CN105233827A - Supported hollow graphene microsphere catalyst and preparation method and application thereof - Google Patents
Supported hollow graphene microsphere catalyst and preparation method and application thereof Download PDFInfo
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- CN105233827A CN105233827A CN201510708931.1A CN201510708931A CN105233827A CN 105233827 A CN105233827 A CN 105233827A CN 201510708931 A CN201510708931 A CN 201510708931A CN 105233827 A CN105233827 A CN 105233827A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000004005 microsphere Substances 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 48
- 239000010439 graphite Substances 0.000 claims abstract description 48
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 16
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 16
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000007921 spray Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- -1 graphite alkene Chemical class 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000001694 spray drying Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a hollow graphene microsphere catalyst loaded with metal oxide, which is prepared by the following method: firstly, adding graphite oxide into deionized water, performing ultrasonic dispersion to form a graphene oxide dispersion liquid, then adding ascorbic acid, performing ultrasonic treatment, then reducing to obtain a graphene dispersion liquid, then adding a compound containing metal ions, placing the obtained graphene dispersion liquid doped with the metal ions into a spray dryer, performing spray drying, and collecting a solid obtained by spray drying, namely the catalyst; the catalyst can be applied to catalyzing organic pollutants in hydrogen peroxide to be oxidized and degraded; the method is simple, easy to operate and suitable for large-scale production, and the prepared catalyst has excellent performance.
Description
(1) technical field
The present invention relates to a kind of metal oxide-loaded hollow graphite alkene microspherical catalyst and preparation method thereof and application.
(2) background technology
Graphene is a kind of new material of the individual layer laminated structure be made up of carbon atom.A kind of by carbon atom SP
2the hexagon of hybridized orbit composition is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Novoselov in 2004 etc. utilize adhesive tape micromechanics to peel off highly oriented pyrolytic graphite and obtain self-existent Graphene.Along with the research to Graphene further deeply, the both sides finding its planar structure all can carrying metal particle, and the carrier material as catalyst is more promising.Compared with other material with carbon elements, Graphene is made up of the most stable phenyl ring, is plane polycyclic aromatic hydrocarbons (PAH) atomic crystal, has larger theoretical specific surface area and (is about 2630m
2g
-1) and better electron transport ability (be about 2 × 10
5cm
2v
-1s
-1), be more suitable for the carrier making catalyst.Different with other carriers, Graphene, due to its superior electric conductivity, except the application in fuel cell, also has the purposes of its uniqueness in photochemical catalyzing.Research shows: loaded to by semiconductor and Graphene carries out light-catalyzed reaction can improve activity, mainly because electronics can more easily be derived by Graphene participate in reaction.But, in grapheme material prepared by current chemical method graphene sheet layer be all easy to reunite and stacking, this can hinder the transmission of electronics, reduces its electric conductivity.This problem constrains further developing of Graphene carrier to a great extent.
(3) summary of the invention
The invention provides a kind of metal oxide-loaded hollow graphite alkene microspherical catalyst and preparation method thereof, described catalyst can be applicable to catalysis hydrogen peroxide (H
2o
2) in oxidation reaction.Further, carrier hollow graphite alkene microballoon that present invention also offers described catalyst and preparation method thereof.
The graphene dispersing solution being mixed with metal ion prepared is carried out spraying dry by spray drying process by the present invention, the droplet produced can constantly evaporate in spray dryer, can Brownian movement be there is in the graphene sheet layer of the inside, close to gas-liquid interface, form metal oxide-loaded hollow graphite alkene microspherical catalyst.
The present invention adopts following technical scheme:
A metal oxide-loaded hollow graphite alkene microspherical catalyst, described metal oxide-loaded hollow graphite alkene microspherical catalyst prepares as follows:
A graphite oxide is added in deionized water by (), form graphene oxide dispersion in the ultrasonic 1 ~ 3h dispersion of 40 ~ 60Hz; The quality consumption of described graphite oxide counts 2 ~ 6g/L with the volume of deionized water;
B () adds ascorbic acid in step (a) gained graphene oxide dispersion, prior to the ultrasonic 1 ~ 3h of 40 ~ 60Hz, again in 30 ~ 60 DEG C of reduction 8 ~ 24h, obtain graphene dispersing solution, in gained graphene dispersing solution, add the compound containing metal ion, obtain the graphene dispersing solution being mixed with metal ion; The quality consumption of described ascorbic acid counts 2 ~ 10g/L with the volume of graphene oxide dispersion; The quality consumption of the described compound containing metal ion counts 0.5 ~ 1g/L with the volume of graphene dispersing solution; Metallic element in the described compound containing metal ion is the mixing of one or more arbitrary proportions in iron, zinc, copper, manganese, nickel, cobalt;
C the graphene dispersing solution that step (b) gained is mixed with metal ion is placed in spray dryer by (), spray dryer intake air temperature be 230 ~ 250 DEG C, air outlet temperature is 150 ~ 160 DEG C, flow velocity is 12 ~ 20mL/min, drying time be the condition of 1 ~ 1.5s under carry out spraying dry, collect spraying dry gained solid, be described metal oxide-loaded hollow graphite alkene microspherical catalyst.
