CN104525174A - Graphene-based composite material preparing method based on oxidized graphene self-assembling - Google Patents
Graphene-based composite material preparing method based on oxidized graphene self-assembling Download PDFInfo
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- CN104525174A CN104525174A CN201510001525.1A CN201510001525A CN104525174A CN 104525174 A CN104525174 A CN 104525174A CN 201510001525 A CN201510001525 A CN 201510001525A CN 104525174 A CN104525174 A CN 104525174A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 144
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 201
- 239000004005 microsphere Substances 0.000 claims abstract description 107
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 100
- 229910052709 silver Inorganic materials 0.000 claims abstract description 58
- 239000004332 silver Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 5
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 56
- 239000006185 dispersion Substances 0.000 claims description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 240000007651 Rubus glaucus Species 0.000 claims description 6
- 235000011034 Rubus glaucus Nutrition 0.000 claims description 6
- 235000009122 Rubus idaeus Nutrition 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 238000004220 aggregation Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 230000009881 electrostatic interaction Effects 0.000 claims description 5
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000010956 nickel silver Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000011238 particulate composite Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/50—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention relates to a seal-assembling method of oxidized graphene on a non-planar substrate surface and a silicon dioxide/graphene/silver nanoparticle composite microsphere built based on the method and of a unique raspberry-shape structure, and belongs to the technical field of graphene-based composite material preparing. Firstly, tetraethyl orthosilicate serves as a silicon source, and a slightly-improved S ber method is adopted to prepare a silicon dioxide microsphere; secondly, cationic polyelectrolyte is assembled to the surface of the silicon dioxide microsphere, and the surface of the silicon dioxide microsphere is made to be electrochemical; thirdly, a small-sized oxidized graphene piece is self assembled to the surface of the microsphere through the electrostatic action under the continuously powerful ultrasonic condition; fourthly, silver nanoparticles are arranged on the surface of the composite microsphere in an in-situ deposition mode; fifthly, the oxidized graphene is changed into graphene in a reduction mode through hydrazine hydrate, and the silicon dioxide/graphene/silver nanoparticle composite microsphere of the raspberry-shape structure is obtained. The composite microsphere has good water dispersibility, excellent catalytic activity is represented for catalytic reduction of 4-nitrobenzene and wide application prospects are presented.
Description
Technical field
The invention belongs to technical field prepared by graphene-based composite, be specifically related to a kind of graphene oxide under ultrasonic wave added in the method for non-planar substrate (silicon dioxide microsphere) surface self-organization and having of constructing based on the method is high-dispersed and raspberry shape structural silica dioxide/Graphene/silver nano-grain complex microsphere that is high catalytic performance.
Background technology
Graphene makes it become the focus in investigation of materials field due to the structure of its uniqueness and excellent physical and chemical performance, and the various composite based on Graphene and functional material also emerge in an endless stream.In report in the past, often by various nano particle (as metal oxide, metal sulfide, noble metal, conductive polymer nanometer particle etc.), (radial dimension scope is about 500 nm to people to be carried on larger-size graphene film
~5 μm) surface prepare graphene/nanometer particulate composite.In these graphene/nanometer particulate composite processes of preparation, nano particle is normally as the graphenic surface that guest species deposits or is grown on as main substance, Graphene act as the role of substrate or backing material, take this strategy easily to cause Assembling Behavior on the one hand, be also unfavorable for preparing the graphene-based composite that pattern is more complicated, performance is more outstanding on the other hand.On the contrary, by substrate material surface, especially non-planar substrate surface is introduced graphene oxide or Graphene to construct the research of graphene-based composite then relatively less.Recently, people start to pay close attention to this problem, and attempt at various microballoon as titanium dioxide, cobaltosic oxide, cadmium sulfide microsphere surface coated one deck graphene oxide also prepare graphene-based composite [(a) Lee, J. S. based on this; You, K. H.; Park, C. B.
adv. Mater.2012,
24, 1084
-1088. (b) Yang, S.; Feng, X.; Ivanovici, S.; M ü llen, K.
