CN104226362A - Heterogeneous Fenton catalyst and purpose thereof - Google Patents
Heterogeneous Fenton catalyst and purpose thereof Download PDFInfo
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- CN104226362A CN104226362A CN201410546489.2A CN201410546489A CN104226362A CN 104226362 A CN104226362 A CN 104226362A CN 201410546489 A CN201410546489 A CN 201410546489A CN 104226362 A CN104226362 A CN 104226362A
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Abstract
The invention relates to heterogeneous Fenton catalyst and a purpose thereof, in particular to graphene modified mesoporous molecular sieve (MCM-41) complex heterogeneous Fenton catalyst and purpose thereof for catalyzing to remove organic pollutant from water body, wherein hematite is loaded to the surface of the graphene modified mesoporous molecular sieve complex. The heterogeneous Fenton catalyst is prepared through steps that doping graphene in a mesoporous molecular sieve to modify through an in-situ synthesis thermal reduction method so as to form the graphene modified mesoporous MCM-41 complex, loading ferric iron to the surface thereof through a dipping method, and roasting under a high temperature under nitrogen atmosphere protection to enable the ferric iron to generate hematite (alpha-Fe2O3) crystal, and forming the graphene-MCM-41 complex loaded with iron oxide. The heterogeneous Fenton catalyst is composed of the graphene, mesoporous molecular sieve and hematite, so that the catalyst has a good catalyzing effect for the organic pollutant (especially phenol, nitrogen heterocyclic ring and the like) in water, enables the reaction time to be shortened, enables the iron ion dissolution to be lowered, and is capable of simultaneously lowering the COD and TOC in waste water.
Description
Technical field
The present invention relates to a kind of heterogeneous fenton catalyst and uses thereof, specifically, relate to the purposes that a kind of Graphene-mesopore molecular sieve complex surfaces modifies the heterogeneous fenton catalyst of bloodstone and catalytic elimination organic pollutants in water body thereof.
Background technology
High-level oxidation technology is persistent organic pollutants in the oxidation degradation water such as dehydrogenation reaction, electro transfer, electrophilic addition utilizing OH.As the one of high-level oxidation technology, Fenton's reaction is usually used in the processing procedure of persistent organic pollutants in water, and the OH with strong oxidizing property that reaction produces persistent organic pollutants degraded in water body can be removed and mineralising is the CO of environmentally safe
2and H
2o is a kind of eco-friendly green catalysis technique.Although homogeneous phase Fenton's reaction catalytic efficiency is higher, in system, dissolubility concentration of iron is high, in processing procedure, easily produce a large amount of iron mud, increases subsequent treatment cost, simultaneously catalyst be difficult to be separated with reclaim, iron ion runs off and causes secondary pollution.And heterogeneous fenton catalyst causes the extensive concern of researcher gradually owing to can overcome these shortcomings.Heterogeneous Fenton's reaction can obviously reduce iron stripping, controls a large amount of generations of iron mud, and catalyst is easy to be separated and reclaim, reduce the secondary pollution in reacting.Develop the key that highly active fenton catalyst is this research field.
Graphene is a kind of New Type of Carbon nanometer light material of the individual layer laminated structure be made up of carbon atom, has unique two-dimension plane structure, and it has larger specific area, high chemical stability, preferably adsorption capacity and stronger electron transport performance.As a kind of ideal carrier material, Graphene has been applied in the advanced function materials such as electronic material, thin-film material, energy storage material, liquid crystal material, catalysis material now gradually.Wherein, Graphene is doped in catalysis material, the good electron transport performance of Graphene, large specific area and strong adsorption capacity can be made full use of, thus improve the efficiency of catalytic reaction.
More report has been had for the catalyst based on Graphene in prior art.Such as, patent of invention (patent publication No.: CN103272650A) reports amphipathic composite of a kind of Graphene modified mesoporous molecular sieve and preparation method thereof, Graphene is doped in mesopore molecular sieve carries out modification by adding hot reflux or hydrothermal crystallizing mode, be applied to as emulsifying agent and improve oil water boundary to improve reaction efficiency.Material prepared by this method does not have load Fenton active metal, so cannot be applied in heterogeneous Fenton's reaction system.
Patent of invention (patent publication No.: CN 103877997A) reports a kind of high-efficient carrier method of Graphene carried photocatalyst, add Zinc vitriol, four nitric hydrate indiums, thioacetamide, prepare graphene-sulfur indium zinc, in light-catalyzed reaction.Patent of invention (patent publication No.: CN 102921422A) reports a kind of magnetic Nano Cu-Fe
3o
4/ graphene composite catalyst and the application in nitro compound reducing thereof.Patent of invention (patent publication No.: CN 102974350A) reports a kind of graphene-supported metal oxide nano-material and its preparation method and application, under hydrothermal conditions, obtained by graphene oxide and acetylacetone metallic compound, and apply to Fischer-Tropsch synthesis.Patent of invention (patent publication No.: CN102350357A) reports a kind of load nano nickel catalyst on Graphene and preparation method thereof, it is carrier with Graphene, add nickel hydroxide stir post-drying directly under argon atmosphere roasting namely obtain catalyst.Catalysis material Graphene prepared by above method and active component do not adopt carrier loaded, or directly using Graphene as carrier, expensive, active component can not obtain abundant efficiency utilization.
Patent of invention (patent publication No.: CN 102847536A) reports a kind of composite photocatalyst material and preparation method thereof, by Graphene ethanolic solution, the butyl titanate aqueous solution and r-Fe
2o
3/ SiO
2be uniformly mixed for a long time, utilize the hydrolysis of butyl titanate, carry out high-temperature roasting after forming colloidal sol oven dry and obtain this composite photo-catalyst r-Fe
2o
3/ SiO
2/ GSs/TiO
2, under being applied to visible light conditions, remove hardly degraded organic substance.Patent of invention (patent publication No.: CN 103464122A) reports 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, add glutaraldehyde solution and carry out cross-linking reaction, dry after grinding is sieved and obtain titanium dioxide-Graphene-shitosan composite resin particle, energy photocatalytic degradation and the dyestuff adsorbed in dyeing waste water.
