CN102910625A - Graphene oxide aerogel, preparation method and application - Google Patents
Graphene oxide aerogel, preparation method and application Download PDFInfo
- Publication number
- CN102910625A CN102910625A CN2012104578204A CN201210457820A CN102910625A CN 102910625 A CN102910625 A CN 102910625A CN 2012104578204 A CN2012104578204 A CN 2012104578204A CN 201210457820 A CN201210457820 A CN 201210457820A CN 102910625 A CN102910625 A CN 102910625A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- aerogel
- solution
- oxide aerogel
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 270
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 237
- 239000004964 aerogel Substances 0.000 title claims abstract description 163
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000017 hydrogel Substances 0.000 claims abstract description 41
- -1 ester compounds Chemical class 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 11
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 33
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- 239000010439 graphite Substances 0.000 claims description 30
- 150000003141 primary amines Chemical class 0.000 claims description 28
- 150000003335 secondary amines Chemical class 0.000 claims description 28
- 150000003512 tertiary amines Chemical group 0.000 claims description 21
- 239000000499 gel Substances 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 17
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 241000446313 Lamella Species 0.000 claims description 14
- 238000007710 freezing Methods 0.000 claims description 13
- 230000008014 freezing Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 6
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 6
- 229960003681 gluconolactone Drugs 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000412 dendrimer Substances 0.000 claims description 5
- 229920000736 dendritic polymer Polymers 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 238000000352 supercritical drying Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 238000004108 freeze drying Methods 0.000 abstract description 4
- 239000004971 Cross linker Substances 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 1
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000003756 stirring Methods 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 238000013019 agitation Methods 0.000 description 13
- 230000000274 adsorptive effect Effects 0.000 description 12
- 238000001132 ultrasonic dispersion Methods 0.000 description 12
- 238000007906 compression Methods 0.000 description 11
- 230000001105 regulatory effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 150000001457 metallic cations Chemical class 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000011240 wet gel Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Abstract
The invention relates to a graphene oxide aerogel, a preparation method and an application, belonging to the application field of nanophase materials. The preparation method comprises the following steps: assembling graphene oxide sheets into a three-dimensional net structure in an edge joint manner through a cross linker; adding metal hydroxide colloid or metal carbonate colloid to basic graphene oxide aqueous solution, or adding molecules containing primary amine, secondary amine or tertiary amine functional groups; adding ester compounds after mixing uniformly; stewing to obtain graphene oxide hydrogel; and obtaining the graphene oxide aerogel disclosed by the invention after freeze drying or supercritical drying. The aerogel has hierarchical aperture, extra-high specific area and three-dimensional structure, and combines excellent physical and chemical properties of graphene oxide and ultra-light porosity characteristic of aerogel.
Description
Technical field
The present invention relates to a kind of graphene oxide aerogel, preparation method and application, belong to fields of nano material application.
Background technology
Aerogel is employing special process (generally referring to supercritical drying) does not significantly change the liquid in the wet gel gel network with gas displacement structure and volume, and the highly porous nano material with low density and high-specific surface area that obtains.The preparation core of aerogel is sol-gel chemistry.Theoretically, if certain material has the sol-gel transition phenomenon, adopting dry this kind wet gel of special process can obtain aerogel (but has exception.(see Chemical Communications such as the poly-alcoxyl sulfonic group ethylenedioxy thiophene hydrogel with two-dimensional framework unit that we have reported, 2011,47 (22), 6287-6289) then can not be transformed into corresponding aerogel by the supercritical drying drying process and (see Journal of Materials Chemistry, 2012,22,8579-8584)).1932, Americanized scholar Samuel StephensKistler reported first case aerogel, i.e. aerosil.Nineteen sixty-eight rises, and professor S.J.Teichner of Lyons, France Cloud university (the UniversityClaude) has reported the aerogel of a series of metal oxides and bimetallic oxide.1986, U.S. Sandia National Laboratory reported borate (ester) aerogel.
The excellent properties such as that aerogel has is ultralight, abundant pore passage structure and high porosity, extremely low thermal conductivity, ultralow acoustic resistance, utmost point low-k, high voltage breakdown.The characteristic of aerogel is mainly determined by the framework material that forms aerogel.Therefore need to the framework material of aerogel be screened and design.The mechanical property of framework material is also determining the mechanical property of aerogel.Usually, inorganic aerogels fragility is very large, and organic aerogel then has good snappiness.Aerogel is with a wide range of applications, as: ultralow thermal conductivity and ultralow acoustic resistance are so that aerogel can be applied to construction work, chemical engineering (chilling process, pyroprocess, moulding, casting etc.), automobile engineering (engine, exhaust system etc.), medicine engineering, electro-engineering etc.The transparency of optics or translucency are so that aerogel can be applied to construction work (front of heat insulation window or heat insualting building) and sensor.Ultralow dielectric is so that aerogel can be applied to the electronic engineering field.Superelevation porosity and huge specific surface area are so that aerogel can be applied to chemistry, medicine, the energy and environmental engineering etc.The mechanical property of extremely-low density and enhancing is so that aerogel can be applied to aerospace (man-made satellite, space shuttle and detector etc.) and automotive field as super light material.The fragility of aerosil is so that its absorbing material that can be used as shockwave is applied to the mechanical protection materials such as the helmet, automobile impacting snubber.In the deep space probing field, aerogel is as outer space particle-capture agent, success caught the space particle.Aerogel even can be applied to the fine chemistry industries such as coating and makeup and filed of daily-use chemical industry etc.
Graphene oxide generates through the strong oxidizer oxidation normally take graphite as raw material, and the constraint that then makes the mono-layer graphite lamella break away from Van der Waals force through special processing independently exists.Graphene oxide is substantially identical with the structure of Graphene, just because acting on the unlimited basal plane that extends of the two dimension that is made of carbon atom of oxygenant is connected with multiple oxygen-content active group.High-resolution solid-state
13C-NMR, the FT-IR test result shows hydroxyl, epoxide group and a large amount of sp
2-C-structure unit is present in the graphene oxide surface, and carboxyl, carbonyl are present in the graphene oxide edge.The existence of these active function groups is for the assembling of the three-dimensional of graphene oxide provides feasible chemical technology route.The whole basal plane main body of graphene oxide is made of two different zones, be respectively not oxidized fragrant phenyl ring and the aliphatics six-ring of sealing, the relative number in these two zones is determined by the degree of oxidation of graphite, the existence of phenyl ring, two key and epoxide group has determined the grid structure of graphene oxide almost flat jointly, because the carbon atom that links to each other with hydroxyl can form the tetrahedral structure of torsional deformation, thereby cause the graphene oxide plane that the part fold occurs.Graphene oxide has excellent processability and solvability, but effective application is in the graphene oxide based composites.The graphene oxide of modifying through chemistry functional can stable dispersion in multiple organic solvent commonly used, form stable graphene oxide suspension, be the starting point for preparing on a large scale Graphene and graphene-based matrix material.In addition, theory and experimental study all show, graphene oxide has very excellent mechanical property, and this is the basis that graphene oxide can be used in many matrix materials.Therefore, can be with graphene oxide as skeleton, preparation graphene oxide aerogel.
Summary of the invention
The purpose of this invention is to provide a kind of graphene oxide aerogel, preparation method and application.Described graphene oxide aerogel has excellent mechanics, absorption and electric property.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of graphene oxide aerogel, described aerogel is assembled into three-dimensional net structure with the graphene oxide lamella with the edge mode of connection by linking agent.
Wherein, described linking agent is divalence or the above metal ion of divalence, perhaps is protonated primary amine, secondary amine or tertiary amine ion.
Preferred described graphene oxide aerogel has vesicular structure, and the aperture is 1nm ~ 20 μ m, and specific surface area is 100 ~ 2000m
2g
-1, density is 10 ~ 500mg cm
-3
The preparation method of a kind of graphene oxide aerogel of the present invention, described method steps is as follows:
(1) preparation graphite oxide aqueous solution;
Described graphite oxide aqueous solution adopts the ordinary method in the Graphene preparation field to make, and is 201001263656.4 such as application number, and denomination of invention is the preparation method of graphene oxide solution in " a kind of graphene aerogel and preparation method thereof ";
After obtaining the graphite oxide aqueous solution, water is formulated as 2～20mg/mL with the concentration of graphene oxide.
