CN107413368A - A kind of polynary magnetic Fe3O4‑QDs@g‑C3N4The Preparation method and use of/ATP composite photo-catalysts - Google Patents
A kind of polynary magnetic Fe3O4‑QDs@g‑C3N4The Preparation method and use of/ATP composite photo-catalysts Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229960000892 attapulgite Drugs 0.000 claims abstract description 86
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 86
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- -1 dimercapto phenylpropyl Chemical group 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical group OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 238000005375 photometry Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 238000005276 aerator Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
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- 230000036651 mood Effects 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- DOFIAZGYBIBEGI-UHFFFAOYSA-N 3-sulfanylphenol Chemical compound OC1=CC=CC(S)=C1 DOFIAZGYBIBEGI-UHFFFAOYSA-N 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 208000010476 Respiratory Paralysis Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
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- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- 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
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- 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
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- 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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Abstract
The invention provides a kind of polynary magnetic Fe3O4‑QDs@g‑C3N4The Preparation method and use of/ATP composite photo-catalysts, step are as follows：The preparation of step 1, modified attapulgite (ATP)；Step 2, g C3N4The preparation of/ATP photochemical catalysts；Step 3, Fe3O4‑QDs@g‑C3N4/ ATP preparation.Fe prepared by method of the present invention3O4‑QDs@g‑C3N4The separation and recovery of/ATP composite photo-catalysts is more convenient, efficient；The Fe3O4‑QDs@g‑C3N4/ ATP composite photo-catalysts have preferable photocatalytic activity and stability.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to one kind is based on ferroso-ferric oxide quantum dot (Fe3O4-
QDs) and concave convex rod (ATP) modification carbonitride (g-C3N4) composite photo-catalyst preparation method composite photo-catalyst preparation
Method and purposes.
Background technology
Mercaptan is the organic compound of a kind of sulfur-bearing, is that organic group is connected with sulfydryl to be formed by chemical bond,
It is expressed as R-SH.Wherein, R group is usually some common aliphatic or fragrant same clan's compound, while also can be by halogen family member
Element, nitrogen, phosphate etc. substitute.The physicochemical property of mercaptan is relevant with alkyl or other groups in combination.Mercaptan
(Mercaptan) class organic pollution mainly includes common methyl mercaptan, ethyl mercaptan, propanethiol, tert-butyl mercaptan, benzenethiol etc.,
Its waste water often has unpleasant stink.The cause for the most critical being related in the Taihu Lake water contamination accident of report in 2007 is smelling material just
It is thio-alcohol organic pollution.
Because city develop rapidly and the increase of population so that original build urban periphal defence sewage treatment plant, chemical industry
Caused by the sewage that enterprise and pharmaceutical engineering enterprise are constantly discharged close to the residential quarter of resident and living area, these enterprises
Foul gas is bound to cause the living environment on resident periphery to be deteriorated.Moreover, these foul gas are also polluting simultaneously
Air, serious harm is brought to ecological environment.Stench caused by sulphur-containing substance is to compare in the current odor pollution in China
More serious, its pollution triggered often has generation so that the physical and mental health of nearby residents and life are all on the hazard.From environment and
The angle analysis of economic development, if a region has the odor pollutions such as mercaptan, caused harm will influence whether one
The economic development and social stability in area.
Poisonous and bad smell can be given out after mercaptan volatilization, if the derivative of some mercaptan and thio-alcohol is discharged into me
Natural environment in, to caused by the life and health of the mankind harm be inevitable[6].In addition, mercaptan is as a kind of organic
Sulphur compound, because it has volatility, micro sulfur alcohol compound is exposed to mood and the work that people can be influenceed in air
Mood, if inhalation of low concentration gas may result in the problem of some are more serious, it can such as cause headache, nausea.Higher concentration goes out
Central nervous system now can be then acted on, vomiting, diarrhoea occurs, it is lethal to even result in respiratory paralysis.In addition, mercaptan gases density
It is bigger than air, quite remote place can be diffused into lower, chance naked light, which can draw, to strile-back.If meeting high temperature, the pressure inside container
Power will become big, might have the danger such as blast, therefore take the mercaptan of this slightly solubility organic odoriferous of suitable technological means removal
Pollutant is necessary.