The composite based on Graphene-carrier or Graphene-active component prepared in published prior art above, has no and is applied in heterogeneous Fenton's reaction system.Due to the remarkable speciality that Graphene itself has, be used in the preparation process of fenton catalyst carrier as altered contents, obtain Graphene-carrier complex, then catalytic active component is modified in complex surfaces, obtain the novel heterogeneous fenton catalyst of Graphene-carrier-active metal component, this catalyst is expected to play the height absorption of Graphene, strong Electron Transfer, and then obtains the high heterogeneous fenton catalyst of a kind of catalytic efficiency.
Summary of the invention
The present inventor is through test of many times, find: modify bloodstone composite catalyst based on Graphene-mesostructured material complex surfaces and effectively can be used as heterogeneous fenton catalyst, Graphene is doped in MCM-41 structure by fabricated in situ thermal reduction by this catalysis material, form Graphene-mesoporous MCM-41 complex, then finishing bloodstone.Three combines by this catalysis material, the organic pollution (comprising phenol, nitrogen heterocyclic ring etc.) in water rapidly and efficiently can be removed as heterogeneous fenton catalyst, excellent catalytic effect, shorten the reaction time, decrease iron stripping, and effectively can reduce COD and TOC in waste water simultaneously.
Heterogeneous fenton catalyst of the present invention is first doped in MCM-41 structure by fabricated in situ thermal reduction by Graphene; form Graphene-mesoporous MCM-41 complex; then put method load ferric iron by leaching, through nitrogen atmosphere protection high-temperature calcination, trivalent iron salt forms bloodstone (α-Fe
2o
3) crystal formation, form Graphene-MCM-41 complex surfaces and modify the heterogeneous Fenton catalysis material of bloodstone.
Therefore, one object of the present invention is to provide one efficiently to remove Organic Pollutants In Water (such as phenol, nitrogen heterocyclic ring etc.) heterogeneous Fenton catalysis material, it comprises mesostructured material-graphene complex, and described complex surfaces modify by bloodstone.
Present invention also offers the preparation method of described heterogeneous fenton catalyst of the present invention; described method bag following steps alive: Graphene is doped in MCM-41 structure by fabricated in situ thermal reduction; form Graphene-mesoporous MCM-41 complex; then method load ferric iron is put by leaching; through nitrogen atmosphere protection high-temperature calcination, trivalent iron salt generates bloodstone (α-Fe
2o
3) crystal formation, form Graphene-MCM-41 complex surfaces and modify the heterogeneous Fenton catalysis material of bloodstone.
Another object of the present invention is to provide the purposes of heterogeneous fenton catalyst of the present invention in process water in persistent organic pollutants.
Another object of the present invention is to provide the purposes of heterogeneous fenton catalyst of the present invention in process water pollutant phenol or quinoline.
Another object of the present invention is to provide the purposes of heterogeneous fenton catalyst of the present invention in process water pollutant phenol.
For achieving the above object; in a technical scheme of the present invention; Graphene is first doped in MCM-41 structure by fabricated in situ thermal reduction by the present invention; form Graphene-mesoporous MCM-41 complex; then method load ferric iron is put by leaching; through nitrogen atmosphere protection high-temperature calcination, trivalent iron salt generates bloodstone (α-Fe
2o
3) crystal formation, thus obtain the catalyst of the present invention that Graphene-MCM-41 complex surfaces modifies bloodstone.
As well known to those skilled in the art: mesoporous between micropore and macropore, refer to the hole of aperture between 2 to 50 nanometers (or claiming mesopore).The aperture of mesoporous material is in macropore range, and mesoporous material has huge specific area and three-dimensional open-framework.Mesoporous supports described in the present invention is not limited to MCM-41, but preferred MCM-41 mesopore molecular sieve.
The present invention one concrete in; heterogeneous fenton catalyst of the present invention is that the method by comprising the following steps is obtained: be first doped in MCM-41 structure by fabricated in situ thermal reduction by Graphene; form Graphene-mesoporous MCM-41 complex; then method load ferric iron is put by leaching; through nitrogen atmosphere protection high-temperature calcination, trivalent iron salt generates bloodstone (α-Fe
2o
3) crystal formation, form Graphene-MCM-41 complex surfaces and modify the heterogeneous Fenton catalysis material of bloodstone.
In one embodiment of the invention, metallic iron compound of the present invention is selected from trivalent iron salt reagent, and especially, metallic iron salt compound of the present invention is selected from Fe(NO3)39H2O.
The present invention one aspect more specifically, heterogeneous fenton catalyst of the present invention is that the method by comprising the following steps is obtained: silicon source solution, template (bromohexadecane base trimethylamine) and graphene oxide solution are mixed, adjust ph, heating crystallization or utilize reflux heating mode to carry out ageing in a kettle., cooling, filter, washing, dry, by the black powdery solid high-temperature calcination under nitrogen protection obtained, obtain Graphene and be doped in complex carrier in mesoporous MCM-41 structure; Get 1 part of above-mentioned complex carrier leaching and put trivalent iron salt, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection high-temperature calcination, obtain Graphene-MCM-41 complex load hematite catalyst of the present invention.
The present invention is an aspect more specifically, heterogeneous fenton catalyst of the present invention is that the method by comprising the following steps is obtained: part by weight, 6 ~ 10 parts of sodium metasilicate being heated 40 DEG C is dissolved in 20 ~ 30 parts of deionizations, be 8 ~ 10 with 3M sulphur acid for adjusting pH, 300 ~ 360r/min stirs 0.5h, makes solution become viscous gel shape; Add 4 ~ 6 parts of bromohexadecane base trimethylamines (CTAB), 10 ~ 40 parts of concentration are the graphene oxide solution of 7.75mg/L, and 300 ~ 360r/min stirs 4 ~ 6h to forming grey black gelatinous mixture; Put it in reactor and heat 100 ~ 130 DEG C of crystallization 16 ~ 36h, room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection 500 ~ 700 DEG C calcining 4 ~ 6h, obtains Graphene Modified MCM-41 carrier; Get 1 part of above-mentioned carrier leaching and put metallic iron compound; concussion; ultrasonic; filter; drying, afterwards through nitrogen protection 550 DEG C calcining 5 ~ 6h, obtains the Graphene-MCM-41 complex load hematite catalyst that heating crystallization legal system of the present invention is standby; be designated as JH-gh-MCM-41-Fe (wherein JH represents that preparation method is heating crystallization method, and gh represents Graphene).
