CN107282134A - A kind of ZnO photocatalyst of graphene coated and preparation method thereof - Google Patents
A kind of ZnO photocatalyst of graphene coated and preparation method thereof Download PDFInfo
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- CN107282134A CN107282134A CN201610223771.6A CN201610223771A CN107282134A CN 107282134 A CN107282134 A CN 107282134A CN 201610223771 A CN201610223771 A CN 201610223771A CN 107282134 A CN107282134 A CN 107282134A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 154
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 327
- 239000011787 zinc oxide Substances 0.000 claims abstract description 157
- 238000005253 cladding Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 235000014692 zinc oxide Nutrition 0.000 claims description 149
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- 238000005406 washing Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000005576 amination reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZAJSWGDRWVXLES-UHFFFAOYSA-N [O-2].N[Zn+2] Chemical compound [O-2].N[Zn+2] ZAJSWGDRWVXLES-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 5
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 5
- 235000013904 zinc acetate Nutrition 0.000 claims description 5
- 230000009881 electrostatic interaction Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 21
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005215 recombination Methods 0.000 abstract description 7
- -1 ZnO compound Chemical class 0.000 abstract description 6
- 230000006798 recombination Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
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- 239000004575 stone Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
Abstract
The present invention relates to a kind of ZnO photocatalyst of graphene coated and preparation method thereof, the ZnO surfaces is carried electropositive, then with being combined on graphene oxide with electronegative oxygen-containing functional group, obtain graphene oxide cladding ZnO photocatalyst.The ZnO compound photochemical catalysts of graphene coated prepared by the present invention, because the graphene film footpath used is larger, the number of plies is relatively thin, and ZnO is more to be combined with plane with it, reduces stress between the two, the structure that can greatly retain graphene is not destroyed.Simultaneously, ZnO and graphene oxide recombination energy is set graphene is coated on ZnO surfaces well by electrostatic force self assembly, so as to increase the contact area between graphene and ZnO and reduce graphene reunion, strengthen the effect between graphene and zinc oxide, the separation and transmission of the photo-generated carrier of ZnO catalyst generation are more beneficial for, this structure can significantly improve photocatalysis effect.
Description
Technical field
The present invention relates to a kind of photochemical catalyst and preparation method thereof, the ZnO photocatalyst of particularly a kind of graphene coated and
Its preparation method.
Background technology
Organic dyestuff and Wastewater Pollutant are the primary pollution source in the industry such as weaving, papermaking, plastics.ZnO is a kind of weight
The photochemical catalyst wanted, with wider energy gap (3.37eV) and larger exciton binding energy (60meV), has to light
Stronger sensitiveness, is conducive to the organic matter in wastewater by photocatalysis.
Due to light excite that ZnO produces excite electronics and hole be easy to it is quick compound be converted into luminous energy, cause catalytic performance
Decline.Therefore scientific research personnel suppresses photo-generate electron-hole using all multi-methods to being combined, and widens the region of photoresponse, such as
Control ZnO pattern, mix other metal ions and other metals or semiconductors coupling etc., risen to improving photocatalysis performance
Effect is well arrived.It is noted that scientific research personnel is by by ZnO and carbon material (graphene, CNT etc.)
It is combined with all multi-methods, ZnO photocatalysis efficiency can be significantly improved, ZnO is combined with graphene and prepares photochemical catalyst
Into the focus of current research.
ZnO/ graphene complex photochemical catalysts and preparation method thereof in spite of many document reports, but still have and much ask
Topic, such as ZnO and graphene composite effect are poor, with the presence of many free graphite alkene, graphene agglomeration in compound
Seriously, graphene-structured destroys the situation such as more serious, is unfavorable for the raising of photocatalytic activity.
The content of the invention
In view of the above-mentioned problems, increasing graphene and ZnO contact area it is an object of the invention to provide a kind of, stone is improved
The preparation method of the graphene coated ZnO photocatalyst of the composite effect of black alkene and ZnO.
