CN110227461A - It is a kind of to have magnetic heterogeneous photosynthetic Fenton catalyst and the preparation method and application thereof - Google Patents
It is a kind of to have magnetic heterogeneous photosynthetic Fenton catalyst and the preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 230000000243 photosynthetic effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000013246 bimetallic metal–organic framework Substances 0.000 claims abstract description 14
- 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 claims abstract description 11
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 11
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 10
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 9
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical class OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 36
- 238000006731 degradation reaction Methods 0.000 abstract description 36
- 230000003197 catalytic effect Effects 0.000 abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 229940106691 bisphenol a Drugs 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000012621 metal-organic framework Substances 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract description 2
- 239000004568 cement Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 6
- 230000005389 magnetism Effects 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JIGWWGDIEUWCOR-UHFFFAOYSA-N 3-(1,4-diazabicyclo[3.2.2]nonan-4-yl)-6-fluorodibenzothiophene 5,5-dioxide Chemical compound C1=C2S(=O)(=O)C=3C(F)=CC=CC=3C2=CC=C1N1CCN2CCC1CC2 JIGWWGDIEUWCOR-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of magnetic heterogeneous photosynthetic Fenton catalyst of tool and the preparation method and application thereof.The present invention is by first preparing a kind of bimetallic MOF precursor material, and reaction forms MOF under high-temperature and high-pressure conditions, then calcine to obtain a kind of holdings original MOF structure and has magnetic efficient heterogeneous photosynthetic Fenton catalyst.This kind of catalyst is used for heterogeneous photosynthetic Fenton reaction system and carrys out efficient process organic wastewater with difficult degradation thereby, the organic wastewater different for methylene blue, Congo red, bisphenol-A etc., removal rate can reach 90-95%, and catalytic agent reuse is high-efficient, can achieve 10 times or more.The obtained method for preparing catalyst of the present invention is simple, stable in catalytic performance is high, the problems such as homogeneous Fenton system iron cement largely deposits, utilization efficiency is low and uses pH narrow range can not only effectively be solved, Magnetic Isolation can also be passed through, it is easily recycled, catalytic performance with higher has very good application prospect.
Description
(1) technical field
The present invention relates to a kind of function admirable, mild condition, the Fenton catalyst being easily isolated and preparation method thereof, institutes
The Fenton catalyst stated is used for degradation of organic waste water, belongs to water-treatment technology field.
(2) background technique
With world economy and industrialized fast development, the industries such as weaving, pesticide, pharmacy, petrochemical industry generate it is a large amount of it is toxic,
Organic pollutant difficult to degrade constitutes greatly harm to ecological environment and human health.In order to solve this burning issue,
Through having attempted the conventional treatment including absorption, filtering, flocculation and biodegrade, but still it is difficult to meet required discharge mark
It is quasi-.Find the Important Problems that new effective obstinate organic pollutant degradation method has become global concern.
" high-level oxidation technology " (Advanced Oxidation Process, AOPs), which has been developed in recent years, to be used for
The new technology of the hardly degraded organic substance in water body is removed, and shows clear superiority.Firstly, high-level oxidation technology can be normal
It is carried out under temperature, normal pressure, reduces the requirement to processing equipment；Secondly, it can be achieved that the targeting to certain pollutants is degraded；Finally, can
For soil and the in-situ immobilization of water body, repair process is quick and does not have a negative impact to ecosystem.High-level oxidation technology
Research emphasis is to probe into highly effective reaction system and design synthetic catalyst.Wherein the representative are (1) photochemical catalytic oxidation skills
Art, photochemically reactive activation energy derive from luminous energy, use up predominantly ultraviolet light, such as UV/O3、UV/H2O2、UV/Fenton
Deng having important application prospect in environmental area；(2) electro-catalysis technology, including two aspects of electrode reaction and catalytic action, grind
Studying carefully emphasis is modified electrode, it is made to have the function of catalyst during the energization, and itself does not change；(3) optical-electronic is multiple
Catalysis technique is closed, uses the semiconductor catalyst of surface modification as electrode to accelerate optical electro-chemistry to react；(4) catalytic wet
Oxidation technology using oxygen is oxidant under the catalytic action of catalyst in high-temperature and high-pressure conditions, and degradation high-concentration hardly-degradable has
Machine waste water；(5) catalytic ozonation technology degrades to pollutant using the strong oxidizing property of ozone；(6) Fenton/ class
Fenton catalytic oxidation generates the free radical with strong oxidizing property, using Fenton reagent with mineralising organic pollutant of degrading.