angew. Chem. Int. Ed.2010,
49, 8404
-8411. (c) Chen, Z.; Liu, S.; Yang, M.-Q.; Xu, Y.-J.
aCS Appl. Mater. Interfaces2013,
5, 4309
-4319.].But often oxidized Graphene institute adhesion between microballoon in coated process, produce serious clustering phenomena, cause the water dispersible of final prepared graphene-based composite very poor, significantly limit the various performance of material and further functional modification.Therefore, how to overcome adhesion and clustering phenomena that graphene oxide easily produces when non-planar substrate surface-assembled, then prepare structure uniqueness, Focal point and difficult point that water dispersible graphene-based composite that is good, excellent performance becomes current relevant Graphene research.
Summary of the invention
One of the object of the invention is to provide a kind of convenient, simple method in non-planar substrate (silicon dioxide microsphere) surface self-organization graphene oxide in order to overcome graphene oxide adhesion common in substrate surface self assembling process and clustering phenomena; Two of object be prepare further on the basis of the method there is high-dispersed, high catalytic activity and unique raspberry shape structure silica/Graphene/silver nano-grain complex microsphere in order to realize the catalytic reduction of 4-nitrophenol high selectivity.
the present invention is achieved by the following technical solutions, first silicon dioxide colloid microballoon is prepared, cationic polyelectrolyte diallyl dimethyl ammoniumchloride is assembled by electrostatic interaction on its surface, make the positive electrification in its surface, the assembling of small size graphene oxide sheet at microsphere surface is realized by electrostatic interaction again under continuous strong ultrasound condition, then utilize the reproducibility of this graphene oxide clad itself that freshly prepd silver ammonia complex in-situ reducing is become silver nano-grain and be deposited on its surface, with hydrazine hydrate, deposited graphene oxide composition is reduced into Graphene again, thus obtain there is unique raspberry shape structure and there is high-dispersed silica/Graphene/silver nano-grain complex microsphere, then this complex microsphere is applied to the catalytic reduction of 4-nitrophenol, specifically comprise the following steps:
(1) employing concentration is the tetraethyl orthosilicate of 0.2 M is silicon source, by it with containing ammonia, (concentration range is 0.8
~2.5 M) and water (concentration is 34 M) ethanolic solution equal-volume mixing, vigorous stirring overnight.Tetraethyl orthosilicate is hydrolyzed and obtains silicon dioxide colloid microballoon under the catalysis of ammonia in ethanol medium.Prepared silicon dioxide colloid Microsphere Size can be controlled by the concentration of regulation and control ammonia.
(2) silicon dioxide microsphere ultrasonic disperse step (1) prepared is in water, then by itself and excessive diallyl dimethyl ammoniumchloride aqueous solution, vigorous stirring overnight, make cationic polyelectrolyte diallyl dimethyl ammoniumchloride be assembled in silicon dioxide microsphere surface by electrostatic interaction, obtain the silicon dioxide microsphere of the positive electrification in surface.
(3) by small size graphene oxide sheet in advance ultrasonic disperse in water, form certain density aqueous dispersions, by this aqueous dispersions centrifugal 5 min at high speeds, removing a small amount of aggregation wherein, and get upper strata dispersion liquid ultrasonic 30 min again, for ensuing assembling.
(4) the silicon dioxide microsphere ultrasonic disperse of the positive electrification in the surface of step (2) being prepared is in water, it be dropwise added in the small size graphene oxide aqueous dispersions in excessive step (3) under continuous strong ultrasound condition, then ultrasonic 30 min are to complete the assembling on small size graphene oxide sheet silicon dioxide microsphere surface of positive electrification on surface.Then silica/graphene oxide complex microsphere is separated reaction system centrifugal 5 min under certain rotating speed with the free oxygen functionalized graphene aqueous dispersions on unassembled.
(5) by the silica in step (4)/graphene oxide complex microsphere ultrasonic disperse in water, itself and excessive brand-new silver ammino solution are uniformly mixed, in 85
oreact 45 min under C, utilize the reproducibility of graphene oxide itself silver ammonia complex in-situ reducing is become silver nano-grain and is deposited on complex microsphere surface, thus obtain silica/graphene oxide/silver nano-grain complex microsphere.
