CN102910625B - Graphene oxide aerogel, preparation method and application - Google Patents
Graphene oxide aerogel, preparation method and application Download PDFInfo
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- CN102910625B CN102910625B CN201210457820.4A CN201210457820A CN102910625B CN 102910625 B CN102910625 B CN 102910625B CN 201210457820 A CN201210457820 A CN 201210457820A CN 102910625 B CN102910625 B CN 102910625B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 269
- 239000004964 aerogel Substances 0.000 title claims abstract description 161
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000017 hydrogel Substances 0.000 claims abstract description 40
- -1 ester compounds Chemical class 0.000 claims abstract description 27
- 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 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 11
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 11
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract 5
- 229910002804 graphite Inorganic materials 0.000 claims description 125
- 239000010439 graphite Substances 0.000 claims description 125
- 239000000243 solution Substances 0.000 claims description 111
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 31
- 150000003141 primary amines Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000499 gel Substances 0.000 claims description 18
- 150000003512 tertiary amines Chemical group 0.000 claims description 17
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
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- 238000007710 freezing Methods 0.000 claims description 13
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- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
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- 229910002012 Aerosil® Inorganic materials 0.000 description 2
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 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
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
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 graphite oxide aerogel, preparation method and application, belong to fields of nano material application.
Background technology
Aerogel is the structure and the volume that adopt special process (generally referring to supercritical drying) the liquid gas displacement in wet gel significantly not to be changed gel network, and the highly porous nano material with low density and high-specific surface area obtained.The preparation core of aerogel is sol-gel chemistry.Theoretically, if certain material has sol-gel transition phenomenon, adopting dry this kind of wet gel of special process can obtain aerogel (but has exception.The poly-alcoxyl sulfonic group ethylenedioxy thiophene hydrogel with two-dimensional framework unit reported as us is (see Chemical Communications, 2011,47 (22), 6287-6289) be not then transformed into corresponding aerogel (see Journal of Materials Chemistry by supercritical drying process, 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) reports the aerogel of a series of metal oxide and bimetallic oxide.1986, Sandia National Laboratory of the U.S. reported borate (ester) aerogel.
Aerogel has the excellent properties such as ultralight, abundant pore passage structure and high porosity, extremely low thermal conductivity, ultralow acoustic resistance, pole low-k, high voltage breakdown.The characteristic of aerogel is mainly determined by the framework material forming aerogel.Therefore need to carry out screening to the framework material of aerogel and design.The mechanical property of framework material also determine 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 make aerogel can be applied to construction work, chemical engineering (chilling process, pyroprocess, shaping, casting etc.), automobile engineering (engine, exhaust system etc.), medicine engineering, electro-engineering etc.The transparency of optics or translucency make aerogel can be applied to construction work (front of heat insulation window or heat insualting building) and sensor.Ultralow dielectric makes aerogel can be applied to electronic engineering field.Superelevation porosity and huge specific surface area make aerogel can be applied to chemistry, medicine, the energy and environmental engineering etc.The mechanical property of extremely-low density and enhancing makes 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 makes it can be applied to the mechanical protection material such as the helmet, automobile impacting snubber as the absorbing material of shockwave.In deep space probing field, aerogel, as outer space particle-capture agent, successfully captures space particle.Aerogel even can be applied to the fine chemistry industry such as coating and makeup and filed of daily-use chemical industry etc.
Graphene oxide is normally raw material with graphite, and generate through strong oxidizer oxidation, the constraint then making mono-layer graphite lamella depart from Van der Waals force through special processing independently exists.The structure of graphene oxide and Graphene is substantially identical, just because acting on basal plane that the two dimension that is made up of carbon atom infinitely extends of oxygenant is connected with multiple oxygen-content active group.High-resolution solid-state
13c-NMR, FT-IR test result shows hydroxyl, epoxide group and a large amount of sp
2-C-structure unit is present in surface of graphene oxide, and carboxyl, carbonyl are present in graphene oxide edge.The existence of these active function groups, for the three-dimensional assembling of graphene oxide provides feasible chemical technology route.The whole basal plane main body of graphene oxide is made up of two different zones, the aliphatics six-ring being respectively not oxidized fragrant phenyl ring and closing, the relative number in these two regions is determined by the degree of oxidation of graphite, the existence of phenyl ring, double bond and epoxide group determines the grid structure of graphene oxide almost flat jointly, because the carbon atom be connected with hydroxyl can form the tetrahedral structure of torsional deformation, thus cause graphene oxide plane generating portion fold.Graphene oxide has excellent processability and solvability, can effectively be applied to graphene oxide based composites.Through chemistry functional modify graphene oxide can stable dispersion in multiple conventional organic solvent, forming stable graphene oxide suspension, is the starting point preparing Graphene and graphene-based matrix material on a large scale.In addition, Theoretical and Experimental Study all shows, graphene oxide has very excellent mechanical property, and this is the basis that graphene oxide can be used in many matrix materials.Therefore, can using graphene oxide as skeleton, preparation graphite oxide aerogel.