The present invention is another aspect more specifically, heterogeneous fenton catalyst of the present invention is that the method by comprising the following steps is obtained: part by weight, 4 ~ 6 parts of bromohexadecane base trimethylamines (CTAB) are added in 100 ~ 150 parts of deionized waters, heat 40 DEG C of 300 ~ 360r/min stirring and dissolving, adding 10 ~ 40 parts of concentration is the graphene oxide solution of 7.75mg/L, 300 ~ 360r/min stirs 15 ~ 30min mixing, add 10 ~ 15 parts of concentrated ammonia liquors, regulate pH to 9 ~ 11, form grey black gelatinous mixture; Add 8 ~ 12 parts of ethyl orthosilicates (TEOS), 300 ~ 360r/min mechanical agitation, reflux heating 100 ~ 130 DEG C carries out ageing 16 ~ 36h, obtains black mixture; Room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection 500 ~ 700 DEG C calcining 4 ~ 6h, obtains Graphene Modified MCM-41 carrier; Get 1 part of above-mentioned carrier leaching and put metallic iron compound; concussion; ultrasonic; filter; drying, afterwards through nitrogen protection 550 DEG C calcining 5 ~ 6h, obtains the Graphene-MCM-41 complex load hematite catalyst that reflux heating legal system of the present invention is standby; be designated as HL-gh-MCM-41-Fe (wherein HL represents that preparation method is reflux heating method, and gh represents Graphene).
In the preparation method of heterogeneous fenton catalyst of the present invention, silicon source, template and graphene oxide solution can be made to react under heating crystallization condition, also silicon source, template and graphene oxide solution can be made to react under reflux heating condition, graphene oxide dosage and Fe(NO3)39H2O dosage can be adjusted as required, heating-up temperature and crystallization time can also be controlled, reflux temperature and digestion time can also be controlled.Preferred catalyst of the present invention is: adulterated to molecular sieve MCM-41 by Graphene by fabricated in situ thermal reduction; obtain Graphene-mesoporous MCM-41 complex; then iron nitrate solution is put in leaching; concussion; ultrasonic; filter; dry; afterwards through nitrogen protection 550 DEG C calcining 5 ~ 6h; obtain Graphene of the present invention-heterogeneous fenton catalyst of mesoporous MCM-41 load bloodstone; be designated as the standby catalysis material JH-gh-MCM-41-Fe of heating crystallization legal system and the standby catalysis material HL-gh-MCM-41-Fe of reflux heating legal system respectively, be black solid powder.
The present inventor examines the catalytic effect of heterogeneous fenton catalyst of the present invention, find and H
2o
2under existent condition, catalyst of the present invention can remove the organic pollution (particularly phenol, nitrogen heterocyclic ring etc.) in water fast, and excellent catalytic effect, shortens the reaction time, decrease iron stripping, and effectively can reduce COD and TOC in waste water simultaneously.Therefore be a kind of heterogeneous Fenton's reaction catalyst of better performances.
Accompanying drawing explanation
Fig. 1 is the SEM SEM picture group of JH-gh-MCM-41-Fe, HL-gh-MCM-41-Fe.
Fig. 2 is the infrared Fourier picture group of JH-gh-MCM-41-Fe, JH-gh-MCM-41 and graphene oxide.
Fig. 3 is the X-ray diffraction picture group of JH-gh-MCM-41-Fe, JH-gh-MCM-41, MCM-41-Fe and MCM-41.
Fig. 4 is the X-ray diffraction picture group of JH-gh-MCM-41-Fe, HL-gh-MCM-41-Fe graphene oxide.
Fig. 5 is JH-gh-MCM-41-Fe/H
2o
2and MCM-41-Fe/H
2o
2heterogeneous Fenton-like system catalytic degradation water body phenol curve map over time.
Fig. 6 is JH-gh-MCM-41-Fe/H
2o
2and MCM-41-Fe/H
2o
2heterogeneous Fenton-like system catalytic degradation water body quinoline curve map over time.
Fig. 7 is HL-gh-MCM-41-Fe/H
2o
2and MCM-41-Fe/H
2o
2heterogeneous Fenton-like system catalytic degradation water body phenol curve map over time.
Fig. 8 is JH-gh-MCM-41-Fe/H
2o
2and MCM-41-Fe/H
2o
2heterogeneous Fenton-like system catalytic degradation water body phenol COD clearance curve map over time.
Fig. 9 is JH-gh-MCM-41-Fe/H
2o
2and MCM-41-Fe/H
2o
2heterogeneous Fenton-like system catalytic degradation water body phenol TOC clearance curve map over time.
Detailed description of the invention
Following example is non-limiting implementation of the present invention.Providing of these embodiments is only for illustrative purposes, and should not be construed as limitation of the present invention.It will be understood by those skilled in the art that and without departing from the spirit and scope of the present invention, many changes and adjustment can be carried out to the present invention, and do not depart from object of the present invention, spirit and scope.In description of the present invention and following instance, unless stated otherwise, concentration used is all percetage by weight.
Preparation embodiment
The preparation method of heterogeneous fenton catalyst of the present invention is described for following embodiment:
First by fabricated in situ thermal reduction, Graphene is carried out modification to MCM-41; obtain Graphene-mesoporous MCM-41 complex; then iron nitrate solution is put in leaching; concussion; ultrasonic; filter; dry; afterwards through nitrogen protection high-temperature calcination; thus obtain the heterogeneous Fenton catalysis material of the three based on Graphene-mesoporous MCM-41-bloodstone of the present invention combination, be designated as the standby catalysis material JH-gh-MCM-41-Fe of heating crystallization legal system and the standby catalysis material HL-gh-MCM-41-Fe of reflux heating legal system respectively.
