CN104190422B - Heterogeneous light fenton catalyst and application thereof - Google Patents
Heterogeneous light fenton catalyst and application thereof Download PDFInfo
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- CN104190422B CN104190422B CN201410483396.XA CN201410483396A CN104190422B CN 104190422 B CN104190422 B CN 104190422B CN 201410483396 A CN201410483396 A CN 201410483396A CN 104190422 B CN104190422 B CN 104190422B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001868 water Inorganic materials 0.000 claims abstract description 30
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- OHZCFWMJMWFNFP-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;iron(2+) Chemical compound [Fe+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O OHZCFWMJMWFNFP-ZVGUSBNCSA-L 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- MDXRFOWKIZPNTA-UHFFFAOYSA-L butanedioate;iron(2+) Chemical compound [Fe+2].[O-]C(=O)CCC([O-])=O MDXRFOWKIZPNTA-UHFFFAOYSA-L 0.000 description 1
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- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Catalysts (AREA)
Abstract
The invention relates to a novel heterogeneous light fenton catalyst and application thereof, in particular to a goethite-graphene complex surface modified mesoporous carrier light fenton catalyst and an application thereof to catalyzing and removing organic pollutants in water. According to the novel heterogeneous light fenton catalyst provided by the invention, based on the combination of goethite, graphene and mesoporous carrier materials, the catalytic effect on the organic pollutants (particularly phenol, nitrogen-contained heterocyclic rings and the like) in the water is good, the application range of pH value is wide, the repeated practical performance is good, and the COD (chemical oxygen demands) and TOC (Total Organic Carbon) in wastewater can be simultaneously and effectively reduced.
Description
Technical field
The present invention relates to a kind of new heterogeneous light Fenton catalyst and application thereof, specifically, it is related to a kind of goethite-stone
Mesoporous supports light fenton catalyst and its purposes of catalytic elimination organic pollutants that black alkene complex surfaces are modified.
Background technology
Fenton's reaction is usually used in the processing procedure of persistent organic pollutants in water, and what reaction produced has strong oxidizing property
OH living radical can by water body persistent organic pollutants degraded remove and mineralising be environmentally safe CO2With
H2O, is a kind of eco-friendly green catalysis technique.Fenton's reaction is generally carried out under homogeneous, although catalytic efficiency higher and
Reaction is easily controlled, but requires harshness (generally only just to have high urging in the range of pH2.5～3.5 pH value of reaction system
Change activity), and also have that catalyst is difficult to separate and reclaim, iron ion runs off the shortcomings of cause secondary pollution, these problems
Presence with shortcoming greatly limit application in degraded Organic Pollutants In Water for the Fenton's reaction.Thus, people increasingly turn
To the research to out-phase Fenton's reaction catalyst.The research of out-phase Fenton's reaction catalyst is concentrated mainly on two aspects：(1) seek
Look for or prepare suitable catalyst carrier, so that metal active composition is uniformly carried on securely on carrier, to improve catalysis
The catalytic performance of agent and its solid- liquid separation ability；(2) choose and optimize catalytic active component, by optimizing preparation condition to urging
In agent active component, metal form (crystal formation, crystalline size) is regulated and controled, to prepare that catalytic efficiency is higher, adaptability more preferably,
The wider array of efficient composite catalyst of the pH scope of application.In recent years, process the organic dirt of difficult degradation in waste water using solar energy photocatalytic
Dye thing has caused the common concern of Chinese scholars.Sunshine is introduced in Fenton's reaction, forms light Fenton's reaction system, permissible
Improve the removal efficiency of organic pollution further.Light Fenton's reaction process reaction speed is fast, is widely used in organic wastewater
In degradation technique.Wherein heterogeneous light Fenton reaction system especially has catalyst itself and easily reclaims, repeatedly using remaining to
The advantage keeping goodish catalysis activity, thus avoid the secondary pollution causing because of iron ion loss, decrease processing cost.
Graphene is a kind of New Type of Carbon nanometer light material, has the monoatomic layer two dimensional crystal structure of uniqueness, has relatively
Big specific surface area, high chemical stability, preferable adsorption capacity and stronger electron transport performance, turn in solar photoelectric
Change field has broad application prospects, and is a kind of ideal carrier material.Catalytic active component is combined with Graphene, permissible
Make full use of the good electron transport performance of Graphene, big specific surface area and strong adsorption capacity thus improving light Fenton's reaction
Efficiency；Can solve the problems, such as that active catalytic nano-particle is easily reunited simultaneously.Graphene is used for surface modification catalyst
Carrier, can play Graphene to greatest extent and carry out the effect such as co-catalysis or absorption of opto-electronic conversion in carrier interface.
There is more report for based on the catalyst of Graphene and carrier in prior art.For example, Huai-ping
(the Macroscopic Multifunctional Graphene-Based Hydragels and Aerogels by a such as cong
Metal Ion Induced Self-Assembly Process, ACS nano, 2012,6 (3)：2693-2703) report stone
Black alkene/R-FeOOH and magnetic graphene/Fe3O4Preparation method；Patent of invention (patent publication No.：CN102921422A) report
A kind of magnetic Nano Cu-Fe3O4/ graphene composite catalyst and its application in nitro compound reducing.Both approaches
The catalysis material of preparation does not adopt carrier loaded, so active component can not obtain abundant efficient utilization.
Patent of invention (patent publication No.：CN 103272650A) report a kind of Graphene modified mesoporous molecular sieve amphiphilic
Property composite and preparation method thereof, be applied to improve oil water boundary to improve reaction efficiency as emulsifying agent, Graphene
Method of modifying is to be heated to reflux-high temperature nitrogen atmosphere roasting method and hydrothermal crystallizing-high temperature nitrogen atmosphere roasting method.