Summary of the invention
The object of this invention is to provide a kind of graphite oxide aerogel, preparation method and application.Described graphite 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 graphite oxide aerogel, graphene oxide lamella, by linking agent, is assembled into three-dimensional net structure in edge conjunction mode by described aerogel.
Wherein, described linking agent is metal ion more than divalence or divalence, or is protonated primary amine, secondary amine or tertiary amine ion.
Preferred described graphite oxide aerogel has vesicular structure, and aperture is 1nm ~ 20 μm, and specific surface area is 100 ~ 2000m
2g
-1, density is 10 ~ 500mg cm
-3.
The preparation method of a kind of graphite oxide aerogel of the present invention, described method steps is as follows:
(1) graphene oxide water solution is prepared;
Described graphene oxide water solution adopts the ordinary method in field of preparation of graphene to obtain, and if application number is 201001263656.4, denomination of invention is the preparation method of graphene oxide solution in " a kind of graphene aerogel and preparation method thereof ";
After obtaining graphene oxide water solution, with water, the concentration of graphene oxide is formulated as 2 ~ 20mg/mL.
(2) in graphene oxide water solution, alkaline solution (as NaOH or KOH) adjust ph is added to alkalescence (7 ~ 14), then the colloidal solution of metal hydroxides or metal carbonate is added, or the molecule added containing primary amine, secondary amine or tertiary amine functional group, dispersion obtains solution 1;
The quality of preferred described graphene oxide: the quality=2 ~ 50:1 of metal hydroxides, metal carbonate or the molecule containing secondary amine, tertiary amine or quarternary amine functional group; Described metal hydroxides or metal carbonate are for can form colloidal solution, and the metal hydroxides containing metal ion more than divalence or divalence or metal carbonate, 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 containing primary amine, secondary amine or tertiary amine functional group is the small molecules or the polymer that contain two or more primary amine, secondary amine or tertiary amine functional group, as trimeric cyanamide, polyethylene polyamine, diethylenetriamine, triethylene tetramine or polyamidoamine dendrimer.
(3) in solution 1, add ester compound, dispersion obtains solution 2; Solution 2 is left standstill and obtains even immobilising graphene oxide hydrogel.
Preferred described ester compound is selected from ethyl acetate, Gluconolactone or vovocan.
Described ester compound slowly can be hydrolyzed in water, acid due to hydrolysis is a kind of molecule containing carboxyl, slowly can reduce the pH value of graphene oxide water solution, thus slowly metal ion is discharged from metal hydroxides or metal carbonate colloidal solution, obtain metallic cation; Or slowly by protonated to the primary amine in the molecule containing primary amine, secondary amine or tertiary amine functional group, secondary amine or tertiary amine functional group, 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 conjunction mode (edge to edge).So the add-on of ester compound amount, metal hydroxides, metal carbonate all can be converted into metal ion, be maybe as the criterion all protonated to the primary amine in the molecule containing primary amine, secondary amine or tertiary amine functional group, secondary amine or tertiary amine functional group.
Preferred described static conditions is that solution 2 is left standstill 0.5 ~ 48h under 20 ° of C ~ 70 ° C.
(4) graphene oxide hydrogel is carried out drying, obtain graphite oxide aerogel of the present invention.
In preferred steps (4), described drying process is lyophilize, be specially and add water in graphene oxide hydrogel, after soaking 0.5 ~ 10h, water is poured out, repeat 2 ~ 8 times, then by graphene oxide hydrogel freezing >=30min under ° C of-50 ° of C ~-5,10 ° of C ~ 100, the dry 30min ~ 48h of ° C, obtains graphite oxide aerogel; Freezing and drying process is all carried out under the vacuum tightness of 1 ~ 10000Pa.
Described freeze drying process by the restriction of freeze drying equipment, can any business or non-commercial freeze drying equipment in complete.Graphene oxide hydrogel also first can adopt liquid nitrogen freezing, then proceeds to vacuum-drying in lyophilizer; Also can direct lyophilize in lyophilizer.Freezing mode can adopt directed freezing (controlling freezing direction), and non-directional also can be adopted freezing.
In preferred steps (4), described drying process is that supercutical fluid mode is dry, concrete mode adds ethanol or acetone in 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 graphite oxide aerogel.
Described supercritical drying process by the restriction of supercritical drying equipment, can any business or non-commercial supercritical drying equipment in complete the supercritical drying of graphite oxide enol (or ketone) gel, to obtain graphite oxide aerogel.