The preparation method of described catalysis material JH-gh-MCM-41-Fe is: part by weight, 6 ~ 10 parts of sodium metasilicate being heated 40 DEG C is dissolved in 20 ~ 30 parts of deionizations, with 3M sulphur acid for adjusting pH be 8 ~ 10,300 ~ 360r/min stir 0.5h, make solution become viscous gel shape; Add 4 ~ 6 parts of bromohexadecane base trimethylamines (CTAB), 10 ~ 40 parts of concentration are the graphene oxide solution of 7.75mg/L, and 300 ~ 360r/min stirs 4 ~ 6h to forming grey black gelatinous mixture; Put it in reactor and heat 100 ~ 130 DEG C of crystallization 16 ~ 36h, room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection 500 ~ 700 DEG C calcining 4 ~ 6h, obtains Graphene-MCM-41 complex JH-gh-MCM-41; Get 1 part of above-mentioned complex leaching and put metallic iron compound, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection 550 DEG C calcining 5 ~ 6h, obtain the JH-gh-MCM-41-Fe catalysis material of heating crystallization method of the present invention.
The preparation method of described catalysis material HL-MCM-41-Fe is: part by weight, 4 ~ 6 parts of bromohexadecane base trimethylamines (CTAB) are added in 100 ~ 150 parts of deionized waters, heat 40 DEG C of 300 ~ 360r/min stirring and dissolving, adding 10 ~ 40 parts of concentration is the graphene oxide solution of 7.75mg/L, 300 ~ 360r/min stirs 15 ~ 30min mixing, add 10 ~ 15 parts of concentrated ammonia liquors, regulate pH to 9 ~ 11, form grey black gelatinous mixture; Add 8 ~ 12 parts of ethyl orthosilicates (TEOS), 300 ~ 360r/min mechanical agitation, reflux heating 100 ~ 130 DEG C carries out ageing 16 ~ 36h, obtains black mixture; Room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection 500 ~ 700 DEG C calcining 4 ~ 6h, obtains Graphene-MCM-41 complex HL-MCM-41; Get 1 part of above-mentioned complex leaching and put metallic iron compound, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection 550 DEG C calcining 5 ~ 6h, obtain the HL-gh-MCM-41-Fe catalysis material of reflux heating method of the present invention.
Graphene oxide can be obtained by commercially available purchase, or also prepares by following illustrative methods.
The preparation method of described graphene oxide solution: adopt the Hummers method revised, takes 4g 32 order expansible graphite and the mixing of 2g sodium nitrate, measures 80ml 98%H
2sO
4join in said mixture, ice bath, with 350r/min mechanical agitation 5min, slowly add 12g potassium permanganate wherein, stir 15min, remove ice bath, be warming up to 35 DEG C, reaction 4 ~ 6h; Continue to be warming up to 97 DEG C, slowly add the ultra-pure water of 150ml wherein, after reaction 15min, add 200ml deionized water; In above-mentioned mixed solution, add at a slow speed 40ml 30% hydrogen peroxide until solution colour becomes golden yellow, stir 15min; Preparation 900ml 5%HCl solution, with the above-mentioned golden yellow mixed solution twice of this hydrochloric acid solution cleaning, then uses the above-mentioned golden yellow mixed solution of 1000ml washed with de-ionized water three times; Above-mentioned golden yellow mixed solution is carried out 7000 ~ 8000r/min high speed centrifugation, the dark yellow dope obtained is joined in 450ml deionized water, ultrasonic 30min ~ the 60min of 100W, the mixed solution obtained is carried out 7000r/min high speed centrifugation, get upper solution, be described graphene oxide solution, concentration is 7.75mg/ml.
The mesoporous supports MCM-41 of Experimental comparison's material in contrast, its preparation method is: part by weight, get 4.8 parts of bromohexadecane base trimethylamines (CTAB) to join in 200 ~ 250 parts of deionized waters and carry out heating 40 DEG C of 300 ~ 360r/min stirring and dissolving, 20 ~ 25 parts of concentrated ammonia liquors are dripped in gained solution, regulate pH to 10 ~ 11, dropwise add 20 ~ 25 parts of ethyl orthosilicates (TEOS), 300 ~ 360r/min mechanical agitation, 4 ~ 6h, obtain off-white color mixing suspension, still aging 1 ~ 2day, filtration obtains white depositions, 105 DEG C of bulging hot-air seasonings, pulverize last in Muffle furnace air atmosphere 550 DEG C calcining 5 ~ 6h, obtain mesoporous supports MCM-41.
The catalysis material MCM-41-Fe of Experimental comparison's material in contrast, its preparation method is: part by weight, take 1 part of above-mentioned MCM-41 carrier leaching and put metallic iron compound, concussion, ultrasonic, filter, dry, place 550 DEG C of calcining 5 ~ 6h in Muffle furnace air atmosphere afterwards, obtain MCM-41-Fe catalysis material.
1. the structure of catalyst material and constituent analysis
The catalysis material (JH-gh-MCM-41-Fe and HL-gh-MCM-41-Fe) obtained in above-mentioned preparation embodiment is carried out the analysis of SEM electron-microscope scanning, all pick and place the SEM scanning electron microscope (SEM) photograph of large 100,000 times, result as shown in Figure 1, the mesoporous supports MCM-41 of two kinds of catalysis materials is all by Graphene modification, catalysis material is the distribution of independent uniform particles, the flaky graphite alkene of not independent distribution, illustrates that Graphene is uniformly doped and form Graphene-MCM-41 complex in mesoporous supports MCM-41.Wherein JH-gh-MCM-41-Fe particle size is less than the particle size of HL-gh-MCM-41-Fe and be more evenly distributed, and the Graphene distribution be doped is more even.