In order to solve the above problems, the invention provides a kind of ZnO photocatalyst of graphene coated, make the ZnO tables
Face carries electropositive, then with being combined on graphene oxide with electronegative oxygen-containing functional group, obtains graphene oxide cladding
ZnO photocatalyst.
Due in graphene carbon atom with sp2Hydridization form formation planar structure, and single electron and other carbon atoms will be provided
Single electron forms the big pi bond of delocalization in the plane, therefore, and graphene has good electronic conductivity energy and heat conductivility.This
Outside, graphene is as the two-dimensional material that thickness is Nano grade, with very high specific surface area.When graphene and ZnO are combined
When carrying out photocatalysis to organic dyestuff, on the one hand, graphene can adsorb organic matter, it is more preferably contacted with catalyst.It is another
Aspect, graphene can receive and shift photo-excited electron, reduce the recombination probability of photo-generate electron-hole pair.Graphene with
The ZnO compound band gap for also reducing ZnO, has widened the light abstraction width of catalyst, has improved the efficiency of light energy utilization, so that
Effectively improve ZnO photocatalysis performance.The present invention makes ZnO surfaces carry electropositive, so that with being carried on graphene oxide
Electronegative oxygen-containing functional group produces the composite effect that electrostatic interaction has been formd, and makes the ZnO of the graphene coated of the invention provided
Photochemical catalyst has strong photocatalysis performance.
It is preferred that ZnO is six rib laminated structures in the ZnO photocatalyst of the graphene coated.Graphene bag of the present invention
The structure of the zinc oxide covered is six rib laminated structures, may be such that zinc oxide increases with graphene contact area.
It is preferred that the graphene number of plies of the ZnO outer claddings is below 5 layers.
It is preferred that the ZnO particle diameters are 400nm~1 μm.
It is preferred that by making ZnO surface aminations so that the ZnO surfaces carry electropositive.
Present invention also offers a kind of preparation method of the ZnO photocatalyst of graphene coated, including：
By ZnO surface aminations, ZnO surfaces are made to carry electropositive, so that with carrying electronegative oxygen-containing function on graphene oxide
Group produces electrostatic interaction and is combined, and obtains graphene oxide cladding ZnO compounds；
Gained graphene oxide cladding ZnO compounds are warming up to 500~800 DEG C in reducibility gas, annealed 2~3 hours,
Obtain the ZnO photocatalyst of graphene coated.It is preferred that the speed of the heating is 10~20 DEG C/min.
It is preferred that the preparation of the ZnO includes：1-METHYLPYRROLIDONE and deionized water are pressed into (4~9)：6 mixing systems
It is standby go out mixed solvent；3.5~5.5g zinc acetates are mixed with 200mL mixed solvents and stirred 4~5 hours at 90~98 DEG C；
Product is subjected to centrifuge washing and after drying after having reacted, the ZnO is obtained.
It is preferred that the preparation of the graphene oxide includes with screening：Graphene oxide using improve Hummers methods according to
Document (J.Am.Chem.Soc., 2008,130,5856-5857) is prepared；By the graphene oxide prepared in centrifuge
In with rotating speed >=8000 rev/min centrifuge 20~30 minutes, obtain upper strata graphene oxide solution；Graphene oxide is dispersed in one
Determine in volumes of deionized water, ultrasonically treated 0.5~1 hour, it is the dispersed oxidation stones of 0.5~1.5mg/mL to obtain concentration
Black aqueous solution.
It is preferred that the amination includes：ZnO is added to 3- aminopropyls-trimethoxy silane and absolute ethyl alcohol volume
Than for 1：In the mixed liquor of (10~20), it is ultrasonically treated and after 55~65 DEG C of heating stirrings are reacted 8~12 hours with anhydrous
Ethanol carries out centrifuge washing and is dried to obtain amino zinc oxide.