The application of a kind of graphite oxide aerogel of the present invention, described application is as anti-ballistic materials using graphite oxide aerogel.The Young's modulus being obtained described aerogel by compression verification is 0.5 ~ 50MPa, and yield strength is 0.1 ~ 5MPa, and shock resistance energy absorption is 10 ~ 200J g
-1.Be 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 graphite oxide aerogel can be used as anti-ballistic materials and uses.
The application of a kind of graphite oxide aerogel of the present invention, described application is as dye adsorption material using graphite oxide aerogel.Under temperature 20 ° of C ~ 80 ° C, the adsorptive capacity of described aerogel to dyestuff (as methylene blue, C.I. 42685, magenta and rhodamine B) is 100 ~ 2000mg g
-1.Graphite oxide aerogel is not only confined to above-mentioned dyestuff to the adsorptive power of dyestuff.
The application of a kind of graphite oxide aerogel of the present invention, described application is as heavy metal ion adsorbing material using graphite oxide aerogel.Under temperature 20 ° of C ~ 80 ° C, described aerogel heavy metal ion is (as Pb
2+, Cu
2+, Ag
+, Hg
2+, Cr
3+) adsorptive capacity be 20 ~ 200mg g
-1.The adsorptive power of graphite oxide aerogel heavy metal ion is not only confined to above-mentioned heavy metal ion.
The application of a kind of graphite oxide aerogel of the present invention, described application is as gas adsorption material using graphite oxide aerogel.Be 20 ~ 200mmol g to the adsorptive capacity of gas (as sulfurous gas, hydrogen sulfide and hydrogen iodide) under temperature 20 ° of C ~ 80 ° C
-1.The adsorptive power of graphite oxide aerogel to gas is not only confined to above-mentioned gas.
The application of a kind of graphite oxide aerogel of the present invention, described application is as electrode materials using graphite oxide aerogel.Such as in ultracapacitor, using Ni film as working electrode, Pt electrode is as to electrode, and the KOH solution of 5moL/L is electrolytic solution, is 200 ~ 500F/g by the ratio capacitance of the graphite oxide aerogel of cyclic voltammetry.Graphite oxide aerogel uses as electrode materials and is not only confined to above-mentioned ultracapacitor.
Beneficial effect
1. the invention provides a kind of graphite oxide aerogel, described aerogel is with metal ion or protonated primary amine, secondary amine or tertiary amine ion for linking agent, carries out crosslinked assembling between graphene oxide lamella with the particular form of edge edge.There is classification aperture, superhigh specific surface area and three-dimensional structure, combine the physical and chemical performance of graphene oxide excellence and the ultralight porosity characteristic of aerogel.
2. the invention provides the preparation method of described graphite oxide aerogel, described method utilizes 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, graphene oxide transform hydrogel is become corresponding aerogel.Described method overcomes in graphene oxide two-dimensional lamella assembling process, and the graphene oxide sheet layer segment that between lamella with lamella, strong interaction causes is overlapping, causes the technical bottleneck that specific surface area is too small.
3. in the forming process of graphene oxide hydrogel, gel promotor (ester compound namely mentioned in the present invention) need be added in Gel Precursor (solution 1), described ester compound slowly can be hydrolyzed in water, acid due to hydrolysis is a kind of molecule containing carboxyl, slowly can reduce the pH value of graphene oxide water solution, thus slowly metal ion is discharged from oxyhydroxide or carbonate colloidal sol, obtain metallic cation; Or slowly by protonated to the primary amine in the molecule containing primary amine, secondary amine or tertiary amine functional group, secondary amine or tertiary amine functional group, 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 conjunction mode (edgeto edge).
4. present invention also offers the application of described graphite oxide aerogel, described graphite oxide aerogel has excellent mechanical property, has good application prospect in shock resistance; In addition, graphite oxide aerogel has outstanding chemisorption effect to a series of reducing gas, dye molecule and metal ion, in ultracapacitor etc., also have good application.
Accompanying drawing explanation
Fig. 1 is two class graphite 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 graphite oxide aerogel that La is cross-linked.
Fig. 3 is SEM figure and the digital photograph of the graphite oxide aerogel that Ni is cross-linked.
Fig. 4 is SEM figure and the digital photograph of the graphite oxide aerogel that polyethylene polyamine is cross-linked.
Fig. 5 is the nitrogen adsorption/desorption curve figure of two class graphite oxide aerogel.
Fig. 6 is the digital photograph of two class graphite oxide aerogel in quasistatic compression process and stress-strain(ed) curve, wherein scheme (a) for metal ion crosslinked aerogel before compression after digital photograph, figure (b) for protonated primary amine, secondary amine or tertiary amine ion be cross-linked aerogel before compression after digital photograph, figure (c) compression curve that is metal ion crosslinked aerogel, figure (d) is cross-linked the compression curve of aerogel for protonated primary amine, secondary amine or tertiary amine ion.