(6) by the silica/graphene oxide in step (5)/silver nano-grain complex microsphere ultrasonic disperse in water, then dropwise add excess hydrazine hydrate under stirring condition, then in 85
oreact 1 h under C, graphene oxide composition wherein will be reduced into Graphene, thus obtain silica/Graphene/silver nano-grain complex microsphere.
(7) by the silica/Graphene in step (6)/silver nano-grain complex microsphere ultrasonic disperse in water, be diluted to finite concentration again, get 1 mL wherein, it is fully mixed with the sodium borohydride aqueous solution of 1 mL and the 4-nitrophenol aqueous solution of 1 mL successively, then this reactant mixture is transferred in cuvette and reacts.This course of reaction adopts ultraviolet
-visible spectrum in-situ monitoring, to measure the catalytic activity of the catalyst (i.e. silica/Graphene/silver nano-grain complex microsphere) of speed constant also prepared by qualification of this reaction.
silicon dioxide microsphere size of the present invention is very homogeneous, and its particle diameter increases with the increase of catalyst ammonia concentration in step (1), and its size adjustable scope is 200
~500 nm, and all there is good water dispersible.
small size graphene oxide sheet of the present invention, its radial dimension is all no more than 200 nm.For avoiding graphene oxide incident adhesion and clustering phenomena in silicon dioxide microsphere surface self-organization process, small size graphene oxide aqueous dispersions before for assembling need under at a high speed (rotating speed is higher than 15000 rpm) centrifugal 5 min, to remove wherein a small amount of aggregation.
Of the present invention ultrasonic to be continuous strong ultrasonic, and its power is higher than 150W.
compared with prior art, tool of the present invention has the following advantages and effect:
1, the present invention assembles in silicon dioxide microsphere surface under continuous strong ultrasound condition by adopting small size graphene oxide sheet, efficiently solving incident adhesion and clustering phenomena in graphene oxide and microballoon recombination process, providing effective method for realizing graphene oxide in the assembling on other non-planar substrate surface.
2, prepared in the present invention graphite oxide thiazolinyl and graphene-based complex microsphere (as silica/graphene oxide, silica/graphene oxide/silver nano-grain, silica/Graphene/silver nano-grain complex microsphere) all have good water dispersible, by after its vacuum drying can again ultrasonic disperse in water, and obvious sedimentation does not occur after hold over night yet or produces massive aggregates body, thus there is good application potential.
3, silica/Graphene/silver nano-grain complex microsphere that prepared by the present invention has unique raspberry shape structure, and its good water dispersible and the synergy between silver nano-grain and Graphene make its catalytic performance be better than the similar catalyst of the silver-containing nanoparticles that other has been reported far away.
4, the standby and course of reaction of the ownership in the present invention is all using water or ethanol as medium, and reaction condition temperature, and method of operating is easy, with low cost, pollutes minimum.In addition, prepared target material silica/Graphene/silver nano-grain complex microsphere also has lasting chemical stability and catalytic activity.
Accompanying drawing explanation
fig. 1 be silica/Graphene/silver nano-grain complex microsphere prepare schematic diagram.
fig. 2 is the SEM figure of silicon dioxide microsphere under different multiplying.
Fig. 3 is the AFM figure of small size graphene oxide sheet.
fig. 4 is the SEM figure of silica under different multiplying/graphene oxide complex microsphere.
fig. 5 is the TEM figure of silica under different multiplying/graphene oxide complex microsphere.
fig. 6 is the ultraviolet of silica/graphene oxide complex microsphere aqueous dispersions
-visible ray spectrogram.
fig. 7 is the electronic photo after silica/graphene oxide complex microsphere aqueous dispersions hold over night.
fig. 8 is the SEM figure of silica/graphene oxide/silver nano-grain complex microsphere under different multiplying.
fig. 9 is the SEM figure of silica/Graphene/silver nano-grain complex microsphere under different multiplying.