It is preferred that the 3- aminopropyls-amount of the trimethoxy silane relative to ZnO should be enough (to 3- ammonia before and after reaction
The concentration influence of base propyl-trimethoxysilane is little).
It is preferred that described be complex as 5~10ml 0.5~1.5mg/ml graphene oxide water solutions with 1.0~2.0g's
Amino zinc oxide, which is added in deionized water, to carry out ultrasonically treated, and is reacted 6~10 hours in 55~65 DEG C of heating stirrings,
Then reacted suspension is subjected to centrifuge washing and is dried to obtain graphene oxide cladding ZnO compounds.
It is preferred that the reducibility gas is hydrogen nitrogen mixed gas or hydrogen-argon-mixed, the molal weight of the hydrogen is reduction
The 9-11% of property gas total moles quality.
The ZnO compound photochemical catalysts of the graphene coated prepared relative to prior art, the present invention, due to the stone used
Black alkene piece footpath is larger, and the number of plies is relatively thin, and ZnO is more to be combined with plane with it, reduces stress between the two, can greatly
The structure for retaining graphene is not destroyed.Meanwhile, ZnO and graphene oxide recombination energy is made graphite by electrostatic force self assembly
Alkene can be coated on ZnO surfaces well, so as to increase the contact area between graphene and ZnO and reduce graphene group
It is poly-, the effect between graphene and zinc oxide strengthen, be more beneficial for the photo-generated carrier of ZnO catalyst generation separation and
Transmission, this structure can significantly improve photocatalysis effect.
Brief description of the drawings
Fig. 1 is AFM (a) shape appearance figures and (b) cross-section analysis figure of graphene oxide prepared by embodiment 1；
The SEM figures that Fig. 2 is six rib sheet ZnO prepared by embodiment 1；
Fig. 3 is six rib sheet ZnO of graphene coated prepared by embodiment 1 (a) EDS carbon distribution maps, (b) SEM and (c-
F) TEM schemes；
Fig. 4 is the rib sheet ZnO of graphene coated six prepared by embodiment 1 Raman spectrogram；
The rib piece of graphene/six that Fig. 5 is six rib sheet ZnO, the rib sheet ZnO of graphene coated six prepared by embodiment 1 and prepared by comparative example
The photocatalysis efficiency of shape ZnO mixture powders and catalysis time graph of a relation；
Fig. 6 is six rib sheet ZnO prepared by embodiment 1 and the rib sheet ZnO of graphene coated six UV-Vis DRS spectrum；
Fig. 7 is six rib sheet ZnO prepared by embodiment 1 and the rib sheet ZnO of graphene coated six photoluminescence spectra.
Embodiment
Implementation below further illustrates the present invention, it should be appreciated that following embodiments are merely to illustrate the present invention, rather than
The limitation present invention.
The present invention makes ZnO surfaces carry electropositive, then with being answered on graphene oxide with electronegative oxygen-containing functional group
Close, obtain graphene oxide cladding ZnO photocatalyst.Wherein, ZnO can in the ZnO photocatalyst of the graphene coated
For six rib laminated structures.The graphene number of plies of ZnO outer claddings is below 5 layers.As shown in figure 3, Fig. 3 a are graphene coateds
Zinc oxide EDS carbon distribution maps, it can be seen that zinc oxide surface is covered by carbon, and the presence of these carbons shows
ZnO surfaces are by graphene coated.Fig. 3 b are the SEM figures of graphene coated zinc oxide, therefrom it can be seen that ZnO tables
There is one layer very thin transparent graphene cladding in face, it is further seen that graphene sticks up layer and fold.Fig. 3 c-3f are the TEM of sample
Figure, from Fig. 3 c, we can see very thin graphene and have been coated in ZnO outward flange, for the seldom graphite of the number of plies
Alkene, we are observed by high-resolution TEM, such as Fig. 3 d, in 3f, and we observed individual layer respectively and three layer graphenes exist
ZnO coated with uniform, it is seen that method provided by the present invention can effectively achieve graphene coated ZnO purpose.Separately
Outside, interplanar distance can be obtained in Fig. 3 e for 0.28nm, correspondence ZnO (100) crystal face, crystallinity is good.Wherein,
The ZnO particle diameters are 400nm~1 μm.As shown in Fig. 2 Fig. 2 is six rib sheet zinc oxides prepared by embodiment 1
SEM shape appearance figures, it can be seen that zinc oxide is in six rib laminated structures of rule, and size is 400nm~1 μm, and in its one side
On have six rib sheet-shaped patterns of regular shape, all faces are plane.This shape can make graphene be easier to be coated on
ZnO surfaces, are combined relative to Irregular Boundary Surface, the recombination energy of graphene and ZnO planes reduce between the two should
Power, reduces the destruction to graphene-structured, and then strengthen interaction between the two.