In step (a) of the present invention, the quality consumption of preferred described graphite oxide counts 3 ~ 5g/L with the volume of deionized water.
In step (b), the quality consumption of preferred described ascorbic acid counts 4 ~ 8g/L with the volume of graphene oxide dispersion.
In step (b), concrete, the described compound containing metal ion can be selected from the mixture of one or more arbitrary proportions in ferric nitrate, copper acetate, manganese acetate, cobalt nitrate, nickel acetate, zinc nitrate.
Metal oxide-loaded hollow graphite alkene microspherical catalyst of the present invention can be applicable to the organic pollution (as: phenol, industrial dye etc.) in catalysis hydrogen peroxide oxidation degradation water; Usually, in the reaction of catalysis hydrogen peroxide oxidation, the quality consumption of described metal oxide-loaded hollow graphite alkene microspherical catalyst is 10% ~ 20% of reaction substrate organic pollution quality.
Present invention also offers a kind of hollow graphite alkene microballoon as described catalyst carrier, described hollow graphite alkene microballoon prepares as follows:
(1) graphite oxide is added in deionized water, forms graphene oxide dispersion in the ultrasonic 1 ~ 3h dispersion of 40 ~ 60Hz; The quality consumption of described graphite oxide counts 2 ~ 6g/L (preferably 3 ~ 5g/L) with the volume of deionized water;
(2) in step (1) gained graphene oxide dispersion, add ascorbic acid, prior to the ultrasonic 1 ~ 3h of 40 ~ 60Hz, then in 30 ~ 60 DEG C of reduction 8 ~ 24h, obtain graphene dispersing solution; The quality consumption of described ascorbic acid counts 2 ~ 10g/L (preferably 4 ~ 8g/L) with the volume of graphene oxide dispersion;
(3) step (2) gained graphene dispersing solution is placed in spray dryer, spray dryer intake air temperature be 230 ~ 250 DEG C, air outlet temperature is 150 ~ 160 DEG C, flow velocity is 12 ~ 20mL/min, drying time be the condition of 1 ~ 1.5s under carry out spraying dry, collect spraying dry gained solid, be described hollow graphite alkene microballoon.
Compared with prior art, the invention has the advantages that:
(1) adopt ascorbic acid to be reducing agent reduction-oxidation graphite, asepsis environment-protecting, and some can be provided to contain oxygen group, to keep the dispersiveness of Graphene in water, and ascorbic acid is cheap;
(2) hollow graphite alkene microspherulite diameter of the present invention is between 2 ~ 5 μm, compared with millimetre-sized at present, size reduces a lot, in addition by controlling the size of the adjustable hollow graphite alkene microballoon of viscosity (viscosity regulates by the concentration of graphene dispersing solution) of graphene dispersing solution, thus can the excellent metal oxide-loaded hollow graphite alkene microspherical catalyst of processability;
(3) prepare support type hollow graphite alkene microspherical catalyst by spray drying process, method is simple, easy to operate, is applicable to large-scale production.
(4) accompanying drawing explanation
Fig. 1 is embodiment 2 gained Fe
2o
3the scanning electron microscope (SEM) photograph of/RGOS microballoon.
Fig. 2 is embodiment 2 gained Fe
2o
3the transmission electron microscope picture of/RGOS microballoon.
Fig. 3 is photocatalysis apparatus figure in embodiment 2.
(5) detailed description of the invention
Below by specific embodiment, the present invention is further detailed, but protection scope of the present invention is not limited in this.
Prepared by embodiment 1RGOS microballoon
(1) be added in 100mL deionized water by 0.4g graphite oxide, in the ultrasonic 2h of 50Hz, then the centrifugal graphite oxide removing bottom and dissociate, obtains graphene oxide dispersion.
(2) be added to by 0.4g ascorbic acid in step (1) gained graphene oxide dispersion, reduce to solution viscosity prior to the ultrasonic 1h of 50Hz, color burn is to black.Again in 30 DEG C of reduction 12h, obtain graphene dispersing solution.