In summary, the problems such as thio-alcohol organic pollution is brought to the mankind food chain product safety and environmental pollution, is
Through getting worse.So realize effective removal to thio-alcohol organic contamination, reducing it, existing risk is still long in the environment
Urgent problem to be solved since phase.At present, the processing method for the organic pollution has a lot, such as, absorption method, biology drop
Solution, micro-electrolysis method, the methods of photocatalysis.Wherein, the research in terms of removal organic polluter is gone to take using photocatalysis technology
Obtain and be necessarily in progress.It is a kind of preferable green technology, can be given birth to organic matter degradation for the small molecule of environmental sound, even
It is carbon dioxide, water etc..
g-C3N4As a kind of new organic photochemical catalyst, it has been widely used in photocatalysis field, such as Shi reports
Road g-C3N4Composite photocatalyst for degrading rhodamine B (Hydrothermal synthesis of InVO4/graphitic
carbon nitride heterojunctions and excellent visible-light-driven
Photocatalytic performance for rhodamine B.J. Alloy.Compd.2014,612,143-148.),
And (Wang X C, KazuhikoM, Arne T, the et al.A metal-free polymeric such as Wang
photocatalyst for hydrogen production from water under visible light[J].
Nature Material,2009,8:76-80.) report g-C3N4Decomposable asymmetric choice net aquatic products H under visible light2Deng.Researcher at present
To g-C3N4Research be also to deepen continuously.But due to g-C3N4Smaller than surface, hardly possible reclaims, and photo-generate electron-hole is easily multiple
The problems such as conjunction make its application receive a certain degree of limitation.Synthesized herein with high-temperature calcination and deposition technique with can
See the magnetic Fe of photocatalytic activity3O4-QDs@g-C3N4/ ATP composite photo-catalysts, the composite photo-catalyst not only have preferable
Magnetic simultaneously also greatly strengthen photocatalytic activity of the composite photo-catalyst to mercaptan pollutant (di-mercaptobenzothiazolby).
In addition, we select Fe3O4Quantum dot mainly considers that its good Magneto separate characteristic reduces financial cost, pole as magnetic material
Big improves cost recovery and secondary use rate, and the quantum effect enhancing of itself improves light and urged to the absorbability of light
Change effect.
The content of the invention
The present invention prepares a kind of Fe with high-temperature calcination and deposition technique preparation means3O4-QDs@g-C3N4/ ATP is multiple
The preparation method of closing light catalyst, can be good at degrade environmental wastewater in di-mercaptobenzothiazolby, have synthesis simply and
The characteristics of degradation rate is high.
The technical scheme is that：
A kind of polynary magnetic Fe3O4-QDs@g-C3N4The preparation method of/ATP composite photo-catalysts, step are as follows：
The preparation of step 1, modified attapulgite (ATP)：Concave convex rod is added in hydrochloric acid, sealing magnetic is stirred to scattered equal
It is even, stood after ultrasound, be centrifugally separating to obtain solid sample, be dried in vacuo, that is, obtain modified attapulgite；
Step 2, g-C3N4The preparation of/ATP photochemical catalysts：Modified attapulgite that step 1 is obtained is finely ground to be distributed to ethanol
In, urea is added, sealing magnetic stirring dissolves solute, solid product is dried in vacuo；Solid product is placed on Muffle again
Calcined in stove, after muffle furnace is cooled to room temperature, crucible is taken out and by the solid sample grind into powder in crucible, done
It is dry, obtain the g-C that ATP is modified after being cooled to room temperature3N4；Labeled as g-C3N4/ ATP photochemical catalysts；
Step 3, Fe3O4-QDs@g-C3N4/ ATP preparation：The g-C that step 2 is obtained3N4/ ATP be added to containing go from
Stirred in the beaker of sub- water and ethanol, add FeCl3·6H2O and FeCl2·4H2O, obtain mixed liquor；By mixed liquor
Stir at a constant temperature, then inject ammoniacal liquor rapidly, then stirring reaction, question response naturally cool to after terminating at a constant temperature
Room temperature, washing is standby by sample drying, obtains polynary magnetic Fe3O4-QDs@g-C3N4/ ATP composite photo-catalysts.What is obtained is heavy
Starch is dried for further characterizing.