figure 10 is the TEM figure of silica/Graphene/silver nano-grain complex microsphere under different multiplying.
figure 11 is that the high-resolution TEM of silica/Graphene/silver nano-grain complex microsphere surface silver nano-grain schemes.
figure 12 is the ultraviolet of silica/Graphene/silver nano-grain complex microsphere aqueous dispersions
-visible ray spectrogram.
figure 13 is the electronic photo after silica/Graphene/silver nano-grain complex microsphere aqueous dispersions hold over night.
figure 14 is silica/Graphene/silver nano-grain complex microsphere catalysis sodium borohydride reduction 4-nitrophenol design sketch.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is further described in detail below by embodiment.
Embodiment 1: method provided by the invention is used for the assembling of small size graphene oxide sheet on silicon dioxide microsphere surface:
(1) be that the tetraethyl orthosilicate ethanolic solution of 0.2 M mixes with the ethanolic solution that 100 mL contain ammonia (concentration is 1.6 M) and water (concentration is 34 M) by 100 mL concentration, vigorous stirring overnight.Employing ethanol is solvent, and silicon dioxide colloid microballoon tetraethyl orthosilicate being hydrolyzed under ammonia catalysis generation is repeatedly centrifugal
-washing final vacuum is dry.The size of prepared silicon dioxide colloid microballoon is very homogeneous, its average grain diameter ~ 280 nm (Fig. 2).
(2) the silicon dioxide microsphere ultrasonic disperse 1 g step (1) prepared, in 100 mL water, is configured to the aqueous dispersions of 10 mg/mL; By 5 g mass fractions be again 20% diallyl dimethyl ammoniumchloride be dissolved in 95 mL water, and stir 1 more than h.Then by silica aqueous dispersion and diallyl dimethyl ammoniumchloride aqueous solution, vigorous stirring overnight, makes cationic polyelectrolyte diallyl dimethyl ammoniumchloride be assembled in silicon dioxide microsphere surface by electrostatic interaction.Employing water is solvent, by repeatedly centrifugal for the silicon dioxide microsphere of positive for this obtained surface electrification
-washing final vacuum is dry.
(3) small size graphene oxide sheet is scattered in water in advance, ultrasonic 60 min, form the aqueous dispersions of 0.2 mg/mL, by this aqueous dispersions centrifugal 5 min under the rotating speed of 16000 rpm, removing a small amount of aggregation wherein, and get upper strata dispersion liquid ultrasonic 30 min again, gained small size graphene oxide aqueous dispersions is used for ensuing assembling, and its radial dimension is all no more than 200 nm (Fig. 3).
(4) the silicon dioxide microsphere ultrasonic disperse of the positive electrification in the surface of 0.8 g step (2) being prepared is in 100 mL water, form the aqueous dispersions that concentration is 8 mg/mL, it is dropwise added under the continuous strong ultrasound condition of 200 W in the small size graphene oxide aqueous dispersions in 100 mL steps (3), then ultrasonic 30 min are to complete the assembling on small size graphene oxide sheet positive electrochemical silicon dioxide microsphere surface on surface, thus obtain silica/graphene oxide complex microsphere.Then by reaction system centrifugal 5 min under the rotating speed of 8000 rpm, silica/graphene oxide complex microsphere is separated with unassembled free oxygen functionalized graphene aqueous dispersions, and be that silica/graphene oxide complex microsphere ultrasonic disperse washs by solvent with water, and centrifugation final vacuum is dry again.
(5) take silica/graphene oxide complex microsphere prepared by 9 mg steps (4), by its ultrasonic disperse in 3 mL water, form the aqueous dispersions that concentration is 3 mg/mL, after hold over night, observe sedimentation situation.
Not oxidized Graphene institute adhesion (Fig. 4 and Fig. 5) between prepared silica/graphene oxide complex microsphere, and silicon dioxide microsphere surface to assemble coated graphene oxide layer very even, average thickness ~ 6 nm (Fig. 5), its assembling amount accounts for 1.45% of silica/graphene oxide complex microsphere quality.