The catalysis material JH-gh-MCM-41-Fe, catalyst carrier gh-MCM-41 and the graphene oxide that obtain in above-mentioned preparation embodiment are carried out Fourier infrared (FTIR) to analyze, result as shown in Figure 2, in the FTIR spectrogram of catalysis material JH-gh-MCM-41-Fe and catalyst complex carrier gh-MCM-41, the characteristic peak of all oxygen-containing functional groups (C=O, O-H, C-OH and C-O-C) almost all disappears or greatly weakens, the wherein O-H characteristic absorption peak 3425 ~ 3198cm of graphene oxide
-1, C-H characteristic absorption peak 2912 ~ 2850cm
-1, C-O characteristic absorption peak 1720cm
-1, O-H & C=C characteristic absorption peak 1625cm
-1, C-O characteristic absorption peak 1401 ~ 1181cm
-1all all disappear in the FTIR spectrogram of catalysis material JH-gh-MCM-41-Fe and catalyst complex carrier gh-MCM-41 or greatly weaken, confirm that Graphene is incorporated in mesostructured material, form Graphene modified mesoporous molecular sieve, i.e. Graphene-MCM-41 complex.
The catalysis material JH-gh-MCM-41-Fe obtained in above-mentioned preparation embodiment and the Graphene-MCM-41 complex JH-gh-MCM-41, the catalysis material MCM-41-Fe and mesoporous supports MCM-41 that are used for comparing are carried out X-ray diffraction spectrogram (XRD) analysis, result as shown in Figure 3, four kinds of materials have a main peak in 2 θ=15 ~ 30 °, are SiO
2characteristic absorption peak, Graphene before modified after MCM-41 carrier and JH-gh-MCM-41 modification complex XRD spectra basically identical, illustrate that Graphene is to the doping of MCM-41 and modification, do not change basic structure and the pore morphology of MCM-41 carrier, illustrate that the basic structure of Graphene-MCM-41 complex and pore morphology are still basic structure and the pore morphology of MCM-41 carrier.The catalysis material JH-gh-MCM-41-Fe prepared after putting method load trivalent iron salt by leaching has two weak absorbing peaks in 2 θ=30 ~ 35 °, is bloodstone (a-Fe
2o
3) characteristic absorption peak, illustrate that iron nitrate solution is put in Graphene-MCM-41 complex JH-gh-MCM-41 leaching and trivalent iron salt generates bloodstone crystal formation (a-Fe after nitrogen atmosphere protection high-temperature calcination
2o
3) and finishing is surperficial in Graphene-MCM-41 complex JH-gh-MCM-41, and the bloodstone (a-Fe formed
2o
3) brilliant complete and tiny, be evenly distributed.The catalysis material MCM-41-Fe prepared after putting iron nitrate solution for mesoporous supports MCM-41 leaching, it has the weak absorbing peak moved after in 2 θ=35 ~ 37 °, be also a-Fe
2o
3characteristic absorption peak, the shaping integrality of brilliant growth is not so good as catalysis material JH-gh-MCM-41-Fe with the uniformity of distribution.The Graphene being used for carrier MCM-41 being carried out to doping and modification is described, for bloodstone (a-Fe
2o
3) growth of brilliant plays favourable facilitation with being uniformly distributed.
Catalysis material JH-gh-MCM-41-Fe and HL-gh-MCM-41-Fe obtained in above-mentioned preparation embodiment and graphene oxide are carried out X-ray diffraction spectrogram (XRD) analysis, result as shown in Figure 4,2 θ=10 ~ 15 ° are the characteristic absorption peak of graphene oxide, all almost disappear completely in above-mentioned two kinds of catalysis materials, illustrate that the graphene oxide be doped in MCM-41 carrier synthesizes in thermal reduction process in position and be reduced to Graphene and by doping, modification carried out thus formation Graphene-MCM-41 complex to MCM-41.All there is weak absorbing peak in 2 θ=30 ~ 37 ° in the catalysis material that two kinds of different preparation methods obtain, is a-Fe
2o
3characteristic absorption peak, but the a-Fe of catalysis material JH-gh-MCM-41-Fe load
2o
3integrality and the distributing homogeneity of brilliant growth are all better than HL-gh-MCM-41-Fe.
2. Graphene modified mesoporous molecular sieve carried metal iron composite material is as the catalytic activity of heterogeneous fenton catalyst
(2.1) JH-gh-MCM-41-Fe/H
2o
2the removal effect of heterogeneous Fenton-like system catalytic degradation water body phenol and quinoline
(2.1.1) the preparation embodiment of catalysis material JH-gh-MCM-41-Fe
8 parts of sodium metasilicate are heated 40 DEG C and are dissolved in 25 parts of deionizations by part by weight, be that 9 ~ 10,360r/min stirs 0.5h, make solution become viscous gel shape with 3M sulphur acid for adjusting pH; Add 6 parts of bromohexadecane base trimethylamines (CTAB), 30 parts of concentration are the graphene oxide solution of 7.75mg/L, and 360r/min stirs 5h to forming grey black gelatinous mixture; Put it in reactor and heat 130 DEG C of crystallization 24h, room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection 550 DEG C calcining 6h, obtains Graphene-MCM-41 complex JH-gh-MCM-41; Taking 0.3670 part of Fe(NO3)39H2O is dissolved in 20ml ethanol water (1: 1v%); Take 1 part of above-mentioned complex JH-gh-MCM-41 leaching and be placed in above-mentioned ferric salt solution, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection 550 DEG C calcining 6h, obtain the catalysis material JH-gh-MCM-41-Fe of heating crystallization method of the present invention.Recording above-mentioned complex JH-gh-MCM-41 specific area (BET) is 546.778m
2/ g, aperture is 3.081nm; Recording catalysis material JH-gh-MCM-41-Fe specific area (BET) is 521.228m
2/ g, aperture is 2.745nm.
(2.1.2) the preparation embodiment of catalysis material MCM-41-Fe
In order to carry out the comparison of catalysis efficiency, preparing the catalysis material MCM-41-Fe not adding Graphene simultaneously and having compared.