The present invention obtains graphene oxide cladding by by ZnO surface aminations, then after fully being reacted with graphene oxide
ZnO compounds.Gained graphene oxide cladding ZnO compounds are made annealing treatment in reducing atmosphere again, stone is finally obtained
The ZnO photocatalyst of black alkene cladding.The ZnO for the graphene coated that the explanation present invention of following exemplary is provided is combined object light and urged
The preparation method of agent.
ZnO preparation.1-METHYLPYRROLIDONE and deionized water are pressed into (4~9)：6 are mixed with out mixed solvent；Will
Proper amount of acetic acid zinc is mixed with 200mL mixed solvents and stirred 4~5 hours at 90~98 DEG C；Product is centrifuged after having reacted
After washing and drying, the ZnO is obtained.As an example, 1-METHYLPYRROLIDONE (NMP) is pressed with deionized water
1:1 is mixed with out mixed solvent；3.5~5.5g zinc acetates are mixed with 200mL mixed solvents and small in 95 DEG C of stirrings 4
When；Product is subjected to centrifuge washing after having reacted, and dried 10~12 hours at 80 DEG C.
The preparation of graphene oxide.Graphene oxide in the present invention can be using improvement Hummers methods according to document (J.Am.
Chem.Soc., 2008,130,5856-5857) prepare, can also be obtained using other modes.
The screening of graphene oxide.It is different dense further according to configuration is needed by the graphene oxide of preparation after the processing such as centrifugation
Spend graphene oxide water solution.As an example, by the graphene oxide prepared in centrifuge with rotating speed >=8000 turn/
Separate the heart 20~30 minutes, obtain upper strata graphene oxide solution.Graphene oxide is dispersed in certain volume deionized water
In, ultrasonically treated 1 hour, it was the dispersed graphene oxide water solutions of 0.5~1.5mg/mL to obtain concentration.
ZnO surface aminations.It is 1 that ZnO is added into 3- aminopropyls-trimethoxy silane with absolute ethyl alcohol volume ratio：
It is ultrasonically treated and entered after 55~65 DEG C of heating stirrings are reacted 8~12 hours with absolute ethyl alcohol in the mixed liquor of (10~20)
Row centrifuge washing is simultaneously dried to obtain amino zinc oxide.Wherein, the 3- aminopropyls-trimethoxy silane is relative to ZnO's
Amount should be enough (influenceing little to the concentration of 3- aminopropyls-trimethoxy silane before and after reaction).The present invention is by six ribs
Sheet ZnO surface aminations, make ZnO surfaces carry electropositive, so that with carrying electronegative oxygen-containing official on graphene oxide
Can group's generation electrostatic interaction, raising composite effect.As an example, six rib sheet ZnO are added to 3- aminopropyls-three
In the mixed liquor of methoxy silane/absolute ethyl alcohol, after ultrasonically treated 5~10 minutes at 55~65 DEG C stir 10 hours, fully
Centrifuge washing is carried out with absolute ethyl alcohol after reaction and dried 10~12 hours at 80 DEG C, obtain amino zinc oxide.
