CN109772285A - A kind of preparation method and application of heterogeneous light Fenton catalyst - Google Patents
A kind of preparation method and application of heterogeneous light Fenton catalyst Download PDFInfo
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- CN109772285A CN109772285A CN201910158881.2A CN201910158881A CN109772285A CN 109772285 A CN109772285 A CN 109772285A CN 201910158881 A CN201910158881 A CN 201910158881A CN 109772285 A CN109772285 A CN 109772285A
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Abstract
The present invention relates to a kind of preparation method and applications of new heterogeneous light Fenton catalyst, it is more particularly to the preparation of one quasi-metal oxides-graphene oxide different-phase catalyst and the purposes of catalytic elimination Organic substance in water pollutant.The invention aims to (1) to solve existing homogeneous fenton catalyst pH narrow application range, and the iron cement that catalyst can not be recycled and be generated causes secondary pollution problems；(2) it solves for the problems such as preparation process such as the preparation method such as hydro-thermal method, coprecipitation of existing different-phase catalyst are complicated, the time is longer.Metal oxide-graphene oxide prepared by the present invention has the characteristics that pH is applied widely, easily separated and good recycling for the good catalytic activity of Organic substance in water, and can reach higher mineralization rate.
Description
Technical field
The present invention relates to a kind of preparation method and application of heterogeneous light Fenton catalyst.
Background technique
Fenton's reaction is a kind for the treatment of process for being usually used in degradation organic pollutants.In Fenton's reaction, homogeneous two
Organic matter can be decomposed into CO by the hydroxyl radical free radical (OH) that valence iron ion and hydrogen peroxide generate strong oxidizing property2And water, it is one
The environmental-friendly green catalysis technique of kind.However, in Fenton's reaction system, to more demanding (usual pH < 4) of pH, and
A large amount of iron cement can be generated during catalysis, can cause secondary pollution to environment.Therefore preparation has high catalytic activity, is easy to
Separation and the different-phase catalyst that secondary pollution will not be led to the problem of to environment recycle the tool of hardly possible for solving traditional fenton catalyst
It is significant.Cause to learn both at home and abroad using hardly degraded organic substance in ultraviolet light (account for solar radiation 5%) catalytic treatment water
The extensive concern of person.Ultraviolet light is introduced into Fenton's reaction system, the mineralization rate of organic pollutant, and energy can be further increased
Sunlight is made full use of, energy consumption is reduced.
Graphene oxide is a kind of New Type of Carbon nanometer light material, and surface is rich in functions such as hydroxyl, carboxyl and alkoxies
Group has high active, big specific surface area and strong adsorption capacity, is a kind of ideal carrier material.By metal oxide
With the compound electronics capture ability that can make full use of graphene oxide of graphene oxide, transmittability；Gold can be prevented simultaneously
The reunion for belonging to oxide nano particles, to improve the efficiency of Fenton's reaction.
Currently, being mostly used greatly for published prepare in metal oxide/graphene oxide different-phase catalyst technology
The preparation such as hydro-thermal method, coprecipitation, and these method preparation steps are cumbersome, energy consumption is high, the time is longer.Therefore, in the prior art
In there is higher catalytic activity there is an urgent need to inventing a kind of preparation of preparation step is simple, the reaction time is short method, be easily recycled
Fenton catalyst.
Summary of the invention
The present inventor is prepared for metal oxide (MO by the method for self assembly on active metal surfacexMiddle M is active gold
Belong to element)/graphene oxide (GO) composite material, it is found that it can be used as heterogeneous light Fenton catalyst, can rapidly and efficiently go
Organic pollutant in water removal has the characteristics that pH is applied widely, easily separated and good recycling, and can reach
To higher mineralization rate.
Heterogeneous light Fenton catalyst of the invention is that pretreated active metal is immersed in graphene oxide solution,
By the way of heating, graphene oxide is self-assembled to active metal surface.Since surface of graphene oxide contains largely
Carboxyl, the functional groups such as hydroxyl can generate metal ion simultaneously during heating, and metal ion can be attached to graphene oxide
Graphene oxide partial reduction is graphene by surface, and itself forms metal oxide.Thus MO is obtainedx/ GO complex,
Heterogeneous light Fenton catalyst i.e. of the invention.
