CN105233827B - 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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- CN105233827B CN105233827B CN201510708931.1A CN201510708931A CN105233827B CN 105233827 B CN105233827 B CN 105233827B CN 201510708931 A CN201510708931 A CN 201510708931A CN 105233827 B CN105233827 B CN 105233827B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 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 45
- 239000010439 graphite Substances 0.000 claims abstract description 45
- 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 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 16
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 16
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 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 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- -1 graphite alkene Chemical class 0.000 claims description 30
- 238000002604 ultrasonography Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 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 4
- 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 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 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
- 239000002184 metal Substances 0.000 claims 2
- 229940071125 manganese acetate Drugs 0.000 claims 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 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 11
- 238000002474 experimental method Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012530 fluid Substances 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
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003643 water by type Substances 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 239000003595 mist Substances 0.000 description 1
- 150000002823 nitrates Chemical class 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
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- 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 and application.
(2) background technology
Graphene is a kind of new material for the individual layer laminated structure being made up of carbon atom.Be one kind by carbon atom SP2Hydridization
The hexagon of track composition is in the flat film of honeycomb lattice, the two-dimensional material of only one carbon atom thickness.2004
Novoselov etc. peels off highly oriented pyrolytic graphite using adhesive tape micromechanics and obtains self-existent graphene.With to graphene
Research further deeply, it is found that the both sides of its planar structure can be with carrying metal particle, the carrier material as catalyst
Material is more promising.Compared with other carbon materials, graphene is made up of most stable of phenyl ring, is plane polycyclic aromatic hydrocarbons (PAH) atom
Crystal, there is bigger theoretical specific surface area (about 2630m2·g-1) and more preferable electron transport ability (about 2 ×
105cm2·V-1·s-1), it is more suitable for the carrier for making catalyst.It is different with other carriers, graphene due to its superior electric conductivity,
In addition to the application in terms of fuel cell, also there is its unique purposes in terms of photochemical catalyzing.Research shows：To partly it lead
Body, which loads to progress light-catalyzed reaction on graphene, can improve activity, and being primarily due to graphene can be by electronics more easily
Export participates in reaction.But graphene sheet layer is all easy to reunite and stack in the grapheme material that at present prepared by chemical method, this
The transmission of electronics can be hindered, reduces its electric conductivity.This problem largely constrains the further hair of graphene carrier
Exhibition.
(3) content of the invention
It is described the invention provides a kind of metal oxide-loaded hollow graphite alkene microspherical catalyst and preparation method thereof
Catalyst can be applied to be catalyzed hydrogen peroxide (H2O2) in oxidation reaction.Also, present invention also offers the carrier of the catalyst
Hollow graphite alkene microballoon and preparation method thereof.
The graphene dispersing solution mixed with metal ion prepared is spray-dried by the present invention by spray drying process,
Caused droplet can constantly evaporate in spray dryer, and Brownian movement can occur for the graphene sheet layer of the inside, to gas-liquid
Interface is close, forms metal oxide-loaded hollow graphite alkene microspherical catalyst.
The present invention adopts the following technical scheme that：
A kind of metal oxide-loaded hollow graphite alkene microspherical catalyst, described metal oxide-loaded hollow stone
Black alkene microspherical catalyst is prepared as follows obtaining：
(a) graphite oxide is added in deionized water, forms graphene oxide and disperse in 40~60Hz ultrasounds, 1~3h is scattered
Liquid；The quality dosage of the graphite oxide is calculated as 2~6g/L with the volume of deionized water；
(b) ascorbic acid is added in graphene oxide dispersion obtained by the step (a), prior to 40~60Hz, 1~3h of ultrasound,
Then at 30~60 DEG C of 8~24h of reduction, graphene dispersing solution is obtained, is added in gained graphene dispersing solution and contains metal ion
Compound, obtain the graphene dispersing solution mixed with metal ion；The quality dosage of the ascorbic acid is with graphene oxide point
The volume of dispersion liquid is calculated as 2~10g/L；The quality dosage of the compound containing metal ion is with the volume of graphene dispersing solution
It is calculated as 0.5~1g/L；Metallic element in the compound containing metal ion is iron, one kind in zinc, copper, manganese, nickel, cobalt
Or the mixing of two or more arbitrary proportions；
(c) graphene dispersing solution obtained by step (b) mixed with metal ion is placed in spray dryer, be spray-dried
Device intake air temperature is 230~250 DEG C, air outlet temperature is 150~160 DEG C, flow velocity is 12~20mL/min, drying time is
Be spray-dried under conditions of 1~1.5s, collect spray drying gained solid, be it is described it is metal oxide-loaded in
Empty graphene microspherical catalyst.