The preparation method of catalysis material MCM-41-Fe:
Part by weight, get 4.8 parts of bromohexadecane base trimethylamines (CTAB) to join in 240 parts of deionized waters and carry out heating 40 DEG C of 360r/min stirring and dissolving, 25 parts of concentrated ammonia liquors are dripped in gained solution, regulate pH to 10 ~ 11, dropwise add 24 parts of ethyl orthosilicates (TEOS), 360r/min mechanical agitation 4h, obtain off-white color mixing suspension, still aging 36h, filtration obtains white depositions, 105 DEG C of bulging hot-air seasonings, pulverize last in Muffle furnace air atmosphere 550 DEG C calcining 6h, obtain mesoporous supports MCM-41; Taking 0.3662 part of Fe(NO3)39H2O is dissolved in 20ml ethanol water (1: 1v%); Take 1 part of carrier MCM-41 leaching and be placed in above-mentioned ferric salt solution, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection 550 DEG C calcining 6h, obtain catalysis material MCM-41-Fe.Recording this catalysis material specific area (BET) is 684.983m
2/ g, aperture is 4.970nm.
(2.1.3) catalysis material JH-gh-MCM-41-Fe is as the embodiment of the method for heterogeneous fenton catalyst catalytic degradation water body phenol
Configuration 200ml initial concentration be the phenol solution of 100mg/L in the there-necked flask of 250mL as simulative organic wastewater, HCl and NaOH of 0.1M is used to regulate reaction solution pH to be 3.5, add 0.1g catalysis material wherein, stir 30min to make after catalysis material reaches adsorption equilibrium (phenol clearance is 5.15%), to add H
2o
2and make water body H
2o
2initial concentration is 10mM, starts clock reaction.Overall reaction is 210min, samples at regular intervals and instills 1 0.1M NaOH stopped reaction.The filtrate obtained is adopted high performance liquid chromatograph analysis of Phenol content (result as shown in Figure 5), and adopt spectrophotometric determination o-phenanthroline iron stripping concentration, calculate clearance and the iron stripping concentration (the results are shown in Table 1) of phenol.
From Fig. 5 and table 1, the catalysis material JH-gh-MCM-41-Fe added after Graphene shortens the reaction time of phenol degrading, in the reaction 15min moment, the clearance of JH-gh-MCM-41-Fe catalytic degradation phenol reaches 91.20%, far above the phenol degrading rate (4.57%) of MCM-41-Fe; Correspondingly, react the 210min moment, the iron stripping of catalysis material JH-gh-MCM-41-Fe reduces 53.4% than MCM-41-Fe, and iron stripping decreases.Illustrate that Graphene enhances the heterogeneous Fenton's reaction catalytic effect of catalyst of the present invention to the doping of MCM-41 and modification, better decrease iron stripping.
Table 1JH-gh-MCM-41-Fe/H
2o
2system and MCM-41-Fe/H
2o
2system compares the effect of water body phenol degrading and iron stripping concentration results
In addition, because carrier MCM-41 and Graphene-MCM-41 complex JH-MCM-41 does not have supported active metals, so the catalytic effect of its heterogeneous Fenton's reaction is very poor; Catalytic active component gh-Fe
2o
3(gh represents Graphene), when adding same amount, the active component amount ratio of Kaolinite Preparation of Catalyst was comparatively large, and cost significantly improves, and using Graphene as carrier, expensive, active component can not obtain abundant efficiency utilization owing to not having carrier.Therefore, Graphene, mesostructured material, bloodstone (a-Fe in catalyst JH-gh-MCM-41-Fe of the present invention
2o
3) Graphene-mesostructured material complex surfaces that formed of triplicity modifies bloodstone catalysis material, its heterogeneous Fenton's reaction catalytic degradation effect is better than binary combination material and unitary material; In catalysis material of the present invention, the combination of Graphene, mesostructured material and bloodstone shows good chemiluminescence in heterogeneous Fenton catalytic degradation reaction system.
(2.1.4) catalysis material JH-gh-MCM-41-Fe is as the embodiment of the method for heterogeneous fenton catalyst catalytic degradation water body quinoline
Configuration 200ml initial concentration be the quinoline solution of 50mg/L in the there-necked flask of 250mL as simulative organic wastewater, HCl and NaOH of 0.1M is used to regulate reaction solution pH to be 3.5, add 0.1g catalysis material wherein, stir 30min to make after catalysis material reaches adsorption equilibrium (quinoline clearance is 6.63%), to add H
2o
2and make water body H
2o
2initial concentration is 10mM, starts clock reaction.Overall reaction is 150min, samples at regular intervals and instills 1 0.1M NaOH stopped reaction.The filtrate obtained is adopted efficient liquid phase chromatographic analysis isoquinoline level (result as shown in Figure 6), and adopts spectrophotometric determination o-phenanthroline iron stripping concentration, calculate clearance and the iron stripping concentration (the results are shown in Table 2) of quinoline.
From Fig. 6 and table 2, the catalysis material JH-gh-MCM-41-Fe added after Graphene shortens the reaction time of quinoline-degrading, in the reaction 60min moment, the clearance of JH-gh-MCM-41-Fe catalytic degradation quinoline reaches 80.80%, far above the quinoline-degrading rate (21.46%) of MCM-41-Fe; Correspondingly, react the 150min moment, the iron stripping of catalysis material JH-gh-MCM-41-Fe reduces 59.8% than MCM-41-Fe, and iron stripping decreases.Illustrate that Graphene enhances the heterogeneous Fenton's reaction catalytic effect of catalyst of the present invention to the doping of MCM-41 and modification, better decrease iron stripping.
Table 2JH-gh-MCM-41-Fe/H
2o
2system and MCM-41-Fe/H
2o
2system compares the effect of water body quinoline-degrading and iron stripping concentration results
(2.2) HL-gh-MCM-41-Fe/H
2o
2the removal effect of heterogeneous Fenton-like system catalytic degradation water body phenol
(2.2.1) the preparation embodiment of catalysis material HL-gh-MCM-41-Fe:
Part by weight, 6 parts of bromohexadecane base trimethylamines (CTAB) are added in 150 parts of deionized waters, heat 40 DEG C of 320r/min stirring and dissolving, adding 35 parts of concentration is the graphene oxide solution of 7.75mg/L, 360r/min stirs 25min mixing, add 15 parts of concentrated ammonia liquors, regulate pH to 10 ~ 11, form grey black gelatinous mixture; Add 10 parts of ethyl orthosilicates (TEOS), 360r/min mechanical agitation, reflux heating 120 DEG C carries out ageing 24h, obtains black mixture; Room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection 550 DEG C calcining 5.5h, obtains Graphene-MCM-41 complex HL-gh-MCM-41; Taking 0.3645 part of Fe(NO3)39H2O is dissolved in 20ml ethanol water (1: 1v%); Get 1 part of above-mentioned complex leaching and be placed in above-mentioned ferric salt solution, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection 550 DEG C calcining 6h, obtain the HL-gh-MCM-41-Fe catalysis material of reflux heating method of the present invention.Recording above-mentioned complex HL-gh-MCM-41 specific area (BET) is 556.705m
2/ g, aperture is 3.165nm; Recording catalysis material HL-gh-MCM-41-Fe specific area (BET) is 549.304m
2/ g, aperture is 2.939nm.