Therefore, one object of the present invention is just to provide a kind of catalyst material of efficiently removal water pollutant, is
Graphene oxide-loaded γ-Fe2O3Nano particle catalytic composite materials.
Another object of the present invention is to solve the problems such as existing different-phase catalyst preparation step is complicated, the time is long,
And provide a kind of preparation method and application of different-phase catalyst in active metal surface self-organization film forming.
The present invention provides the simple preparation methods of heterogeneous light Fenton catalyst of the present invention.The method includes with
Lower step: pre-processing firstly the need of by active metal surface, and pretreated relatively active metal piece is then immersed in oxygen
Heating water bath in graphite alkene solution, keep the temperature the regular hour after, will be deposited with certain thickness graphene oxide film together with
Active metal piece is put into air dry oven, is removed film from sheet metal after keeping the temperature two hours at 60 DEG C, is obtained certain matter
The film of amount.
It is another object of the present invention to provide heterogeneous light Fenton catalyst of the present invention in processing water pollutant
The purposes of methylene blue.
To achieve the above object, in a technical solution of the invention, the present invention, will be pre- by using the mode of heating
Processed active metal is soaked in graphene oxide solution, the carboxyl that surface is contained, the functional groups such as hydroxyl, in heating
It can be oxidized metal in the process as metal ion, the metal ion of formation can be attached to surface of graphene oxide, by graphite oxide
Alkene partial reduction is graphene, and its own forms metal oxide.Thus MO is obtainedx/ GO complex, i.e., out-phase of the invention
Light fenton catalyst.
The specific aspect of of the invention one, heterogeneous light Fenton catalyst of the invention is through the following steps that with method system
(by taking the iron of active metal as an example) obtained: pretreated active metal iron is soaked in graphene oxide solution, graphite oxide
Iron can be oxidized to iron ion by the oxygen-containing functional group on alkene surface such as carboxyl etc., and iron ion enters solution, immobilized in graphene oxide
Graphene oxide is reduced to graphene simultaneously by surface, its own forms ferriferous oxide and the effect with oxygen.
In one embodiment of the invention, it is zinc, iron, cobalt, copper that base material used in the present invention, which is active metal,.
The present invention one more specifically aspect, heterogeneous light Fenton catalyst of the invention be by include the following steps and side
Made from method: pre-processed firstly the need of by active metal surface, successively using 400#SiC sand paper, 800#SiC sand paper,
1200#SiC sand paper, 2000#SiC sand paper and 3000#SiC sand paper polish to active metal piece such as zinc, iron, cobalt and copper, most
After be polished to mirror surface；Ultrasonic cleaning 2 times first is carried out to metal using deionized water, it is then clear to metal ultrasound using dehydrated alcohol
It washes 2 times, is finally dried up using hair dryer, obtain pretreated sheet metal.It secondly is preparation MOx/ GO (M=Zn, Fe, Co, Cu)
Sheet heterogeneous light Fenton catalyst: by certain density graphene oxide solution ultrasonic disperse 30min, then pretreated
It is put into heating water bath in graphene oxide solution compared with active metal piece, after keeping the temperature the regular hour, will be deposited with certain thickness
Graphene oxide film is put into air dry oven together with active metal piece, by film from metal after keeping the temperature two hours at 60 DEG C
Substrate removing, obtains the film of certain mass.Complete a kind of preparation method of out-phase fenton catalyst.
The present inventor examines the catalytic effect of heterogeneous light Fenton catalyst of the invention, finds to shine in the auxiliary of ultraviolet light
Penetrate with existing for hydrogen peroxide under the conditions of, catalyst of the invention can rapidly and efficiently go water removal in organic pollutant (methylene
Base indigo plant etc.).And have the characteristics that pH is applied widely, easily separated and good recycling.
Detailed description of the invention
Fig. 1 is the γ-Fe that the present invention is prepared by substrate of iron2O3/ GO material and the X-ray of graphene oxide and graphite are spread out
Penetrate map.
Fig. 2 is the γ-Fe that the present invention is prepared by substrate of iron2O3The transmission electron microscope figure of/GO material.
Fig. 3 is the γ-Fe that the present invention is prepared by substrate of iron2O3The decoloration of/GO material light Fenton catalytic degradation methylene blue
The comparison diagram that rate changes over time.
Fig. 4 is the γ-Fe that the present invention is prepared by substrate of iron2O3/ GO material is catalyzed at different pH as heterogeneous light Fenton
Catalytic elimination effect of the agent to methylene blue.