Patent of invention (patent publication No.：CN 103272560A) report a kind of Novel composite water treatment material and its system
Graphene or graphene oxide are coated on sepiolite and tourmaline surface using circumfluence method, using Graphene or oxygen by Preparation Method
The larger surface area of graphite alkene is to improve the sepiolite and tourmaline absorption property to organic wastewater.
Patent of invention (patent publication No.：CN 102847536A) report a kind of composite photocatalyst material and its preparation side
Method, by Graphene ethanol solution, the butyl titanate aqueous solution and r-Fe2O3/SiO2Carry out long agitation mixing, using metatitanic acid fourth
Ester hydrolysis, carry out high-temperature roasting after forming colloidal sol drying and obtain this composite photo-catalyst r-Fe2O3/SiO2/GSs/TiO2, should
For removing hardly degraded organic substance under visible light conditions.
Patent of invention (patent publication No.：CN 103464098A) report a kind of preparation of Graphene photocatalytic absorbent
Method, takes the sodium silicate binder of proper ratio, Graphene, photochemical catalyst, adsorbent, dispersant, inorfil to carry out uniformly
Mixing, puts extrusion forming in grinding tool, carries out maintenance and obtain photocatalytic adsorbent, in photochemical catalyst in 20 days in 120 DEG C of vapor
Soak stagnant in colloidal sol, the adsorbent with photocatalytic activity after high-temperature calcination, is obtained.Patent of invention (patent publication No.：CN
103464122A) report a kind of preparation method of graphene/chitosan adsorbent resin, configuration nano titanium oxide suspension,
Graphene oxide solution, chitosan solution, three's high-speed stirred mixes, and adds glutaraldehyde solution to carry out cross-linking reaction, dries
Dry grinding obtains titanium dioxide-Graphene-shitosan composite resin particle after sieving, in energy catalytic degradation and absorption dyeing waste water
Dyestuff.
Mostly using the carrying method of high-temperature calcination or binding agent, Graphene is entered in above disclosed prior art
Row is processed, and preparation process is comparatively laborious, or power consumption is high, and gained catalyst is at aspects such as catalytic efficiency, the pH scope of applications
Not satisfactory.Therefore, prior art still one or more of the problems referred to above in the urgent need to address aspect, particularly needs
Will a kind of high catalytic efficiency, the light fenton catalyst based on Graphene that easily prepared, pH scope is wide.
Content of the invention
The present inventor after test of many times, it was unexpectedly found that：Based on goethite-graphene complex surface modification
The composite catalyst of mesoporous supports can act effectively as heterogeneous light Fenton catalyst, and this catalysis material is by goethite-Graphene-mesoporous
Carrier material three combine, and can rapidly and efficiently go the organic pollution in eliminating water (to include as heterogeneous light Fenton catalyst
Phenol, nitrogen heterocyclic ring etc.), catalytic effect is fabulous, and the pH scope of application is especially wide, and repeat performance is good, and also can
Simultaneously effective reduce COD and TOC in waste water.
The heterogeneous light Fenton catalyst of the present invention is first by graphene oxide heat load in mesoporous supports surface (for example：Logical
Cross the mode being heated to reflux), recycle divalent iron salt reagent that graphene oxide is reduced to Graphene, molysite is attached to stone simultaneously
Black alkene surface forms goethite-graphene complex, thus obtains having been carried out surface modification by goethite-graphene complex
Mesoporous supports, thus obtain the heterogeneous light Fenton catalysis material of the surface modification based on mesoporous supports of the present invention.
Therefore, it is an object of the present invention to provide one kind efficiently removes Organic Pollutants In Water, (such as phenol, contains
Azacyclo- etc.) heterogeneous light Fenton catalysis material, it comprises mesoporous supports, and the surface of described mesoporous supports by goethite-
Graphene complex is modified.
Present invention also offers the preparation method of the described heterogeneous light Fenton catalyst of the present invention, methods described bag is lived following
Step：By graphene oxide heat load in mesoporous supports, thus being modified to described mesoporous supports surface with graphene oxide；
Then with divalent iron salt, graphene oxide is reduced, while making graphene oxide be reduced to Graphene, divalent iron salt is by oxygen
Chemical conversion goethite (a-FeOOH) crystal formation, and it is attached to graphenic surface formation goethite (a-FeOOH)-graphene complex.
Further object is that providing heterogeneous light Fenton catalyst of the present invention difficult fall in processing water
Purposes in solution organic pollution.
Further object is that providing heterogeneous light Fenton catalyst of the present invention to pollute in processing water
Purposes in thing phenol or quinoline.
Further object is that provide heterogeneous light Fenton catalyst of the present invention to live together in reason water polluting
Purposes in thing phenol.
For achieving the above object, in a technical scheme of the present invention, the present invention is aoxidized by mesoporous supports heat load
Graphene, using divalent iron salt redox graphene and immobilized generate goethite (a- in the graphenic surface that generated
FeOOH) crystal formation, forms goethite-graphene complex and modifies in mesoporous supports surface, thus obtaining the table based on mesoporous supports
The catalyst of the present invention that face is modified by goethite-graphene complex.
As well known to those skilled in the art：Mesoporous between micropore and macropore, refer to hole between 2 to 50 nanometers for the aperture
(or claiming mesopore).In macropore range, mesoporous material has huge specific surface area and 3 D pore canal knot in the aperture of mesoporous material
Structure.Heretofore described mesoporous supports, in addition to those mesoporous materials that can be used as carrier as known in the art, especially select
From r-Al2O3、MCM-41、Al-MCM-41.