But also there are respective technical disadvantages in above several catalytic oxidation technologies, as needed artificial light at present in photocatalytic system
Source needs to expend in electro-catalysis system electric energy, and the high-temperature high-voltage reaction condition of wet raw noodles is more harsh, ozone
The ozone generating apparatus of catalyst costly and in operation needs to expend electric energy, in traditional Fenton technology, reaction system
PH needs in acid condition could oxidation efficiency with higher.The intrinsic defect of these technologies limits catalysis oxidation in reality
Application in the engineering of border, with the development of society, there is an urgent need to have the green catalysis that low energy consumption, at low cost, without secondary pollution
Water treatment technology is aoxidized, and lightwave CATV oxidation technology can utilize in the advantage and Fenton oxidation technology use of sunlight often
The feature that normal temperature and pressure and energy free consume makes the two technologies with good application prospect.Therefore, developing one kind can be in temperature
It is catalyzed under the conditions of, is visible light-responded, environmental sound, the Fenton catalyst being easily recycled become lightwave CATV oxygen
The research emphasis of change technology.
(3) summary of the invention
The object of the present invention is to provide a kind of magnetic heterogeneous photosynthetic Fenton catalyst of tool and preparation method thereof.
Technical scheme is as follows:
A kind of magnetic heterogeneous photosynthetic Fenton catalyst of tool, the catalyst is by Fe3O4And Co3O4Composition,
Middle Fe3O4Mass percent in the catalyst is 40%-60%, Co3O4Mass percent in the catalyst is 40%-
60%.
Heterogeneous photosynthetic Fenton catalyst of the present invention is specifically prepared as follows:
(1) cabaltous nitrate hexahydrate and Fe(NO3)39H2O are dissolved in methanol solution, obtain solution A；By trimesic acid
It is dissolved in methanol solution, obtaining concentration is 0.1~0.25mol/L solution B, and the solution A and solution B ultrasonic mixing is equal
It is even, it pours into autoclave, 12h is reacted under the conditions of 150 DEG C, fully reacting obtains reaction mixture, post-treated to obtain
Bimetallic MOF material；In the solution A, the concentration of cabaltous nitrate hexahydrate is 0.05~0.15mol/L, Fe(NO3)39H2O
Concentration be 0.05~0.15mol/L；The volume ratio of the solution A and solution B is 0.6~1:1；
(2) bimetallic MOF material obtained by step (1) is placed in Muffle furnace, at 350 DEG C, calcines 2~6h, obtain non-
Homogeneous photosynthetic Fenton catalyst.
Further, in step (1), the post-processing approach of the bimetallic MOF material are as follows: the reaction solution first that will be obtained
Alcohol centrifuge washing 2-3 times, then taken lower sediment thing to dry at 80 DEG C with ethyl alcohol centrifuge washing to supernatant, obtained in colourless
Bimetallic MOF material.
Further, in step (2), the calcination process is with the heating rate temperature programming of 5 DEG C/min to 350 DEG C.
Further, the heterogeneous photosynthetic Fenton catalyst prepared by the present invention can be applied at the purification of organic wastewater
Reason.
Further, the organic wastewater is the waste water containing methylene blue, Congo red, bisphenol-A or 4- nitrophenols.