(2.2.2) the preparation embodiment of catalysis material MCM-41-Fe
In order to carry out the comparison of catalysis efficiency, preparing the catalysis material MCM-41-Fe not adding Graphene simultaneously and having compared.
The preparation method of catalysis material MCM-41-Fe:
Part by weight, get 4.8 parts of bromohexadecane base trimethylamines (CTAB) to join in 240 parts of deionized waters and carry out heating 40 DEG C of 360r/min stirring and dissolving, 25 parts of concentrated ammonia liquors are dripped in gained solution, regulate pH to 10 ~ 11, dropwise add 24 parts of ethyl orthosilicates (TEOS), 360r/min mechanical agitation 4h, obtain off-white color mixing suspension, still aging 36h, filtration obtains white depositions, 105 DEG C of bulging hot-air seasonings, pulverize last in Muffle furnace air atmosphere 550 DEG C calcining 6h, obtain mesoporous supports MCM-41; Taking 0.3662 part of Fe(NO3)39H2O is dissolved in 20ml ethanol water (1: 1v%); Take 1 part of carrier MCM-41 leaching and be placed in above-mentioned ferric salt solution, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection 550 DEG C calcining 6h, obtain catalysis material MCM-41-Fe.Recording this catalysis material specific area (BET) is 684.983m
2/ g, aperture is 4.970nm.
(2.2.3) catalysis material HL-gh-MCM-41-Fe is as the embodiment of the method for heterogeneous fenton catalyst catalytic degradation water body phenol
Configuration 200ml initial concentration be the phenol solution of 100mg/L in the there-necked flask of 250mL as simulative organic wastewater, HCl and NaOH of 0.1M is used to regulate reaction solution pH to be 3.5, add 0.1g catalysis material wherein, stir 30min to make after catalysis material reaches adsorption equilibrium (phenol clearance is 7.57%), to add H
2o
2and make water body H
2o
2initial concentration is 10mM, starts clock reaction.Overall reaction is 210min, samples at regular intervals and instills 1 0.1M NaOH stopped reaction.The filtrate obtained is adopted efficient liquid phase chromatographic analysis phenol content (result as shown in Figure 7), and adopts spectrophotometric determination o-phenanthroline iron stripping concentration, calculate clearance and the iron stripping concentration (the results are shown in Table 3) of phenol.
From Fig. 7 and table 3, the catalysis material HL-gh-MCM-41-Fe added after Graphene shortens the reaction time of phenol degrading degraded, in the reaction 30min moment, the clearance of HL-gh-MCM-41-Fe catalytic degradation phenol reaches 91.08%, far above the phenol degrading rate (8.05%) of MCM-41-Fe; Correspondingly, react the 210min moment, the iron stripping of catalysis material HL-gh-MCM-41-Fe reduces 46.2% than MCM-41-Fe, and iron stripping decreases.Illustrate that Graphene enhances the heterogeneous Fenton's reaction catalytic effect of catalyst of the present invention to the doping of MCM-41 and modification, better decrease iron stripping.
Table 3HL-gh-MCM-41-Fe/H
2o
2system and MCM-41-Fe/H
2o
2system is to the effect of water body phenol degrading and iron stripping concentration results
(2.3) JH-gh-MCM-41-Fe/H
2o
2cOD and the TOC removal effect of heterogeneous Fenton-like system catalytic degradation phenol water body
(2.3.1) the preparation embodiment of catalysis material JH-gh-MCM-41-Fe
8 parts of sodium metasilicate are heated 40 DEG C and are dissolved in 25 parts of deionizations by part by weight, be that 9 ~ 10,360r/min stirs 0.5h, make solution become viscous gel shape with 3M sulphur acid for adjusting pH; Add 6 parts of bromohexadecane base trimethylamines (CTAB), 30 parts of concentration are the graphene oxide solution of 7.75mg/L, and 360r/min stirs 5h to forming grey black gelatinous mixture; Put it in reactor and heat 130 DEG C of crystallization 24h, room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection 550 DEG C calcining 6h, obtains Graphene-MCM-41 complex JH-gh-MCM-41; Taking 0.3670 part of Fe(NO3)39H2O is dissolved in 20ml ethanol water (1: 1v%); Take 1 part of above-mentioned complex JH-gh-MCM-41 leaching and be placed in above-mentioned ferric salt solution, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection 550 DEG C calcining 6h, obtain the catalysis material JH-gh-MCM-41-Fe of heating crystallization method of the present invention.Recording above-mentioned complex JH-gh-MCM-41 specific area (BET) is 546.778m
2/ g, aperture is 3.081nm; Recording catalysis material JH-gh-MCM-41-Fe specific area (BET) is 521.228m
2/ g, aperture is 2.745nm.
(2.3.2) the preparation embodiment of catalysis material MCM-41-Fe
In order to carry out the comparison of catalysis efficiency, preparing the catalysis material MCM-41-Fe not adding Graphene simultaneously and having compared.