At the present invention one specifically aspect, the heterogeneous light Fenton catalyst of the present invention is the side by comprising the following steps
Method is obtained：By graphene oxide heat load in mesoporous supports, thus being carried out to described mesoporous supports surface with graphene oxide
Modify；Then with divalent iron salt, graphene oxide is reduced, while making graphene oxide be reduced to Graphene, divalent iron salt
It is oxidized to goethite (a-FeOOH) crystal formation, and is attached to graphenic surface formation goethite (a-FeOOH)-Graphene and be combined
Body.
In one embodiment of the invention, the divalent iron salt of the present invention be selected from inorganic salts for example ferrous sulfate, ferrous nitrate,
Frerrous chloride；Organic salt such as ferrous citrate, ferrous succinate, ferrous tartrate, ferrous fumarate etc..The divalence of the present invention
Inorganic molysite can also be composite iron salt such as iron ammonium sulfate.Especially, the divalent iron salt of the present invention is selected from FeSO4·7H2O
(NH4)2Fe(SO4)2·6H2O.
The present invention one more specifically aspect, the heterogeneous light Fenton catalyst of the present invention is the side by comprising the following steps
Method is obtained：Weigh mesoporous supports, add in alcohol solution, add graphene oxide solution thereto, ultrasonic, add in solution
Enter divalent iron salt, filter, washing precipitation, by gained filter cake freeze-drying, grind into powder.
More specifically on one side, the heterogeneous light Fenton catalyst of the present invention is the side by comprising the following steps to the present invention
Method is obtained：Weigh 2g mesoporous supports, be added in 50ml ethanol water (1: 2～2: 1v%), add 10～
40ml7.75mg/ml graphene oxide solution, ultrasonic 20min, heats (90 DEG C～130 DEG C) return stirring 4～8h；Weigh certain
The divalent iron salt reagent of amount is dissolved in reaction 2～4h in above-mentioned hot solution；Reacted hot solution is carried out suction filtration, uses a small amount of ethanol
Solution washing, obtains the filter cake drained, and is carried out freeze-drying 12～24h, grind into powder.
In the preparation method of the heterogeneous light Fenton catalyst of the present invention, mesoporous supports and graphene oxide solution can be made
Reacted under reflux conditions, graphene oxide dosage and divalent iron salt dosage can be adjusted as needed, acceptable
Control the temperature of backflow and the time of backflow.The preferred catalyst of the present invention is to be respectively adopted mesoporous supports r-Al2O3、MCM-
41 or Al-MCM-41 react, with graphene oxide and divalent iron salt, the catalyst obtaining, and it is expressed as：gh-r-Al2O3-
FeOOH, gh-MCM-FeOOH and gh-Al-MCM-FeOOH (wherein gh represents Graphene), they are black powdery solid.
The present inventor examines the catalytic effect of the heterogeneous light Fenton catalyst of the present invention, finds in daylight and H2O2Exist
Under conditions of, the catalyst of the present invention can quickly and efficiently go organic pollution (particularly phenol, the nitrogen heterocyclic ring in eliminating water
Deng), and there is extensive pH scope applicability, it is therefore a kind of heterogeneous light Fenton catalysts of excellent performance.
Brief description
The gh-r-Al that Fig. 1 is prepared for the present invention2O3- FeOOH, gh-MCM-FeOOH and gh-Al-MCM-FeOOH material
FTIR spectrum figure.
The X-ray diffraction spectrogram of the gh-Al-MCM-FeOOH that Fig. 2 is prepared for the present invention and graphene oxide and goethite.
Gh-Al-MCM-FeOOH and gh-Al-MCM-Fe that Fig. 3 is prepared for the present invention3O4、gh-Al-MCM-Fe2O3、gh-
Al-MCM、gh-FeOOH、Al-MCM-Fe2O3Removal efficiency with seven kinds of catalysis material light Fenton catalytic degradation phenol of a-FeOOH
Time dependent comparison diagram.
Gh-Al-MCM-FeOOH material light Fenton and the removal effect of Fenton catalytic degradation phenol that Fig. 4 is prepared for the present invention
The time dependent comparison diagram of rate.
The removal efficiency anaplasia at any time of the gh-MCM-FeOOH material light Fenton catalytic degradation phenol that Fig. 5 is prepared for the present invention
Change figure.
The gh-r-Al that Fig. 6 is prepared for the present invention2O3The removal efficiency of-FeOOH material light Fenton catalytic degradation phenol is at any time
Between variation diagram.
The removal efficiency of the gh-Al-MCM-FeOOH material light Fenton catalytic degradation quinoline that Fig. 7 is prepared for the present invention is at any time
Between variation diagram.
The gh-r-Al that Fig. 8 is prepared for the present invention2O3- FeOOH, gh-MCM-FeOOH and gh-Al-MCM-FeOOH material light
COD the and TOC removal efficiency versus time curve figure of Fenton catalytic degradation phenol.
Graphite alkene hydrogel is dried system
Specific embodiment
The following is the non-limiting example of the present invention.Being given of these embodiments is solely for the purpose of illustration, and should not
It is interpreted as limitation of the invention.It will be understood by those skilled in the art that can be on the basis without departing from the spirit and scope of the present invention
On, the present invention is carried out with many change and adjustment, without deviating from objective, spirit and scope of the present invention.Explanation in the present invention
In book and following instance, unless stated otherwise, concentration used is all percetage by weight.
