CN107983391A - Insoluble magnetic cobalt/defective g-C3N4 composite catalysts and its application in Oxone degrading waste waters are catalyzed - Google Patents
Insoluble magnetic cobalt/defective g-C3N4 composite catalysts and its application in Oxone degrading waste waters are catalyzed Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 54
- 239000010941 cobalt Substances 0.000 title claims abstract description 54
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 230000002950 deficient Effects 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000002351 wastewater Substances 0.000 title claims abstract description 16
- 230000000593 degrading effect Effects 0.000 title abstract 2
- 239000003426 co-catalyst Substances 0.000 claims abstract description 17
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 claims abstract description 7
- 229960003376 levofloxacin Drugs 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 235000013495 cobalt Nutrition 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002604 ultrasonography Methods 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 229960001699 ofloxacin Drugs 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000005389 magnetism Effects 0.000 claims description 8
- 229910052603 melanterite Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 150000007974 melamines Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- -1 melamine Amine Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of insoluble magnetic cobalt/defective g C3N4Composite catalyst and its application in Oxone degrading waste waters are catalyzed, belong to the synthesis of composite catalyzing material and the catalytic degradation technology field of organic wastewater.Technical scheme main points are：Insoluble magnetic cobalt/defective g C3N4The preparation method of composite catalyst, insoluble magnetic cobalt/defective g C that the preparation of magnetic Co catalysts and the mass percentage of cobalt that the mass percentage for specifically including cobalt is 11% are 1.2%3N4The preparation of composite catalyst and etc., the insoluble magnetic cobalt/defective g C3N4Composite catalyst being capable of efficient catalytic Oxone degraded Levofloxacin Wastewaters.Insoluble magnetic cobalt produced by the present invention/defective g C3N4Composite catalyst has preferable insoluble in neutral environment, while has preferable catalytic performance, but also has certain photocatalysis performance, can be applied to the degraded of difficult for biological degradation organic pollution.
Description
Technical field
The invention belongs to the synthesis of composite catalyzing material and the catalytic degradation technology field of organic wastewater, and in particular to a kind of
Insoluble magnetic cobalt/defective g-C3N4The preparation method of composite catalyst and its catalysis Oxone degraded Levofloxacin Wastewater
In application.
Background technology
Lavo-ofloxacin is an antibiotic medicine with light word activity in quinolone drugs, to most of gram positive bacterias
Obvious inhibitory action, and persistent are respectively provided with gram-negative bacteria.Therefore, lavo-ofloxacin has clinically obtained extensively
General application.Since its half-life period is longer, traditional water technology can not effectively remove these medicines, therefore it is good for public
The potential hazard of health causes extensive concern.
Oxone（2KHSO5·KHSO4·K2SO4）For the trade name of peroxosulphuric hydrogen potassium complex salt, its active material is
Single peroxosulphuric hydrogen potassium KHSO5, due to a SO3 −Substitution HOOH forms the unique texture of asymmetric peroxide, makes it easier to
Excite and produce substantial amounts of potentiometric titrations（SO4 •-）.Oxone/Co2+It is a kind of oxidation system similar to Fenton reagent,
Transition metal Co2+Oxone can be catalyzed and produce that a large amount of active, oxidabilities are strong and the SO of non-selectivity4 •-Free radical, by water body
In organic pollution materials exhaustive oxidation be CO2、H2O and inorganic salts.The technology is because treatment effeciency is high, especially in difficult for biological degradation
There is excellent performance in the removal of pollutant, it is become research hotspot of concern always.
Graphite phase carbon nitride（g-C3N4）It is a kind of unique 2D stratiform nonmetallic materials, its band structure is very suitable for light
The production hydrogen in water and the crucial half-reaction step of production oxygen two is catalytically decomposed, while has simple synthetic method, good thermal stability concurrently
The advantages that, therefore generally it is considered as the catalysis material with broad prospect of application, in photocatalysis Decomposition aquatic products hydrogen, manually photosynthetic
There is important researching value into the field such as, organic pollutant degradation and carbon dioxide reduction.