(2) in the graphite oxide aqueous solution, add alkaline solution (such as NaOH or KOH) and regulate the pH value to alkalescence (7～14), then the colloidal solution that adds metal hydroxides or metal carbonate, or add the molecule that contains primary amine, secondary amine or tertiary amine functional group, disperse to obtain solution 1;
The quality of preferred described graphene oxide: metal hydroxides, metal carbonate or contain the quality of the molecule of secondary amine, tertiary amine or quaternary amine functional group=2 ~ 50:1; Described metal hydroxides or metal carbonate contain metal hydroxides or the metal carbonate of the above metal ion of divalence or divalence for can form colloidal solution, and described metal ion is Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zr
4+, Sn
4+, Ti
4+, V
5+, La
3+, Cr
3+, Al
3+, Zn
2+, Ce
4+The described molecule that contains primary amine, secondary amine or tertiary amine functional group is small molecules or the polymer that contains two or more primary amine, secondary amine or tertiary amine functional group, such as trimeric cyanamide, polyethylene polyamine, diethylenetriamine, triethylene tetramine or polyamide-amide type dendrimer.
(3) in solution 1, add ester compound, disperse to obtain solution 2; Solution 2 left standstill obtain even immobilising graphene oxide hydrogel.
Preferred described ester compound is selected from ethyl acetate, Gluconolactone or vovocan.
Described ester compound can slowly be hydrolyzed in water, because the acid of hydrolysis is a kind of molecule that contains carboxyl, can slowly reduce the pH value of graphite oxide aqueous solution, thereby slowly metal ion is discharged from metal hydroxides or metal carbonate colloidal solution, obtain metallic cation; Primary amine, secondary amine or the tertiary amine functional group that perhaps will contain slowly in the molecule of primary amine, secondary amine or tertiary amine functional group are protonated, obtain primary amine, secondary amine or tertiary amine positive ion.By metallic cation or primary amine, secondary amine or the tertiary amine positive ion of positively charged, electronegative graphene oxide is assembled into three-dimensional net structure by edge mode of connection (edge to edge).So the add-on of ester compound amount, metal hydroxides, metal carbonate all can be converted into metal ion, maybe will contain primary amine, secondary amine or tertiary amine functional group molecule in whole protonated being as the criterion of primary amine, secondary amine or tertiary amine functional group.
The preferred described condition that leaves standstill is for to leave standstill 0.5～48h with solution 2 under 20 ° of C～70 ° C.
(4) the graphene oxide hydrogel is carried out drying, obtain graphene oxide aerogel of the present invention.
In the preferred steps (4), described drying process is lyophilize, be specially in the graphene oxide hydrogel and add entry, after soaking 0.5～10h water is poured out, repeat 2～8 times, then with graphene oxide hydrogel freezing 〉=30min under-50 ° of C～-5 ° C, the dry 30min～48h of ° C obtains the graphene oxide aerogel 10 ° of C～100; Freezing and drying process is all carried out under the vacuum tightness of 1～10000Pa.
Described freeze drying process is not subjected to the restriction of freeze drying equipment, can finish in freeze drying equipment any commerce or non-commercial.The graphene oxide hydrogel also can adopt first liquid nitrogen freezing, then changes vacuum-drying in the lyophilizer over to; Also can directly lyophilize in lyophilizer.Freezing mode can adopt directed freezing (controlling freezing direction), also can adopt non-directional freezing.
In the preferred steps (4), described drying process is that the supercutical fluid mode is dry, concrete mode is to add ethanol or acetone in the graphene oxide hydrogel, pour out after soaking 0.5～10h, repeat 1～8 time, obtain graphene oxide alcogel or ketone gel, then with Supercritical Ethanol or supercritical co drying 〉=2h, obtain the graphene oxide aerogel.
Described supercritical drying drying process is not subjected to the restriction of supercritical drying equipment, can finish the supercritical drying of graphite oxide enol (or ketone) gel in supercritical drying equipment any commerce or non-commercial, to obtain the graphene oxide aerogel.
The application of a kind of graphene oxide aerogel of the present invention, described application are as anti-ballistic materials with the graphene oxide aerogel.The Young's modulus that obtains described aerogel by compression verification is 0.5 ~ 50MPa, and yield strength is 0.1 ~ 5MPa, and the shock resistance energy absorption is 10 ~ 200J g
-1Be 5 ~ 5000J g by calculating its specific Young's modulus
-1, be 1 ~ 500J g than yield strength
-1, density distribution is 10 ~ 500mg cm
-3, illustrate that the graphene oxide aerogel can be used as anti-ballistic materials and uses.
The application of a kind of graphene oxide aerogel of the present invention, described application are as dye adsorption material with the graphene oxide aerogel.Under 20 ° of C～80 ° C of temperature, described aerogel is 100～2000mg g to the adsorptive capacity of dyestuff (such as methylene blue, C.I. 42685, magenta and rhodamine B)
-1The graphene oxide aerogel not only is confined to above-mentioned dyestuff to the adsorptive power of dyestuff.
The application of a kind of graphene oxide aerogel of the present invention, described application are as heavy metal ion adsorbing material with the graphene oxide aerogel.Under 20 ° of C～80 ° C of temperature, described aerogel to heavy metal ion (such as Pb
2+, Cu
2+, Ag
+, Hg
2+, Cr
3+) adsorptive capacity be 20 ~ 200mg g
-1Graphene oxide aerogel counterweight metal biosorption ability not only is confined to above-mentioned heavy metal ion.
The application of a kind of graphene oxide aerogel of the present invention, described application are as gas adsorption material with the graphene oxide aerogel.Under 20 ° of C～80 ° C of temperature, be 20～200mmol g to the adsorptive capacity of gas (such as sulfurous gas, hydrogen sulfide and hydrogen iodide)
-1The graphene oxide aerogel not only is confined to above-mentioned gas to the adsorptive power of gas.
The application of a kind of graphene oxide aerogel of the present invention, described application are as electrode materials with the graphene oxide aerogel.For example in ultracapacitor, as working electrode, the Pt electrode is as to electrode with the Ni film, and the KOH solution of 5moL/L is electrolytic solution, and the ratio electric capacity of the graphene oxide aerogel by cyclic voltammetry is 200 ~ 500F/g.The graphene oxide aerogel uses as electrode materials and not only is confined to above-mentioned ultracapacitor.
Beneficial effect
1. the invention provides a kind of graphene oxide aerogel, described aerogel is that the particular form with the edge edge between the graphene oxide lamella is carried out crosslinked assembling take metal ion or protonated primary amine, secondary amine or tertiary amine ion as linking agent.Have classification aperture, superhigh specific surface area and three-dimensional structure, combine the ultralight porosity characteristic of physical and chemical performance and the aerogel of graphene oxide excellence.
2. the invention provides the preparation method of described graphene oxide aerogel, described method is utilized the sol-gel transition phenomenon of graphene oxide, the graphene oxide lamella of two dimension is assembled into three-dimensional Graphene hydrogel block materials, and then adopt supercritical drying or cryodesiccated mode, the graphene oxide hydrogel is transformed into corresponding aerogel.Described method has overcome in graphene oxide two dimension lamella assembling process, and the graphene oxide sheet layer segment that strong interaction causes between lamella and the lamella is overlapping, causes the too small technical bottleneck of specific surface area.
3. in the forming process of graphene oxide hydrogel, need in Gel Precursor (solution 1), to add gel promotor (being the ester compound of mentioning among the present invention), described ester compound can slowly be hydrolyzed in water, because the acid of hydrolysis is a kind of molecule that contains carboxyl, can slowly reduce the pH value of graphite oxide aqueous solution, thereby slowly metal ion is discharged from oxyhydroxide or carbonate colloidal sol, obtain metallic cation; Primary amine, secondary amine or the tertiary amine functional group that perhaps will contain slowly in the molecule of primary amine, secondary amine or tertiary amine functional group are protonated, obtain primary amine, secondary amine or tertiary amine positive ion.Metallic cation or primary amine, secondary amine or tertiary amine positive ion by positively charged are assembled into three-dimensional net structure with electronegative graphene oxide by edge mode of connection (edgeto edge).
4. the present invention also provides the application of described graphene oxide aerogel, and described graphene oxide aerogel has excellent mechanical property, and good application prospect is arranged aspect shock resistance; In addition, the graphene oxide aerogel has outstanding chemisorption effect to a series of reducing gas, dye molecule and metal ion, at aspects such as ultracapacitors good application is arranged also.
Description of drawings
Fig. 1 is two class graphene oxide aerogel mechanism of crosslinking schematic diagram, and left figure is the crosslinked schematic diagram of metal ion, and right figure is the crosslinked schematic diagram of protonated primary amine, secondary amine or tertiary amine ion.
Fig. 2 is scanning electronic microscope (SEM) figure and the digital photograph of the crosslinked graphene oxide aerogel of La.