In step 1, the amount ratio of used concave convex rod and hydrochloric acid is 10~20g：100~200mL, the hydrochloric acid it is dense
Spend for 1mol L-1。
In step 2, used modified attapulgite, ethanol, the amount ratio of urea are 0.001~1g：20mL：5g；It is described
Calcining heat is 500 DEG C, and 2h is kept under the constant temperature, and wherein heating rate is 1.0~10 DEG C/min.
In step 3, the g-C3N4/ATP、FeCl3·6H2O、FeCl2·4H2O, the dosage of ammoniacal liquor, deionized water, ethanol
Than for 0.1~0.3g:0.1mmol~1.0mmol:0.05mmol~0.5mmol:1.0mL~1mL:10~30mL:10~
30mL；Described constant temperature is 60-80 DEG C, and the time of stirring reaction is 3-8h under the constant temperature.
Fe prepared by described method3O4-QDs@g-C3N4/ ATP composite photo-catalyst is used for photocatalytic degradation dimercapto
Phenylpropyl alcohol thiazole.
Beneficial effect：
Fe prepared by method of the present invention3O4-QDs@g-C3N4The separation and recovery of/ATP composite photo-catalysts is more just
It is prompt, efficient；The Fe3O4-QDs@g-C3N4/ ATP composite photo-catalysts have preferable photocatalytic activity and stability.
Brief description of the drawings
Fig. 1 is the XRD of sample prepared by embodiment 1；Respectively g-C3N4,Fe3O4, ATP, g-C3N4/ATP, Fe3O4-
QDs@g-C3N4/ ATP XRD curves；
Fig. 2 a figures are Fe3O4-QDs@g-C3N4/ ATP circulation degraded design sketch, Fig. 2 b are Fe3O4-QDs@g-C3N4/ATP
VSM figure；
Fig. 3 is the photoelectricity flow graph and impedance diagram that different samples are different synthetic samples, and wherein A figures are g-C3N4(a), ATP
(b), g-C3N4/ATP(c),Fe3O4-QDs@g-C3N4/ ATP (d) photoelectricity flow graph；B figures are g-C3N4(a), ATP (b), g-
C3N4/ATP(c),Fe3O4-QDs@g-C3N4/ ATP (d) impedance diagram.
Fig. 4 is the PL figures and FL figures that different samples are different synthetic samples, and wherein a figures are g-C3N4(a), g-C3N4/ATP
And Fe (b)3O4-QDs@g-C3N4/ ATP (c) PL figures；B figures are g-C3N4(a), g-C3N4/ ATP (b) and Fe3O4-QDs@g-
C3N4/ ATP (c) FL figures.
Embodiment
With reference to specific embodiment, the invention will be further described：
Photocatalytic activity evaluation：Carried out in D1 type photochemical reactions instrument (being purchased from Educational Instrument Factory of Yangzhou University), will
100mL 20mg/L di-mercaptobenzothiazolby simulated wastewater is added in reaction bulb, is added magneton and 0.05g photochemical catalysts, is beaten
Open visible photoelectric source and aerator and carry out Dynamic Adsorption, it is 30 to start external thermostatic water-circulator bath to control temperature of reaction system
℃.Illumination reaction is carried out after reaching adsorption equilibrium, every sampling in 15 minutes once, centrifuges, surveys thioresorcin in supernatant
And the concentration of thiazole, pass through C/C0To judge the degradation effect of di-mercaptobenzothiazolby.Wherein, C0For tetracycline after adsorption equilibrium
Concentration, the concentration of di-mercaptobenzothiazolby when C is reaction time T.