Compared with prior art, the beneficial effects of the present invention are:
(1) synthesis step is simple, and preparation cost is low, is suitble to industrialized production；
(2) reaction condition is mild, high catalytic efficiency, can be easily recycled by Magnetic Isolation, number can be recycled
Height, catalytic performance with higher；
(3) by synthesizing a kind of iron-cobalt dual-metal MOF, can be converted into after calcining a kind of holding original MOF structure and
Has magnetic efficiently heterogeneous photosynthetic Fenton catalyst, iron and cobalt are oxidized to Fe respectively3O4And Co3O4, wherein Fe3O4Tool
It is magnetic, the Fenton catalyst can be made to be rapidly separated after completion of the reaction, will not be to environmental pollution, and Co3O4?
It with good catalytic effect, is easily isolated with magnetism, not will cause secondary pollution, environmental sound；
(4) treatment effect to organic wastewater is improved, the organic waste different for methylene blue, Congo red, bisphenol-A etc.
Water, degradation efficiency can reach 90-95%.
(4) Detailed description of the invention
Fig. 1 is the phenogram of heterogeneous photosynthetic Fenton catalyst in the embodiment of the present invention 1: aSEM, bXPS, cEDX；
Fig. 2 is heterogeneous photosynthetic Fenton catalyst first time catalytic effect in the embodiment of the present invention 1；
Fig. 3 is heterogeneous photosynthetic Fenton catalyst first time catalytic effect in comparative example 1 of the present invention.
(5) specific embodiment
Combined with specific embodiments below, the present invention is described in detail, but the present invention is not limited to the following embodiments,
It does not depart from the content of present invention and range, change all should be comprising within the technical scope of the present invention.
Embodiment 1: heterogeneous photosynthetic Fenton catalyst degradation methylene blue
2.9009g cabaltous nitrate hexahydrate and 2.7951g Fe(NO3)39H2O are dissolved in 40mL methanol solution, solution is denoted as
A；1.5962g trimesic acid is dissolved in 40mL methanol solution, solution B is denoted as, A, B solution ultrasonic mixing is uniform,
It pours into 100mL autoclave, reacts 12h under the conditions of 150 DEG C.To which after the reaction was completed, the centrifugation of reaction solution methanol is washed
It washs 2-3 times, then colourless to supernatant liquor with ethyl alcohol centrifuge washing, is dried under the conditions of taking lower sediment thing to be placed in 80 DEG C, obtained double
Metal MOF material.Solid after drying is placed in Muffle furnace with 5 DEG C/min, temperature programming obtains most to calcining at 350 DEG C
Whole heterogeneous photosynthetic Fenton catalyst, color are in black.Using characterization methods such as XPS, EDX, prepared iron-cobalt is learnt
Bimetallic MOF material is Fe by calcined oxide3O4And Co3O4。
Heterogeneous photosynthetic Fenton catalyst is used for catalytic degradation methylene blue:
(1) preparation of organic wastewater
0.01g methylene blue is weighed, is dissolved in 50mL deionized water, ultrasonic 10min makes dissolution completely, with 1000mL capacity
Bottle is settled to graduation mark with deionized water, the methylene blue solution that concentration is 10mg/L is obtained, then by the pH tune of above-mentioned solution
To 5.0-6.5；
(2) heterogeneous Fenton degradation experiment
Take solution 100mL in step (1) that the above-mentioned catalyst stirring of 0.1g is added, starts to count in 250mL conical flask respectively
When 30min adsorption saturation experiment after sample, be then respectively adding 10-50 μ L hydrogen peroxide, sample, survey respectively at regular intervals
Measure absorbance.
(3) catalytic agent reuse is tested
It is cleaned respectively with ethyl alcohol and deionized water after experiment by after catalyst magnetite quick separating in step (2)
Three times, then in baking oven 105 DEG C be dried for standby.It repeats the process in step (2) and presses step (3) again after the end of the experiment
Catalyst is recycled, each degradation efficiency of comparative catalyst after reuse three times.
Experiment show that first time degradation efficiency is 95.2%, and degradation efficiency still reaches 90% or more after recycling three times,
And there is magnetism can quickly be easily isolated.