Graphene oxide coats the preparation of ZnO compounds.5~10ml 0.5~1.5mg/ml graphene oxides is water-soluble
Liquid and 1.0~2.0g amino zinc oxide be added in deionized water carry out it is ultrasonically treated and anti-in 55~65 DEG C of heating stirrings
Answer 6~10 hours, then carry out centrifuge washing by reacted suspension and be dried to obtain graphene oxide cladding ZnO to be combined
Thing.Graphene and ZnO photocatalyst, which be combined, more effectively to be handled sewage.The big ratio of graphene first
Surface area can adsorb organic pollution well, so as to improve the photocatalysis efficiency of catalyst.Graphene is answered with ZnO
Conjunction can improve the absorptivity of catalyst, so as to improve the utilization ratio of light.Importantly, graphene can be used as electronics
Acceptor, receives the photo-excited electron produced on ZnO, the compound probability of electron-hole is reduced, so as to improve catalytic effect
(see Fig. 6, Fig. 7).As an example, by 5~10ml 0.5~1.5mg/ml graphene oxide water solutions with 1.0~
2.0g amino zinc oxides are added in 200mL deionized waters, it is ultrasonically treated after 55~65 DEG C stir 6~10 hours, so
Reacted suspension is subjected to centrifuge washing and after drying afterwards, graphene oxide is obtained and coats six rib sheet ZnO compounds.
Wherein, the drying can be to be dried 10~12 hours at 80 DEG C.
The present invention is reached by being reduced graphene oxide with reducibility gas under high temperature (such as 500~800 DEG C)
To the purpose for preparing graphene coated ZnO compound photochemical catalysts.The reducibility gas is that hydrogen nitrogen mixed gas or hydrogen argon are mixed
Gas, the molal weight of the hydrogen is the 9~11% of reducibility gas total moles quality.For example, hydrogen nitrogen (H2:N2=1:9) mix
Close gas or hydrogen argon (H2:Ar=1:9) gaseous mixture.As an example, graphene oxide is coated into six rib sheet ZnO compounds
In hydrogen nitrogen (H2:N2=1:9) 500~800 DEG C are warming up to 10~20 DEG C/min of heating rates in the reducing atmosphere of gaseous mixture,
Annealing 2~3 hours, the final six rib sheet ZnO photocatalysts for obtaining graphene coated.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this hair
It is bright to be further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential modifications and adaptations that the above is made belong to protection scope of the present invention.Following specific technique ginsengs of example
Number etc. is also only an example in OK range, i.e. those skilled in the art can be done in suitable scope by this paper explanation
Selection, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
4.50g zinc acetates, 100mL 1-METHYLPYRROLIDONEs (NMP) and 100mL deionized waters are added into 250mL conical flasks
It is interior, stirred 4 hours at 95 DEG C, product after completion of the reaction is after eccentric cleaning, in the drying 10 hours of 80 DEG C of drying box,
Obtain six rib sheet ZnO.
Take 1.5g to insert in 250mL conical flasks six ribs sheet ZnO obtained above, and add 5mL 3- aminopropyls-
Trimethoxy silane (APTMS) and 95mL absolute ethyl alcohols, after ultrasonically treated 5 minutes, are stirred 10 hours at 60 DEG C；Instead
Product is subjected to centrifuge washing with absolute ethyl alcohol after having answered, and dried 10 hours at 80 DEG C, amino zinc oxide is obtained.
By crystalline flake graphite using improvement Hummers methods according to document (J.Am.Chem.Soc., 2008,130,5856-
5857) graphene oxide is prepared；By the graphene oxide prepared in centrifuge with 8000 revs/min of rotating speed centrifugation 30
Minute, take upper solution to be dispersed in certain volume deionized water, ultrasonically treated 30 minutes, being configured to concentration was about
Graphene oxide water solution dispersed 1.0mg/mL.