The step of the present invention is as follows：
A kind of polynary magnetic Fe3O4-QDs@g-C3N4The preparation method of/ATP composite photo-catalysts, step are as follows：
The preparation of step 1, modified attapulgite (ATP)：Concave convex rod is added in hydrochloric acid, sealing magnetic is stirred to scattered equal
It is even, stood after ultrasound, be centrifugally separating to obtain solid sample, be dried in vacuo, that is, obtain modified attapulgite；
Step 2, g-C3N4The preparation of/ATP photochemical catalysts：Modified attapulgite that step 1 is obtained is finely ground to be distributed to ethanol
In, urea is added, sealing magnetic stirring dissolves solute, solid product is dried in vacuo；Solid product is placed on Muffle again
Calcined in stove, after muffle furnace is cooled to room temperature, crucible is taken out and by the solid sample grind into powder in crucible, done
It is dry, it will obtain the g-C that ATP is modified after being cooled to room temperature3N4；Labeled as g-C3N4/ ATP photochemical catalysts；
Step 3, Fe3O4-QDs@g-C3N4/ ATP preparation：The g-C that step 2 is obtained3N4/ ATP be added to containing go from
Stirred in the beaker of sub- water and ethanol, add FeCl3·6H2O and FeCl2·4H2O, obtain mixed liquor；By mixed liquor
Stir at a constant temperature, then inject ammoniacal liquor rapidly, then stirring reaction, question response naturally cool to after terminating at a constant temperature
Room temperature, washing is standby by sample drying, obtains polynary magnetic Fe3O4-QDs@g-C3N4/ ATP composite photo-catalysts.What is obtained is heavy
Starch is dried for further characterizing.
Embodiment 1：
In step 1, the concave convex rod quality is 5g, hydrochloric acid (1mol L-1) liquor capacity is 50mL.
In step 2, the calcining heat is 500 DEG C, and 2h is kept under the constant temperature, wherein heating rate be 1.0 DEG C/
min.The g-C3N4, ATP dosage be followed successively by 0.1g, 0.001g；The magnetic agitation time is 2h, ultrasonic time 0.5h.
In step 3, the g-C3N4/ATP、FeCl3·6H2O、FeCl2·4H2O, the dosage of ammoniacal liquor, deionized water, ethanol
It is followed successively by 0.1g, 0.1mmol, 0.05mmol, 1.0mL, 10mL, 10mL；The temperature of solvent thermal reaction is 60 DEG C, reacts 3h.
In step 2, step 3, the drying temperature of sample is 60 DEG C.
Step 4, take Fe in 0.05g steps 33O4-QDs@g-C3N4/ ATP is added to 100mL and contains 20mg L-1Two-mercapto
Lucifuge, which stirs, in the reactor of base benzothiazole solution, at 30 DEG C reaches adsorption equilibrium；Open xenon lamp and be aerated, when one section
Between sample once, take 5mL every time, take clarified solution after centrifugation, and it is the suction at 310nm to be determined with ultraviolet spectrometry photometry in wavelength
Shading value.
Embodiment 2：
In step 1, the concave convex rod quality is 20g, hydrochloric acid (1mol L-1) liquor capacity is 200mL.
In step 2, the calcining heat is 500 DEG C, and 2h is kept under the constant temperature, wherein heating rate be 10 DEG C/
min.The g-C3N4, ATP dosage be followed successively by 2.0g, 1.0g；The magnetic agitation time is 6h, ultrasonic time 1h.
In step 3, the g-C3N4/ATP、FeCl3·6H2O、FeCl2·4H2O, the dosage of ammoniacal liquor, deionized water, ethanol
It is followed successively by 0.3g, 1.0mmol, 0.5mmol, 10mL, 30mL, 30mL；The temperature of solvent thermal reaction is 80 DEG C, reacts 8h.
In step 2, step 3, the drying temperature of sample is 60 DEG C.