Prepared silica/graphene oxide complex microsphere aqueous dispersions has an absworption peak (Fig. 6) at 230 nm places, is the characteristic absorption peak of graphene oxide, this further demonstrates that the successful assembling of graphene oxide on silicon dioxide microsphere surface.
Prepared silica/graphene oxide complex microsphere water dispersible is splendid, dried silica/graphene oxide complex microsphere can be scattered in water through ultrasonic again, form homogeneous brown colored water dispersion liquid, and after hold over night, also do not produce obvious sedimentation or massive aggregates body (Fig. 7).
Embodiment 2: by method provided by the invention for the preparation of having unique texture and high-dispersed graphene-based composite:
(1) by the silica in 0.4 g embodiment 1/graphene oxide complex microsphere ultrasonic disperse in 100 mL water, forming concentration is the aqueous dispersions of 4 mg/mL, and the brand-new silver ammino solution being 40 mM by itself and 100 mL concentration is uniformly mixed, in 85
oreact 45 min under C, utilize the reproducibility of graphene oxide itself silver ammonia complex in-situ reducing is become silver nano-grain and is deposited on complex microsphere surface, thus prepare silica/graphene oxide/silver nano-grain complex microsphere.Employing water is solvent, and it is repeatedly centrifugal
-washing final vacuum is dry.
(2) by the silica/graphene oxide in 0.2 g step (1)/silver nano-grain complex microsphere ultrasonic disperse in 100 mL water, form the aqueous dispersions that concentration is 2 mg/mL, then dropwise hydrazine hydrate is added under stirring condition, its ultimate density is made to reach 10 mg/mL, then in 85
oreact 1 h under C, graphene oxide composition wherein will be reduced into Graphene, thus obtain silica/Graphene/silver nano-grain complex microsphere.Employing water is solvent, and it is repeatedly centrifugal
-washing final vacuum is dry.
(3) take silica/Graphene/silver nano-grain complex microsphere prepared by 0.9 mg step (2), by its ultrasonic disperse in 3 mL water, form the aqueous dispersions that concentration is 0.3 mg/mL, after hold over night, observe sedimentation situation.
Also without adhesion between prepared silica/Graphene/silver nano-grain complex microsphere, and there is unique raspberry shape structure (Fig. 9 and Figure 10), its pattern and silica/graphene oxide/silver nano-grain complex microsphere no significant difference (Fig. 8), illustrate that pattern obtains still to keep after hydrazine hydrate heat treatment.
Prepared silica/Graphene/silver nano-grain complex microsphere surface uniform is dispersed with silver nano-grain, and its particle size range is 2
~50 nm (Figure 10), and its lattice fringe is high-visible, the spacing of lattice of its 0.236 nm corresponds to (111) crystal face (Figure 11) of silver nano-grain well, and this illustrates the successful deposition of silver nano-grain on complex microsphere surface well.
Prepared silica/Graphene/silver nano-grain complex microsphere aqueous dispersions has an absworption peak (Figure 12) at 260 nm places, for the characteristic absorption peak of Graphene, this illustrates that silica/graphene oxide/silver nano-grain complex microsphere is after hydrazine hydrate heat treatment, and wherein deposited graphene oxide composition has been reduced into Graphene really; Meanwhile, prepared silica/Graphene/silver nano-grain complex microsphere aqueous dispersions also has another absworption peak (Figure 12) at 410 nm places, the corresponding well typical surface plasmon absorption peak of institute's depositing silver nano particle.In addition, in prepared silica/Graphene/silver nano-grain complex microsphere, silver content is 4%.
Prepared silica/Graphene/silver nano-grain complex microsphere also has fabulous water dispersible, dried silica/Graphene/silver nano-grain complex microsphere can be scattered in water through ultrasonic again, form homogeneous red aqueous dispersions, and after hold over night, also do not produce obvious sedimentation or massive aggregates body (Figure 13).