(3) step (2) gained graphene dispersing solution is placed in spray dryer, it is 250 DEG C at spray dryer intake air temperature, air outlet temperature is 160 DEG C, flow velocity is 15mL/min, drying time is carry out spraying dry under the condition of 1s, gained solid in receiving flask, is hollow graphite alkene microballoon 0.2g.
Embodiment 2Fe
2o
3prepared by/RGOS microballoon
(1) be added in 100mL deionized water by 0.4g graphite oxide, in the ultrasonic 2h of 50Hz, then the centrifugal graphite oxide removing bottom and dissociate, obtains graphene oxide dispersion.
(2) be added to by 0.4g ascorbic acid in step (1) gained graphene oxide dispersion, reduce to solution viscosity prior to the ultrasonic 1h of 50Hz, color burn is to black.Again in 30 DEG C of reduction 12h, obtain graphene dispersing solution, in gained graphene dispersing solution, add 0.1g ferric nitrate, obtain the graphene dispersing solution being mixed with iron ion.
(3) graphene dispersing solution step (2) gained being mixed with iron ion is placed in spray dryer, spray dryer intake air temperature be 250 DEG C, air outlet temperature is 160 DEG C, flow velocity is 15mL/min, drying time be the condition of 1s under carry out spraying dry, gained solid in receiving flask, is the hollow graphite alkene microspherical catalyst 0.2g of load ferric oxide particle.
The experimental procedure of Photocatalytic activity dyestuff:
First prepare the reactive gaudy red X 3B dye solution that 0.8L concentration is 100mg/L, be added in homemade glass reactor, and with 0.1M sodium hydroxide solution, X-3B dye solution is regulated pH to 6.0; Then the hollow graphite alkene microspherical catalyst taking the load ferric oxide particle of the above-mentioned preparation of 0.01g joins in dye solution, opens magnetic stirring apparatus, is mixed by catalyst with dye solution.Before photocatalytic degradation experiment is carried out, first reactant liquor is stirred under lucifuge condition 30min to reach the adsorption equilibrium of catalyst, every its characteristic peak absorbance of 10min sampling and measuring in adsorption process; Then open sodium vapor lamp, add 0.9mL30wt%H
2o
2solution, reaction formally starts, by regulating cooling water flow velocity to ensure that temperature maintains 25 ± 2 DEG C in course of reaction.Degradation time is 120min, in photocatalytic oxidation degradation process, draws reactant liquor carry out analytical test according to the time interval of 30min.Water sample to be measured surveys its absorbance with visible spectrophotometer after 0.45 μm of micropore acetate fiber membrane filtration.
The change of dye strength is measured according to the change of absorption peak strength under different dyes characteristic wavelength in experiment.
Adopt ultraviolet-visible spectrophotometer to carry out full wavelength scanner to dyestuff in experiment, and measure the absorption peak under its characteristic wavelength, calculate dye decolored rate by following formula: D=(1-A
t/ A
0) × 100%, A in formula
0, A
tbe respectively before light-catalyzed reaction and reaction t time water sample absorbance.
Fe prepared by the present embodiment
2o
3/ RGOS microballoon is at present little in photocatalysis 2, A
0and A
tbe respectively 1.298 and 0.014, calculate and 99.1% is reached to the rate of discoloring of Organic substance in water.
Prepared by embodiment 3CuO/RGOS microballoon
The difference of the present embodiment and embodiment 2 is: in step (2), add 0.1g copper acetate in graphene dispersing solution, other conditions are all identical, final obtained CuO/RGOS microballoon 0.2g.
The experimental procedure of the Photocatalytic activity dyestuff of the CuO/RGOS microballoon prepared by the present embodiment is with embodiment 2, at present little in photocatalysis 2, A
0and A
tbe respectively 1.234 and 0.025, calculate and 97.9% is reached to the rate of discoloring of Organic substance in water.
Embodiment 4MnO
2the preparation of/RGOS microballoon
The difference of the present embodiment and embodiment 2 is: in step (2), add 0.1g manganese acetate in graphene dispersing solution, other conditions are all identical, finally obtained MnO
2/ RGOS microballoon 0.2g.
MnO prepared by the present embodiment
2the experimental procedure of the Photocatalytic activity dyestuff of/RGOS microballoon is with embodiment 2, at present little in photocatalysis 2, A
0and A
tbe respectively 1.118 and 0.115, calculate and 89.8% is reached to the rate of discoloring of Organic substance in water.
Comparative example
The difference of the present embodiment and embodiment 2 is: after adding ascorbic acid in step (2), the recovery time is decided to be 24h, finally obtains Fe
2o
3/ RGOS microballoon 0.2g.