Step 4, take Fe in 0.05g steps 33O4-QDs@g-C3N4/ ATP is added to 100mL and contains 20mg L-1Dimercapto
Lucifuge, which stirs, in the reactor of phenylpropyl alcohol thiazole solution, at 30 DEG C reaches adsorption equilibrium；Open xenon lamp and be aerated, at regular intervals
Sampling once, takes 5mL every time, clarified solution is taken after centrifugation, and it is the absorbance at 310nm to be determined with ultraviolet spectrometry photometry in wavelength
Value.
Embodiment 3：
In step 1, the concave convex rod quality is 10g, hydrochloric acid (1mol L-1) liquor capacity is 100mL.
In step 2, the calcining heat is 500 DEG C, and 2h is kept under the constant temperature, wherein heating rate be 5 DEG C/
min.The g-C3N4, ATP amount ratio be 1.0g:0.05g；The magnetic agitation time is 3h, ultrasonic time 0.6h.
In step 3, the g-C3N4/ATP、FeCl3·6H2O、FeCl2·4H2O, the dosage of ammoniacal liquor, deionized water, ethanol
It is followed successively by 0.2g, 0.5mmol, 0.25mmol, 5mL, 20mL, 20mL；The temperature of solvent thermal reaction is 70 DEG C, reacts 4h.
In step 2, step 3, the drying temperature of sample is 60 DEG C.
Step 4, take Fe in 0.05g steps 33O4-QDs@g-C3N4/ ATP is added to 100mL and contains 20mg L-1Dimercapto
Lucifuge, which stirs, in the reactor of phenylpropyl alcohol thiazole solution, at 30 DEG C reaches adsorption equilibrium；Open xenon lamp and be aerated, at regular intervals
Sampling once, takes 5mL, clarified solution is taken after centrifugation every time, and it is the absorbance at 310nm to be determined with ultraviolet spectrometry photometry in wavelength
Value.
Photocatalytic activity evaluation：Carried out in DW-01 type photochemical reaction instrument, it is seen that light light irradiation, by 100mL 20mg
L-1Dimercapto phenylpropyl alcohol thiazole simulated wastewater adds in reactor and determines its initial value, then adds photochemical catalyst, magnetic agitation
And open aerator and be passed through air and maintain the catalyst in suspension or afloat, sample after dark adsorption equilibrium, During Illumination
Middle interval 20min sampling analyses, take supernatant liquor in spectrophotometer λ after centrifugationmaxAbsorbance is determined at=310nm,
And pass through formula：DC=[(C0-Ci)/C0] × 100% calculates degradation rate, wherein C0The suction of tetracycline during to reach adsorption equilibrium
Luminosity, CiFor timing sampling measure be dimercapto phenylpropyl alcohol thiazole solution absorbance.
It is really g-C that Fig. 1, which is demonstrated in the sample prepared by the application,3N4, ATP and Fe3O4-QDs。
A is Fe in Fig. 23O4-QDs@g-C3N4/ ATP composite photo-catalysts show preferable magnetic, can be with from figure
Draw Fe3O4-QDs@g-C3N4/ ATP composite photo-catalysts still have good catalytic effect after 5 circulation experiments.Fig. 2 b
For sample F e3O4-QDs@g-C3N4/ ATP VSM figures, illustration can be seen that figure Fe3O4-QDs@g-C3N4/ ATP is easy to outside
Attraction, there is preferable magnetic recyclability.
Fig. 3 is the photoelectricity flow graph and impedance diagram that different samples are different synthetic samples, wherein g-C3N4Photoelectric current it is minimum,
ATP takes second place, followed by g-C3N4/ ATP, wherein Fe3O4-QDs@g-C3N4/ ATP photocurrent response is most strong, shows Fe3O4-
QDs@g-C3N4/ ATP has higher electron hole transmission performance；B figures are g-C3N4, ATP, g-C3N4/ATP、 Fe3O4-QDs@
g-C3N4/ ATP impedance diagram, wherein g-C3N4Semicircle it is maximum, show impedance maximum, Fe3O4-QDs@g-C3N4/ ATP semi arches
Minimum, show impedance minimum, further illustrate Fe3O4-QDs@g-C3N4/ ATP has preferable conductive performance, has preferable
Photocatalytic activity.