Fig. 3 is SEM figure and the digital photograph of the crosslinked graphene oxide aerogel of Ni.
Fig. 4 is SEM figure and the digital photograph of the crosslinked graphene oxide aerogel of polyethylene polyamine.
Fig. 5 is the nitrogen adsorption/desorption graphic representation of two class graphene oxide aerogels.
Fig. 6 is digital photograph and the stress-strain(ed) curves of two class graphene oxide aerogels in the quasistatic compression process, wherein figure (a) is the digital photograph of metal ion crosslinked aerogel before and after compression, figure (b) is protonated primary amine, secondary amine or the tertiary amine ionomer aerogel digital photograph before and after compression, figure (c) be the compression curve of metal ion crosslinked aerogel, schemes the compression curve that (d) is protonated primary amine, secondary amine or tertiary amine ionomer aerogel.
The left figure of Fig. 7 is that the graphene oxide aerogel is at H
2Reacted SEM figure in the S gas, right figure is the quality change curve in the reaction process.
Fig. 8 be the graphene oxide aerogel to methylene blue, C.I. 42685, the adsorption curve of magenta and four kinds of dyestuffs of rhodamine B.
Fig. 9 is that the graphene oxide aerogel is to Pb
2+, Ag
+, Cu
2+, Hg
2+The adsorptive capacity data of four heavy metal species ions.
Figure 10 is the spectrogram of x-ray photoelectron power spectrum (XPS), Raman spectrum and the X-ray diffraction spectrum (XRD) of graphene oxide aerogel, wherein figure (a) is XPS figure, figure (b) is the amplification at carbon 1s peak among the figure (a), and figure (c) is Raman figure, and figure (d) is XRD figure.
Figure 11 is with the cyclic voltammetry curve of graphene oxide aerogel as electrode material for super capacitor.
Embodiment
Wherein, the graphite oxide aqueous solution among the embodiment 1 ~ 11 prepares by the following method:
(1) is in the sulfuric acid adding 100mL flask of 98wt% with 25mL concentration, is heated to 90 ° of C, slowly add successively 5g Potassium Persulphate and 5g Vanadium Pentoxide in FLAKES under the agitation condition.Then be cooled to 80 ° of C, add the 6g Graphite Powder 99, stirring reaction 4.5 hours, the distilled water that adds 1L leaves standstill 12h, obtains preoxidation graphite.
(2) with 2L distilled water the preoxidation graphite that obtains is carried out filtering and washing after, with preoxidation graphite dry 12h under 50 ° of C.
(3) getting 230mL concentration is the flask that the sulfuric acid of 98wt% places 1L, cools off 20min with ice bath, then slowly adds successively dried preoxidation graphite and 30g potassium permanganate, magnetic agitation 20min; Flask reacted 2h in 35 ° of C water-baths after, slowly add 460mL distilled water, add the distilled water diluting of 1.4L again, behind the stirring reaction 2h, add the hydrogen peroxide of 25mL 30wt%, this moment, the color of reaction solution became khaki color;
(4) add the hydrochloric acid of 5wt% in the reaction solution, behind the standing sedimentation supernatant liquor is poured out, repeat 3 times; Add again 2L distilled water, behind the standing sedimentation supernatant liquor is poured out, centrifugal after repeating 2 times, obtain graphene oxide, described graphene oxide is made into needs concentration (2～20mg/mL) graphene oxide solution.Concrete grammar is weighed after for the graphene oxide solution oven dry of taking a morsel, and calculates concentration with quality divided by volume, and then thin up needs concentration until reach.
1) get the graphite oxide aqueous solution that 5mL concentration is 15mg/mL, add the sodium hydroxide solution of 0.4mL0.5mol/L under the agitation condition, regulating the pH value is 8, again to the La that wherein adds 0.4mL 30mg/mL (OH)
3Colloidal solution, ultra-sonic dispersion obtain solution 1.
2) add the Gluconolactone of 100mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 24h under 20 ° of C, obtains uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 6h, repeatedly after 5 times, obtain the graphene oxide alcogel.With the dry 24h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the crosslinked graphene oxide aerogel of La.
1) get the graphite oxide aqueous solution that 5mL concentration is 4mg/mL, add the sodium hydroxide solution of 0.2mL0.5mol/L under the agitation condition, regulating the pH value is 9, after being uniformly dispersed again to the Ni that wherein adds 0.3mL 30mg/mL (OH)
2Colloidal solution, dispersed with stirring obtain solution 1.
2) add the ethyl acetate of 40mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 48h under 20 ° of C, obtains uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 0.5h, repeatedly after 8 times, obtain the graphene oxide alcogel.With the dry 12h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, has obtained the crosslinked graphene oxide aerogel of Ni.
1) get the graphite oxide aqueous solution that 6mL concentration is 14mg/mL, add the potassium hydroxide solution of 0.3mL0.5mol/L under the agitation condition, regulating the pH value is 10, is uniformly dispersed, again to the Fe that wherein adds 0.2mL 30mg/mL (OH)
3Colloidal solution, dispersed with stirring obtain solution 1.
2) add the Gluconolactone of 70mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 8h under 40 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 10h, repeatedly after 2 times, obtain the graphene oxide alcogel.With the dry 24h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, has obtained the crosslinked graphene oxide aerogel of Fe.
Embodiment 4
1) get the graphite oxide aqueous solution that 5mL concentration is 9mg/mL, add the sodium hydroxide solution of 0.2mL0.5mol/L under the agitation condition, regulating the pH value is 8, is uniformly dispersed, again to the Co that wherein adds 0.4mL 20mg/mL (OH)
2Colloidal solution, dispersed with stirring obtain solution 1.
2) add the ethyl acetate of 20mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 12h under 20 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add acetone, after soaking 5h acetone is poured out, after repeating 8 times, in the graphene oxide hydrogel, add entry, water poured out after soaking 5h, repeat 4 times after, obtain graphite oxide ketenes gel, with ketone gel freezing 〉=30min under-5 ° of C, then at the dry 48h of 30 ° of C, obtained the crosslinked graphene oxide aerogel of Co.Freezing and drying process is all carried out under the vacuum tightness of 10Pa.
Embodiment 5
1) get the graphite oxide aqueous solution that 5mL concentration is 18mg/mL, add the sodium hydroxide solution of 0.3mL0.5mol/L under the agitation condition, regulating the pH value is 8, is uniformly dispersed, again to the Ce that wherein adds 0.4mL 30mg/mL (OH)
3Colloidal solution, dispersed with stirring obtain solution 1.
2) add the vovocan of 50mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 24h under 20 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, after soaking 10h ethanol is poured out, after repeating 2 times, in the graphene oxide hydrogel, add entry, water poured out after soaking 10h, repeat 2 times after, obtain the graphene oxide alcogel, with alcogel freezing 〉=30min under-25 ° of C, then at the dry 30min of 70 ° of C, obtained the crosslinked graphene oxide aerogel of Ce.Freezing and drying process is all carried out under the vacuum tightness of 1000Pa.
1) get the graphite oxide aqueous solution that 4mL concentration is 6mg/mL, add the potassium hydroxide solution of 0.2mL 0.5mol/L under the agitation condition, regulating the pH value is 8, is uniformly dispersed, again to the FeCO that wherein adds 0.3mL 30mg/mL
3Colloidal solution, dispersed with stirring obtain solution 1.
2) add the Gluconolactone of 50mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 7h under 50 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 10h, repeatedly after 2 times, obtain the graphene oxide alcogel.With the dry 24h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, has obtained the crosslinked graphene oxide aerogel of Fe.
Embodiment 7
1) get the graphite oxide aqueous solution that 7mL concentration is 6mg/mL, add the potassium hydroxide solution of 0.4mL 0.5mol/L under the agitation condition, regulating the pH value is 9, is uniformly dispersed, again to the NiCO that wherein adds 0.2mL 30mg/mL
3Colloidal solution, dispersed with stirring obtain solution 1.
2) add the ethyl acetate of 40mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 8h under 40 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 10h, repeatedly after 2 times, obtain the graphene oxide alcogel.With the dry 24h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, has obtained the crosslinked graphene oxide aerogel of Ni.
1) gets the graphite oxide aqueous solution that 5mL concentration is 8mg/mL, add the sodium hydroxide solution of 0.3mL0.5mol/L under the agitation condition, regulating the pH value is 9, is uniformly dispersed, to the polyethylene polyamine solution that wherein adds 0.3mL 10mg/mL, dispersed with stirring obtains solution 1 again.