The above-mentioned graphene oxide solutions of 5mL and 1.5g aminations ZnO obtained above are added to 200mL deionized waters
In, ultrasonically treated 10 minutes, then stirred 6 hours at 60 DEG C；Reacted suspension is subjected to centrifuge washing, and 80
DEG C dry 10 hours, obtain graphene oxide coat six rib sheet ZnO compounds.
Obtained graphene oxide is coated into six rib sheet ZnO compounds reducing atmosphere (hydrogen nitrogen is used in tube furnace
(H2:N2=1:9) gaseous mixture or hydrogen argon (H2:Ar=1:9) gaseous mixture) in made annealing treatment.With 20 DEG C/min of heating rates
550 DEG C are warming up to, is annealed 2 hours, the final six rib sheet ZnO photocatalysts for obtaining graphene coated.
Comparative example zinc oxide is combined without amination and graphene.
4.50g zinc acetates, 100mL 1-METHYLPYRROLIDONEs (NMP) and 100mL deionized waters are added into 250mL cones
In shape bottle, stirred 4 hours at 95 DEG C, product after completion of the reaction is small in 80 DEG C of dryings 10 of drying box after eccentric cleaning
When, obtain six rib sheet ZnO.
By crystalline flake graphite using improvement Hummers methods according to document (J.Am.Chem.Soc., 2008,130,5856-
5857) graphene oxide is prepared；By the graphene oxide prepared in centrifuge with 8000 revs/min of rotating speed centrifugation 30
Minute, take upper solution to be dispersed in certain volume deionized water, ultrasonically treated 30 minutes, being configured to concentration was about
Graphene oxide water solution dispersed 1.0mg/mL.
The above-mentioned graphene oxide solutions of 5mL and the rib sheet ZnO of 1.5g six obtained above are added to 200mL deionizations
In water, ultrasonically treated 10 minutes, then stirred 6 hours at 60 DEG C；By reacted suspension progress centrifuge washing, and
80 DEG C of dryings 10 hours, obtain the rib sheet ZnO mixture powders of graphene oxide/six.
The rib sheet ZnO mixture powders of obtained graphene oxide/six are used into reducing atmosphere (hydrogen nitrogen in tube furnace
(H2:N2=1:9) gaseous mixture or hydrogen argon (H2:Ar=1:9) gaseous mixture) in made annealing treatment.With 20 DEG C/min of heating rates
It is warming up to 550 DEG C, anneals 2 hours, finally gives the rib sheet ZnO mixture powders of graphene/six.
Photocatalysis methyl blue is comprised the following steps that：
10mg/L methyl blue (MB) solution is prepared with deionized water, takes 100mL to insert in beaker, 20mg catalyst is added
And ultrasound is uniform, then makes up within 1 hour adsorption-desorption with magnetic agitation in the dark and balance.Photocatalytic Degradation Process is being urged
Middle progress is put in makeup, by the use of 300W xenon lamps as light source come Degradation of Methyl Blueness by Photocatalysis, and is constantly stirred with magnetic stirring apparatus
Mix, every taking supernatant liquor after 10min sampling and testings, centrifugation, methyl blue solution is surveyed using ultraviolet-uisible spectrophotometer
In the absorbance of maximum absorption wave strong point.Degradation efficiency can be used to following formula subrepresentation：
The sign of sample
AFM (AFM) is the detection maximally effective instrument of graphene, and the pattern of graphene is surveyed by AFM
Examination, we can intuitively find out the size and the number of plies in graphene film footpath.We will prepare and garbled surface of graphene oxide
Characterized, as shown in figure 1, Fig. 1 be embodiment 1 prepare preparation graphene oxide AFM (a) shape appearance figures and
(b) cross-section analysis figure, it can be seen that graphene oxide major part thickness is no more than 3 layers, and thickness is no more than 5 layers, oxygen
The piece footpath of graphite alkene is less than 300nm.
