CN110479384A - Hud typed Fe3O4The preparation method and application of@hydrogel composite nano-catalyst - Google Patents
Hud typed Fe3O4The preparation method and application of@hydrogel composite nano-catalyst Download PDFInfo
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims abstract description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 Methylene acrylamide Chemical compound 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 239000010919 dye waste Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- PEAGNRWWSMMRPZ-UHFFFAOYSA-L woodstain scarlet Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 PEAGNRWWSMMRPZ-UHFFFAOYSA-L 0.000 description 7
- 239000000017 hydrogel Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of hud typed Fe3O4The preparation method and application of@hydrogel composite nano-catalyst.The present invention is first by FeCl3·6H2O and FeCl2·4H2O is dissolved in deionized water, and Fe is prepared2+/Fe3+Mixed solution.Secondly under nitrogen protection and 50 DEG C of water bath conditions, NaOH solution is instilled into Fe dropwise2+/Fe3+In mixed solution.Then sodium carboxymethyl cellulose solution is instilled dropwise.Finally successively by acrylic acid, acrylamide,N,NMethylene acrylamide and ammonium persulfate, are added rapidly in reaction solution, are acted on by externally-applied magnetic field and separate black product, and to get to target product after deionized water repeatedly wash.Present invention improves Fe3O4Shape, partial size, recycling property and the dispersion performance of nanoparticle have the advantages such as high catalytic efficiency, catalytic rate are fast, the pH value of solution scope of application is wide.
Description
Technical field
The present invention relates to material synthesis method, specifically a kind of magnetic core-shell Fe3O4@CMC-g-p (AA-co-AM) is i.e.
Fe3O4The preparation method of@hydrogel nano-particle catalyst and the application in industrial organic dye waste water.
Background technique
With the rapid development of printing and dyeing industry, the usage amount of dyestuff increasingly increases.In the Industry Waste of China's discharge at present
35% is dyeing waste water.Waste water from dyestuff tool is difficult to degrade, COD, it is easily carcinogenic the features such as, and will cause serious water body
Pollute the broken ring ecological balance.That there are discharge amounts is big for the processing of waste water from dyestuff at present, component is more, content is high, coloration is deep and difficult to degrade
The problems such as.
Advanced oxidation Fenton method is one of research topic concerned in water-treatment technology field, because to environment dirt
Dye degree is small and low energy consumption and is acknowledged as " green catalysis water treatment technology ".Extensive development and application has been obtained in recent years.
The shortcomings that homogeneous Fenton process is overcome due to Fenton-like system heterogeneous in Fenton's reaction, to Fe3O4Magnetic nanoparticle
(abbreviation Fe3O4MNPs research) is more.It has the characteristics that stability is high, catalytic is strong, it is convenient to recycle.However
Fe3O4MNPs activates H2O2Ability it is poor, this makes the H in Fenton's reaction2O2Utilization rate and catalysis degradation modulus it is weaker.
Fe3O4MNPs generates agglomeration easily so as to cause the reduction of its catalytic activity.In addition, Fe3O4MNPs pH degradation range compared with
To be narrow, recycling and reusing is more difficult.Therefore, current water treatment technology there is still a need for one kind to recycle, catalytic activity is high and
To the Fenton reagent of pH value wide adaptation range.
The performance of composite oxide catalysts receives the concern of scholars, and composite oxide catalysts are with particle for load
Body overlays on advantageous material made of particle surface.The physical and chemical performance that composite catalyst not only retains catalyst, which makes full use of, urges
The effective component of agent is also influenced by the physical and chemical performance of carrier.Experiment shows hydrogel as a kind of natural polymer material
Material has the characteristics that green, cheap, and there are the groups such as a large amount of carboxyl, hydroxyl and carbonyl in its polymer network, easily
Complex compound is formed with the oxide of Fe.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of Fe of core-shell structure3O4@CMC-g-p (AA-co-AM) is i.e.
Fe3O4The preparation method and application of@hydrogel nanocatalyst.Utilize the catalysis of the nanocomposite waste water from dyestuff of preparation
Agent, it may be achieved to the catalytic degradation of waste water from dyestuff.The preparation method is simple, Fe3O4@hydrogel nanocomposite applications dye
Material waste water has the characteristics that Ke Xunhuanliyong, catalytic activity height and to pH value wide adaptation range.