2) add the vovocan of 20mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 0.5h under 70 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 6h, repeatedly after 5 times, obtain the graphene oxide alcogel.With the dry 24h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, has obtained the crosslinked graphene oxide aerogel of polyethylene polyamine.
Embodiment 9
1) gets the graphite oxide aqueous solution that 5mL concentration is 10mg/mL, add the potassium hydroxide solution of 0.2mL0.5mol/L under the agitation condition, regulating the pH value is 8, is uniformly dispersed, to the melamine solution that wherein adds 0.2mL 10mg/mL, dispersed with stirring obtains solution 1 again.Contain three primary amine functional groups in the described trimeric cyanamide.
2) add the vovocan of 10mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 1h under 70 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 6h, repeatedly after 5 times, obtain the graphene oxide alcogel.With the dry 24h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, has obtained the crosslinked graphene oxide aerogel of trimeric cyanamide.
1) gets the graphite oxide aqueous solution that 5mL concentration is 9mg/mL, add the sodium hydroxide solution of 0.1mL 0.5mol/L under the agitation condition, regulating the pH value is 10, is uniformly dispersed, to the polyamide-amide type dendrimer solution that wherein adds 0.1mL 10mg/mL, dispersed with stirring obtains solution 1 again.Contain a plurality of primary amine and secondary amine functional groups in the described polyamide-amide type dendrimer.
2) add the Gluconolactone solution of 50mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 3h under 70 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 6h, repeatedly after 5 times, obtain the graphene oxide alcogel.With the dry 24h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, has obtained the crosslinked graphene oxide aerogel of polyamide-amide type dendrimer.
Embodiment 11
1) gets the graphite oxide aqueous solution that 5mL concentration is 7mg/mL, add the sodium hydroxide solution of 0.2mL0.5mol/L under the agitation condition, regulating the pH value is 9, is uniformly dispersed, to the diethylenetriamine solution that wherein adds 0.2mL 10mg/mL, dispersed with stirring obtains solution 1 again.Contain two primary amine and a secondary amine functional groups in the described diethylenetriamine.
2) add the ethyl acetate solution of 30mg in the solution 1, ultra-sonic dispersion obtains solution 2, and solution 2 is left standstill 3h under 60 ° of C, has namely obtained uniform graphene oxide hydrogel.
3) in the graphene oxide hydrogel, add ethanol, ethanol is poured out after soaking 6h, repeatedly after 5 times, obtain the graphene oxide alcogel.With the dry 24h of supercritical co drying instrument that U.S. SFT company produces, the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, has obtained the crosslinked graphene oxide aerogel of diethylenetriamine.
The graphene oxide aerogel that embodiment 1 ~ 11 obtains is tested, and the result is as follows:
Fig. 1 is the crosslinking method schematic diagram of two kinds of dissimilar graphene oxide aerogels, the mechanism of crosslinking that has reflected graphene oxide, be metallic cation (left figure) by positively charged or protonated primary amine, secondary amine or tertiary amine ion (right figure), electronegative graphene oxide is assembled into three-dimensional net structure by edge mode of connection (edge to edge).Fig. 2 is SEM figure and the digital photograph of the crosslinked graphene oxide aerogel of the La that obtains of embodiment 1, Fig. 3 is SEM figure and the digital photograph of the crosslinked graphene oxide aerogel of the Ni that obtains of embodiment 2, and Fig. 4 is SEM figure and the digital photograph of the crosslinked graphene oxide aerogel of the polyethylene polyamine that obtains of embodiment 8.Can find out from Fig. 2, Fig. 3 and Fig. 4, described graphene oxide aerogel is a kind of three-dimensional porous structure.SEM figure and the digital photograph result of the graphene oxide aerogel that embodiment 3 ~ 7,9 ~ 11 obtains are similar.
In Fig. 5, a is the nitrogen adsorption/desorption curve of the graphene oxide aerogel that obtains of embodiment 1, b is the nitrogen adsorption/desorption curve of the graphene oxide aerogel that obtains of embodiment 8, wherein transverse axis is test pressure, the longitudinal axis is adsorptive capacity, illustrate that described graphene oxide aerogel is vesicular structure, the specific surface area that calculates embodiment 1 is 890m
2/ g, the specific surface area of embodiment 8 is 750m
2/ g, the aperture is between 1nm ~ 20 μ m.The specific surface area of the graphene oxide aerogel that embodiment 1 ~ 11 obtains is 100 ~ 2000m
2/ g, density is 10 ~ 500mg cm
-3, the aperture is between 1nm ~ 20 μ m.
Fig. 6 is digital photograph and the stress-strain(ed) curves of two class graphene oxide aerogels in the quasistatic compression process, wherein (a) figure is the crosslinked digital photograph of graphene oxide aerogel before and after compression of La that embodiment 1 obtains, (b) digital photograph of graphene oxide aerogel before and after compression that the polyethylene polyamine that obtains for embodiment 8 is crosslinked illustrates that from (a) and (b) figure graphene oxide aerogel width before and after pressurized does not increase.The compression curve of the graphene oxide aerogel that the La that (c) obtains for embodiment 1 is crosslinked, the compression curve of the graphene oxide aerogel that the polyethylene polyamine that (d) obtains for embodiment 8 is crosslinked, wherein X-coordinate is strain, ordinate zou is stress.By stress-strain(ed) curve, can find out that the graphene oxide aerogel has good mechanical strength, wherein the Young's modulus of embodiment 1 is 10MPa, and yield strength is 1MPa, and the energy absorption of the opposing external force that calculates is 45J g
-1The Young's modulus of embodiment 8 is 20MPa, and yield strength is 1.8MPa, and the energy absorption of the opposing external force that calculates is 55J g
-1The Young's modulus of the graphene oxide aerogel that embodiment 1 ~ 11 obtains is 5 ~ 50MPa, and yield strength is 1 ~ 5MPa.The energy absorption of the opposing external force that calculates is 10 ~ 200J g
-1Illustrate that the graphene oxide aerogel has good shock resistance.
Figure 10 is to XPS, the Raman of graphene oxide aerogel and the characterization data of XRD among embodiment 1 and the embodiment 8.
Wherein figure (a) is x-ray photoelectron power spectrum (XPS) figure, be followed successively by from top to bottom the graphene oxide aerogel that embodiment 1 obtains, the graphene oxide aerogel that embodiment 8 obtains, the spectral line of pure zirconia Graphene, X-coordinate is for becoming bond energy, and ordinate zou is intensity.Front two spectral lines contain respectively N 1s peak and La 4d peak, illustrate that N and La are present in respectively in the graphene oxide aerogel that embodiment 1 and embodiment 8 obtain.
Figure (b) is the C-C peak for the amplification at carbon 1s peak among the figure (a) in transverse axis 284.8 positions, and 286.9 positions are the C-O peak, illustrate in three kinds of materials all to contain graphene oxide.The figure (a) and (b) illustrate cross-linker molecules and the existence of graphene oxide in the aerogel network jointly.
Figure (c) be that Raman spectrum (Raman) is schemed, and is followed successively by from top to bottom the graphene oxide aerogel that embodiment 1 obtains, the graphene oxide aerogel that embodiment 8 obtains, the spectral line of pure zirconia Graphene, and X-coordinate is Raman shift, and ordinate zou is intensity.The characteristic peak of graphene oxide all appears in explanation in three kinds of materials.
Figure (d) be that X-ray diffraction spectrum (XRD) is schemed, and is followed successively by from top to bottom the graphene oxide aerogel that embodiment 1 obtains, the graphene oxide aerogel that embodiment 8 obtains, the spectral line of pure zirconia Graphene, and X-coordinate is diffraction angle, and ordinate zou is intensity.Wherein the pure zirconia Graphene has fixing interlamellar spacing, therefore diffraction peak occurs, and the graphene oxide lamella is that the edge is crosslinked in the graphene oxide aerogel, therefore without diffraction peak.XPS, Raman and the XRD result of the graphene oxide aerogel that embodiment 2 ~ 7,9 ~ 11 obtains are similar.
The graphene oxide aerogel that embodiment 1 is obtained is placed on and is connected with reducing gas H
2In the test tube of S, under 20 ° of C, continue to place 30h, the quality change of results of regular determination reaction gas gel between the reaction period, to graphene oxide aerogel quality without considerable change, stop to measure.
The left figure of Fig. 7 is the SEM photo of reaction rear oxidation graphene aerogel, and right figure is the quality change curve of graphene oxide aerogel in the reaction process.As can be seen from the figure, obvious variation occurs in the three-dimensional porous nano structure of graphene oxide aerogel after reaction, adhered to a mass of cylindrical sulphur simple substance at original graphene oxide lamella, and the weight of aerogel also has significant increase, illustrate that graphene oxide has oxidisability, can be with S
2-Be reduced to elemental sulfur, the reflection graphene oxide is to H
2S has obvious adsorption effect.