Preparation embodiment
The preparation method of the heterogeneous light Fenton catalyst of the present invention taking following embodiments is as a example described：
Weigh 2g carrier (r-Al2O3, MCM-41 or Al-MCM-41), add 50ml ethanol water (1: 2～2: 1v%)
In, add 10～40ml 7.75mg/ml graphene oxide solution, ultrasonic 20min, heat (90 DEG C～130 DEG C) return stirring 3
～6h；Weigh a certain amount of divalent iron salt reagent (FeSO4·7H2O、(NH4)2Fe(SO4)2·6H2O) it is dissolved in above-mentioned hot solution
Reaction 2～4h；Reacted hot solution is carried out suction filtration, is washed with a small amount of ethanol water, the filter cake after being drained, by it
Carry out freeze-drying 12～24h, grind into powder, obtain the powdery solid catalyst gh-r-Al of black2O3- FeOOH, gh-
MCM-FeOOH and gh-Al-MCM-FeOOH.
In addition, heretofore described r-Al2O3, MCM-41, Al-MCM-41 be mesoporous supports as known in the art,
It all can be commercially available by commercially available, or also can be prepared by example below method.
Described r-Al2O3Preparation method be：The amount of taking fully spherolite activated alumina, grinds after 30min with pulverizer, sieve
Point 100 mesh～200 mesh particle diameter carrier granulars, deionized water is repeatedly washed, and the mealy solid particle that will obtain after centrifugation is in 105
8～12h being dried in DEG C baking oven, and 300～500 DEG C of roasting 1～3h in Muffle furnace, will obtain through pretreated powdery
Grain carrier is dried preservation.
The preparation method of described MCM-41：Take 4.8gCTAB (cetyl trimethylammonium bromide), be added to 40 DEG C
Dissolved in 240ml deionized water, drip 20ml 25% concentrated ammonia liquor in resulting solution, make pH=10～11, be added dropwise over
20ml TEOS (tetraethyl orthosilicate), is stirred vigorously 4h with 360r/min, will be still aging for obtained off-white color mixing suspension
24～48h, is filtrated to get sediment, dries 12h, grind into powder 550 DEG C of roastings in Muffle furnace in 105 DEG C of baking ovens
5h, the carrier obtaining is dried preservation.
The preparation method of described Al-MCM-41：Take 4.8gCTAB (cetyl trimethylammonium bromide), be added to 40 DEG C
240ml deionized water in dissolved；Weigh the aluminum sulfate solid 2.9875g that sial mass ratio is 10, be added dropwise to
In 20ml TEOS (tetraethyl orthosilicate), stir 15min；Dropwise add 20ml 25% concentrated ammonia liquor in above-mentioned resulting solution, make
PH=10～11, are stirred vigorously 4h with 360r/min, and still aging for gained off-white color mixed solution 24～48h is filtrated to get
Sediment, dries 12h, grind into powder 550 DEG C of roasting 5h in Muffle furnace in 105 DEG C of baking ovens, the carrier obtaining is entered
Row kept dry.
Graphene oxide can be commercially available by commercially available, or also can be prepared by example below method.
The preparation method of described graphene oxide solution：Using the Hummers method revised, weighing 4g 32 mesh can be swollen
Swollen graphite and the mixing of 2g sodium nitrate, measure 40ml 98%H2SO4It is added in said mixture, ice bath, with 350r/min machinery
Stirring 5min, slowly adds 12g potassium permanganate thereto, stirs 15min, removes ice bath, be warming up to 35 DEG C, reacts 4～6h；Continue
Continue and be warming up to 97 DEG C, slowly add the ultra-pure water of 150ml thereto, after reaction 15min, add 200ml deionized water；To above-mentioned
Add at a slow speed 40ml 30% hydrogen peroxide in mixed solution until solution colour is changed into golden yellow, stir 15min；Prepare 900ml
5%HCl solution, cleans above-mentioned golden yellow mixed solution twice, then is cleaned with 1000ml deionized water above-mentioned with this hydrochloric acid solution
Golden yellow mixed solution three times；Above-mentioned golden yellow mixed solution is carried out 7000～8000r/min high speed centrifugation, dark by obtain
Clear yellow viscous thing is added in 450ml deionized water, the ultrasonic 30min～60min of 100W, and the mixed solution obtaining is carried out
7000r/min high speed centrifugation, takes upper solution, as described graphene oxide solution, and concentration is 7.75mg/ml.
1. the structure of catalyst material and constituent analysis
Sample (the gh-r-Al that will obtain in above-mentioned preparation embodiment2O3- FeOOH, gh-MCM-FeOOH and gh-Al-MCM-
FeOOH) carry out Fourier's infrared analysis, result is as shown in figure 1, wave number 3434～3423cm-1There is the O-H of a-FeOOH in display
Feature stretching vibration peak, 1631～1628cm-1With 1406～1384cm-1There is loaded the flexible of Graphene C=O and shake in display
Dynamic peak, 1137～1081cm-1With 1237～1226cm-1There is the stretching vibration peak of loaded Graphene C-O in display.Above-mentioned red
Outer analysis result confirms that Graphene is incorporated into the surface of mesoporous supports, and divalent iron salt is raw during redox graphene
Become goethite (a-FeOOH) crystal formation.