The preparation method that the present invention uses, includes the following steps:
(1) by FeCl3·6H2O and FeCl2·4H2O is dissolved in deionized water, and Fe is prepared2+/Fe3+Mixed solution.
(2) under nitrogen protection and 50 DEG C of water bath conditions, NaOH solution is instilled to Fe made from step (1) dropwise2+/Fe3+
In mixed solution, 30 min are reacted with continuous stirring.
(3) sodium carboxymethylcellulose (CMC) aqueous solution is instilled dropwise in step (2), in nitrogen protection and 50 DEG C of water
30 min are persistently stirred under the conditions of bath.
(4) successively by acrylic acid (AA), acrylamide (AM),N,NMethylene acrylamide (MBA) and ammonium persulfate
(APS), it is added rapidly in step (3) resulting reaction solution, and this mixture is stirred to react 3 h at 70 DEG C, entirely
Reaction is in N2Protection is lower to be carried out.Then it is acted on by externally-applied magnetic field and separates black product, and repeatedly washed through deionized water
Afterwards to get arrive Fe3O4@CMC-g-p (AA-co-AM) magnetic Nano complex, abbreviation Fe3O4@hydrogel, and can be in 4 DEG C of items
It is stored under part.
Further, FeCl in step (1)3·6H2O and FeCl2·4H2O is dissolved in 100 mL deionized waters, FeCl3·
6H2O and FeCl2·4H2Both O concentration is 66.667 mmol/L, and Fe is made2+/Fe3+Mixed liquor；NaOH is molten in step (2)
Liquid additional amount is 20 mL, and concentration is 1.5 mol/L；Sodium carboxymethylcellulose (CMC) aqueous solution additional amount is 100 in step (3)
ML, concentration are 15 mmol/L.
Further, prepared core-shell structure Fe3O4The partial size of@hydrogel nanoparticle is 10 nm.
Further, prepared core-shell structure Fe3O4The brilliant saturation magnetic intensity of@hydrogel nanoparticle is 44.8
emu/g。
Further, prepared a kind of Fe3O4The application process of@hydrogel magnetic Nano complex include: by
Fe3O4@hydrogel catalyst is added in industrial organic dye waste water, and hydrogen peroxide is added and carries out degradation reaction.
It is demonstrated experimentally that the physical chemistry that the composite oxide catalysts of prepared core-shell structure had both had hydrogel is special
Property remains script Fe again3O4The physical and chemical performance of MNPs, so that NEW TYPE OF COMPOSITE oxide catalyst has stronger catalytic performance,
Broader pH degrades range, and higher the features such as obtaining recycling rate.
Beneficial effects of the present invention are as follows:
One, magnetic core-shell Fe of the invention3O4@hydrogel nano-particle catalyst preparation method have it is simple and easy, can grasp
The features such as property made is strong, low cost, low pollution, simple process.
Two, the magnetic core-shell Fe prepared by the present invention3O4@hydrogel nano-particle catalyst, due to the cladding of hydrogel
So that the specific surface area of catalyst changes, catalyst agglomeration phenomenon is improved therewith, is more connect in catalysis
Touching plane product is reacted with pollutant；Therefore it is significantly improved in catalysis Fenton degradation of contaminant efficiency, compared with pure Fe3O4 MNPs
Show stronger catalytic degradation activity.
Three, the magnetic core-shell Fe prepared by the present invention3O4Physics of the@hydrogel nano-particle catalyst by hydrogel
The influence of chemical property is suitable for wider array of pH range, such as is widened by pH=3 or so of script as pH=3 ~ 4.5.
Four, the magnetic core-shell Fe prepared by the present invention3O4@hydrogel nano-particle catalyst, the agglomeration of nanoparticle
It can reduce, recycling property is strong, highly beneficial to processing organic wastewater.
Detailed description of the invention
Fig. 1 a is the Fe of core-shell structure prepared by inventive embodiments 13O4The transmission electron microscope picture of@hydrogel nanocatalyst.
Fig. 1 b is Fe3O4The transmission electron microscope picture of MNPs catalyst.
Fig. 2 is the Fe of core-shell structure prepared by inventive embodiments 13O4@hydrogel nanocatalyst to acid red 73 into
6 circulation degradation effect figures of row.
Fig. 3 is the Fe of core-shell structure prepared by inventive embodiments 13O4@hydrogel nanocatalyst is urged acid red 73
Change active testing datagram.