Embodiment 13
It is 20mg L that the graphene oxide aerogel of the 5mg that embodiment 1 is obtained is put into 20mL concentration
-1The methylene blue dye solution in, under 20 ° of C, stir 3000min, survey the absorbancy of solution with UV-Vis spectrum, obtaining the graphene oxide aerogel is 271.8mg g to the adsorptive capacity of methylene blue
-1
Fig. 8 be the graphene oxide aerogel that obtains of embodiment 1 according to the method described above to the adsorption curve of different dyes, be followed successively by from top to bottom the adsorptive capacity to methylene blue, magenta, C.I. 42685 and rhodamine B, scope is at 100～2000mg g
-1, transverse axis is the time, the longitudinal axis is absorbancy.
Embodiment 14
It is 50mg L that the graphene oxide aerogel that embodiment 1 is obtained is put into 20mL concentration
-1PbCl
2In the solution, stir 24h under 20 ° of C, survey the variation of absorbancy by atomic absorption spectrum, then utilize typical curve to obtain the graphene oxide aerogel to Pb
2+The adsorptive capacity of ion is 72.1mg g
-1
Fig. 9 is that the graphene oxide aerogel that obtains of embodiment 1 is to the adsorptive capacity of different metal ion, under 20 ° of C ~ 80 ° C, to Pb
2+, Ag
+, Cu
2+And Hg
2+Adsorptive capacity be 20 ~ 200mg g
-1
The graphene oxide aerogel that obtains is used as electrode of super capacitor, and step is as follows.
After the graphene oxide aerogel ground with mortar, according to aerogel: acetylene black: the PVDF(polyvinylidene difluoride (PVDF), as binding agent) mass ratio=87:10:3 be mixed with mixture and in mortar, grind, until form the high viscosity solution of homogeneous; With tabletting machine high viscosity solution is pressed in the Ni film, placed 120 ° of C dry 6 hours, then be assembled into two electrode systems, the Ni film is as working electrode, and the conduct of Pt electrode is to electrode.Electrolytic solution is the KOH solution of 5moL/L.All electro-chemical tests (tests such as cyclic voltammetric and constant current charge-discharge) all become to produce in CHI660D(Shanghai occasion China company) carry out in the electrochemical workstation.Figure 11 is the cyclic voltammetry curve when the graphene oxide aerogel uses as electrode of super capacitor among the embodiment 1, and calculating the ratio capacitance that integral area must this aerogel is 120F/g.The ratio electric capacity of the graphene oxide aerogel that embodiment 2 ~ 9 obtains is 200 ~ 500F/g.
Graphene oxide aerogel overcritical or that lyophilize obtains is a kind of special three-dimensional assembling network structure, its singularity is mainly manifested in three aspects: the singularity of (1) assembling mode, cross-linker molecules by from different graphene oxide sheets between electrostatic interaction, the mode of connection of graphene oxide lamella with special edge edge fitted together the final three dimensional gel network that forms macroscopic view.(2) singularity of forming process, the formation of graphene oxide hydrogel is different from general synthetic method.Need to add a kind of gel promotor (being the ester compound of mentioning among the present invention) in Gel Precursor, it is controlled that the adding of this gel promotor not only allows the forming process of gel become, and greatly improved gel quality affects, is conducive to further drying treatment; (3) singularity of structure, its special gel formation process has given the graphene oxide aerogel significant constructional feature, namely the partly overlapping probability between the graphene oxide lamella genetic horizon of two dimension and the layer is very little, and the three-dimensional assembly and connection of graphene oxide mainly occurs in the edge section of graphene oxide.The graphene oxide aerogel that adopts this assembling mode to obtain had both had large specific surface area (100 ~ 2000m
2g
-1), (Young's modulus is 0.5 ~ 50MPa, and yield strength is 0.1 ~ 5MPa, and the shock resistance energy absorption is 10 ~ 200J g to have again good mechanical strength
-1).The graphene oxide aerogel that adopts above-mentioned preparation method to obtain, in the lamella of graphene oxide, still contain a large amount of oxygen-containing functional groups, contain simultaneously a small amount of metallic element or nitrogen element (these elements are mainly derived from employed linking agent) in the edge section of graphene sheet layer, and do not occur or rare overlapping phenomenon between the graphene oxide lamella as the structural unit use.
In sum, above is preferred embodiment of the present invention only, is not for limiting protection scope of the present invention.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. graphene oxide aerogel is characterized in that: described aerogel is assembled into three-dimensional net structure with the graphene oxide lamella with the edge mode of connection by linking agent;
Wherein, described linking agent is divalence or the above metal ion of divalence, perhaps is protonated primary amine, secondary amine or tertiary amine ion.
2. a kind of graphene oxide aerogel according to claim 1, it is characterized in that: described graphene oxide aerogel has vesicular structure, and the aperture is 1nm ~ 20 μ m, and specific surface area is 100 ~ 2000m
2g
-1, density is 10 ~ 500mg cm
-3
3. the preparation method of a kind of graphene oxide aerogel as claimed in claim 1 or 2, it is characterized in that: described method steps is as follows:
(1) preparation graphite oxide aqueous solution;
(2) in the graphite oxide aqueous solution, add the alkaline solution adjust pH to alkalescence, then add the colloidal solution of metal hydroxides or metal carbonate, or add the molecule that contains primary amine, secondary amine or tertiary amine functional group, disperse to obtain solution 1;
(3) in solution 1, add ester compound, disperse to obtain solution 2; Solution 2 left standstill obtain the graphene oxide hydrogel;
(4) the graphene oxide hydrogel is carried out drying, obtain described graphene oxide aerogel.
4. the preparation method of a kind of graphene oxide aerogel as claimed in claim 3 is characterized in that: after step (1) obtains the graphite oxide aqueous solution, the concentration of graphene oxide is formulated as 2～20mg/mL.
5. the preparation method of a kind of graphene oxide aerogel as claimed in claim 3, it is characterized in that: in the step (2), the quality of described graphene oxide: metal hydroxides, metal carbonate or contain the quality of the molecule of primary amine, secondary amine or tertiary amine functional group=2 ~ 50:1; Described metal hydroxides or metal carbonate are oxyhydroxide or the carbonate that contains the metal ion more than divalence or the divalence; The described molecule that contains primary amine, secondary amine or tertiary amine functional group is the molecule that contains two or more primary amine, secondary amine or tertiary amine functional group.
6. the preparation method of a kind of graphene oxide aerogel as claimed in claim 5, it is characterized in that: the metal ion in the described metal hydroxides of step (2) or the metal carbonate is Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zr
4+, Sn
4+, Ti
4+, V
5+, La
3+, Cr
3+, Al
3+, Zn
2+Or Ce
4+The described molecule that contains primary amine, secondary amine or tertiary amine functional group is trimeric cyanamide, polyethylene polyamine, diethylenetriamine, triethylene tetramine or polyamide-amide type dendrimer.
7. the preparation method of a kind of graphene oxide aerogel as claimed in claim 3, it is characterized in that: the described ester compound of step (3) is selected from ethyl acetate, Gluconolactone or vovocan.
8. the preparation method of a kind of graphene oxide aerogel as claimed in claim 3, it is characterized in that: in the step (4), described drying process is for to add entry in the graphene oxide hydrogel, after soaking 0.5～10h water is poured out, repeat 2～8 times, then with graphene oxide hydrogel freezing 〉=30min under-50 ° of C～-5 ° C, the dry 30min～48h of ° C obtains the graphene oxide aerogel 10 ° of C～100; Freezing and drying process is all carried out under the vacuum tightness of 1～10000Pa.
9. the preparation method of a kind of graphene oxide aerogel as claimed in claim 3, it is characterized in that: in the step (4), described drying process is that the supercutical fluid mode is dry, for in the graphene oxide hydrogel, adding ethanol or acetone, pour out after soaking 0.5～10h, repeat 1～8 time, obtain graphene oxide alcogel or ketone gel, then with Supercritical Ethanol or supercritical co drying 〉=2h, obtain the graphene oxide aerogel.