Oxone/Co2+In oxidation system Co will be ionized into as catalyst, cobaltous sulfate frequently with water miscible cobaltous sulfate2+
It is present in aqueous solution, Co in reaction process2+It can promote SO as catalyst4 •-A large amount of generations of free radical, so as to ensure oxygen
Change being smoothed out for reaction.Soluble cobalt salt can be discharged with water after the completion of reaction, and still, cobalt belongs to heavy metal element, energy
It is enriched with, can be accumulated in human body by food chain in vivo, therefore has to ecological environment and human health potential
Damaging effect.Experimental studies have found that：Oxone/Co2+PH value no requirement (NR) when oxidation system is to processing waste water, in most cases
To the better processing effect of neutral waste water.Therefore in order to avoid the pollution of soluble heavy metal cobalt, in the present invention, with melamine
Amine, sodium hydroxide, ferrous sulfate, iron chloride and cobaltous sulfate are raw material, have prepared and have not been found in the literature, neutral ring
Not soluble in water under border, recyclable insoluble magnetic cobalt/defective g-C3N4Composite catalyst.
The content of the invention
The technical problem to be solved by the present invention is to provide a kind of insoluble magnetic cobalt/defective g-C3N4Composite catalyst
Preparation method and its application in catalysis Oxone degraded Levofloxacin Wastewaters, insoluble magnetic cobalt made from this method/have
Defect g-C3N4The oxidation system of composite catalyst and Oxone composition can not only effectively degrade Levofloxacin Wastewater, and not
Dissolubility magnetic cobalt/defective g-C3N4Composite catalyst can recycling, avoid causing secondary pollution to environment.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, insoluble magnetic cobalt/defective g-C3N4It is compound
The preparation method of catalyst, it is characterised in that concretely comprise the following steps：
（1）Take 2.703g FeCl3·6H2O、2.780g FeSO4·7H2O and 6.033g CoSO4·7H2O be dissolved in 20mL go from
It is to be dissolved to obtain orange red mixed solution completely in sub- water, above-mentioned mixed solution is placed in water-bath and is heated to 60 DEG C and is added dropwise
In the ammonia spirit for being 3mol/L to 45mL molar concentrations, there is black solid generation in reaction process, after reaction, will contain
The troubled liquor of a large amount of black solids, in 60 DEG C of ultrasound 30min, is then cooled to room temperature under the ultrasound condition of 20KHz, 100W,
With deionized water rinsing black solid to neutrality after separation of solid and liquid, then filter, the air-dried mass percentage for obtaining cobalt is 11%
Magnetic Co catalysts；
（2）0.7g melamines, 0.07g sodium hydroxides and 0.07g magnetism Co catalysts are taken to be put into crucible and be uniformly mixed, by crucible
It is put into Muffle furnace and is heated to 550 DEG C of insulation 4h, the black that the mass percentage of cobalt is 1.2% is obtained after natural cooling
Powdered insoluble magnetic cobalt/defective g-C3N4Composite catalyst.
Insoluble magnetic cobalt of the present invention/defective g-C3N4Composite catalyst is in catalysis Oxone degraded levofloxacins
Application in star waste water, it is characterised in that detailed process is：Under room temperature, it is 0.01mol/L's by 10mL molar concentrations
The insoluble magnetic cobalt of black powder/defective g-C that the mass percentage of Oxone solution and 0.005g cobalts is 1.2%3N4It is multiple
The oxidation system for closing catalyst composition is added in the Levofloxacin Wastewater that 50mL mass concentrations are 10mg/L, 20min degradeds
Efficiency is 96.68%, insoluble magnetic cobalt/defective g-C3N4Composite catalyst it is filtered or centrifuge recycling after circulate again
Utilize.
Insoluble magnetic cobalt produced by the present invention/defective g-C3N4Composite catalyst has preferable in neutral environment
It is insoluble, while there is preferable catalytic performance, but also there is certain photocatalysis performance, it can be applied to difficult for biological degradation
The degraded of organic pollution.Under room temperature, the Oxone solution and 0.005g cobalts by 10mL molar concentrations for 0.01mol/L
Mass percentage is 1.2% insoluble magnetic cobalt/defective g-C3N4The oxidation system of composite catalyst composition is added to
50mL mass concentrations are in the Levofloxacin Wastewater of 10mg/L, and 20min degradation efficiencies are 96.68%.The present invention passes through simplicity
The controllable g-C of alkali auxiliary one-step synthesis nitrogen defect level3N4Material, the synthetic method with raw material than change can obtain one
The g-C of serial difference nitrogen defect density3N4Sample, energy gap can carry out continuous controllable adjusting between 2.7-2.3eV,
G-C is greatly widened3N4Visible absorption ability, visible light catalytic efficiency is obtained tremendous increase.