The left figure of Fig. 7 is that graphite oxide aerogel is at H
2reacted SEM figure in S gas, right figure is the mass-change curve in reaction process.
Fig. 8 be graphite oxide aerogel to methylene blue, C.I. 42685, the adsorption curve of magenta and rhodamine B four kinds of dyestuffs.
Fig. 9 is that graphite 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 the x-ray photoelectron power spectrum (XPS) of graphite oxide aerogel, Raman spectrum and X-ray diffraction spectrum (XRD), wherein scheme (a) for XPS figure, figure (b) is the amplification at carbon 1s peak in figure (a), and figure (c) is Raman figure, and figure (d) is XRD figure.
Figure 11 is using the cyclic voltammetry curve of graphite oxide aerogel as electrode material for super capacitor.
Embodiment
Wherein, the graphene oxide water solution in embodiment 1 ~ 11 prepares by the following method:
(1) be that the sulfuric acid of 98wt% adds in 100mL flask by 25mL concentration, be heated to 90 ° of C, under agitation condition, slowly add 5g Potassium Persulphate and 5g Vanadium Pentoxide in FLAKES successively.Then be cooled to 80 ° of C, add 6g Graphite Powder 99, stirring reaction 4.5 hours, the distilled water adding 1L leaves standstill 12h, obtains preoxidation graphite.
(2) after carrying out filtering and washing with 2L distilled water to the preoxidation graphite obtained, by preoxidation graphite dry 12h under 50 ° of C.
(3) getting 230mL concentration is the flask that the sulfuric acid of 98wt% is placed in 1L, and be cooled with an ice bath 20min, then slowly adds dried preoxidation graphite and 30g potassium permanganate successively, magnetic agitation 20min; After flask is reacted 2h in 35 ° of C water-baths, slowly add 460mL distilled water, then add the distilled water diluting of 1.4L, after stirring reaction 2h, add the hydrogen peroxide of 25mL 30wt%, now the color of reaction solution becomes khaki color;
(4) in reaction solution, add the hydrochloric acid of 5wt%, after standing sedimentation, supernatant liquor is poured out, repeat 3 times; Add 2L distilled water again, after standing sedimentation, supernatant liquor is poured out, centrifugal after repeating 2 times, obtain graphene oxide, described graphene oxide is made into the graphene oxide solution needing concentration (2 ~ 20mg/mL).Concrete grammar, for weighing after the graphene oxide solution oven dry that takes a morsel, calculates concentration by quality divided by volume, then thin up, needs concentration until reach.
Embodiment 1
1) get the graphene oxide water solution that 5mL concentration is 15mg/mL, add the sodium hydroxide solution of 0.4mL0.5mol/L under agitation condition, adjust ph is 8, then adds the La (OH) of 0.4mL 30mg/mL wherein
3colloidal solution, ultrasonic disperse obtains solution 1.
2) in solution 1, add the Gluconolactone of 100mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 24h under 20 ° of C, obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 6h and ethanol is poured out, repeatedly after 5 times, obtain graphene oxide alcogel.The dry 24h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that La is crosslinked.
Embodiment 2
1) get the graphene oxide water solution that 5mL concentration is 4mg/mL, add the sodium hydroxide solution of 0.2mL0.5mol/L under agitation condition, adjust ph is 9, adds the Ni (OH) of 0.3mL 30mg/mL after being uniformly dispersed again wherein
2colloidal solution, dispersed with stirring obtains solution 1.
2) in solution 1, add the ethyl acetate of 40mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 48h under 20 ° of C, obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 0.5h and ethanol is poured out, repeatedly after 8 times, obtain graphene oxide alcogel.The dry 12h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that Ni is crosslinked.
Embodiment 3
1) get the graphene oxide water solution that 6mL concentration is 14mg/mL, add the potassium hydroxide solution of 0.3mL0.5mol/L under agitation condition, adjust ph is 10, is uniformly dispersed, then adds the Fe (OH) of 0.2mL 30mg/mL wherein
3colloidal solution, dispersed with stirring obtains solution 1.
2) in solution 1, add the Gluconolactone of 70mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 8h under 40 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 10h and ethanol is poured out, repeatedly after 2 times, obtain graphene oxide alcogel.The dry 24h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that Fe is crosslinked.
Embodiment 4
1) get the graphene oxide water solution that 5mL concentration is 9mg/mL, add the sodium hydroxide solution of 0.2mL0.5mol/L under agitation condition, adjust ph is 8, is uniformly dispersed, then adds the Co (OH) of 0.4mL 20mg/mL wherein
2colloidal solution, dispersed with stirring obtains solution 1.