Fig. 4 is the PL figures and FL figures that different samples are different synthetic samples, and wherein a figures are g-C3N4, g-C3N4/ ATP and
Fe3O4-QDs@g-C3N4/ ATP PL figures, wherein g-C3N4Peak value is higher, illustrates that its electron-hole recombination rate is higher, and Fe3O4-
QDs@g-C3N4/ ATP peak values are relatively low, illustrate that its electron-hole recombination rate is relatively low, can make full use of photo-generate electron-hole；B figures are
g-C3N4, g-C3N4/ ATP and Fe3O4-QDs@g-C3N4/ ATP FL schemes, as can be seen from the figure Fe3O4-QDs@g-C3N4/ATP
With the shorter electron-hole recombinations time, electron hole caused by explanation preferably utilizes.
Claims (5)
- A kind of 1. polynary magnetic Fe3O4-QDs@g-C3N4The preparation method of/ATP composite photo-catalysts, it is characterised in that step is such as Under：The preparation of step 1, modified attapulgite：Concave convex rod is added in hydrochloric acid, sealing magnetic is stirred to being uniformly dispersed, after ultrasound Stand, be centrifugally separating to obtain solid sample, be dried in vacuo, that is, obtain modified attapulgite；Step 2, g-C3N4The preparation of/ATP photochemical catalysts：Modified attapulgite that step 1 is obtained is finely ground to be distributed in ethanol, then Urea is added, sealing magnetic stirring dissolves solute, solid product is dried in vacuo；Solid product is placed in Muffle furnace again and forged Burn, after muffle furnace is cooled to room temperature, crucible is taken out and the solid sample grind into powder in crucible, drying is cold But to the g-C of acquisition ATP modifications after room temperature3N4；Labeled as g-C3N4/ ATP photochemical catalysts；Step 3, Fe3O4-QDs@g-C3N4/ ATP preparation：The g-C that step 2 is obtained3N4/ ATP is added to containing deionized water Stirred with the beaker of ethanol, add FeCl3·6H2O and FeCl2·4H2O, obtain mixed liquor；By mixed liquor in perseverance Stirred under temperature, then inject ammoniacal liquor rapidly, then stirring reaction, question response naturally cool to room after terminating at a constant temperature Temperature, washing is standby by sample drying, obtains polynary magnetic Fe3O4-QDs@g-C3N4/ ATP composite photo-catalysts.
- A kind of 2. polynary magnetic Fe according to claim 13O4-QDs@g-C3N4The preparation side of/ATP composite photo-catalysts Method, it is characterised in that in step 1, the amount ratio of used concave convex rod and hydrochloric acid is 10~20g：100~200mL, the salt The concentration of acid is 1mol L-1。
- A kind of 3. polynary magnetic Fe according to claim 13O4-QDs@g-C3N4The preparation side of/ATP composite photo-catalysts Method, it is characterised in that in step 2, used modified attapulgite, ethanol, the amount ratio of urea are 0.001~1g：20mL： 5g；The calcining heat is 500 DEG C, and 2h is kept under the constant temperature, and wherein heating rate is 1.0~10 DEG C/min.
- A kind of 4. polynary magnetic Fe according to claim 13O4-QDs@g-C3N4The preparation side of/ATP composite photo-catalysts Method, it is characterised in that in step 3, the g-C3N4/ATP、FeCl3·6H2O、FeCl2·4H2O, ammoniacal liquor, deionized water, ethanol Amount ratio be 0.1~0.3g:0.1mmol~1.0mmol:0.05mmol~0.5mmol:1.0mL~1mL:10~30mL:10 ~30mL；Described constant temperature is 60-80 DEG C, and the time of stirring reaction is 3-8h under the constant temperature.
- 5. Fe prepared by the method described in Claims 1 to 4 any one3O4-QDs@g-C3N4/ ATP composite photo-catalyst is used In the purposes of photocatalytic degradation dimercapto phenylpropyl alcohol thiazole.
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