Embodiment 3: the catalytic reduction graphene-based composite wood prepared in the present invention being used for 4-nitrophenol:
(1) silica/Graphene/silver nano-grain complex microsphere in 3 mg embodiments 2 is taken, by its ultrasonic disperse in 20 mL water, form the aqueous dispersions that concentration is 0.15 mg/mL, get wherein 1 mL, be then diluted to the aqueous dispersions that concentration is 1.5 μ g/mL.
(2) 1 mL of the aqueous dispersions in step (1) after dilution is got, the 4-nitrophenol aqueous solution of to be the sodium borohydride aqueous solution of 30 mM and 1 mL concentration successively with 1 mL concentration by it be 0.3 mM fully mixes, and is then transferred in cuvette by this reactant mixture and reacts.
(3) the whole process of this catalytic reaction adopts ultraviolet
-visible spectrum carries out in-situ monitoring, to measure the catalytic activity of the catalyst (i.e. silica/Graphene/silver nano-grain complex microsphere) of speed constant also prepared by qualification of this reaction.
Figure 14 is silica/Graphene/silver nano-grain complex microsphere catalysis sodium borohydride reduction 4-nitrophenol design sketch, therefrom can see the ultraviolet of reaction system described in step (2)
-visible spectrum over time.Clearly, this catalytic reaction just can complete within 9 min, and conversion ratio is more than 99.5%; In addition, this reaction is similar to first order reaction, and its speed constant is 0.7 min
1.As can be seen here, prepared silica/Graphene/silver nano-grain complex microsphere has very outstanding catalytic performance, far above the similar catalyst of silver-containing nanoparticles, illustrates that it has a good application prospect.
Claims (6)
1. the method at non-planar substrate surface self-organization graphene oxide, it is characterized in that not sticking together and Assembling Behavior in self assembling process, non-planar substrate is silicon dioxide microsphere, its particle size range is 200 ~ 500 nm, and needs in self assembling process to complete under the continuous strong ultrasound condition of power higher than 150 W.
2. graphene oxide as claimed in claim 1, is characterized in that its radial dimension is no more than 200 nm.
3. the assembling of graphene oxide on silicon dioxide microsphere surface as claimed in claim 1, it is characterized in that assembled graphene oxide layer thickness is about 6 nm, and the silica/graphene oxide complex microsphere formed after assembling has splendid water dispersible, the aqueous dispersions that this complex microsphere is formed after ultrasonic disperse still produces without obvious sedimentation or aggregation after hold over night.
4. graphene oxide as claimed in claim 1 is as follows in the concrete steps of non-planar substrate surface self-organization:
(1) employing concentration is the tetraethyl orthosilicate of 0.2 M is silicon source, it is mixed with the ethanolic solution equal-volume containing ammonia (concentration range is 0.8 ~ 2.5 M) and water (concentration is 34 M), vigorous stirring overnight, tetraethyl orthosilicate is hydrolyzed and obtains silicon dioxide colloid microballoon under the catalysis of ammonia in ethanol medium, and prepared silicon dioxide colloid Microsphere Size can be controlled by the concentration of regulation and control ammonia;
(2) silicon dioxide microsphere ultrasonic disperse step (1) prepared is in water, then by itself and excessive diallyl dimethyl ammoniumchloride aqueous solution, vigorous stirring overnight, make cationic polyelectrolyte diallyl dimethyl ammoniumchloride be assembled in silicon dioxide microsphere surface by electrostatic interaction, obtain the silicon dioxide microsphere of the positive electrification in surface;
(3) by small size graphene oxide sheet in advance ultrasonic disperse in water, form certain density aqueous dispersions, by this aqueous dispersions centrifugal 5 min at high speeds, removing a small amount of aggregation wherein, and get upper strata dispersion liquid ultrasonic 30 min again, for ensuing assembling;
(4) the silicon dioxide microsphere ultrasonic disperse of the positive electrification in the surface of step (2) being prepared is in water, it be dropwise added in the small size graphene oxide aqueous dispersions in excessive step (3) under continuous strong ultrasound condition, then ultrasonic 30 min are to complete the assembling on small size graphene oxide sheet silicon dioxide microsphere surface of positive electrification on surface; Then silica/graphene oxide complex microsphere is separated reaction system centrifugal 5 min under certain rotating speed with the free oxygen functionalized graphene aqueous dispersions on unassembled.