Comparative example 1:
1.4543g cabaltous nitrate hexahydrate and 3.9617g Fe(NO3)39H2O are dissolved in 40mL methanol solution, solution is denoted as
A；1.5962g trimesic acid is dissolved in 40mL methanol solution, solution B is denoted as, A, B solution ultrasonic mixing is uniform,
It pours into 100mL autoclave, reacts 12h under the conditions of 150 DEG C.To which after the reaction was completed, the centrifugation of reaction solution methanol is washed
It washs 2-3 times, then colourless to supernatant liquor with ethyl alcohol centrifuge washing, is dried under the conditions of taking lower sediment thing to be placed in 80 DEG C, obtained double
Metal MOF material.Solid after drying is placed in Muffle furnace with 5 DEG C/min, temperature programming obtains most to calcining at 350 DEG C
Whole heterogeneous photosynthetic Fenton catalyst, color are in black.Using characterization methods such as XPS, EDX, prepared iron-cobalt is learnt
Bimetallic MOF material is Fe by calcined oxide3O4And Co3O4。
Heterogeneous photosynthetic Fenton catalyst is used for catalytic degradation methylene blue:
(1) preparation of organic wastewater
0.01g methylene blue is weighed, is dissolved in 50mL deionized water, ultrasonic 10min makes dissolution completely, with 1000mL capacity
Bottle is settled to graduation mark with deionized water, the methylene blue solution that concentration is 10mg/L is obtained, then by the pH tune of above-mentioned solution
To 5.0-6.5；
(2) heterogeneous Fenton degradation experiment
Take solution 100mL in step (1) that the above-mentioned catalyst stirring of 0.1g is added, starts to count in 250mL conical flask respectively
When 30min adsorption saturation experiment after sample, be then respectively adding 10-50 μ L hydrogen peroxide, sample, survey respectively at regular intervals
Measure absorbance.
(3) catalytic agent reuse is tested
It is cleaned respectively with ethyl alcohol and deionized water after experiment by after catalyst magnetite quick separating in step (2)
Three times, then in baking oven 105 DEG C be dried for standby.It repeats the process in step (2) and presses step (3) again after the end of the experiment
Catalyst is recycled, each degradation efficiency of comparative catalyst after reuse three times.
Experiment show that first time degradation efficiency is 86.1%, and degradation efficiency can reach 80% or more after recycling three times,
And there is magnetism can quickly be easily isolated.
Embodiment 2: heterogeneous photosynthetic Fenton catalyst degradation is Congo red
2.9009g cabaltous nitrate hexahydrate and 2.7951g Fe(NO3)39H2O are dissolved in 40mL methanol solution, solution is denoted as
A；1.5962g trimesic acid is dissolved in 40mL methanol solution, solution B is denoted as, A, B solution ultrasonic mixing is uniform,
It pours into 100mL autoclave, reacts 12h under the conditions of 150 DEG C.To which after the reaction was completed, the centrifugation of reaction solution methanol is washed
It washs 2-3 times, then colourless to supernatant liquor with ethyl alcohol centrifuge washing, is dried under the conditions of taking lower sediment thing to be placed in 80 DEG C, obtained double
Metal MOF material.Solid after drying is placed in Muffle furnace with 5 DEG C/min, temperature programming obtains most to calcining at 350 DEG C
Whole heterogeneous photosynthetic Fenton catalyst, color are in black.Using characterization methods such as XPS, EDX, prepared iron-cobalt is learnt
Bimetallic MOF material is Fe by calcined oxide3O4And Co3O4。
It is Congo red that heterogeneous photosynthetic Fenton catalyst is used for catalytic degradation:
(1) preparation of organic wastewater
It is Congo red to weigh 0.01g, is dissolved in 50mL deionized water, ultrasonic 10min makes dissolution completely, with 1000mL volumetric flask
It is settled to graduation mark with deionized water, the Congo red solution that concentration is 10mg/L is obtained, is then adjusted to the pH of above-mentioned solution
5.0-6.5；
(2) heterogeneous Fenton degradation experiment
Take solution 100mL in step (1) that the above-mentioned catalyst stirring of 0.1g is added, starts to count in 250mL conical flask respectively
When 30min adsorption saturation experiment after sample, be then respectively adding 10-50 μ L hydrogen peroxide, sample, survey respectively at regular intervals
Measure absorbance.