In step (a) of the present invention, the quality dosage of preferably described graphite oxide is calculated as 3 with the volume of deionized water~
5g/L。
In step (b), the quality dosage of preferably described ascorbic acid is calculated as 4 with the volume of graphene oxide dispersion~
8g/L。
In step (b), specifically, the compound containing metal ion can be selected from ferric nitrate, copper acetate, acetic acid
The mixture of one or both of manganese, cobalt nitrate, nickel acetate, zinc nitrate any of the above ratio.
Metal oxide-loaded hollow graphite alkene microspherical catalyst of the present invention can be applied to be catalyzed hydrogen peroxide oxidation
Organic pollution in degradation water is (such as：Phenol, industrial dye etc.)；Generally, in catalysis hydrogen peroxide oxidation reaction, the load
The quality dosage of the hollow graphite alkene microspherical catalyst of metal oxide be reaction substrate organic pollution quality 10%~
20%.
Present invention also offers a kind of hollow graphite alkene microballoon as the catalyst carrier, described hollow graphite alkene
Microballoon is prepared as follows obtaining：
(1) graphite oxide is added in deionized water, forms graphene oxide and disperse in 40~60Hz ultrasounds, 1~3h is scattered
Liquid；The quality dosage of the graphite oxide is calculated as 2~6g/L (preferably 3~5g/L) with the volume of deionized water；
(2) ascorbic acid is added in graphene oxide dispersion obtained by the step (1), prior to 40~60Hz, 1~3h of ultrasound,
Then at 30~60 DEG C of 8~24h of reduction, graphene dispersing solution is obtained；The quality dosage of the ascorbic acid is with graphene oxide point
The volume of dispersion liquid is calculated as 2~10g/L (preferably 4~8g/L)；
(3) graphene dispersing solution obtained by step (2) is placed in spray dryer, is in spray dryer intake air temperature
230~250 DEG C, air outlet temperature be 150~160 DEG C, the condition that flow velocity is 12~20mL/min, drying time is 1~1.5s
Under be spray-dried, collect spray drying gained solid, be described hollow graphite alkene microballoon.
Compared with prior art, the advantage of the invention is that：
(1) ascorbic acid is used as reducing agent reduction-oxidation graphite, asepsis environment-protecting, and some oxygen-containing groups can be provided, with
Dispersiveness of the graphene in water is kept, and ascorbic acid is cheap；
(2) hollow graphite alkene microspherulite diameter of the present invention is between 2~5 μm, and compared with millimetre-sized at present, size reduces very
It is more, in addition by controlling the viscosity (viscosity can be adjusted by the concentration of graphene dispersing solution) of graphene dispersing solution adjustable
The size of hollow graphite alkene microballoon, urged so as to the excellent metal oxide-loaded hollow graphite alkene microballoon of processability
Agent；
(3) support type hollow graphite alkene microspherical catalyst is prepared by spray drying process, method is simple, easy to operate, is applicable
In large-scale production.
(4) illustrate
Fig. 1 is the gained Fe of embodiment 22O3The scanning electron microscope (SEM) photograph of/RGOS microballoons.
Fig. 2 is the gained Fe of embodiment 22O3The transmission electron microscope picture of/RGOS microballoons.
Fig. 3 is photocatalysis apparatus figure in embodiment 2.
(5) embodiment
The present invention is further detailed below by specific embodiment, but protection scope of the present invention and not only limited
In this.
It is prepared by embodiment 1RGOS microballoons
(1) 0.4g graphite oxides are added in 100mL deionized waters, in 50Hz ultrasound 2h, are then centrifuged for removing bottom trip
From graphite oxide, obtain graphene oxide dispersion.
(2) 0.4g ascorbic acid is added in graphene oxide dispersion obtained by step (1), prior to 50Hz ultrasounds 1h to molten
Fluid viscosity reduces, color burn to black.Then at 30 DEG C of reduction 12h, graphene dispersing solution is obtained.
(3) graphene dispersing solution obtained by step (2) is placed in spray dryer, is in spray dryer intake air temperature
250 DEG C, air outlet temperature is 160 DEG C, flow velocity 15mL/min, and drying time to be spray-dried under conditions of 1s, collects
Gained solid, as hollow graphite alkene microballoon 0.2g in bottle.