2) in solution 1, add the ethyl acetate of 20mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 12h under 20 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, acetone is added, after soaking 5h, acetone is poured out, after repeating 8 times, in graphene oxide hydrogel, add water, water is poured out, after repeating 4 times after soaking 5h, obtain graphite oxide ketenes gel, by freezing under-5 ° of C for ketone gel >=30min, then at the dry 48h of 30 ° of C, obtain the graphite oxide aerogel that Co is crosslinked.Freezing and drying process is all carried out under the vacuum tightness of 10Pa.
Embodiment 5
1) get the graphene oxide water solution that 5mL concentration is 18mg/mL, add the sodium hydroxide solution of 0.3mL0.5mol/L under agitation condition, adjust ph is 8, is uniformly dispersed, then adds the Ce (OH) of 0.4mL 30mg/mL wherein
3colloidal solution, dispersed with stirring obtains solution 1.
2) in solution 1, add the vovocan of 50mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 24h under 20 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, ethanol is added, after soaking 10h, ethanol is poured out, after repeating 2 times, in graphene oxide hydrogel, add water, water is poured out, after repeating 2 times after soaking 10h, obtain graphene oxide alcogel, by freezing under-25 ° of C for alcogel >=30min, then at the dry 30min of 70 ° of C, obtain the graphite oxide aerogel that Ce is crosslinked.Freezing and drying process is all carried out under the vacuum tightness of 1000Pa.
Embodiment 6
1) get the graphene oxide water solution that 4mL concentration is 6mg/mL, add the potassium hydroxide solution of 0.2mL 0.5mol/L under agitation condition, adjust ph is 8, is uniformly dispersed, then adds the FeCO of 0.3mL 30mg/mL wherein
3colloidal solution, dispersed with stirring obtains solution 1.
2) in solution 1, add the Gluconolactone of 50mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 7h under 50 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 10h and ethanol is poured out, repeatedly after 2 times, obtain graphene oxide alcogel.The dry 24h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that Fe is crosslinked.
Embodiment 7
1) get the graphene oxide water solution that 7mL concentration is 6mg/mL, add the potassium hydroxide solution of 0.4mL 0.5mol/L under agitation condition, adjust ph is 9, is uniformly dispersed, then adds the NiCO of 0.2mL 30mg/mL wherein
3colloidal solution, dispersed with stirring obtains solution 1.
2) in solution 1, add the ethyl acetate of 40mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 8h under 40 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 10h and ethanol is poured out, repeatedly after 2 times, obtain graphene oxide alcogel.The dry 24h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that Ni is crosslinked.
Embodiment 8
1) graphene oxide water solution that 5mL concentration is 8mg/mL is got, add the sodium hydroxide solution of 0.3mL0.5mol/L under agitation condition, adjust ph is 9, is uniformly dispersed, add the polyethylene polyamine solution of 0.3mL 10mg/mL more wherein, dispersed with stirring obtains solution 1.
2) in solution 1, add the vovocan of 20mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 0.5h under 70 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 6h and ethanol is poured out, repeatedly after 5 times, obtain graphene oxide alcogel.The dry 24h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that polyethylene polyamine is crosslinked.
Embodiment 9
1) graphene oxide water solution that 5mL concentration is 10mg/mL is got, add the potassium hydroxide solution of 0.2mL0.5mol/L under agitation condition, adjust ph is 8, is uniformly dispersed, add the melamine solution of 0.2mL 10mg/mL more wherein, dispersed with stirring obtains solution 1.Containing three primary amine functional groups in described trimeric cyanamide.
2) in solution 1, add the vovocan of 10mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 1h under 70 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 6h and ethanol is poured out, repeatedly after 5 times, obtain graphene oxide alcogel.The dry 24h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that trimeric cyanamide is crosslinked.
Embodiment 10
1) graphene oxide water solution that 5mL concentration is 9mg/mL is got, the sodium hydroxide solution of 0.1mL 0.5mol/L is added under agitation condition, adjust ph is 10, be uniformly dispersed, add the polyamidoamine dendrimer solution of 0.1mL 10mg/mL more wherein, dispersed with stirring obtains solution 1.Containing multiple primary amine and secondary amine functional groups in described polyamidoamine dendrimer.
2) in solution 1, add the Gluconolactone solution of 50mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 3h under 70 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 6h and ethanol is poured out, repeatedly after 5 times, obtain graphene oxide alcogel.The dry 24h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that polyamidoamine dendrimer is crosslinked.