Fig. 5 is the γ-Fe that the present invention is prepared by substrate of iron2O3The circulation of/GO material light Fenton catalytic degradation methylene blue
Service performance test.
Fig. 6 is the MO that the present invention is prepared using zinc, cobalt, copper as substratex/ GO material is urged with the light Fenton for not adding catalyst
Change the comparison diagram that the percent of decolourization of degradation of methylene blue changes over time.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, carries out to technical solution in the embodiment of the present invention clear, complete
Whole description.Obviously, these embodiments provide merely to illustration purpose, rather than limitation of the invention.This field skill
Art personnel should be understood that every other embodiment obtained without making creative work, belong to of the invention
Protection scope.
Prepare embodiment
Illustrate the method that the present invention prepares heterogeneous light Fenton catalyst by taking following embodiments as an example.
Pre-processed firstly the need of by active metal surface, successively using 400#SiC sand paper, 800#SiC sand paper,
1200#SiC sand paper, 2000#SiC sand paper and 3000#SiC sand paper polish to active metal piece such as zinc, iron, cobalt and copper, most
After be polished to mirror surface；Ultrasonic cleaning 2 times first is carried out to metal using deionized water, it is then clear to metal ultrasound using dehydrated alcohol
It washes 2 times, is finally dried up using hair dryer, obtain pretreated sheet metal.It secondly is preparation MOx/ GO (M=Zn, Fe, Co, Cu)
Sheet heterogeneous light Fenton catalyst: by certain density graphene oxide solution ultrasonic disperse 30min, then pretreated
It is put into heating water bath in graphene oxide solution compared with active metal piece, after keeping the temperature the regular hour, will be deposited with certain thickness
Graphene oxide film is put into air dry oven together with active metal piece, by film from metal after keeping the temperature two hours at 60 DEG C
Substrate removing, obtains the film of certain mass.
Zinc of the present invention, iron, cobalt, copper sheet can be commercially available by commercially available.
Graphene oxide solution of the present invention can be commercially available by commercially available, can also be prepared by Hummers method.
1.γ-Fe2O3Structure and morphology analysis of/the GO material as heterogeneous light Fenton catalyst
By sample obtained in above-mentioned preparation embodiment (using iron as substrate, γ-Fe2O3/ GO material) with the oxidation stone that compares
Black alkene and graphite carry out X-ray diffractogram spectrum analysis, as a result as shown in Figure 1.As seen from the figure, the Qiang Fengwei graphite of 2 θ=26.9 °
Characteristic peak, after being graphene by graphite oxidation, this peak disappears, and occurs stronger peak at 2 θ=10.6 °, passes through calculating
The interlamellar spacing of the graphene oxide prepared is 0.85nm.In 2 θ=30.5 °, 35.8 °, 43.5 °, 53.8 °, 57.4 °,
63.0 ° respectively correspond γ-Fe2O3(220), (311), (400), (422), (511), (440) crystal face illustrates γ-Fe2O3
Success is modified onto graphene oxide carrier.
The analysis that sample obtained in above-mentioned preparation embodiment is carried out to microscopic appearance under transmission electron microscope, as a result such as Fig. 2 institute
Show.As can be seen from the figure granular γ-Fe2O3It is evenly affixed in the graphene oxide carrier of silk shape, it follows that oxygen
Graphite alkene and γ-Fe2O3Compound can prevent γ-Fe2O3The reunion of nano particle, and can be mentioned for the transmission of electronics
For necessary channel.
2.γ-Fe2O3Catalytic activity of/GO the material as heterogeneous light Fenton catalyst.
2.1 γ-Fe prepared by the present invention2O3The catalytic elimination effect of/GO material to methylene blue
It 2.1.1 is γ-Fe in the proof present invention2O3/GO+H2O2It is fragrant that+UV combination enhances out-phase light of the present invention
The catalytic effect for the process of pausing, devises with UV, H2O2+ UV, γ-Fe2O3+H2O2+ UV, γ-Fe2O3/GO+H2O2+ Dark, γ-
Fe2O3/GO+H2O2+ UV is the comparative experiments of experimental comparison group.