10. the application of a kind of graphene oxide aerogel as claimed in claim 1 or 2, described application are as anti-ballistic materials, dye adsorption material, heavy metal ion adsorbing material, gas adsorption material or electrode materials with the graphene oxide aerogel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210457820.4A CN102910625B (en) | 2012-11-14 | 2012-11-14 | Graphene oxide aerogel, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210457820.4A CN102910625B (en) | 2012-11-14 | 2012-11-14 | Graphene oxide aerogel, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102910625A true CN102910625A (en) | 2013-02-06 |
| CN102910625B CN102910625B (en) | 2015-07-01 |
Family
ID=47609236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210457820.4A Expired - Fee Related CN102910625B (en) | 2012-11-14 | 2012-11-14 | Graphene oxide aerogel, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102910625B (en) |
Cited By (49)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145118A (en) * | 2013-03-04 | 2013-06-12 | 哈尔滨工业大学 | Preparation method of three-dimensional interpenetrating macroporous graphene high-efficiency oil absorption material |
| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
| CN103910356A (en) * | 2014-04-28 | 2014-07-09 | 南京新月材料科技有限公司 | Preparation method of three-dimensional graphene |
| CN103977748A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Magnetic aerogel and preparation method thereof |
| CN104071785A (en) * | 2014-07-14 | 2014-10-01 | 中国科学院福建物质结构研究所 | Method for preparing graphene with three-dimensional macroscopic porous structure |
| CN104085881A (en) * | 2014-06-10 | 2014-10-08 | 南京邮电大学 | Method of preparing three-dimensional graphene |
| CN104174424A (en) * | 2014-08-19 | 2014-12-03 | 中南大学 | Preparation method of nitrogen-doped graphene aerogel supported non-precious metal oxygen reduction catalyst |
| CN104401979A (en) * | 2014-10-31 | 2015-03-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Phase-transfer preparation method of graphene-based composite aerogel |
| CN104815357A (en) * | 2015-04-27 | 2015-08-05 | 复旦大学 | Inorganic-organic hybrid three-dimensional interpenetrating network hydrogel materials and preparation method and application thereof |
| CN104828807A (en) * | 2015-04-10 | 2015-08-12 | 中国科学院重庆绿色智能技术研究院 | Preparation method of three-dimensional graphene oxide aerogel with high specific surface area |
| CN105271185A (en) * | 2014-06-25 | 2016-01-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Two-dimensional lamellar structure stable dispersion liquid and gel, and preparation method and application thereof |
| WO2016037565A1 (en) * | 2014-09-11 | 2016-03-17 | 中国科学院上海应用物理研究所 | Graphene hydrogel and graphene aerogel as well as preparation methods therefor and applications thereof |
| CN105645400A (en) * | 2016-03-16 | 2016-06-08 | 浙江大学 | Graphene self-supporting material subjected to ion-induced assembly and preparation method thereof |
| CN105647249A (en) * | 2016-03-16 | 2016-06-08 | 浙江大学 | Method for preparing graphene coating through ion-induced assembly |
| CN105692607A (en) * | 2016-04-18 | 2016-06-22 | 齐鲁工业大学 | Graphene compressible aerogel on basis of chemical reduction, method for preparing graphene compressible aerogel and application thereof |
| CN104250005B (en) * | 2014-09-11 | 2016-07-06 | 中国科学院上海应用物理研究所 | A kind of graphene aerogel and its preparation method and application |
| CN106823830A (en) * | 2017-02-27 | 2017-06-13 | 中南大学 | A kind of preparation method of the self-supporting graphene oxide film with water phase stability high |
| CN107051404A (en) * | 2017-04-07 | 2017-08-18 | 南京信息工程大学 | A kind of hydrophobic adsorbent based on graphene oxide |
| CN107051392A (en) * | 2017-05-23 | 2017-08-18 | 深圳大学 | The functionalization aeroge and preparation method acted on heavy metal ion adsorption desorption |
| CN107335253A (en) * | 2016-04-29 | 2017-11-10 | 北京化工大学常州先进材料研究院 | A kind of method that supercritical carbon dioxide prepares blocky graphite alkene porous material |
| CN107501594A (en) * | 2017-08-23 | 2017-12-22 | 成都新柯力化工科技有限公司 | A kind of method with gel state nylon blown foams |
| CN107500284A (en) * | 2017-09-07 | 2017-12-22 | 北京师范大学 | A kind of carboxylated graphene oxide hydrogel and preparation method thereof |
| CN107583607A (en) * | 2017-10-05 | 2018-01-16 | 王干 | Composite material and preparation method thereof based on graphene oxide processing heavy metal in water ion |
| WO2018027035A1 (en) * | 2016-08-04 | 2018-02-08 | The Board Of Trustees Of The University Of Arkansas | Cross-linked graphene oxide compositions and applications thereof |
| CN105983380B (en) * | 2015-02-09 | 2018-06-12 | 南京理工大学 | A kind of super-hydrophobic MTMS/ graphite oxides composite aerogel and preparation method thereof |
| CN108178152A (en) * | 2018-03-01 | 2018-06-19 | 济南开发区星火科学技术研究院 | It is a kind of can efficient absorption heavy metal ion graphite oxide aerogel preparation method |
| CN108264372A (en) * | 2016-12-30 | 2018-07-10 | 四川大学 | High intensity, the non-ignitable aerogel type foam of A grades of low heat conduction and its preparation and application |
| CN108341410A (en) * | 2018-01-11 | 2018-07-31 | 南京大学 | A kind of preparation method and applications of graphene aerogel |
| CN108404879A (en) * | 2018-04-25 | 2018-08-17 | 苏州凌科特新材料有限公司 | A kind of preparation method of high-performance Dye Adsorption material |
| CN108745287A (en) * | 2018-06-15 | 2018-11-06 | 福建工程学院 | The preparation method of three-dimensional graphene oxide group carbonic anhydride adsorption agent |
| CN109437180A (en) * | 2018-12-07 | 2019-03-08 | 四川聚创石墨烯科技有限公司 | The preparation method of low layer number graphene oxide and the freeze-drying method of graphene oxide |
| CN110142022A (en) * | 2019-04-17 | 2019-08-20 | 南京工业大学 | A kind of preparation method of air cleaning graphene aerogel |
| CN110143810A (en) * | 2019-05-22 | 2019-08-20 | 哈尔滨工业大学 | A kind of preparation method of oriented alignment graphene/alumina composite ceramic |
| CN110451493A (en) * | 2019-09-02 | 2019-11-15 | 内蒙古农业大学 | A kind of graphene aerogel and its preparation method and application |
| CN110940701A (en) * | 2019-11-26 | 2020-03-31 | 西安戴森电子技术有限公司 | Preparation method of graphene-based gas sensor |
| CN111389372A (en) * | 2020-05-15 | 2020-07-10 | 安阳工学院 | Special graphene oxide aerogel solid-phase extraction column for perfluorinated acid compounds and preparation method thereof |
| CN111482147A (en) * | 2019-01-25 | 2020-08-04 | 天津工业大学 | Continuous preparation method and continuous preparation device of self-assembled aerogel particles of low-dimensional material |
| CN111676591A (en) * | 2020-06-11 | 2020-09-18 | 南京信息工程大学 | Graphene oxide aerogel fiber fabric and preparation method and application thereof |
| CN111847430A (en) * | 2020-07-15 | 2020-10-30 | 广东墨睿科技有限公司 | Preparation method of high-strength high-resilience graphene aerogel |
| CN111871389A (en) * | 2020-08-06 | 2020-11-03 | 哈尔滨工业大学 | Preparation method of lanthanum hydroxide modified aerogel phosphorus removal adsorbent |
| US10864498B2 (en) | 2015-05-29 | 2020-12-15 | Adelaide Research & Innovation Pty Ltd | Composite graphene-based material |
| CN112724935A (en) * | 2021-01-15 | 2021-04-30 | 大连理工大学 | Sound-heat energy conversion type composite phase change energy storage material and preparation method and application thereof |
| CN112816111A (en) * | 2020-12-25 | 2021-05-18 | 哈尔滨工业大学（深圳） | Flexible touch sensor and manufacturing method thereof |
| CN113148996A (en) * | 2021-04-27 | 2021-07-23 | 南京信息工程大学 | Three-dimensional porous graphene aerogel wave-absorbing material and preparation method thereof |
| CN113477236A (en) * | 2021-08-24 | 2021-10-08 | 西北有色金属研究院 | Preparation method of graphene oxide-polyethyleneimine/silicon dioxide composite aerogel |
| CN113651593A (en) * | 2021-09-23 | 2021-11-16 | 青岛裕王智能科技床业有限公司 | Electrothermal fabric, graphene oxide aerogel and preparation method and application thereof |