Fe prepared by the present embodiment
2o
3the experimental procedure of the Photocatalytic activity dyestuff of/RGOS microballoon is with embodiment 2, at present little in photocatalysis 2, A
0and A
tbe respectively 1.221 and 0.095, rate of discoloring is reduced to 92.3% on the contrary, illustrates that the recovery time is not that the longer the better, the short recovery time can make sheet interlayer spacing larger, electric conductivity is better, and this is conducive to promoting the electro transfer in catalytic process, thus improves the performance of catalyst.
Claims (7)
1. a metal oxide-loaded hollow graphite alkene microspherical catalyst, is characterized in that, described metal oxide-loaded hollow graphite alkene microspherical catalyst prepares as follows:
A graphite oxide is added in deionized water by (), form graphene oxide dispersion in the ultrasonic 1 ~ 3h dispersion of 40 ~ 60Hz; The quality consumption of described graphite oxide counts 2 ~ 6g/L with the volume of deionized water;
B () adds ascorbic acid in step (a) gained graphene oxide dispersion, prior to the ultrasonic 1 ~ 3h of 40 ~ 60Hz, again in 30 ~ 60 DEG C of reduction 8 ~ 24h, obtain graphene dispersing solution, in gained graphene dispersing solution, add the compound containing metal ion, obtain the graphene dispersing solution being mixed with metal ion; The quality consumption of described ascorbic acid counts 2 ~ 10g/L with the volume of graphene oxide dispersion; The quality consumption of the described compound containing metal ion counts 0.5 ~ 1g/L with the volume of graphene dispersing solution; Metallic element in the described compound containing metal ion is the mixing of one or more arbitrary proportions in iron, zinc, copper, manganese, nickel, cobalt;
C the graphene dispersing solution that step (b) gained is mixed with metal ion is placed in spray dryer by (), spray dryer intake air temperature be 230 ~ 250 DEG C, air outlet temperature is 150 ~ 160 DEG C, flow velocity is 12 ~ 20mL/min, drying time be the condition of 1 ~ 1.5s under carry out spraying dry, collect spraying dry gained solid, be described metal oxide-loaded hollow graphite alkene microspherical catalyst.
2. hollow graphite alkene microspherical catalyst metal oxide-loaded as claimed in claim 1, is characterized in that, in step (a), the quality consumption of described graphite oxide counts 3 ~ 5g/L with the volume of deionized water.
3. hollow graphite alkene microspherical catalyst metal oxide-loaded as claimed in claim 1, is characterized in that, in step (b), the quality consumption of described ascorbic acid counts 4 ~ 8g/L with the volume of graphene oxide dispersion.
4. hollow graphite alkene microspherical catalyst metal oxide-loaded as claimed in claim 1, it is characterized in that, in step (b), the described compound containing metal ion is selected from the mixture of one or more arbitrary proportions in ferric nitrate, copper acetate, manganese acetate, cobalt nitrate, nickel acetate, zinc nitrate.
5. the application in the organic pollution of hollow graphite alkene microspherical catalyst metal oxide-loaded as claimed in claim 1 in catalysis hydrogen peroxide oxidation degradation water.
6. apply as claimed in claim 5, it is characterized in that, in the reaction of catalysis hydrogen peroxide oxidation, the quality consumption of described metal oxide-loaded hollow graphite alkene microspherical catalyst is 10% ~ 20% of reaction substrate organic pollution quality.
7. a hollow graphite alkene microballoon, is characterized in that, described hollow graphite alkene microballoon prepares as follows:
(1) graphite oxide is added in deionized water, forms graphene oxide dispersion in the ultrasonic 1 ~ 3h dispersion of 40 ~ 60Hz; The quality consumption of described graphite oxide counts 2 ~ 6g/L with the volume of deionized water;
(2) in step (1) gained graphene oxide dispersion, add ascorbic acid, prior to the ultrasonic 1 ~ 3h of 40 ~ 60Hz, then in 30 ~ 60 DEG C of reduction 8 ~ 24h, obtain graphene dispersing solution; The quality consumption of described ascorbic acid counts 2 ~ 10g/L with the volume of graphene oxide dispersion;
(3) step (2) gained graphene dispersing solution is placed in spray dryer, spray dryer intake air temperature be 230 ~ 250 DEG C, air outlet temperature is 150 ~ 160 DEG C, flow velocity is 12 ~ 20mL/min, drying time be the condition of 1 ~ 1.5s under carry out spraying dry, collect spraying dry gained solid, be described hollow graphite alkene microballoon.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404544A (en) * | 2019-07-26 | 2019-11-05 | 华东理工大学 | A kind of bimetallic catalytic material and its preparation method and application method |
| CN110577215A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | high-dispersion graphene oxide powder and preparation method and application thereof |
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