The preparation method of catalysis material MCM-41-Fe:
Part by weight, get 4.8 parts of bromohexadecane base trimethylamines (CTAB) to join in 240 parts of deionized waters and carry out heating 40 DEG C of 360r/min stirring and dissolving, 25 parts of concentrated ammonia liquors are dripped in gained solution, regulate pH to 10 ~ 11, dropwise add 24 parts of ethyl orthosilicates (TEOS), 360r/min mechanical agitation 4h, obtain off-white color mixing suspension, still aging 36h, filtration obtains white depositions, 105 DEG C of bulging hot-air seasonings, pulverize last in Muffle furnace air atmosphere 550 DEG C calcining 6h, obtain mesoporous supports MCM-41; Taking 0.3662 part of Fe(NO3)39H2O is dissolved in 20ml ethanol water (1: 1v%); Take 1 part of carrier MCM-41 leaching and be placed in above-mentioned ferric salt solution, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection 550 DEG C calcining 6h, obtain catalysis material MCM-41-Fe.Recording this catalysis material specific area (BET) is 684.983m
2/ g, aperture is 4.970nm.
(2.3.3) catalysis material JH-gh-MCM-41-Fe reduces the embodiment of the method for phenol water body COD and TOC as heterogeneous fenton catalyst
Configuration 200ml initial concentration be the phenol solution of 100mg/L in the there-necked flask of 250mL as simulative organic wastewater, HCl and NaOH of 0.1M is used to regulate reaction solution pH to be 3.5, add 0.1g catalysis material wherein, stir 30min and make after catalysis material reaches adsorption equilibrium, to add H
2o
2and make water body H
2o
2concentration is 10mM, starts clock reaction.Overall reaction is 90min, samples at regular intervals and instills 1 0.1M NaOH stopped reaction.The filtrate obtained is carried out COD and TOC to measure, calculate phenol water body COD and TOC clearance in reaction system, the results are shown in Figure 8 and Fig. 9.
From Fig. 8 and Fig. 9, the catalysis material JH-gh-MCM-41-Fe added after Graphene shortens the reaction time of phenol degrading, in the reaction 90min moment, phenol water body COD and TOC is reduced to 38.04% and 61.11% respectively, itself COD and TOC clearance is all far above COD and the TOC clearance (being respectively 18.52% and 14.68%) of MCM-41-Fe simultaneously.Illustrate that Graphene enhances the heterogeneous Fenton's reaction catalytic effect of catalyst of the present invention to the doping of MCM-41 and modification, promote that it reduces COD and the TOC value of polluted-water preferably simultaneously.
Claims (10)
1. a heterogeneous fenton catalyst, it comprises mesoporous supports, and described mesoporous supports forms Graphene-mesoporous supports complex by doped graphene, and this complex surfaces is modified by bloodstone.
2. heterogeneous fenton catalyst according to claim 1, wherein said mesoporous supports is selected from MCM-41.
3. heterogeneous fenton catalyst according to claim 1 and 2; it is that method by comprising the following steps is obtained: be doped in MCM-41 carrier by fabricated in situ thermal reduction by Graphene; form Graphene-mesoporous MCM-41 complex; then method area load ferric iron is put by leaching; through nitrogen atmosphere protection high-temperature calcination, trivalent iron salt generates bloodstone (α-Fe
2o
3) crystal formation, form Graphene-MCM-41 complex load bloodstone.
4. the heterogeneous fenton catalyst according to any one of claim 1-3, wherein said trivalent iron salt is selected from Fe(NO3)39H2O.
5. the heterogeneous fenton catalyst according to any one of claim 3-4, it is that method by comprising the following steps is obtained: silicon source solution, template (bromohexadecane base trimethylamine) and graphene oxide solution are mixed, adjust ph, heating crystallization or utilize reflux heating mode to carry out ageing in a kettle., cooling, filter, washing, dry, by the black powdery solid high-temperature calcination under nitrogen protection obtained, obtain Graphene and be doped in complex carrier in mesoporous MCM-41 structure; Get 1 part of above-mentioned complex carrier leaching and put trivalent iron salt, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection high-temperature calcination, obtain Graphene-MCM-41 complex load hematite catalyst of the present invention.
6. the heterogeneous fenton catalyst according to any one of claim 3-4, it is that method by comprising the following steps is obtained: part by weight, by 6 ~ 10 parts of sodium metasilicate heating for dissolving in 20 ~ 30 parts of deionizations, be 8 ~ 10 with acid for adjusting pH, stir and make solution become viscous gel shape; Add 4 ~ 6 parts of bromohexadecane base trimethylamines (CTAB), 10 ~ 40 parts of graphene oxide solution, be stirred to and form grey black gelatinous mixture; Put it into heating crystallization in reactor, room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection high-temperature calcination, obtains Graphene Modified MCM-41 carrier; Get 1 part of above-mentioned carrier leaching and put trivalent iron salt, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection high-temperature calcination, obtain heating crystallization legal system of the present invention standby Graphene-MCM-41 complex load hematite catalyst.
7. the heterogeneous fenton catalyst according to any one of claim 3-4, it is that method by comprising the following steps is obtained: part by weight, 4 ~ 6 parts of bromohexadecane base trimethylamines (CTAB) are added in 100 ~ 150 parts of deionized waters, heating stirring and dissolving, add 10 ~ 40 parts of graphene oxide solution, stir and evenly mix, add 10 ~ 15 parts of concentrated ammonia liquors, regulate pH to 9 ~ 11, form grey black gelatinous mixture; Add 8 ~ 12 parts of ethyl orthosilicates (TEOS), mechanical agitation, adopt reflux heating mode to carry out ageing, obtain black mixture; Room temperature cools, and filters, and washing is dry, obtains black powdery solid, and through nitrogen protection high-temperature calcination, obtains Graphene Modified MCM-41 carrier; Get 1 part of above-mentioned carrier leaching and put trivalent iron salt, concussion, ultrasonic, filter, dry, afterwards through nitrogen protection high-temperature calcination, obtain reflux heating legal system of the present invention standby Graphene-MCM-41 complex load hematite catalyst.
8. the purposes of the heterogeneous fenton catalyst according to any one of claim 1-7 in process water in persistent organic pollutants.
9. the purposes of the heterogeneous fenton catalyst according to any one of claim 1-7 in process water pollutant phenol or quinoline.
10. the purposes of the heterogeneous fenton catalyst according to any one of claim 1-7 in process water pollutant phenol.
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Application publication date: 20141224 |