Brief description of the drawings
Fig. 1 is insoluble magnetic cobalt made from embodiment 4/defective g-C3N4The SEM figures of composite catalyst 200nm, by scheming
Understand, regular lamellar structure is defective g-C3N4, spherical particle is to be supported on defective g-C3N4There is magnetic in lamellar structure
The Co catalysts of property；
Fig. 2 is insoluble magnetic cobalt made from embodiment 4/defective g-C3N4The SEM figures of composite catalyst 200nm, can by figure
Know, particle is in pellet shapes, and average grain diameter 150nm, these particle packings are together.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
（1）Take 2.703g FeCl3·6H2O、2.780g FeSO4·7H2O and 6.033g CoSO4·7H2O be dissolved in 20mL go from
It is to be dissolved to obtain orange red mixed solution completely in sub- water, above-mentioned mixed solution is placed in water-bath and is heated to 60 DEG C and is added dropwise
In the ammonia spirit for being 3mol/L to 45mL molar concentrations, there is black solid generation in reaction process, after reaction, will contain
The troubled liquor of a large amount of black solids, in 60 DEG C of ultrasound 30min, is then cooled to room temperature under the ultrasound condition of 20KHz, 100W,
With deionized water rinsing black solid to neutrality after separation of solid and liquid, then filter, the air-dried mass percentage for obtaining cobalt is 11%
Magnetic Co catalysts；
（2）0.7g melamines, 0.07g sodium hydroxides and 0.07g magnetism Co catalysts are taken to be put into crucible and be uniformly mixed, by crucible
It is put into Muffle furnace and is heated to 550 DEG C of insulation 4h, the black that the mass percentage of cobalt is 1.2% is obtained after natural cooling
Powdered insoluble magnetic cobalt/defective g-C3N4Composite catalyst, grinding are spare.
（3）Under room temperature, by the insoluble magnetic cobalts of 0.005g/defective g-C3N4Composite catalyst is added to 50mL
In the lavo-ofloxacin solution of 10mg/L, mixed solution is placed on magnetic stirring apparatus and is degraded, is almost no longer dropped after 42min
Solution, degradation efficiency 7%.
Embodiment 2
（1）Take 2.703g FeCl3·6H2O、2.780g FeSO4·7H2O and 6.033g CoSO4·7H2O be dissolved in 20mL go from
It is to be dissolved to obtain orange red mixed solution completely in sub- water, above-mentioned mixed solution is placed in water-bath and is heated to 60 DEG C and is added dropwise
In the ammonia spirit for being 3mol/L to 45mL molar concentrations, there is black solid generation in reaction process, after reaction, will contain
The troubled liquor of a large amount of black solids, in 60 DEG C of ultrasound 30min, is then cooled to room temperature under the ultrasound condition of 20KHz, 100W,
With deionized water rinsing black solid to neutrality after separation of solid and liquid, then filter, the air-dried mass percentage for obtaining cobalt is 11%
Magnetic Co catalysts；
（2）Under room temperature, it is 10mg/L the Oxone that 10mL molar concentrations are 0.01mol/L to be added to 50mL mass concentrations
Lavo-ofloxacin solution in, mixed solution is placed on magnetic stirring apparatus and is degraded, is almost no longer degraded after 45min, drop
It is 3.13% to solve efficiency.
Embodiment 3
（1）Take 2.703g FeCl3·6H2O、2.780g FeSO4·7H2O and 6.033g CoSO4·7H2O be dissolved in 20mL go from
It is to be dissolved to obtain orange red mixed solution completely in sub- water, above-mentioned mixed solution is placed in water-bath and is heated to 60 DEG C and is added dropwise
In the ammonia spirit for being 3mol/L to 45mL molar concentrations, there is black solid generation in reaction process, after reaction, will contain
The troubled liquor of a large amount of black solids, in 60 DEG C of ultrasound 30min, is then cooled to room temperature under the ultrasound condition of 20KHz, 100W,
With deionized water rinsing black solid to neutrality after separation of solid and liquid, then filter, the air-dried mass percentage for obtaining cobalt is 11%
Magnetic Co catalysts；
（2）0.1.77g melamines, 0.177g sodium hydroxides and 0.07g magnetism Co catalysts are taken to be put into crucible and be uniformly mixed, will
Crucible, which is put into Muffle furnace, is heated to 550 DEG C of insulation 4h, and the mass percentage that cobalt is obtained after natural cooling is 0.5%
The insoluble magnetic cobalt of black powder/defective g-C3N4Composite catalyst, grinding are spare.