Gh-Al-MCM-FeOOH in above-mentioned sample is carried out X-ray with the graphene oxide compareing and goethite mark product spread out
Penetrate spectrum analysis, result is as shown in Figure 2.As seen from the figure, 2 θ=11.6 ° are the characteristic peak of graphene oxide, gh-Al-MCM-
FeOOH does not have peak in this 2 θ, illustrates to modify the graphene oxide in mesoporous supports surface and is reduced to Graphene by ferrous iron；2 θ=
21.4 °, 2 θ=33.3 °, 2 θ=34.8 °, 2 θ=36.1 °, 2 θ=36.8 °, 2 θ=39.5 °, 2 θ=40.0 °, 2 θ=41.1 °, 2
θ=45.7,2 θ=53.3 °, 2 θ=57.6 °, 2 θ=59.0 °, 2 θ=61.5 °, 2 θ=64.1 °, 2 θ=68.4 ° are goethite
(a-FeOOH) characteristic peak, illustrating to modify the crystal formation in the Graphene institute carried metal active component iron on mesoporous supports surface is
Goethite (a-FeOOH).
2.gh-r-Al2O3- FeOOH, gh-MCM-FeOOH and gh-Al-MCM-FeOOH are as heterogeneous light Fenton catalyst
Catalysis activity
(2.1) the catalytic elimination effect of the gh-Al-MCM-FeOOH material Pyrogentisinic Acid of present invention preparation
(2.1.1) the preparation embodiment of gh-Al-MCM-FeOOH material：
Weigh 2g carrier Al-MCM-41, add in 50ml ethanol water (1: 1v%), add 30ml 7.75mg/ml oxygen
Graphite alkene solution, ultrasonic 20min, 118 DEG C are heated to reflux stirring 4h.Weigh 0.4913g FeSO4·7H2O is dissolved in above-mentioned thermosol
In liquid, react 2h.Reacted hot solution is carried out suction filtration, is washed with a small amount of ethanol water, the filter cake after being drained, will
It carries out freeze-drying 24h, grind into powder, obtains black powdery solid catalyst gh-Al-MCM-FeOOH.Record this catalysis
Material specific surface area (BET) is 861.752m2/ g, pore volume is 0.452cc/g, and aperture is 3.829nm.
(2.1.2) it is to prove that the inventive method intermediary hole carrier, Graphene, the combination of goethite enhance the present invention
The catalytic degradation effect of described heterogeneous light Fenton catalysis material, devises with gh-Al-MCM-Fe3O4、gh-Al-MCM-Fe2O3、
gh-Al-MCM、gh-FeOOH、Al-MCM-Fe2O3With a-FeOOH for experimental comparison group contrast experiment.Specific experiment is as follows：
(2.1.2.1)gh-Al-MCM-Fe3O4、gh-Al-MCM-Fe2O3、gh-Al-MCM、gh-FeOOH、Al-MCM-
Fe2O3Prepare example with a-FeOOH as experimental comparison group material：
(A)gh-Al-MCM-Fe3O4The preparation embodiment of material：
On the basis of above-mentioned (2.1.1) preparation embodiment, the gh-Al-MCM-FeOOH obtaining material is placed in tube furnace
550 DEG C of nitrogen atmosphere roasting 6h are warming up to 10 DEG C/min heating rate, obtain gh-Al-MCM-Fe3O4.Record this catalysis material and compare table
Area (BET) is 958.512m2/ g, pore volume is 0.936cc/g, and aperture is 1.935nm.
(B) the preparation embodiment of gh-Al-MCM material：
Weigh 2g carrier Al-MCM-41, add in 50ml ethanol water (1: 1v%), add 30ml 7.75mg/ml oxygen
Graphite alkene solution, ultrasonic 20min, 118 DEG C are heated to reflux stirring 3h, are slowly added dropwise 0.5ml hydrazine hydrate solution thereto and carry out
Reduction reaction 2h.Reacted hot solution is carried out suction filtration, is washed with a small amount of ethanol water, the filter cake after being drained, will
It carries out freeze-drying 24h, grind into powder, obtains black powdery solid catalyst gh-Al-MCM.Record this catalysis material ratio
Surface area (BET) is 664.221m2/ g, pore volume is 0.541cc/g, and aperture is 3.063nm.
(C)gh-Al-MCM-Fe2O3The preparation embodiment of material：
Weigh 1g above-mentioned (B) carrier gh-Al-MCM and 0.3643gFe (NO)3·9H2O adds into 10ml ethanol water (1
: 1v%) in, stirring, ultrasonic 15min, it is placed in shaking table room temperature with 150r/min overnight, suction filtration, in 105 DEG C of drying of baking oven, grinds
Clay into power, in tube furnace, 550 DEG C of nitrogen atmosphere roasting 5h, obtain catalysis material gh-Al-MCM-Fe2O3.Record this catalysis material
Specific surface area (BET) is 648.522m2/ g, pore volume is 0.516cc/g, and aperture is 3.025nm.
(D) the preparation embodiment of gh-FeOOH material：
Repeat above-mentioned (2.1.1) preparation embodiment, simply without mesoporous supports, remaining step is constant, obtains powdery black
Color solid gh-FeOOH.
(E)Al-MCM-Fe2O3The preparation embodiment of material：
Weigh 1g carrier Al-MCM-41, be added to and fill in 10ml ethanol water (2: 1v%) 50ml conical flask, Xiang Qi
Middle addition 0.3631g Fe (NO3)3·9H2O, stirring, ultrasonic 20min mixes, and puts in shaking table and puts 12h with the leaching of 150r/min room temperature,
Suction filtration, 105 DEG C of drying 12h, grind 550 DEG C of roasting 6h in rearmounted Muffle furnace, obtain catalysis material Al-MCM-Fe2O3.Record this
Catalysis material specific surface area (BET) is 1037.756m2/ g, pore volume is 0.572cc/g, and aperture is 2.313nm.