Fig. 4 is the Fe of core-shell structure prepared by inventive embodiments 13O4@hydrogel nanocatalyst is at different pH to acid
The degradation curve figure of property red 73.
Specific embodiment
Following case study on implementation can make those skilled in the art more fully understand the present invention, but therefore not limit the present invention to
In following embodiments.
Embodiment 1
One, the Fe of core-shell structure3O4@hydrogel nanocatalyst the preparation method is as follows:
(1) under nitrogen protection, by FeCl3·6H2O and FeCl2·4H2O is dissolved in 100 mL deionized waters, FeCl3·6H2O
And FeCl2·4H2Both O concentration is 66.667 mmol/L, and Fe is prepared2+/Fe3+Mixed solution.
(2) under nitrogen protection and 50 DEG C of water bath conditions, 20 mL, 1.5 mol/L NaOH solution is instilled into step dropwise
(1) in ferrous solution made from, 30 min of reaction are continuously stirred.
(3) 100 15 mmol of mL/L CMC aqueous solution is instilled dropwise in the solution of step (2), in 50 DEG C of water-baths
Under the conditions of persistently stir 30 min after.
It (4) successively will be successively by 0.5 mL acrylic acid (AA), 0.5 g acrylamide (AM), 25 mgN,NMethylene third
Acrylamide (MBA) and 25 mg ammonium persulfates (APS), are added rapidly to reaction solution, this mixture are stirred at 70 DEG C anti-
3 h are answered entirely to react in N2Protection is lower to be carried out.It is acted on externally-applied magnetic field and separates black product, as Fe3O4@CMC-g-p
(AA-co-AM), abbreviation Fe3O4@hydrogel is stored in 4 after deionized water is repeatedly washedoUnder the conditions of C.
The scanning electron microscope (SEM) photograph Fe as shown in Figure 1a for the nuclear shell structure nano catalyst that the present embodiment step (4) obtains3O4@
About 10 nm of hydrogel nanocatalyst average grain diameter or so, hence it is evident that be greater than pure Fe3O4The partial size of MNPs, Fig. 1 b, and reunite
Phenomenon tool improves significantly.
Two, the Fe of core-shell structure3O4The application of@hydrogel nanocatalyst is as follows:
(A) acid red 73 (AR73) dissolution is made to the solution of 50 mg/L in deionized water, AR73 solution 100mL is taken to use
The HCl solution of the NaOH solution of 0.1 M and 0.1 M adjust pH (3,3.5,4,5,6,7).
(B) Fe in 4 DEG C of deionised waters will be stored in3O4@hydrogel nanocatalyst, which takes out, carries out rapid filtration under suction
Moisture is removed, is added in the solution of step (A) after the catalyst measured needed for quick weigh.
(C) by the way that H is added2O2(various dose) causes class Fenton catalytic degradation reaction, at constant temperature oscillator (250 rmp)
(25 ~ 28 DEG C) 5 h of reaction at room temperature.Interval sampling 2-4mL is until reaction terminates to schedule.
(D) it after taking the reaction solution of each period in step (C) to use 0.45 μm of pin hole membrane filtration on a small quantity, is suitably diluted
Afterwards, its absorbance is tested at 510 nm of ultraviolet specrophotometer, passes through the drop with initial absorbance comparing calculation acid red 73
Solution rate.
(E) by the Fe in step (C)3O4@hydrogel nanocatalyst carries out recycling and reusing weight under the influence of a magnetic field
Multiple (A) (B) (C) step, Fe as shown in Figure 23O4@hydrogel nanocatalyst can still reach 95% after circulation degradation 6 times
Above degradation rate.
The Fe for the core-shell structure that the present embodiment step (D) obtains3O4@hydrogel nanocatalyst is urged acid red 73
Change active effect figure as shown in figure 3, Fe3O4@hydrogel nanocatalyst is compared with Fe3O4MNPs is imitated with stronger catalysis
Fruit can degrade 73 quick catalysis of acid red to 99% or more in 3h.
The Fe that the present embodiment step (D) obtains3O4Under appropriate conditions, different pH are to acid for@hydrogel nanocatalyst
The degradation effect Fe as shown in Figure 4 of property red 733O4@hydrogel nanocatalyst has broader pH range compared with Fe3O4
It widens as pH=3-4.5 pH=3 of MNPs.