Embodiment 2Fe2O3It is prepared by/RGOS microballoons
(1) 0.4g graphite oxides are added in 100mL deionized waters, in 50Hz ultrasound 2h, are then centrifuged for removing bottom trip
From graphite oxide, obtain graphene oxide dispersion.
(2) 0.4g ascorbic acid is added in graphene oxide dispersion obtained by step (1), prior to 50Hz ultrasounds 1h to molten
Fluid viscosity reduces, color burn to black.Then at 30 DEG C of reduction 12h, graphene dispersing solution is obtained, in gained graphene dispersing solution
In, 0.1g ferric nitrates are added, obtain the graphene dispersing solution mixed with iron ion.
(3) graphene dispersing solution obtained by step (2) mixed with iron ion is placed in spray dryer, in spray dryer
Sprayed under conditions of intake air temperature is 250 DEG C, air outlet temperature is 160 DEG C, flow velocity 15mL/min, drying time are 1s
Mist is dried, gained solid in receiving flask, as loads the hollow graphite alkene microspherical catalyst 0.2g of ferric oxide particle.
The experimental procedure of Photocatalytic activity dyestuff：
The reactive gaudy red X 3B dye solution that 0.8L concentration is 100mg/L is prepared first, and it is anti-to be added into homemade glass
Answer in device, and X-3B dye solutions are adjusted into pH to 6.0 with 0.1M sodium hydroxide solutions；Then the above-mentioned preparations of 0.01g are weighed
The hollow graphite alkene microspherical catalyst of load ferric oxide particle is added in dye solution, is opened magnetic stirring apparatus, will be urged
Agent is well mixed with dye solution.Before photocatalytic degradation experiment is carried out, reaction solution is first stirred into 30min under the conditions of lucifuge
To reach the adsorption equilibrium of catalyst, its characteristic peak absorbance is measured by sampling per 10min in adsorption process；It is then turned on sodium
Lamp, add 0.9mL 30wt%H2O2Solution, react formal and start, ensured during the course of the reaction by adjusting cooling water flow velocity
Temperature maintains 25 ± 2 DEG C.Degradation time is 120min, during photocatalytic oxidation degradation, according to 30min time interval
Draw reaction solution and carry out analysis test.Water sample to be measured uses visible spectrophotometer after 0.45 μm of micropore acetate fiber membrane filtration
Survey its absorbance.
The change of dye strength is determined according to the change of absorption peak strength under different dyes characteristic wavelength in experiment.
Full wavelength scanner is carried out to dyestuff using ultraviolet-visible spectrophotometer in experiment, and determines its characteristic wavelength
Under absorption peak, dye decolored rate is calculated by following formula：D=(1-At/A0) × 100%, A in formula0, AtRespectively photocatalysis
The absorbance of water sample when reaction is preceding and reacts t.
Fe prepared by the present embodiment2O3/ RGOS microballoons are small at present in photocatalysis 2, A0And AtRespectively 1.298 Hes
0.014, the discoloration rate to Organic substance in water is calculated and reaches 99.1%.
It is prepared by embodiment 3CuO/RGOS microballoons
The difference of the present embodiment and embodiment 2 is：In step (2), 0.1g second is added in graphene dispersing solution
Sour copper, other conditions are all identical, finally obtained CuO/RGOS microballoons 0.2g.
The experimental procedure of the Photocatalytic activity dyestuff of CuO/RGOS microballoons prepared by the present embodiment with embodiment 2,
Small at present, the A in photocatalysis 20And AtRespectively 1.234 and 0.025, the discoloration rate to Organic substance in water is calculated and reaches
97.9%.
Embodiment 4MnO2The preparation of/RGOS microballoons
The difference of the present embodiment and embodiment 2 is：In step (2), 0.1g second is added in graphene dispersing solution
Sour manganese, other conditions are all identical, and MnO is finally made2/ RGOS microballoons 0.2g.
MnO prepared by the present embodiment2The experimental procedure of the Photocatalytic activity dyestuff of/RGOS microballoons with embodiment 2,
Small at present, the A in photocatalysis 20And AtRespectively 1.118 and 0.115, the discoloration rate to Organic substance in water is calculated and reaches
89.8%.
Comparative example
The present embodiment and the difference of embodiment 2 are：After adding ascorbic acid in step (2), the recovery time is set to
24h, finally give Fe2O3/ RGOS microballoons 0.2g.