Embodiment 11
1) graphene oxide water solution that 5mL concentration is 7mg/mL is got, add the sodium hydroxide solution of 0.2mL0.5mol/L under agitation condition, adjust ph is 9, is uniformly dispersed, add the diethylenetriamine solution of 0.2mL 10mg/mL more wherein, dispersed with stirring obtains solution 1.Containing two primary amine and a secondary amine functional groups in described diethylenetriamine.
2) in solution 1, add the ethyl acetate solution of 30mg, ultrasonic disperse obtains solution 2, solution 2 is left standstill 3h under 60 ° of C, namely obtains uniform graphene oxide hydrogel.
3) in graphene oxide hydrogel, add ethanol, soak after 6h and ethanol is poured out, repeatedly after 5 times, obtain graphene oxide alcogel.The dry 24h of the supercritical co drying instrument produced with SFT company of the U.S., the critical temperature of supercritical co drying is 31.05 ° of C, and emergent pressure is 7.38Pa, obtains the graphite oxide aerogel that diethylenetriamine is crosslinked.
Test the graphite oxide aerogel that embodiment 1 ~ 11 obtains, result is as follows:
Fig. 1 is the crosslinking method schematic diagram of two kinds of dissimilar graphite oxide aerogel, reflect the mechanism of crosslinking of graphene oxide, be the 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 conjunction mode (edge to edge).Fig. 2 is SEM figure and the digital photograph of the graphite oxide aerogel that La that embodiment 1 obtains is cross-linked, Fig. 3 is SEM figure and the digital photograph of the graphite oxide aerogel that Ni that embodiment 2 obtains is cross-linked, and Fig. 4 is SEM figure and the digital photograph of the graphite oxide aerogel that polyethylene polyamine that embodiment 8 obtains is cross-linked.As can be seen from Fig. 2, Fig. 3 and Fig. 4, described graphite oxide aerogel is a kind of three-dimensional porous structure.The graphite oxide aerogel that embodiment 3 ~ 7,9 ~ 11 obtains SEM figure and digital photograph result similar.
In Figure 5, a is the nitrogen adsorption/desorption curve of the graphite oxide aerogel that embodiment 1 obtains, b is the nitrogen adsorption/desorption curve of the graphite oxide aerogel that embodiment 8 obtains, wherein transverse axis is test pressure, the longitudinal axis is adsorptive capacity, illustrate that described graphite oxide aerogel is vesicular structure, the specific surface area calculating embodiment 1 is 890m
2/ g, the specific surface area of embodiment 8 is 750m
2/ g, aperture is between 1nm ~ 20 μm.The specific surface area of the graphite oxide aerogel that embodiment 1 ~ 11 obtains is 100 ~ 2000m
2/ g, density is 10 ~ 500mg cm
-3, aperture is between 1nm ~ 20 μm.
Fig. 6 is the digital photograph of two class graphite oxide aerogel in quasistatic compression process and stress-strain(ed) curve, wherein (a) figure be the graphite oxide aerogel that is cross-linked of La that embodiment 1 obtains before compression after digital photograph, the graphite oxide aerogel that b polyethylene polyamine that () obtains for embodiment 8 is cross-linked before compression after digital photograph, illustrate that graphite oxide aerogel width before and after pressurized does not increase from (a) and (b) figure.The compression curve of the graphite oxide aerogel that c La that () obtains for embodiment 1 is cross-linked, the compression curve of the graphite oxide aerogel that the polyethylene polyamine that (d) obtains for embodiment 8 is cross-linked, wherein X-coordinate is strain, and ordinate zou is stress.By stress-strain(ed) curve, can find out that graphite 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 calculated is 45J g
-1; The Young's modulus of embodiment 8 is 20MPa, and yield strength is 1.8MPa, and the energy absorption of the opposing external force calculated is 55J g
-1; The Young's modulus of the graphite oxide aerogel that embodiment 1 ~ 11 obtains is 5 ~ 50MPa, and yield strength is 1 ~ 5MPa.The energy absorption of the opposing external force calculated is 10 ~ 200J g
-1.Illustrate that graphite oxide aerogel has good shock resistance.
Figure 10 is the characterization data to XPS, Raman and XRD of graphite oxide aerogel in embodiment 1 and embodiment 8.
Wherein scheming (a) is x-ray photoelectron power spectrum (XPS) figure, be followed successively by the spectral line of graphite oxide aerogel that embodiment 1 obtains, graphite oxide aerogel that embodiment 8 obtains, pure zirconia Graphene from top to bottom, X-coordinate is for becoming bond energy, and ordinate zou is intensity.Front two spectral lines, respectively containing N 1s peak and La 4d peak, illustrate that N and La is present in the graphite oxide aerogel that embodiment 1 and embodiment 8 obtain respectively.