(F) control sample a-FeOOH is purchased from the geothite mark product of SIGMA-ALDRICH, and No. CAS is 20344-49-4,
It is 243-746-4 that EINECS numbers.
(2.1.2.2) comparative example of above-mentioned reference substance：
Take the phenol solution that 200ml concentration is 100mg/L respectively in beaker, weigh 0.1g catalysis material (a- simultaneously
FeOOH is exception, and reaction dosage is 80mg) and add 0.3% hydrogen peroxide (10mM) in above-mentioned simulative organic wastewater, it is placed in
Vertical 25cm under 500W xenon lamp (light source distance reactant liquor identity distance from) place carries out light Fenton catalytic degradation reaction.Wherein, in pH=6
In water body environment, the effect of gh-Al-MCM-FeOOH catalysis material catalytic elimination phenol is best；Gh-FeOOH and gh-Al-MCM-
Fe3O4Take second place；But gh-FeOOH is not due to having carrier, the active component preparing catalyst in the case of adding same amount is used
Amount ratio is larger, and cost significantly improves；gh-Al-MCM-Fe3O4Catalysis material need to through high temperature nitrogen atmosphere roasting 6h on the basis of the former,
Power consumption is than larger hence it is evident that uneconomical.After seven kinds of material catalytic degradation phenol 1h, COD clearance see table (table 1), its reaction power
Learn experimental result as shown in Figure 3.Under remaining ph condition (4,5,7,8,9) water body environment, gh-Al-MCM-FeOOH catalysis material is urged
It is also best for changing degradation of phenol removal effect.
COD clearance (%) after seven kinds of material catalytic degradation phenol 1h under the conditions of table 1 pH=6 water body environment
From the above results, gh-Al-MCM-FeOOH catalysis material intermediary hole carrier (Al-MCM- of the present invention
41), Graphene, goethite three combine the mesoporous supports of formation goethite-graphene complex surface modification, its light Fenton
Catalytic degradation performance is substantially than binary combination material (gh-Al-MCM-41, gh-FeOOH, Al-MCM-Fe2O3) and unitary material
(a-FeOOH) effect will be got well.Especially, under same input amount, the COD clearance of Al-MCM-FOOH is significantly higher than Al-
MCM-Fe2O3With the COD clearance sum of a-FeOOH it is clear that catalysis material intermediary hole carrier (Al-MCM-41) of the present invention, graphite
The combination of alkene and goethite shows good synergy in heterogeneous light Fenton catalytic degradation reaction system.
(2.1.3) gh-Al-MCM-FeOOH material is as heterogeneous light Fenton catalyst and fenton catalyst catalytic degradation water
The embodiment of the method for phenol in body：
Take the phenol solution that 200ml concentration is 100mg/L as simulative organic wastewater respectively in two beakers, claim simultaneously
Take 0.1g catalyst gh-Al-MCM-FeOOH and add 0.3% hydrogen peroxide (10mM) in above-mentioned simulative organic wastewater, one anti-
Answer system to be placed under 500W xenon lamp vertical 25cm (light source distance reactant liquor identity distance from) place and carry out light Fenton catalytic degradation reaction, separately
One reaction system is to wrap up whole beaker using aluminium-foil paper to carry out the Fenton catalytic degradation reaction under dark room conditions.In water body ring
Under conditions of border pH is respectively 4,5,6,7,8,9, after reaction 10min, phenol clearance see table (table 2), degradation kinetics
Experimental result is as shown in Figure 4.From experimental result, when pH=4～9, with 10min reaction moment as a comparison, gh-
The reaction rate of Al-MCM-FeOOH material catalytic degradation phenol in the light Fenton's reaction system sweet smell more simple than under dark room conditions
Reaction system of pausing is fast；As pH=9, in this catalysis material simple Fenton's reaction system under dark room conditions to water body in phenol
Substantially there is no catalytic degradation effect, and the removal effect of catalytic degradation phenol reacts the moment in 1h in light Fenton's reaction system
Reach 100%, illustrate this catalysis material as heterogeneous light Fenton catalyst can rapidly and efficiently catalytic elimination water body phenol, and ph fits
Substantially will be extensively with scope.
The smooth Fenton catalystic converter system of table 2 and Fenton catalystic converter system react phenol after 10min respectively under different pH
Clearance (%)
(2.2) the catalytic elimination effect of the gh-MCM-FeOOH material Pyrogentisinic Acid of present invention preparation
(2.2.1) the preparation embodiment of gh-M-FeOOH material：
Weigh 2g carrier MCM-41, add in 50ml ethanol water (2: 1v%), add 30ml 7.75mg/ thereto
Ml graphene oxide solution, ultrasonic 20min, 114 DEG C are heated to reflux stirring 5h.Weigh 0.4937gFeSO4·7H2O is dissolved in above-mentioned
3h is reacted in hot solution.Reacted hot solution is carried out suction filtration, and is washed with a small amount of ethanol water, the filter after being drained
Cake, carries out freeze-drying 24h, grind into powder, obtains black powdery solid catalyst gh-MCM-FeOOH.Record this catalysis material
The specific surface area (BET) of material is 768.871m2/ g, pore volume is 0.660cc/g, and aperture is 3.065nm.