| CN114534695A (en) * | 2022-01-05 | 2022-05-27 | 安徽农业大学 | Preparation method and application of modified nano-cellulose aerogel |
| CN115650221A (en) * | 2022-10-28 | 2023-01-31 | 航天特种材料及工艺技术研究所 | Antioxidant elastic graphene aerogel and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837972A (en) * | 2010-05-28 | 2010-09-22 | 南京邮电大学 | Graphene three-dimensional structure and preparation method thereof |
| US20120034442A1 (en) * | 2010-08-06 | 2012-02-09 | Lawrence Livermore National Security, Llc | Graphene aerogels |
| CN102718210A (en) * | 2012-07-03 | 2012-10-10 | 新疆大学 | Method for preparing graphene oxide three-dimensional self-assembled aerogel and application of graphene oxide three-dimensional self-assembled aerogel |
-
2012
- 2012-11-14 CN CN201210457820.4A patent/CN102910625B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837972A (en) * | 2010-05-28 | 2010-09-22 | 南京邮电大学 | Graphene three-dimensional structure and preparation method thereof |
| US20120034442A1 (en) * | 2010-08-06 | 2012-02-09 | Lawrence Livermore National Security, Llc | Graphene aerogels |
| CN102718210A (en) * | 2012-07-03 | 2012-10-10 | 新疆大学 | Method for preparing graphene oxide three-dimensional self-assembled aerogel and application of graphene oxide three-dimensional self-assembled aerogel |
Cited By (70)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145118B (en) * | 2013-03-04 | 2015-08-19 | 哈尔滨工业大学 | A kind of preparation method of three-dimensional intercommunication macropore graphene high-efficiency oil absorption material |
| CN103145118A (en) * | 2013-03-04 | 2013-06-12 | 哈尔滨工业大学 | Preparation method of three-dimensional interpenetrating macroporous graphene high-efficiency oil absorption material |
| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
| CN103413689B (en) * | 2013-07-19 | 2016-08-10 | 北京科技大学 | Prepare graphene aerogel and the method for graphene/metal oxide aeroge |
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
| CN103537236B (en) * | 2013-10-22 | 2015-12-02 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene aerogel |
| CN103910356A (en) * | 2014-04-28 | 2014-07-09 | 南京新月材料科技有限公司 | Preparation method of three-dimensional graphene |
| CN103910356B (en) * | 2014-04-28 | 2019-07-16 | 南京新月材料科技有限公司 | A kind of preparation method of three-dimensional grapheme |
| CN103977748A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Magnetic aerogel and preparation method thereof |
| CN103977748B (en) * | 2014-05-23 | 2015-10-28 | 苏州大学 | A kind of magnetic aeroge and preparation method thereof |
| CN104085881A (en) * | 2014-06-10 | 2014-10-08 | 南京邮电大学 | Method of preparing three-dimensional graphene |
| CN105271185A (en) * | 2014-06-25 | 2016-01-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Two-dimensional lamellar structure stable dispersion liquid and gel, and preparation method and application thereof |
| CN104071785B (en) * | 2014-07-14 | 2016-01-13 | 中国科学院福建物质结构研究所 | A kind of method preparing the Graphene with three-dimensional macro vesicular structure |
| CN104071785A (en) * | 2014-07-14 | 2014-10-01 | 中国科学院福建物质结构研究所 | Method for preparing graphene with three-dimensional macroscopic porous structure |
| CN104174424A (en) * | 2014-08-19 | 2014-12-03 | 中南大学 | Preparation method of nitrogen-doped graphene aerogel supported non-precious metal oxygen reduction catalyst |
| CN104174424B (en) * | 2014-08-19 | 2016-06-15 | 中南大学 | The preparation of the aerogel carried non noble metal oxygen reduction catalyst of a kind of nitrogen-doped graphene |
| WO2016037565A1 (en) * | 2014-09-11 | 2016-03-17 | 中国科学院上海应用物理研究所 | Graphene hydrogel and graphene aerogel as well as preparation methods therefor and applications thereof |
| CN104250005B (en) * | 2014-09-11 | 2016-07-06 | 中国科学院上海应用物理研究所 | A kind of graphene aerogel and its preparation method and application |
| CN104401979A (en) * | 2014-10-31 | 2015-03-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Phase-transfer preparation method of graphene-based composite aerogel |
| CN105983380B (en) * | 2015-02-09 | 2018-06-12 | 南京理工大学 | A kind of super-hydrophobic MTMS/ graphite oxides composite aerogel and preparation method thereof |
| CN104828807A (en) * | 2015-04-10 | 2015-08-12 | 中国科学院重庆绿色智能技术研究院 | Preparation method of three-dimensional graphene oxide aerogel with high specific surface area |
| CN104815357A (en) * | 2015-04-27 | 2015-08-05 | 复旦大学 | Inorganic-organic hybrid three-dimensional interpenetrating network hydrogel materials and preparation method and application thereof |
| US10864498B2 (en) | 2015-05-29 | 2020-12-15 | Adelaide Research & Innovation Pty Ltd | Composite graphene-based material |
| CN105645400A (en) * | 2016-03-16 | 2016-06-08 | 浙江大学 | Graphene self-supporting material subjected to ion-induced assembly and preparation method thereof |
| CN105647249A (en) * | 2016-03-16 | 2016-06-08 | 浙江大学 | Method for preparing graphene coating through ion-induced assembly |
| CN105647249B (en) * | 2016-03-16 | 2017-12-26 | 浙江大学 | A kind of method of ion induction assembling graphite ene coatings |
| CN105692607A (en) * | 2016-04-18 | 2016-06-22 | 齐鲁工业大学 | Graphene compressible aerogel on basis of chemical reduction, method for preparing graphene compressible aerogel and application thereof |
| CN107335253A (en) * | 2016-04-29 | 2017-11-10 | 北京化工大学常州先进材料研究院 | A kind of method that supercritical carbon dioxide prepares blocky graphite alkene porous material |
| EP3494088A4 (en) * | 2016-08-04 | 2020-02-12 | The Board of Trustees of the University of Arkansas | Cross-linked graphene oxide compositions and applications thereof |
| WO2018027035A1 (en) * | 2016-08-04 | 2018-02-08 | The Board Of Trustees Of The University Of Arkansas | Cross-linked graphene oxide compositions and applications thereof |
| CN108264372B (en) * | 2016-12-30 | 2021-08-24 | 四川大学 | High-strength low-heat-conductivity A-grade non-combustible aerogel foam and preparation and application thereof |
| CN108264372A (en) * | 2016-12-30 | 2018-07-10 | 四川大学 | High intensity, the non-ignitable aerogel type foam of A grades of low heat conduction and its preparation and application |
| CN106823830A (en) * | 2017-02-27 | 2017-06-13 | 中南大学 | A kind of preparation method of the self-supporting graphene oxide film with water phase stability high |
| CN106823830B (en) * | 2017-02-27 | 2019-03-29 | 中南大学 | A kind of preparation method of the self-supporting graphene oxide film with high water phase stability |
| CN107051404A (en) * | 2017-04-07 | 2017-08-18 | 南京信息工程大学 | A kind of hydrophobic adsorbent based on graphene oxide |
| CN107051392A (en) * | 2017-05-23 | 2017-08-18 | 深圳大学 | The functionalization aeroge and preparation method acted on heavy metal ion adsorption desorption |
| CN107501594B (en) * | 2017-08-23 | 2021-05-25 | 长沙争明新材料有限公司 | Method for foaming foamed plastic by using gel state nylon |
| CN107501594A (en) * | 2017-08-23 | 2017-12-22 | 成都新柯力化工科技有限公司 | A kind of method with gel state nylon blown foams |
| CN107500284A (en) * | 2017-09-07 | 2017-12-22 | 北京师范大学 | A kind of carboxylated graphene oxide hydrogel and preparation method thereof |
| CN107583607A (en) * | 2017-10-05 | 2018-01-16 | 王干 | Composite material and preparation method thereof based on graphene oxide processing heavy metal in water ion |
| CN107583607B (en) * | 2017-10-05 | 2019-12-20 | 贵州美瑞特环保科技有限公司 | Preparation method of composite material for treating heavy metal ions in water body based on graphene oxide |
| CN108341410A (en) * | 2018-01-11 | 2018-07-31 | 南京大学 | A kind of preparation method and applications of graphene aerogel |
| CN108341410B (en) * | 2018-01-11 | 2021-09-10 | 南京大学 | Preparation method and application of graphene aerogel |
| CN108178152A (en) * | 2018-03-01 | 2018-06-19 | 济南开发区星火科学技术研究院 | It is a kind of can efficient absorption heavy metal ion graphite oxide aerogel preparation method |