2.1.1.1 the comparative example of above-mentioned reference substance
It takes the methylene blue solution that 50ml concentration is 50mg/L in beaker respectively, while weighing 10mg catalysis material, and
Add 10ml H2O2In above-mentioned simulative organic wastewater (comparative experiments only has except ultraviolet light), it is placed under 500W mercury lamp vertical
Light Fenton catalytic degradation reaction is carried out at 15cm (light source from reaction solution identity distance from).As a result as shown in Figure 3, wherein γ-Fe2O3/
GO+H2O2The catalytic effect of+UV is best, it has just reached 99% to the percent of decolourization of methylene blue after reaction 80 minutes, and compares real
Test UV, H2O2+ UV, γ-Fe2O3+H2O2+ UV, γ-Fe2O3/GO+H2O2The colour fading rate of+Dark after reaction 120 minutes is right respectively
11%, 36%, 35%, 25% is answered, illustrates the γ-Fe using the preparation of simple self-assembly method2O3/ GO material can significantly increase
The catalytic effect of this reaction system.
From the above results, the γ-Fe prepared using simple self-assembly method2O3/ GO material can be in H2O2With UV light spoke
The synergistic effect of light reaction and Fenton's reaction is given full play in the case where penetrating, to significantly increase the degradation speed of organic pollutant
Rate.
2.1.2 γ-Fe2O3/ GO material goes the catalysis of methylene blue at different pH as heterogeneous light Fenton catalyst
Except effect.
2.1.2.1 γ-Fe2O3/ GO material is at different pH to methylene blue catalytic elimination effect example
The pH that methylene blue is adjusted using the concentrated hydrochloric acid and sodium hydroxide of mass fraction 36%-38%, finally obtains a system
The methylene blue solution of different pH is arranged, pH is respectively 2.0,4.2,5.7,8.2,10.2,11.91.The 50ml concentration is taken to be respectively
The methylene blue solution of 50mg/L and difference pH weigh 10mg γ-Fe in beaker2O3/ GO material simultaneously adds 10ml H2O2In
In above-mentioned simulative organic wastewater, it is placed under 500W mercury lamp at vertical 15cm (light source from reaction solution identity distance from) and carries out the catalysis of light Fenton
Degradation reaction.As a result as shown in Figure 4, when pH value of solution is in the range of 4.2-11.91, methylene blue is completely de- by 80 minutes
Color；And pH value of solution is when being 2.0, methylene blue then needs decoloration completely in 100 minutes, and decolorization rate slowed down.
From the above results, γ-Fe2O3/ GO material is still with higher to methylene blue under wider pH value of solution
Catalytic elimination effect.And when pH value of solution is 2.0, γ-Fe2O3Why/GO material can be to the decolorization rate of methylene blue
Slow down, it may be possible to due in higher H+Under concentration, one side Fe2+It will form [Fe (H2O)]2+, another aspect H2O2It also can be with H+Shape
At stable [H3O2]+, so that the formation of the OH in influence system with strong oxidizing property, has finally slowed down γ-Fe2O3/ GO material
Expect the catalytic elimination effect to methylene blue.
2.1.3 γ-Fe2O3/ GO material is as heterogeneous light Fenton catalyst to the recycling performance of degradation of methylene blue.
2.1.3.1 γ-Fe2O3The recycling performance embodiment of/GO material to degradation of methylene blue
It takes the methylene blue solution that 50ml concentration is 50mg/L in beaker respectively, weighs 10mg γ-Fe2O3/ GO material is simultaneously
Add 10ml H2O2In above-mentioned simulative organic wastewater, it is placed under 500W mercury lamp at vertical 15cm (light source from reaction solution identity distance from)
Carry out light Fenton catalytic degradation reaction.As a result as shown in figure 5, γ-Fe2O3/ GO material still has after 8 times are recycled
There are higher catalytic activity, and γ-Fe2O3/ GO material to the complete decoloration of methylene blue by 80 minutes of the 1st time it is less to
60 minutes of 8th recycling, accelerate the decolorization rate of methylene blue instead.
From the above results, γ-Fe2O3/ GO material to methylene blue have good recycling performance, and with
The increase of access times, complete bleaching time has been reduced to last 60 minutes by 80 minutes at the beginning, and finally stablizes
At 60 minutes.γ-Fe2O3/ GO material may be due to during magneton stirs to the raising of the decolorization rate of methylene blue
Sheet γ-Fe2O3/ GO material is torn into smaller fragment, increases γ-Fe2O3Suction of/GO the material to methylene blue molecule
Attached property, further increases to be still bleached rate.