Fig. 4 is the rib sheet ZnO of graphene coated six prepared by embodiment 1 Raman spectrogram, it can be clearly seen that stone
The D peaks and G peaks of black alkene, and the strength ratio I at D peaks and G peaksD/IG=0.91<1, illustrate that the defect of graphene is less, structure
It is more complete, there is the sp of large area2Composition.
Photocatalysis is tested
Fig. 5 is that photocatalysis methyl blue tests methyl blue percentage and time chart, the six rib sheets that we prepare embodiment 1
The rib sheet ZnO mixture powders of graphene prepared by ZnO, six rib sheet ZnO of graphene coated and comparative example/six carry out light
Catalysis experiments are tested.As seen from the figure, relative to six rib sheet ZnO of preparation, six rib sheet zinc oxides of graphene coated
The catalytic efficiency of (ZnO@Gr) is improved significantly.At 50 minutes, ZnO catalyst only degrades 61%, and graphene
Six rib sheet ZnO of cladding are almost degradable by methyl blue.It can be seen that graphene and ZnO's is compounded in raising photocatalysis efficiency
In serve important function.And the rib sheet ZnO mixture powders of graphene/six prepared without ZnO surface aminations are (not
Modified ZnO/Gr) in the photocatalysis efficiencies of 50 minutes it is 41.3%, prepared well below ZnO surface aminations
ZnO@Gr, six rib sheet ZnO not being combined with graphene even below.This illustrate in unmodified ZnO/Gr not only ZnO with
Graphene composite effect is very poor, and presence of the graphene in powder also absorbs more luminous energy, reduces the work of ZnO and light
With so that its photocatalysis efficiency is even below six rib sheet ZnO.Further, since the presence of graphene, ZnO@Gr with not
Modified ZnO/Gr shows stronger adsorption capacity to methyl blue.
Photocatalysis performance improves mechanism
As seen from Figure 5, ZnO@Gr have stronger suction-operated to methyl blue in photocatalytic process, so as to methyl blue
Have more preferable contact action, when light action on a catalyst when, photoexcitation carrier can be acted on more easily on methyl blue,
It is allowed to degrade.After the methyl blue adsorbed on catalyst is degraded, catalyst continues the methyl blue in adsorbent solution, is allowed to continue to
In adsorption-desorption poised state.
Fig. 6 is (the α h ν) calculated by sample UV-Vis DRS spectrum2- h ν curves, it can be deduced that embodiment 1 is made
Standby ZnO and ZnO@Gr band gap is respectively 3.26 and 3.22eV, it is seen that the cladding reduction ZnO of graphene band gap,
So as to reduce the excitation wavelength of light induced electron, ZnO is more also easy to produce photoexcitation carrier, and then improves ZnO photocatalysis speed
Rate.Be can be seen that from UV-vis DRS spectrum compared with ZnO, ZnO@Gr light absorbs have obvious red shift and
It can be seen that increasing near ultraviolet band absorptivity so that the photoinduction scope of compound broadens, the light that can improve catalyst is utilized
Rate.
Fig. 7 is ZnO and ZnO@Gr prepared by embodiment 1 photoluminescence spectra figure, wherein, it is 398nm in wavelength
Black light produced by photo-excited electron and hole-recombination, when photo-generate electron-hole is larger to recombination probability, produce
Luminous intensity it is bigger, and light induced electron and the compound of hole reduce the quantity in high energy electron and hole, are unfavorable for catalyst pair
The catalysis of methyl blue.Six rib sheet ZnO photoluminescence intensities of graphene coated are big it can be seen from photoluminescence intensity figure
Big reduction, this shows that light induced electron and the probability of hole-recombination are greatly reduced in the compound, and photo-generated carrier has been obtained effectively
Separation.This is due to that graphene can undertake the reception and transmission effect of electronics, and the photo-excited electron that ZnO surfaces are produced is transferred to
On graphene, and graphene has conduction well to electronics, therefore can quickly transmit electronics, thus by electronics with
Hole is efficiently separated.