| CN108404879A (en) * | 2018-04-25 | 2018-08-17 | 苏州凌科特新材料有限公司 | A kind of preparation method of high-performance Dye Adsorption material |
| CN108745287A (en) * | 2018-06-15 | 2018-11-06 | 福建工程学院 | The preparation method of three-dimensional graphene oxide group carbonic anhydride adsorption agent |
| CN108745287B (en) * | 2018-06-15 | 2020-12-01 | 福建工程学院 | Preparation method of three-dimensional graphene oxide based carbon dioxide adsorbent |
| CN109437180A (en) * | 2018-12-07 | 2019-03-08 | 四川聚创石墨烯科技有限公司 | The preparation method of low layer number graphene oxide and the freeze-drying method of graphene oxide |
| CN111482147A (en) * | 2019-01-25 | 2020-08-04 | 天津工业大学 | Continuous preparation method and continuous preparation device of self-assembled aerogel particles of low-dimensional material |
| CN110142022A (en) * | 2019-04-17 | 2019-08-20 | 南京工业大学 | A kind of preparation method of air cleaning graphene aerogel |
| CN110143810A (en) * | 2019-05-22 | 2019-08-20 | 哈尔滨工业大学 | A kind of preparation method of oriented alignment graphene/alumina composite ceramic |
| CN110451493B (en) * | 2019-09-02 | 2021-10-22 | 内蒙古农业大学 | Graphene aerogel and preparation method and application thereof |
| CN110451493A (en) * | 2019-09-02 | 2019-11-15 | 内蒙古农业大学 | A kind of graphene aerogel and its preparation method and application |
| CN110940701A (en) * | 2019-11-26 | 2020-03-31 | 西安戴森电子技术有限公司 | Preparation method of graphene-based gas sensor |
| CN111389372B (en) * | 2020-05-15 | 2023-03-24 | 安阳工学院 | Special graphene oxide aerogel solid-phase extraction column for perfluorinated acid compounds and preparation method thereof |
| CN111389372A (en) * | 2020-05-15 | 2020-07-10 | 安阳工学院 | Special graphene oxide aerogel solid-phase extraction column for perfluorinated acid compounds and preparation method thereof |
| CN111676591A (en) * | 2020-06-11 | 2020-09-18 | 南京信息工程大学 | Graphene oxide aerogel fiber fabric and preparation method and application thereof |
| CN111847430A (en) * | 2020-07-15 | 2020-10-30 | 广东墨睿科技有限公司 | Preparation method of high-strength high-resilience graphene aerogel |
| CN111871389A (en) * | 2020-08-06 | 2020-11-03 | 哈尔滨工业大学 | Preparation method of lanthanum hydroxide modified aerogel phosphorus removal adsorbent |
| CN112816111A (en) * | 2020-12-25 | 2021-05-18 | 哈尔滨工业大学（深圳） | Flexible touch sensor and manufacturing method thereof |
| CN112724935A (en) * | 2021-01-15 | 2021-04-30 | 大连理工大学 | Sound-heat energy conversion type composite phase change energy storage material and preparation method and application thereof |
| CN112724935B (en) * | 2021-01-15 | 2022-06-10 | 大连理工大学 | Sound-heat energy conversion type composite phase change energy storage material and preparation method and application thereof |
| CN113148996A (en) * | 2021-04-27 | 2021-07-23 | 南京信息工程大学 | Three-dimensional porous graphene aerogel wave-absorbing material and preparation method thereof |
| CN113477236A (en) * | 2021-08-24 | 2021-10-08 | 西北有色金属研究院 | Preparation method of graphene oxide-polyethyleneimine/silicon dioxide composite aerogel |
| CN113651593B (en) * | 2021-09-23 | 2023-02-03 | 青岛裕王智能科技床业有限公司 | Electrothermal fabric, graphene oxide aerogel and preparation method and application thereof |
| CN113651593A (en) * | 2021-09-23 | 2021-11-16 | 青岛裕王智能科技床业有限公司 | Electrothermal fabric, graphene oxide aerogel and preparation method and application thereof |
| CN114534695A (en) * | 2022-01-05 | 2022-05-27 | 安徽农业大学 | Preparation method and application of modified nano-cellulose aerogel |
| CN114534695B (en) * | 2022-01-05 | 2022-11-29 | 安徽农业大学 | Preparation method and application of modified nano-cellulose aerogel |
| CN115650221A (en) * | 2022-10-28 | 2023-01-31 | 航天特种材料及工艺技术研究所 | Antioxidant elastic graphene aerogel and preparation method thereof |
| CN115650221B (en) * | 2022-10-28 | 2023-11-21 | 航天特种材料及工艺技术研究所 | Antioxidant elastic graphene aerogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102910625B (en) | 2015-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102910625B (en) | Graphene oxide aerogel, preparation method and application | |
| Fan et al. | Ti3C2-MXene composite films functionalized with polypyrrole and ionic liquid-based microemulsion particles for supercapacitor applications | |
| Xie et al. | MOF-derived CoFe2O4 nanorods anchored in MXene nanosheets for all pseudocapacitive flexible supercapacitors with superior energy storage | |
| Shaheen et al. | Fabrication of different conductive matrix supported binary metal oxides for supercapacitors applications | |
| Huang et al. | Synthesis of polyaniline/nickel oxide/sulfonated graphene ternary composite for all-solid-state asymmetric supercapacitor | |
| Yang et al. | Novel hybrid nanoparticles of vanadium nitride/porous carbon as an anode material for symmetrical supercapacitor | |
| Xing et al. | Three dimensional nitrogen-doped graphene aerogels functionalized with melamine for multifunctional applications in supercapacitors and adsorption | |
| Wang et al. | Modified hollow glass microspheres/reduced graphene oxide composite aerogels with low thermal conductivity for highly efficient solar steam generation | |
| Andikaey et al. | Synthesis of engineered graphene nanocomposites coated with NiCo metal-organic frameworks as electrodes for high-quality supercapacitor | |
| Shi et al. | Synthesis of aminopyrene-tetraone-modified reduced graphene oxide as an electrode material for high-performance supercapacitors | |
| Purty et al. | Chemically grown mesoporous f-CNT/α-MnO 2/PIn nanocomposites as electrode materials for supercapacitor application | |
| Ates et al. | The synthesis of rGO/RuO 2, rGO/PANI, RuO 2/PANI and rGO/RuO 2/PANI nanocomposites and their supercapacitors | |
| Sahoo et al. | Facile synthesis of polypyrrole nanofiber and its enhanced electrochemical performances in different electrolytes. | |
| Zhang et al. | Graphitic carbon coated CuO hollow nanospheres with penetrated mesochannels for high-performance asymmetric supercapacitors | |
| CN103971941B (en) | Graphene/polyaniline/oxidation tin composite material applied to ultracapacitor and preparation method thereof | |
| CN103971942B (en) | Graphene/polyaniline/ferric oxide composite material applied to supercapacitor and manufacturing method thereof | |
| Wang et al. | Ruthenium oxide/reduced graphene oxide nanoribbon composite and its excellent rate capability in supercapacitor application | |
| Ma et al. | A novel core-shell polyaniline/graphene oxide/copper nanocomposite for high performance and low-cost supercapacitors | |
| Sandhiya et al. | Boosting the energy density of flexible supercapacitors by redox-additive hydrogels | |
| Yang et al. | MnO 2-assisted fabrication of PANI/MWCNT composite and its application as a supercapacitor | |
| Khan et al. | Development of 1.6 V hybrid supercapacitor based on ZnO nanorods/MnO2 nanowires for next-generation electrochemical energy storage | |
| Kowsari et al. | Geminal dicationic ionic liquid functionalized graphene nanoribbon/POAP composite film: synthesis, characterization and electrochemical pseudocapacitance performance | |
| Yang et al. | Graphene covalently functionalized with 2, 6-diaminoanthraquinone (DQ) as a high performance electrode material for supercapacitors | |
| Zhang et al. | 2, 6-Diaminopyridine decorated reduced graphene oxide as integrated electrode with excellent electrochemical properties for aqueous supercapacitors | |
| Balaji et al. | Symmetric electrochemical supercapacitor performance evaluation of N-doped graphene prepared via supercritical fluid processing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160620 Address after: 100022 Beijing City, Chaoyang District No. 39 East Third Ring Road, SOHO7-503 Patentee after: Tao Li Address before: 100081 No. 5, Zhongguancun South Street, Haidian District, Beijing Patentee before: BEIJING INSTITUTE OF TECHNOLOGY |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150701 |