3. utilizing the method for the invention, the MO prepared using other active metals as substratex/ GO (M=Zn, Co, Cu) piece
Catalytic activity of the shape material as heterogeneous light Fenton catalyst.
3.1 MO prepared using other active metals as substrate using the method for the inventionx/ GO (M=Zn, Co, Cu) piece
Catalytic elimination effect of the shape material to methylene blue.
3.1.1 the MO prepared using other active metals as substrate using the method for the inventionx/ GO (M=Zn, Co, Cu)
Catalytic elimination effect example of the flaky material to methylene blue
Take respectively 50ml concentration be 50mg/L methylene blue solution in beaker, weigh respectively 10mg ZnO/GO,
CoOx/ GO and CuOx/ GO flaky material simultaneously adds 10ml H2O2In above-mentioned simulative organic wastewater, it is placed under 500W mercury lamp vertical
Light Fenton catalytic degradation reaction is carried out at 15cm (light source from reaction solution identity distance from).As shown in Figure 6, as a result CoOx/ GO and CuOx/
GO was 60 minutes to the complete bleaching time of methylene blue, and ZnO/GO declines the percent of decolourization of methylenum careuleum, at 120 minutes
Its percent of decolourization only reaches 47% afterwards, but its percent of decolourization is still higher than the system (H for not adding catalyst2O2+UV)。
From the above results, ZnO/GO, the CoO prepared using method of the present inventionx/ GO and CuOx/ GO sheet material
Material still has catalytic elimination effect to methylene blue, wherein CoOx/ GO and CuOx/ GO material is as heterogeneous light Fenton catalyst
It to methylene blue decolorization rate with higher, can only decolourize completely within 60 minutes, therefore prepare out-phase light using self-assembly method
Fenton catalyst has certain universality.
Claims (5)
1. a kind of preparation method of heterogeneous light Fenton catalyst, it is characterised in that a kind of preparation method of heterogeneous light Fenton catalyst
Specifically complete according to the following steps:
A, compared with active metal surface preparation:
Successively use 400#SiC sand paper, 800#SiC sand paper, 1200#SiC sand paper, 2000#SiC sand paper and 3000#SiC sand paper pair
Active metal such as zinc, iron, cobalt and copper are polished, and mirror surface is finally polished to；Ultrasound is carried out to metal using deionized water first
Then cleaning 2 times is cleaned by ultrasonic metal 2 times using dehydrated alcohol, is finally dried up using hair dryer, obtain pretreated metal
Substrate.
B, metal oxide-graphene oxide (MO is preparedx/ GO) heterogeneous light Fenton catalyst
By certain density graphene oxide solution ultrasonic disperse 30min, then pretreated relatively active metal substrate is put
Enter heating water bath in graphene oxide solution, after keeping the temperature the regular hour, certain thickness graphene oxide film will be deposited with
It is put into drying box together with active metal substrate, film is removed from metallic substrates after keeping the temperature two hours at 60 DEG C, obtains one
Determine the film of quality.
2. a kind of preparation method of heterogeneous light Fenton catalyst according to claim 1 is it is characterized in that described in step 1
Active metal such as zinc, iron, cobalt and copper.
3. the use of heterogeneous light Fenton catalyst according to claim 1 to 2 hardly degraded organic substance pollutant in processing water
On the way.
4. heterogeneous light Fenton catalyst according to claim 1 to 2 is in the purposes of processing water pollutant methylene blue.
5. persistent organic pollutants methylene blue in heterogeneous light Fenton catalyst treatment water according to claim 4,
It is characterized in that the MO of sheetx/ GO (M=Zn, Fe, Co, Cu), which is added directly in methylene blue solution, to degrade.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560029A (en) * | 2019-09-16 | 2019-12-13 | 中国科学院生态环境研究中心 | graphene-based metal-free Fenton catalyst, and preparation method and application thereof |
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| CN102173500A (en) * | 2011-02-25 | 2011-09-07 | 华中师范大学 | Method for treating water by Fenton oxidization of activated molecular oxygen |
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| CN110560029A (en) * | 2019-09-16 | 2019-12-13 | 中国科学院生态环境研究中心 | graphene-based metal-free Fenton catalyst, and preparation method and application thereof |
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Application publication date: 20190521 |