Claims (9)
1. a kind of ZnO photocatalyst of graphene coated, it is characterised in that make the ZnO surfaces carry electropositive, then with being combined on graphene oxide with electronegative oxygen-containing functional group, obtain graphene oxide cladding ZnO photocatalyst.
2. the ZnO photocatalyst of graphene coated according to claim 1, it is characterised in that ZnO is six rib laminated structures in the ZnO photocatalyst of the graphene coated.
3. the ZnO photocatalyst of graphene coated according to claim 1 or 2, it is characterised in that the graphene number of plies of the ZnO outer claddings is below 5 layers.
4. the ZnO photocatalyst of the graphene coated according to any one of claim 1-3, it is characterised in that the ZnO particle diameters are 400 nm~1 μm.
5. a kind of preparation method of the ZnO photocatalyst of the graphene coated as described in claim 1-4, it is characterised in that including：
By ZnO surface aminations, ZnO surfaces is carried electropositive, so as to be combined with producing electrostatic interaction with electronegative oxygen-containing functional group on graphene oxide, obtain graphene oxide cladding ZnO compounds；
Gained graphene oxide cladding ZnO compounds are warming up to 500~800 DEG C in reducibility gas, anneals 2~3 hours, obtains the ZnO photocatalyst of graphene coated.
6. preparation method according to claim 5, it is characterised in that the preparation of the ZnO includes：1-METHYLPYRROLIDONE is pressed with deionized water（4~9）：6 are mixed with out mixed solvent；3.5~5.5g zinc acetates are mixed with 200mL mixed solvents and stirred 4~5 hours at 90~98 DEG C；Product is subjected to centrifuge washing and after drying after having reacted, the ZnO is obtained.
7. the preparation method according to claim 5 or 6, it is characterised in that the amination includes：It is 1 that ZnO is added into 3- aminopropyls-trimethoxy silane with absolute ethyl alcohol volume ratio：（10~20）Mixed liquor in, it is ultrasonically treated and carry out centrifuge washing with absolute ethyl alcohol after 55~65 DEG C of heating stirrings are reacted 8~12 hours and be dried to obtain amino zinc oxide.
8. the preparation method according to any one of claim 5-7, it is characterized in that, it is described be complex as the amino zinc oxide of 5~10 ml 0.5~1.5 mg/ml graphene oxide water solutions and 1.0~2.0 g being added in deionized water carry out it is ultrasonically treated, and reacted 6~10 hours in 55~65 DEG C of heating stirrings, reacted suspension is then subjected to centrifuge washing and graphene oxide cladding ZnO compounds are dried to obtain.
9. the preparation method according to any one of claim 5-8, it is characterised in that the reducibility gas is hydrogen nitrogen mixed gas or hydrogen-argon-mixed, the molal weight of the hydrogen is the 9~11% of reducibility gas total moles quality.
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| CN109266893A (en) * | 2018-09-21 | 2019-01-25 | 宜春学院 | A kind of method of coating zinc oxide graphene enhancing composite material of magnesium alloy |
| CN109273605A (en) * | 2018-10-01 | 2019-01-25 | 河北工程大学 | A kind of graphene solar battery and preparation method thereof |
| CN109701515A (en) * | 2019-01-28 | 2019-05-03 | 中国建筑材料科学研究总院有限公司 | Air cleaning nano zine oxide/graphene optic catalytic composite material and preparation method thereof |
| CN111054419A (en) * | 2019-12-23 | 2020-04-24 | 湖南大学 | For CO2Reduced semiconductor/g-C3N4Photocatalyst and preparation method thereof |
| CN111054419B (en) * | 2019-12-23 | 2023-03-24 | 湖南大学 | For CO 2 Reduced semiconductor/g-C 3 N 4 Photocatalyst and preparation method thereof |
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