in step c), reacts 30min at 70 DEG C, turned
It moves on in reaction kettle, reacts 4h at 110 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 100 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity of experiment simulation removal organic dyestuff is 95.09%.
Embodiment 7
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor melamine is placed in Muffle furnace, air atmosphere rises in 520 DEG C of heating 2.5h
Warm rate is 3 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 1:1, and are dissolved in the deionized water of 10ml,
Solution is placed at 50 DEG C after mixing and reacts 30min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeSO that will be prepared in step a)4·7H2O and KOH is 1:0.1:0.036 according to mass ratio
Ratio mixing, and be added in the deep eutectic solvent prepared in step b), 30min reacted at 50 DEG C, stirring rate is
600r·min-1；
D) KOH of 0.0252g is added in the mixed solution prepared in step c), 30min is reacted at 80 DEG C, shifted
Into reaction kettle, 5h is reacted at 130 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 80 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity of experiment simulation removal organic dyestuff is 95.49%.
Embodiment 8
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbon nitride precursor melamine is placed in Muffle furnace, air atmosphere rises in 550 DEG C of heating 2.5h
Warm rate is 3.5 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 1.2:1, and is dissolved in the deionized water of 10ml
In, solution is placed at 60 DEG C after mixing and reacts 30min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeSO that will be prepared in step a)4·7H2O and NaOH is 1:0.2 according to mass ratio:
0.072 ratio mixing, and be added in the deep eutectic solvent prepared in step b), 30min, stirring rate are reacted at 50 DEG C
For 600rmin-1；
D) NaOH of 0.0504g is added in the mixed solution prepared in step c), reacts 40min at 70 DEG C, turned
It moves on in reaction kettle, reacts 3h at 120 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 90 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity of experiment simulation removal organic dyestuff is 96.01%.
Embodiment 9
A kind of preparation method of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst, includes the following steps:
A) graphite-like carbonitride thiocarbamide presoma is placed in Muffle furnace, air atmosphere is in 600 DEG C of heating 3.0h, heating speed
Rate is 2.5 DEG C of min-1, it is cooled to room temperature, is crushed into powder, as graphite-like carbonitride；
B) choline chloride and urea are mixed according to the ratio that mass ratio is 2:1, and are dissolved in the deionized water of 15ml,
Solution is placed at 65 DEG C after mixing and reacts 20min, prepares deep eutectic solvent；
C) graphite-like carbonitride, the FeCl that will be prepared in step a)2·4H2O and NaOH is 1:0.1 according to mass ratio:
0.036 ratio mixing, and be added in the deep eutectic solvent prepared in step b), 40min, stirring rate are reacted at 60 DEG C
For 700rmin-1；
D) NaOH of 0.0252g is added in the mixed solution prepared in step c), reacts 20min at 90 DEG C, turned
It moves on in reaction kettle, reacts 4h at 110 DEG C；
E) the step d) material obtained is successively rinsed well with water, ethyl alcohol, is dried at 90 DEG C, be milled to powder, is obtained
Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst.
The photocatalytic activity of experiment simulation removal organic dyestuff is 96.36%.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (9)
1. a kind of ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method, which is characterized in that including such as
Lower step:
A) graphite-like carbon nitride precursor is placed in Muffle furnace, 500~600 DEG C of 2~3.5h of heating, heating rate be 2.5~
3.5℃·min-1, cooled to room temperature is crushed into powder, and obtains graphite-like carbonitride；
It b) is that 1~2g:1g:5~20ml ratio mixes according to choline chloride, urea and deionized water solid-to-liquid ratio, 35~65 DEG C
20~40min of lower reaction, obtains deep eutectic solvent；
C) by graphite-like carbonitride, ferrous salt, inorganic base and deep eutectic solvent by solid-to-liquid ratio be 1g:0.05~1g:0.018~
The ratio of 0.072g:10mL mixes, and 20~40min is reacted at 30~60 DEG C, and stirring rate is 500~700rmin-1, obtain
Mixed solution；
D) ratio for being 0.0126~0.0504g:1g according to the mass ratio of inorganic base and graphite-like carbonitride, continuously adds inorganic
Alkali reacts 20~40min, is then transferred to reaction kettle into above-mentioned mixed solution at 70~90 DEG C, and 100~130 DEG C of reactions 3~
5h, cooled to room temperature；
E) it is successively rinsed well with water, ethyl alcohol, is dried at 80~100 DEG C, be milled to powder, obtain ferroso-ferric oxide-graphite-like
Carbonitride composite magnetic photochemical catalyst.
2. ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method according to claim 1, special
Sign is: graphite-like carbon nitride precursor described in step a) is any one of melamine, dicyandiamide or thiocarbamide.
3. ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method according to claim 1, special
Sign is: graphite-like carbon nitride precursor being placed in Muffle furnace described in step a), 520 DEG C of heating 3.0h.
4. ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method according to claim 1, special
Sign is: it is mixed described in step b) according to the ratio that choline chloride, urea and deionized water solid-to-liquid ratio are 1.2g:1g:10mL,
50 DEG C of reaction 30min.
5. ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method according to claim 1, special
Sign is: ferrous salt described in step c) is FeSO4·7H2O or FeCl2·4H2O；The inorganic base is KOH or NaOH.
6. ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method according to claim 1, special
Sign is: by graphite-like carbonitride, ferrous salt, inorganic base and deep eutectic solvent by solid-to-liquid ratio be 1g:0.1g described in step c):
The ratio of 0.036g:10mL mixes.
7. ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method according to claim 1, special
Sign is: reaction kettle, 110 DEG C of reaction 4h, cooled to room temperature are transferred to described in step d).
8. the ferroso-ferric oxide that-7 any the methods are prepared according to claim 1-graphite-like carbonitride composite magnetic light
Catalyst.
9. a kind of application of ferroso-ferric oxide described in claim 8-graphite-like carbonitride composite magnetic photochemical catalyst, feature exist
In: it is applied to waste water of the Photocatalytic Activity for Degradation containing organic dyestuff.
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|---|---|---|---|---|
| CN105271369A (en) * | 2015-10-27 | 2016-01-27 | 南昌航空大学 | Method for preparing g-C3N4/CdS composite by organic molten salt method |
| CN107649162A (en) * | 2017-10-12 | 2018-02-02 | 江苏大学 | A kind of composite photo-catalyst and preparation method and application |
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| CN105271369A (en) * | 2015-10-27 | 2016-01-27 | 南昌航空大学 | Method for preparing g-C3N4/CdS composite by organic molten salt method |
| CN107649162A (en) * | 2017-10-12 | 2018-02-02 | 江苏大学 | A kind of composite photo-catalyst and preparation method and application |
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