（3）Under room temperature, the Oxone that 10mL molar concentrations are 0.01mol/L is added to 50mL mass concentrations is
In the lavo-ofloxacin solution of 10mg/L, then add 0.005g cobalts mass percentage be 0.5% insoluble magnetic cobalt/
Defective g-C3N4Composite catalyst, mixed solution is placed on magnetic stirring apparatus and is degraded, and degradation efficiency is during 60min
73.9%。
Embodiment 4
（1）Take 2.703g FeCl3·6H2O、2.780g FeSO4·7H2O and 6.033g CoSO4·7H2O be dissolved in 20mL go from
It is to be dissolved to obtain orange red mixed solution completely in sub- water, above-mentioned mixed solution is placed in water-bath and is heated to 60 DEG C and is added dropwise
In the ammonia spirit for being 3mol/L to 45mL molar concentrations, there is black solid generation in reaction process, after reaction, will contain
The troubled liquor of a large amount of black solids, in 60 DEG C of ultrasound 30min, is then cooled to room temperature under the ultrasound condition of 20KHz, 100W,
With deionized water rinsing black solid to neutrality after separation of solid and liquid, then filter, the air-dried mass percentage for obtaining cobalt is 11%
Magnetic Co catalysts；
（2）0.7g melamines, 0.07g sodium hydroxides and 0.07g magnetism Co catalysts are taken to be put into crucible and be uniformly mixed, by crucible
It is put into Muffle furnace and is heated to 550 DEG C of insulation 4h, the black that the mass percentage of cobalt is 1.2% is obtained after natural cooling
Powdered insoluble magnetic cobalt/defective g-C3N4Composite catalyst, grinding are spare.
（3）Under room temperature, the Oxone that 10mL molar concentrations are 0.01mol/L is added to 50mL mass concentrations is
In the lavo-ofloxacin solution of 10mg/L, then add 0.005g cobalts mass percentage be 1.2% insoluble magnetic cobalt/
Defective g-C3N4Composite catalyst, mixed solution is placed on magnetic stirring apparatus and is degraded, is almost no longer degraded after 20min,
Degradation efficiency is 96.68%.
Embodiment 5
（1）Take 2.703g FeCl3·6H2O、2.780g FeSO4·7H2O and 6.033g CoSO4·7H2O be dissolved in 20mL go from
It is to be dissolved to obtain orange red mixed solution completely in sub- water, above-mentioned mixed solution is placed in water-bath and is heated to 60 DEG C and is added dropwise
In the ammonia spirit for being 3mol/L to 45mL molar concentrations, there is black solid generation in reaction process, after reaction, will contain
The troubled liquor of a large amount of black solids, in 60 DEG C of ultrasound 30min, is then cooled to room temperature under the ultrasound condition of 20KHz, 100W,
With deionized water rinsing black solid to neutrality after separation of solid and liquid, then filter, the air-dried mass percentage for obtaining cobalt is 11%
Magnetic Co catalysts；
（2）0.3g melamines, 0.03g sodium hydroxides and 0.07g magnetism Co catalysts are taken to be put into crucible and be uniformly mixed, by crucible
It is put into Muffle furnace and is heated to 550 DEG C of insulation 4h, the black that the mass percentage of cobalt is 2.4% is obtained after natural cooling
Powdered insoluble magnetic cobalt/defective g-C3N4Composite catalyst, grinding are spare.
（3）Under room temperature, the Oxone that 10mL molar concentrations are 0.01mol/L is added to 50mL mass concentrations is
In the lavo-ofloxacin solution of 10mg/L, then add 0.005g cobalts mass percentage be 2.4% insoluble magnetic cobalt/
Defective g-C3N4Composite catalyst, mixed solution is placed on magnetic stirring apparatus and is degraded, and degradation efficiency is during 60min
77.7%。
Embodiment 6
（1）Take 2.703g FeCl3·6H2O、2.780g FeSO4·7H2O and 6.033g CoSO4·7H2O be dissolved in 20mL go from
It is to be dissolved to obtain orange red mixed solution completely in sub- water, above-mentioned mixed solution is placed in water-bath and is heated to 60 DEG C and is added dropwise
In the ammonia spirit for being 3mol/L to 45mL molar concentrations, there is black solid generation in reaction process, after reaction, will contain
The troubled liquor of a large amount of black solids, in 60 DEG C of ultrasound 30min, is then cooled to room temperature under the ultrasound condition of 20KHz, 100W,
With deionized water rinsing black solid to neutrality after separation of solid and liquid, then filter, the air-dried mass percentage for obtaining cobalt is 11%
Magnetic Co catalysts；
（2）0.1g melamines, 0.01g sodium hydroxides and 0.07g magnetism Co catalysts are taken to be put into crucible and be uniformly mixed, by crucible
It is put into Muffle furnace and is heated to 550 DEG C of insulation 4h, the black that the mass percentage of cobalt is 5.0% is obtained after natural cooling
Powdered insoluble magnetic cobalt/C3N4Composite catalyst, grinding are spare.