Figure (b) is the amplification at carbon 1s peak in figure (a), and be C-C peak in transverse axis 284.8 position, 286.9 positions are C-O peak, illustrate in three kinds of materials all containing graphene oxide.Figure (a) and (b) illustrate cross-linker molecules and the existence of graphene oxide in aerogel network jointly.
Figure (c) is Raman spectrum (Raman) figure, and be followed successively by the spectral line of graphite oxide aerogel that embodiment 1 obtains, graphite oxide aerogel that embodiment 8 obtains, pure zirconia Graphene from top to bottom, X-coordinate is Raman shift, and ordinate zou is intensity.The characteristic peak all occurring graphene oxide in three kinds of materials is described.
Figure (d) is X-ray diffraction spectrum (XRD) figure, and be followed successively by the spectral line of graphite oxide aerogel that embodiment 1 obtains, graphite oxide aerogel that embodiment 8 obtains, pure zirconia Graphene from top to bottom, X-coordinate is diffraction angle, and ordinate zou is intensity.Wherein pure zirconia Graphene has fixing interlamellar spacing, therefore occurs diffraction peak, and in graphite oxide aerogel, graphene oxide lamella is that edge is cross-linked, therefore salt free ligands peak.XPS, Raman and XRD result of the graphite oxide aerogel that embodiment 2 ~ 7,9 ~ 11 obtains is similar.
Embodiment 12
The graphite oxide aerogel that embodiment 1 obtains is placed on and is connected with reducing gas H
2in the test tube of S, continue to place 30h, the quality change of results of regular determination reaction gas gel between the reaction period under 20 ° of C, to graphite oxide aerogel quality without considerable change, stop measuring.
The left figure of Fig. 7 is the SEM photo of reaction rear oxidation graphene aerogel, and right figure is the mass-change curve of graphite oxide aerogel in reaction process.As can be seen from the figure, there is obvious change in the three-dimensional porous nano structure of graphite oxide aerogel, native oxide graphene sheet layer attached to a mass of cylindrical sulphur simple substance after the reaction, and the weight of aerogel also has significant increase, illustrate that graphene oxide has oxidisability, can by S
2-be reduced to elemental sulfur, reflection graphene oxide is to H
2s has obvious adsorption effect.
Embodiment 13
It is 20mg L that the graphite oxide aerogel of 5mg embodiment 1 obtained puts into 20mL concentration
-1methylene blue dye solution in, under 20 ° of C, stir 3000min, survey the absorbancy of solution with UV-Vis spectrum, obtaining graphite oxide aerogel to the adsorptive capacity of methylene blue is 271.8mg g
-1.
Fig. 8 be the graphite oxide aerogel that obtains of embodiment 1 according to the method described above to the adsorption curve of different dyes, be followed successively by the adsorptive capacity to methylene blue, magenta, C.I. 42685 and rhodamine B from top to bottom, scope is at 100 ~ 2000mg g
-1, transverse axis is the time, and the longitudinal axis is absorbancy.
Embodiment 14
The graphite oxide aerogel that embodiment 1 obtains being put into 20mL concentration is 50mg L
-1pbCl
2in solution, under 20 ° of C, stir 24h, surveyed the change of absorbancy by atomic absorption spectrum, then utilize typical curve to obtain graphite oxide aerogel to Pb
2+the adsorptive capacity of ion is 72.1mg g
-1.
Fig. 9 be the graphite oxide aerogel that obtains of embodiment 1 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.
Embodiment 15
The graphite oxide aerogel obtained used as electrode of super capacitor, step is as follows.
By graphite oxide aerogel with mortar grind after, according to aerogel: acetylene black: PVDF(polyvinylidene difluoride (PVDF), as binding agent) mass ratio=87:10:3 be mixed with mixture and grind in mortar, until form homogeneous high viscosity solution; With tabletting machine, high viscosity solution is pressed in Ni film, is placed in 120 ° of C dry 6 hours, is then assembled into two electrode systems, Ni film is as working electrode, and Pt electrode is as to electrode.Electrolytic solution is the KOH solution of 5moL/L.All electro-chemical tests (test such as cyclic voltammetric and constant current charge-discharge) all become to produce in CHI660D(Shanghai Chen Hua company) carry out in electrochemical workstation.Figure 11 is cyclic voltammetry curve when graphite oxide aerogel uses as electrode of super capacitor in embodiment 1, and calculating integral area must the ratio capacitance value of this aerogel be 120F/g.The ratio capacitance of the graphite oxide aerogel that embodiment 2 ~ 9 obtains is 200 ~ 500F/g.