(3) catalytic agent reuse is tested
It is cleaned respectively with ethyl alcohol and deionized water after experiment by after catalyst magnetite quick separating in step (2)
Three times, then in baking oven 105 DEG C be dried for standby.It repeats the process in step (2) and presses step (3) again after the end of the experiment
Catalyst is recycled, each degradation efficiency of comparative catalyst after reuse three times.
Experiment show that first time degradation efficiency is 93.6%, and degradation efficiency still reaches 90% or more after recycling three times,
And there is magnetism can quickly be easily isolated.
Embodiment 3: heterogeneous photosynthetic Fenton catalyst degradation 4- nitrophenols
2.9009g cabaltous nitrate hexahydrate and 2.7951g Fe(NO3)39H2O are dissolved in 40mL methanol solution, solution is denoted as
A；1.5962g trimesic acid is dissolved in 40mL methanol solution, solution B is denoted as, A, B solution ultrasonic mixing is uniform,
It pours into 100mL autoclave, reacts 12h under the conditions of 150 DEG C.To which after the reaction was completed, the centrifugation of reaction solution methanol is washed
It washs 2-3 times, then colourless to supernatant liquor with ethyl alcohol centrifuge washing, is dried under the conditions of taking lower sediment thing to be placed in 80 DEG C, obtained double
Metal MOF material.Solid after drying is placed in Muffle furnace with 5 DEG C/min, temperature programming obtains most to calcining at 350 DEG C
Whole heterogeneous photosynthetic Fenton catalyst, color are in black.Using characterization methods such as XPS, EDX, prepared iron-cobalt is learnt
Bimetallic MOF material is Fe by calcined oxide3O4And Co3O4。
Heterogeneous photosynthetic Fenton catalyst is used for catalytic degradation 4- nitrophenols:
(1) preparation of organic wastewater
0.01g 4- nitrophenols is weighed, is dissolved in 50mL deionized water, ultrasonic 10min holds that dissolution with 1000mL completely
Measuring bottle is settled to graduation mark with deionized water, the 4- nitro phenol solution that concentration is 10mg/L is obtained, then by the pH of above-mentioned solution
It is adjusted to 5.0-6.5；
(2) heterogeneous Fenton degradation experiment
Take solution 100mL in step (1) that the above-mentioned catalyst stirring of 0.1g is added, starts to count in 250mL conical flask respectively
When 30min adsorption saturation experiment after sample, be then respectively adding 10-50 μ L hydrogen peroxide, sample, survey respectively at regular intervals
Measure absorbance.
(3) catalytic agent reuse is tested
It is cleaned respectively with ethyl alcohol and deionized water after experiment by after catalyst magnetite quick separating in step (2)
Three times, then in baking oven 105 DEG C be dried for standby.It repeats the process in step (2) and presses step (3) again after the end of the experiment
Catalyst is recycled, each degradation efficiency of comparative catalyst after reuse three times.
Experiment show that first time degradation efficiency is 94.3%, and degradation efficiency still reaches 90% or more after recycling three times,
And there is magnetism can quickly be easily isolated.