To sum up, the heterogeneous fenton catalyst for the dyeing waste water that can degrade being prepared in the present invention, passes through Fe3O4With
The influence of the physicochemical characteristics of the mutual load of hydrogel, improves Fe3O4The shape of nanoparticle, partial size, recycling property
And dispersion performance, there are the advantages such as high catalytic efficiency, catalytic rate are fast, the pH value of solution scope of application is wide, and can be in extraneous magnetic
Catalyst is quickly separated to the recycling for realizing catalyst with the help of with solution.Meanwhile the composite Nano is catalyzed
Agent also have the characteristics that in production application low in cost, chemical stabilization, it is environmentally protective, be easy to realize industrial production.
Claims (8)
1. hud typed Fe3O4The preparation method of@hydrogel composite nano-catalyst, which comprises the following steps:
(1) by FeCl3·6H2O and FeCl2·4H2O is dissolved in deionized water, and Fe is prepared2+/Fe3+Mixed solution；
(2) under nitrogen protection and 50 DEG C of water bath conditions, NaOH solution is instilled to Fe made from step (1) dropwise2+/Fe3+Mixing
In solution, reacted with continuous stirring；
(3) sodium carboxymethyl cellulose solution is instilled in step (2) dropwise, is held under nitrogen protection and 50 DEG C of water bath conditions
Continuous stirring；
(4) successively by acrylic acid, acrylamide,N,NMethylene acrylamide and ammonium persulfate are added rapidly to step (3) institute
In the reaction solution obtained, and this mixture is stirred to react at 70 DEG C, entire reaction is in N2Protection is lower to be carried out；Then by outer
Add magnetic fields to separate black product, and after deionized water is repeatedly washed to get arrive Fe3O4@CMC-g-p(AA-co-
AM) magnetic Nano complex, abbreviation Fe3O4@hydrogel。
2. the method according to claim 1, wherein FeCl in the step (1)3·6H2O and FeCl2·4H2O
It is dissolved in 100 mL deionized waters, FeCl3·6H2O and FeCl2·4H2Both O concentration is 66.667 mmol/L, and Fe is made2 +/Fe3+Mixed liquor.
3. the method according to claim 1, wherein in the step (2) NaOH solution additional amount be 20 mL,
Concentration is 1.5 mol/L, and reaction continues 30 min.
4. the method according to claim 1, wherein sodium carboxymethyl cellulose solution adds in the step (3)
Entering amount is 100 mL, and concentration is 15 mmol/L.
5. the method according to claim 1, wherein mixture is stirred to react 3 at 70 DEG C in the step (4)
h。
6. the method according to claim 1, wherein obtained core-shell structure Fe3O4@hydrogel nanoparticle
Partial size be 10 nm.
7. the method according to claim 1, wherein obtained core-shell structure Fe3O4@hydrogel nanoparticle
Brilliant saturation magnetic intensity be 44.8 emu/g.
8. a kind of hud typed Fe described in claim 13O4@hydrogel composite nano-catalyst is in industrial organic dye waste water
In application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910778283.5A CN110479384A (en) | 2019-08-22 | 2019-08-22 | Hud typed Fe3O4The preparation method and application of@hydrogel composite nano-catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910778283.5A CN110479384A (en) | 2019-08-22 | 2019-08-22 | Hud typed Fe3O4The preparation method and application of@hydrogel composite nano-catalyst |
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| CN105879051A (en) * | 2016-06-02 | 2016-08-24 | 北京林业大学 | Preparation and application of self-assembled nano-drug of core-shell structure |
| CN108676123A (en) * | 2018-04-12 | 2018-10-19 | 浙江理工大学 | A kind of preparation method of evenly dispersed type photocatalysis hydrogel |
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| CN105879051A (en) * | 2016-06-02 | 2016-08-24 | 北京林业大学 | Preparation and application of self-assembled nano-drug of core-shell structure |
| CN108676123A (en) * | 2018-04-12 | 2018-10-19 | 浙江理工大学 | A kind of preparation method of evenly dispersed type photocatalysis hydrogel |
Non-Patent Citations (1)
| Title |
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| JUANLI SHEN，等: "Hydrogel-coated Fe3O4 nanoparticles as an efficient heterogeneous Fenton catalyst for degradation of phenol", 《J. MATER. SCI.》 * |
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