(2.2.2) gh-MCM-FeOOH material is as the method for phenol in heterogeneous light Fenton catalyst degraded water body
Embodiment：
Take the phenol solution that 200ml concentration is 100mg/L as simulative organic wastewater in beaker, organic to above-mentioned simulation
Add 0.1g catalyst gh-MCM-FeOOH and 0.3% hydrogen peroxide (10mM) in waste water, be placed under 500W xenon lamp vertical 25cm (light
Source apart from reactant liquor identity distance from) place carries out light Fenton catalytic reaction, under the conditions of pH is respectively 4,6,7,8,9, after reaction 1.5h
Phenol clearance all reach 100%.Result is as shown in Figure 5.
(2.3) gh-r-Al of present invention preparation2O3The catalytic elimination effect of-FeOOH material Pyrogentisinic Acid
(2.3.1)gh-r-Al2O3The preparation embodiment of-FeOOH material：
Weigh 2g carrier r-Al2O3, it is added in 50ml ethanol water (1: 2v%), add 40ml thereto
7.75mg/ml graphene oxide solution, ultrasonic 20min, 120 DEG C are heated to reflux stirring 6h.Weigh 0.7023g (NH4)2Fe
(SO4)2·6H2O is dissolved in reaction 2.5h in above-mentioned hot solution.Reacted hot solution is carried out suction filtration, and water-soluble with a small amount of ethanol
Liquid washs, and the filter cake after being drained carries out freeze-drying 24h, grind into powder, obtains black powdery solid catalyst gh-
r-Al2O3-FeOOH.The specific surface area (BET) recording this catalysis material is 193.418m2/ g, pore volume is 0.430cc/g, aperture
For 3.826nm.
(2.3.2)gh-r-Al2O3- FeOOH material is degraded the going of phenol in water body as heterogeneous light Fenton catalyst
Except effect：
Take the phenol solution that 200ml concentration is 100mg/L as simulative organic wastewater in beaker, be added thereto to 0.1g
Catalyst gh-r-Al2O3- FeOOH and 0.3% hydrogen peroxide (10mM) are in Beijing time 11:30am～13:The 30pm time period in
The light Fenton catalytic degradation reaction carrying out on windowsill under the conditions of real daylight irradiation is opened wide in certain laboratory, be respectively 4 in pH, 6,7,
8th, under conditions of 9, the phenol clearance after reaction 1.5h all reaches 100%.Result is as shown in Figure 6.
(2.4) the catalytic elimination effect to quinoline for the gh-Al-MCM-FeOOH material
(2.4.1) the preparation embodiment of gh-Al-MCM-FeOOH material：
Weigh 2g carrier Al-MCM-FeOOH, add in 50ml ethanol water (1: 1v%), add thereto
30ml7.75mg/ml graphene oxide solution, ultrasonic 20min, 116 DEG C are heated to reflux stirring 4.5h.Weigh 0.7023g (NH4)2Fe(SO4)2·6H2O is dissolved in reaction 2.5h in above-mentioned hot solution.Reacted hot solution is carried out suction filtration, and uses a small amount of ethanol
Solution washing, the filter cake after being drained, carry out freeze-drying 24h, grind into powder, obtain black powdery solid catalyst
gh-Al-MCM-FeOOH.The specific surface area (BET) recording this catalysis material is 866.678m2/ g, pore volume is 0.472cc/g, hole
Footpath is 3.862nm.
(2.4.2) gh-Al-MCM-FeOOH material is degraded the going of quinoline in water body as heterogeneous light Fenton catalyst
Except effect：
Take the quinoline solution that 200ml concentration is 20mg/L as simulative organic wastewater in beaker, organic to above-mentioned simulation
Add 0.1g catalyst gh-Al-MCM-FeOOH and 0.3% hydrogen peroxide (10mM) in waste water, be placed under 500W xenon lamp vertical 25cm
(light source distance reactant liquor identity distance from) place carries out light Fenton catalytic degradation reaction, is respectively 3.6,4.6,6.5,7,8,9 in pH
Under the conditions of, after reaction 2h, quinoline clearance all reaches 100%.Result is as shown in Figure 7.
(2.5)gh-r-Al2O3- FeOOH, gh-MCM-FeOOH and gh-Al-MCM-FeOOH catalyst degradation of phenol
COD and TOC removal effect
(2.5.1)gh-r-Al2O3The preparation embodiment of-FeOOH, gh-MCM-FeOOH and gh-Al-MCM-FeOOH material：
Weigh 2g carrier (r-Al2O3, MCM-41, Al-MCM-41), add in 50ml ethanol water (1: 1v%), Xiang Qi
In add 30ml 7.75mg/ml graphene oxide solution, ultrasonic 20min, 118 DEG C are heated to reflux stirring 4h.Weigh 0.4913g
FeSO4·7H2O is dissolved in reaction 2h in above-mentioned hot solution.Reacted hot solution is carried out suction filtration, uses a small amount of ethanol aqueous wash
Wash, the filter cake after being drained, carried out freeze-drying 24h, grind into powder, obtain black powdery solid catalyst gh-
r-Al2O3- FeOOH, gh-MCM-FeOOH and gh-Al-MCM-FeOOH.The specific surface area (BET) of catalyst, pore volume and aperture are surveyed
Determine result and see table (table 3).
The BET of 3 three kinds of catalysis materials of table, pore volume and pore size determination result
(2.5.2)gh-r-Al2O3- FeOOH, gh-MCM-FeOOH and gh-Al-MCM-FeOOH material is fragrant as out-phase light
Catalyst is degraded the removal effect of COD and TOC of phenol in water body：
Take the phenol solution that 200ml concentration is 100mg/L as simulative organic wastewater in beaker, add 0.1g thereto
Catalyst (gh-r-Al2O3- FeOOH, gh-MCM-FeOOH or gh-Al-MCM-FeOOH) and 0.3% hydrogen peroxide (10mM), it is placed in
Vertical 25cm under 500W xenon lamp (light source distance reactant liquor identity distance from) place carries out light Fenton catalytic reaction, under the conditions of pH=6, reaction
After 1h, COD the and TOC removal efficiency of three kinds of heterogeneous light Fenton material catalytic degradation phenol see table (table 4).Result such as Fig. 8 institute
Show.