Embodiment 4: heterogeneous photosynthetic Fenton catalyst degradation bisphenol-A
2.9009g cabaltous nitrate hexahydrate and 2.7951g Fe(NO3)39H2O are dissolved in 40mL methanol solution, solution is denoted as
A；1.5962g trimesic acid is dissolved in 40mL methanol solution, solution B is denoted as, A, B solution ultrasonic mixing is uniform,
It pours into 100mL autoclave, reacts 12h under the conditions of 150 DEG C.To which after the reaction was completed, the centrifugation of reaction solution methanol is washed
It washs 2-3 times, then colourless to supernatant liquor with ethyl alcohol centrifuge washing, is dried under the conditions of taking lower sediment thing to be placed in 80 DEG C, obtained double
Metal MOF material.Solid after drying is placed in Muffle furnace with 5 DEG C/min, temperature programming obtains most to calcining at 350 DEG C
Whole heterogeneous photosynthetic Fenton catalyst, color are in black.Using characterization methods such as XPS, EDX, prepared iron-cobalt is learnt
Bimetallic MOF material is Fe by calcined oxide3O4And Co3O4。
Heterogeneous photosynthetic Fenton catalyst is used for catalytic degradation bisphenol-A:
(1) preparation of organic wastewater
0.01g bisphenol-A is weighed, is dissolved in 50mL deionized water, ultrasonic 10min makes dissolution completely, with 1000mL volumetric flask
It is settled to graduation mark with deionized water, the bisphenol-A solution that concentration is 10mg/L is obtained, the pH of above-mentioned solution is then adjusted to 5.0-
6.5；
(2) heterogeneous Fenton degradation experiment
Take solution 100mL in step (1) that the above-mentioned catalyst stirring of 0.1g is added, starts to count in 250mL conical flask respectively
When 30min adsorption saturation experiment after sample, be then respectively adding 10-50 μ L hydrogen peroxide, sample, survey respectively at regular intervals
Measure absorbance.
(3) catalytic agent reuse is tested
It is cleaned respectively with ethyl alcohol and deionized water after experiment by after catalyst magnetite quick separating in step (2)
Three times, then in baking oven 105 DEG C be dried for standby.It repeats the process in step (2) and presses step (3) again after the end of the experiment
Catalyst is recycled, each degradation efficiency of comparative catalyst after reuse three times.
Experiment show that first time degradation efficiency is 92.5%, and degradation efficiency still reaches 90% or more after recycling three times,
And there is magnetism can quickly be easily isolated.
The degradation efficiency data of above embodiments are as shown in table 1.
The degradation efficiency data of 1 catalyst of table
Claims (6)
1. a kind of magnetic heterogeneous photosynthetic Fenton catalyst of tool, which is characterized in that the catalyst is by Fe3O4With
Co3O4It forms, wherein Fe3O4Mass percent in the catalyst is 40%-60%, Co3O4Quality percentage in the catalyst
Than for 40%-60%.
2. one kind has the preparation method of magnetic heterogeneous photosynthetic Fenton catalyst, feature as described in claim 1
It is, the method carries out in accordance with the following steps:
(1) cabaltous nitrate hexahydrate and Fe(NO3)39H2O are dissolved in methanol solution, obtain solution A；Trimesic acid is dissolved in
In methanol solution, obtaining concentration is 0.1~0.25mol/L solution B, and the solution A and solution B ultrasonic mixing is uniform,
Enter in autoclave, 12h is reacted under the conditions of 150 DEG C, fully reacting obtains reaction mixture, post-treated to obtain bimetallic
MOF material；In the solution A, the concentration of cabaltous nitrate hexahydrate is 0.05~0.15mol/L, the concentration of Fe(NO3)39H2O
For 0.05~0.15mol/L；The volume ratio of the solution A and solution B is 0.6~1:1；
(2) bimetallic MOF material obtained by step (1) is placed in Muffle furnace, at 350 DEG C, calcines 2~6h, obtain heterogeneous
Photosynthetic Fenton catalyst.
3. method according to claim 2, it is characterised in that: in step (1), the post-processing of the bimetallic MOF material
Method are as follows: by obtained reaction solution with methanol centrifuge washing 2-3 times, then removed in colourless with ethyl alcohol centrifuge washing to supernatant
Layer sediment is dried at 80 DEG C, obtains bimetallic MOF material.
4. method according to claim 2, it is characterised in that: in step (2), the calcination process is with the liter of 5 DEG C/min
Warm rate program is warming up to 350 DEG C.
5. the purified treatment that a kind of heterogeneous photosynthetic Fenton catalyst as described in claim 1 is applied to organic wastewater.
6. application as claimed in claim 5, it is characterised in that: the organic wastewater is containing methylene blue, Congo red, bis-phenol
The waste water of A or 4- nitrophenols.
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