The graphite oxide aerogel that overcritical or 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 the electrostatic interaction between different graphene oxide sheet, graphene oxide lamella is fitted together with the mode of connection of special edge edge, the final three dimensional gell network forming macroscopic view.(2) singularity of forming process, the formation of graphene oxide hydrogel is different from general synthetic method.A kind of gel promotor (ester compound namely mentioned in the present invention) need be added in Gel Precursor, the adding of this gel promotor not only allow the forming process of gel become controlled, and substantially increase gel quality, be conducive to further drying treatment; (3) singularity of structure, its special gel formation process imparts the significant constructional feature of graphite oxide aerogel, namely the partly overlapping probability between two-dimentional graphene oxide lamella genetic horizon and layer is very little, and the three-dimensional assembly and connection of graphene oxide mainly occurs in the edge section of graphene oxide.The graphite oxide aerogel adopting this assembling mode to obtain both had had large specific surface area (100 ~ 2000m
2g
-1), (Young's modulus is 0.5 ~ 50MPa to the mechanical strength had again, and yield strength is 0.1 ~ 5MPa, and shock resistance energy absorption is 10 ~ 200J g
-1).Adopt the graphite oxide aerogel that above-mentioned preparation method obtains, still containing a large amount of oxygen-containing functional groups in the lamella of graphene oxide, simultaneously contain a small amount of metallic element or nitrogen element (these elements are mainly derived from used linking agent) in the edge section of graphene sheet layer, and do not occur or the phenomenon that seldom overlaps between the graphene oxide lamella used as structural unit.
In sum, these are only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a preparation method for graphite oxide aerogel, is characterized in that: described method steps is as follows: (1) prepares graphene oxide water solution; (2) in graphene oxide water solution, add alkaline solution adjust pH to alkalescence, then add the colloidal solution of metal hydroxides or metal carbonate, or add the molecule containing primary amine, secondary amine or tertiary amine functional group, dispersion obtains solution 1; (3) in solution 1, add ester compound, dispersion obtains solution 2; Solution 2 is left standstill and obtains graphene oxide hydrogel; (4) graphene oxide hydrogel is carried out drying, obtain described graphite oxide aerogel; Wherein, in step (2), described metal hydroxides or metal carbonate are oxyhydroxide containing metal ion more than divalence or carbonate; Metal ion in described metal hydroxides or metal carbonate is Fe
3+, 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 containing primary amine, secondary amine or tertiary amine functional group is trimeric cyanamide, polyethylene polyamine or polyamidoamine dendrimer; Step (3) described ester compound is selected from ethyl acetate, Gluconolactone or vovocan.
2. the preparation method of a kind of graphite oxide aerogel as claimed in claim 1, is characterized in that: after step (1) obtains graphene oxide water solution, the concentration of graphene oxide is formulated as 2 ~ 20 mg/mL.
3. the preparation method of a kind of graphite oxide aerogel as claimed in claim 1, it is characterized in that: in step (2), the quality of described graphene oxide: the quality=2 ~ 50:1 of metal hydroxides, metal carbonate or the molecule containing primary amine, secondary amine or tertiary amine functional group.
4. the preparation method of a kind of graphite oxide aerogel as claimed in claim 1, it is characterized in that: in step (4), water, for add water in graphene oxide hydrogel, is poured out after soaking 0.5 ~ 10 h by described drying process, repeat 2 ~ 8 times, then by graphene oxide hydrogel-50
oc ~-5
ofreezing under C>=30min, 10
oc ~ 100
odry 30 min ~ 48 h of C, obtain graphite oxide aerogel; Freezing and drying process is all carried out under the vacuum tightness of 1 ~ 10000 Pa.
5. the preparation method of a kind of graphite oxide aerogel as claimed in claim 1, it is characterized in that: in step (4), described drying process is that supercutical fluid mode is dry, for adding ethanol or acetone in graphene oxide hydrogel, pour out after soaking 0.5 ~ 10 h, repeat 1 ~ 8 time, obtain graphene oxide alcogel or ketone gel, then with Supercritical Ethanol or supercritical co drying >=2 h, graphite oxide aerogel is obtained.
6. the graphite oxide aerogel prepared of the method for claim 1, is characterized in that: graphene oxide lamella, by linking agent, is assembled into three-dimensional net structure in edge conjunction mode by described aerogel; Described linking agent is the metal ion of more than divalence, or is protonated primary amine, secondary amine or tertiary amine ion.
7. a kind of graphite oxide aerogel according to claim 6, it is characterized in that: described graphite oxide aerogel has vesicular structure, aperture is 1 nm ~ 20 μm, specific surface area is 100 ~ 2000 m
2g
-1, density is 10 ~ 500 mg cm
-3.
8. the application of a kind of graphite oxide aerogel as claimed in claims 6 or 7, described application is as anti-ballistic materials, dye adsorption material, heavy metal ion adsorbing material, gas adsorption material or electrode materials using graphite oxide aerogel.
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| 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 |
| 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 |
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