Fe prepared by the present embodiment2O3The experimental procedure of the Photocatalytic activity dyestuff of/RGOS microballoons with embodiment 2,
Small at present, the A in photocatalysis 20And AtRespectively 1.221 and 0.095, discoloration rate is reduced to 92.3% on the contrary, when illustrating reduction
Between be not that the longer the better, the short recovery time can make it that piece interlamellar spacing is bigger, and electric conductivity is more preferable, and this may advantageously facilitate catalysis
During electronics transfer, so as to improve the performance of catalyst.
Claims (7)
- A kind of 1. metal oxide-loaded hollow graphite alkene microspherical catalyst, it is characterised in that described carried metal oxidation The hollow graphite alkene microspherical catalyst of thing is prepared as follows obtaining：(a) graphite oxide is added in deionized water, disperses to form graphene oxide dispersion in 40~60Hz ultrasounds, 1~3h； The quality dosage of the graphite oxide is calculated as 2~6g/L with the volume of deionized water；(b) ascorbic acid is added in graphene oxide dispersion obtained by the step (a), prior to 40~60Hz, 1~3h of ultrasound, then at 30~60 DEG C of 8~24h of reduction, obtain graphene dispersing solution, the change containing metal ion are added in gained graphene dispersing solution Compound, obtain the graphene dispersing solution mixed with metal ion；The quality dosage of the ascorbic acid is with graphene oxide dispersion Volume be calculated as 2~10g/L；The quality dosage of the compound containing metal ion is calculated as with the volume of graphene dispersing solution 0.5~1g/L；Metallic element in the compound containing metal ion is iron, zinc, copper, manganese, nickel, one kind in cobalt or two The mixing of kind any of the above ratio；(c) graphene dispersing solution obtained by step (b) mixed with metal ion is placed in spray dryer, entered in spray dryer Draught temperature is 230~250 DEG C, air outlet temperature is 150~160 DEG C, flow velocity is 12~20mL/min, drying time be 1~ It is spray-dried under conditions of 1.5s, collects spray drying gained solid, is described metal oxide-loaded hollow Graphene microspherical catalyst.
- 2. metal oxide-loaded hollow graphite alkene microspherical catalyst as claimed in claim 1, it is characterised in that step (a) in, the quality dosage of the graphite oxide is calculated as 3~5g/L with the volume of deionized water.
- 3. metal oxide-loaded hollow graphite alkene microspherical catalyst as claimed in claim 1, it is characterised in that step (b) in, the quality dosage of the ascorbic acid is calculated as 4~8g/L with the volume of graphene oxide dispersion.
- 4. metal oxide-loaded hollow graphite alkene microspherical catalyst as claimed in claim 1, it is characterised in that step (b) in, the compound containing metal ion is in ferric nitrate, copper acetate, manganese acetate, cobalt nitrate, nickel acetate, zinc nitrate One or more kinds of arbitrary proportions mixture.
- 5. metal oxide-loaded hollow graphite alkene microspherical catalyst as claimed in claim 1 is in catalysis hydrogen peroxide oxidation drop The application in organic pollution in Xie Shui.
- 6. application as claimed in claim 5, it is characterised in that in catalysis hydrogen peroxide oxidation reaction, the carried metal oxygen The quality dosage of the hollow graphite alkene microspherical catalyst of compound is the 10%~20% of reaction substrate organic pollution quality.
- 7. a kind of hollow graphite alkene microballoon, it is characterised in that described hollow graphite alkene microballoon is prepared as follows obtaining：(1) graphite oxide is added in deionized water, disperses to form graphene oxide dispersion in 40~60Hz ultrasounds, 1~3h； The quality dosage of the graphite oxide is calculated as 2~6g/L with the volume of deionized water；(2) ascorbic acid is added in graphene oxide dispersion obtained by the step (1), prior to 40~60Hz, 1~3h of ultrasound, then at 30~60 DEG C of 8~24h of reduction, obtain graphene dispersing solution；The quality dosage of the ascorbic acid is with graphene oxide dispersion Volume be calculated as 2~10g/L；(3) graphene dispersing solution obtained by step (2) is placed in spray dryer, is 230 in spray dryer intake air temperature ~250 DEG C, air outlet temperature is 150~160 DEG C, enters under conditions of flow velocity is 12~20mL/min, drying time is 1~1.5s Row spray drying, spray drying gained solid is collected, is described hollow graphite alkene microballoon.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510708931.1A CN105233827B (en) | 2015-10-27 | 2015-10-27 | Supported hollow graphene microsphere catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
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