5. one kind has the silica/Graphene/silver nano-grain complex microsphere of unique raspberry shape structure, it is characterized in that silver nano-grain is uniformly distributed in complex microsphere surface, its size range is 2 ~ 50 nm, this complex microsphere has fabulous water dispersible, the aqueous dispersions formed after ultrasonic disperse still produces without obvious sedimentation or aggregation after hold over night, and shows excellent catalytic activity to the catalytic reduction of 4-nitro.
6. the preparation method of silica/Graphene/silver nano-grain complex microsphere as claimed in claim 5, is characterized in that concrete synthesis step is as follows:
(1) by the silica in claim 3 or 4/graphene oxide complex microsphere ultrasonic disperse in water, itself and excessive brand-new silver ammino solution are uniformly mixed, in 85
oreact 45 min under C, utilize the reproducibility of graphene oxide itself silver ammonia complex in-situ reducing is become silver nano-grain and is deposited on complex microsphere surface, thus obtain silica/graphene oxide/silver nano-grain complex microsphere;
(2) by the silica/graphene oxide in step (1)/silver nano-grain complex microsphere ultrasonic disperse in water, then dropwise add excess hydrazine hydrate under stirring condition, then in 85
oreact 1 h under C, graphene oxide composition wherein will be reduced into Graphene, namely obtain silica/Graphene/silver nano-grain complex microsphere.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110014550A1 (en) * | 2007-12-14 | 2011-01-20 | Nanyang Technological University | Nanostructured material loaded with noble metal particles |
| CN102532620A (en) * | 2010-12-28 | 2012-07-04 | 广东海洋大学 | Method for preparing natural latex composite material based on nano SiO2 and graphite oxide |
| CN102989416A (en) * | 2012-11-30 | 2013-03-27 | 中国农业科学院油料作物研究所 | Aflatoxin adsorbent and method for removing aflatoxins in edible vegetable oil |
| CN103359709A (en) * | 2012-03-27 | 2013-10-23 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013057079A1 (en) * | 2011-10-17 | 2013-04-25 | Fundació Privada Institut Català D'investigació Química (Iciq) | Process for water oxidation comprising the use of a polyoxometalate compound as water oxidation catalyst |
| CN102895938B (en) * | 2012-11-13 | 2014-12-31 | 武汉大学 | Preparation method of graphene covered silica gel |
| CN104148061A (en) * | 2014-07-07 | 2014-11-19 | 上海应用技术学院 | Catalyst for waste water treatment and preparation method thereof |
| CN104157840B (en) * | 2014-08-15 | 2016-06-15 | 南京师范大学 | The preparation method of a kind of lithium ion battery graphene coated silica nanometer pipe composite negative pole material |
-
2015
- 2015-01-05 CN CN201610609321.0A patent/CN106000379A/en active Pending
- 2015-01-05 CN CN201510001525.1A patent/CN104525174B/en active Active
- 2015-01-05 CN CN201610608612.8A patent/CN106345459A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110014550A1 (en) * | 2007-12-14 | 2011-01-20 | Nanyang Technological University | Nanostructured material loaded with noble metal particles |
| CN102532620A (en) * | 2010-12-28 | 2012-07-04 | 广东海洋大学 | Method for preparing natural latex composite material based on nano SiO2 and graphite oxide |
| CN103359709A (en) * | 2012-03-27 | 2013-10-23 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN102989416A (en) * | 2012-11-30 | 2013-03-27 | 中国农业科学院油料作物研究所 | Aflatoxin adsorbent and method for removing aflatoxins in edible vegetable oil |
Non-Patent Citations (1)
| Title |
|---|
| XIAOJING LIANG，: ""Layer-by-layer self-assembled graphene oxide/silica microsphere composites as stationary phase for high performance liquid chromatography"", 《ANALYST》 * |
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