COD the and TOC removal efficiency of the catalytic degradation phenol of 4 three kinds of catalysis materials of table
(2.6) gh-Al-MCM-FeOOH material is as the repetition of phenol in heterogeneous light Fenton catalyst degraded water body
Serviceability
(2.6.1) the preparation embodiment of gh-Al-M-FeOOH material：
Weigh 2g carrier Al-MCM-41, add in 50ml ethanol water (1: 1v%), add 30ml thereto
7.75mg/ml graphene oxide solution, ultrasonic 20min, 118 DEG C are heated to reflux stirring 4h.Weigh 0.4913gFeSO4·7H2O is molten
2h is reacted in above-mentioned hot solution.Reacted hot solution is carried out suction filtration, and is washed with a small amount of ethanol water, drained
Filter cake afterwards, is carried out freeze-drying 24h, grind into powder, obtains black powdery solid catalyst gh-Al-MCM-
FeOOH.Recording this catalysis material specific surface area (BET) is 861.752m2/ g, pore volume is 0.452cc/g, and aperture is 3.829nm.
(2.6.2) gh-Al-MCM-FeOOH material is as the removal of phenol in heterogeneous light Fenton material catalytic degradation water body
Effect：
Take the phenol solution that 800ml concentration is 100mg/L in beaker as simulative organic wastewater, be added thereto to 0.4g and urge
Agent gh-Al-MCM-FeOOH and 0.3% hydrogen peroxide (10mM), are placed under 500W xenon lamp vertical 25cm (light source distance reactant liquor
Identity distance from) place carries out light Fenton catalytic reaction, under the conditions of pH=6, carries out 10 " degraded-reclaim-degraded " repeated experiments,
Take 1h as reaction end, 10 repeated experiment concrete conditions and result see table (table 5).This catalysis material makes at the 10th time
With in, in catalytic degradation water body, the clearance of phenol is maintained at more than 90%, illustrates that this catalysis material is urged as heterogeneous light Fenton
The repeat performance of agent degraded Organic Pollutants In Water is good.
Table 5 10 repeated experiment concrete conditions of gh-Al-MCM-FeOOH catalytic degradation phenol and result
Claims (5)
1. a kind of heterogeneous light Fenton catalyst, it comprises mesoporous supports, and the surface of described mesoporous supports is by goethite-graphite
Alkene complex is modified, and wherein said mesoporous supports are Al-MCM-41, and described heterogeneous light Fenton catalyst is by including
The method of following steps is obtained：Weigh 2g mesoporous supports, be added in the ethanol water of 50mL 1: 2～2: 1v%, add
10～40mL 7.75mg/mL graphene oxide solution, ultrasonic 20min, 90 DEG C～130 DEG C are heated to reflux high-speed stirred 4～8h；
Weigh a certain amount of divalent iron salt reagent and be dissolved in reaction 2～4h in above-mentioned hot solution；Reacted hot solution is carried out suction filtration, uses
A small amount of ethanol water washing, obtains the filter cake drained, is carried out freeze-drying 12～24h, grind into powder.
2. heterogeneous light Fenton catalyst according to claim 1, wherein said divalent iron salt is selected from FeSO4·7H2O and
(NH4)2Fe(SO4)2·6H2O.
3. the use in heterogeneous light Fenton catalyst according to claim 1 and 2 persistent organic pollutants in processing water
On the way.
4. use in processing water pollutant phenol or quinoline for the heterogeneous light Fenton catalyst according to claim 1 and 2
On the way.
5. purposes in processing water pollutant phenol for the heterogeneous light Fenton catalyst according to claim 1 and 2.
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| CN104289223A (en) * | 2014-09-22 | 2015-01-21 | 北京师范大学 | Method for preparing heterogeneous light Fenton catalyst |
| CN105645506B (en) * | 2015-12-29 | 2018-07-03 | 哈尔滨工业大学 | A kind of smooth Fenton catalysis oxidation coal chemical industrial waste water advanced treatment system and its method for handling coal chemical industrial waste water |
| CN105597758A (en) * | 2016-02-05 | 2016-05-25 | 武汉理工大学 | Graphene modified iron mud heterogeneous Fenton catalyst and preparation method thereof |
| CN105921151A (en) * | 2016-04-29 | 2016-09-07 | 华东师范大学 | Preparation method and application of beta-FeOOH-loaded graphene oxide catalyst |
| CN106587326B (en) * | 2016-12-27 | 2019-03-26 | 哈尔滨工业大学 | A kind of preparation method of the graphene oxide of carried magnetic nano particle and conducting polymer Fenton gel |
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| CN111068638A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for oxidation reaction and application thereof |
| CN110026195B (en) * | 2019-05-05 | 2021-09-03 | 河北师范大学 | High-activity alpha-Fe2O3Nanosheet and preparation method and application thereof |
| CN110272058B (en) * | 2019-07-01 | 2022-08-09 | 中南大学 | MCM-41 ordered mesoporous material and preparation method thereof |
| CN110586140B (en) * | 2019-09-30 | 2022-06-24 | 广西民族大学 | photo-Fenton catalyst and preparation method and application thereof |
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