（3）Under room temperature, the Oxone that 10mL molar concentrations are 0.01mol/L is added to 50mL mass concentrations is
In the lavo-ofloxacin solution of 10mg/L, then add 0.005g cobalts mass percentage be 5.0% insoluble magnetic cobalt/
Defective g-C3N4Composite catalyst, mixed solution is placed on magnetic stirring apparatus and is degraded, and degradation efficiency is during 60min
46%。
Basic principle, main features and advantages embodiment above describes the present invention, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the original of the present invention
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. insoluble magnetic cobalt/defective g-C3N4The preparation method of composite catalyst, it is characterised in that concretely comprise the following steps：
（1）Take 2.703g FeCl3·6H2O、2.780g FeSO4·7H2O and 6.033g CoSO4·7H2O be dissolved in 20mL go from
It is to be dissolved to obtain orange red mixed solution completely in sub- water, above-mentioned mixed solution is placed in water-bath and is heated to 60 DEG C and is added dropwise
In the ammonia spirit for being 3mol/L to 45mL molar concentrations, there is black solid generation in reaction process, after reaction, will contain
The troubled liquor of a large amount of black solids, in 60 DEG C of ultrasound 30min, is then cooled to room temperature under the ultrasound condition of 20KHz, 100W,
With deionized water rinsing black solid to neutrality after separation of solid and liquid, then filter, the air-dried mass percentage for obtaining cobalt is 11%
Magnetic Co catalysts；
（2）0.7g melamines, 0.07g sodium hydroxides and 0.07g magnetism Co catalysts are taken to be put into crucible and be uniformly mixed, by crucible
It is put into Muffle furnace and is heated to 550 DEG C of insulation 4h, the black that the mass percentage of cobalt is 1.2% is obtained after natural cooling
Powdered insoluble magnetic cobalt/defective g-C3N4Composite catalyst.
2. insoluble magnetic cobalt made from the method as described in claim 1/defective g-C3N4Composite catalyst is being catalyzed
Application in Oxone degraded Levofloxacin Wastewaters, it is characterised in that detailed process is：Under room temperature, it is dense by 10mL moles
Spend the insoluble magnetism of black powder for being 1.2% for the Oxone solution of 0.01mol/L and the mass percentage of 0.005g cobalts
Cobalt/defective g-C3N4The oxidation system of composite catalyst composition is added to the lavo-ofloxacin that 50mL mass concentrations are 10mg/L
In waste water, 20min degradation efficiencies are 96.68%, insoluble magnetic cobalt/defective g-C3N4Composite catalyst is filtered or centrifugation divides
Recycled again from after recycling.
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| CN109603886A (en) * | 2019-01-09 | 2019-04-12 | 扬州工业职业技术学院 | A kind of novel Fe3O4/g-C3N4Composite material and its application as catalyst |
| CN109985656A (en) * | 2019-04-28 | 2019-07-09 | 上海电力学院 | A kind of synthetic method and application of the carbon nitride catalyst rich in defect |
| CN110180573A (en) * | 2019-05-20 | 2019-08-30 | 河南师范大学 | Heterogeneous magnetic catalyst CoFeO is prepared using old and useless battery positive electrode2The method and its application of@CN |
| CN110252373A (en) * | 2019-06-14 | 2019-09-20 | 湖北中和普汇环保股份有限公司 | A kind of magnetism Co-V/C3N3The preparation method and application of complex carrier particle |
| CN113292150A (en) * | 2021-05-01 | 2021-08-24 | 河南师范大学 | Preparation of Fe by ball milling-calcining method3O4-CuxMethod for degrading LVF in organic wastewater by using O |
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