CN110203910A - The preparation method of modified graphene aeroge - Google Patents
The preparation method of modified graphene aeroge Download PDFInfo
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- CN110203910A CN110203910A CN201910567860.6A CN201910567860A CN110203910A CN 110203910 A CN110203910 A CN 110203910A CN 201910567860 A CN201910567860 A CN 201910567860A CN 110203910 A CN110203910 A CN 110203910A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 89
- 239000000017 hydrogel Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 150000002191 fatty alcohols Chemical class 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005187 foaming Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 244000005700 microbiome Species 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 235000019441 ethanol Nutrition 0.000 description 27
- 238000006722 reduction reaction Methods 0.000 description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 16
- 239000000908 ammonium hydroxide Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 230000002209 hydrophobic effect Effects 0.000 description 12
- 239000004964 aerogel Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- -1 Polyethylene Polymers 0.000 description 8
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- 239000011734 sodium Substances 0.000 description 6
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- 238000001035 drying Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 235000010378 sodium ascorbate Nutrition 0.000 description 5
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 5
- 229960005055 sodium ascorbate Drugs 0.000 description 5
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 5
- 238000010257 thawing Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 108010082495 Dietary Plant Proteins Proteins 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000012520 frozen sample Substances 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229940059939 kayexalate Drugs 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UZIQYAYUUNMDMU-UHFFFAOYSA-N N.[Br+] Chemical compound N.[Br+] UZIQYAYUUNMDMU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241001593750 Turcica Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical group CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical group CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Colloid Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of modified graphene aeroge, include the following steps: that the mixed solution containing graphene oxide, surfactant and reducing agent is made in (1)；(2) mixed solution is foamed, obtains graphene hydrogel；(3) graphene hydrogel is reacted in the presence of monohydric alcohol and alkalescent catalyst, obtains modified graphene hydrogel；(4) modified graphene hydrogel is freezed and is thawed, obtain modified graphene aeroge.The modified graphene aeroge that this method is prepared has good hydrophobicity.
Description
Technical field
The present invention relates to a kind of preparation method of graphene aerogel, in particular to a kind of system of modified graphene aeroge
Preparation Method.
Background technique
Graphene aerogel is a kind of high-intensitive aeroge, has the characteristics that high resiliency, strong absorption, has a extensive future.
Graphene aerogel is although with good performance, but its preparation process is complicated, at high cost, be always its be difficult to it is industrialized
One of the major reasons.Since graphene difficulty is dispersed in water, graphene aerogel generally is prepared by raw material of graphene oxide.But
It is the introducing due to oxygen-containing group, reduces the hydrophobic performance for the graphene aerogel being prepared.
CN104843676A discloses a kind of preparation method of graphene aerogel: (1) preparing containing graphene oxide
Polyethylene aqueous solution, obtaining concentration is 1~10mg/cm3Graphene oxide dispersion；(2) by graphene oxide dispersion,
It is freezed under conditions of not higher than subzero 196 DEG C, obtains frozen samples；(3) frozen samples are dried, it is dry obtains freezing
Dry sample；(4) in the mixed-gas environment of argon gas and hydrogen, freeze drying example progress high temperature reduction is obtained into required stone
Black alkene aeroge.Graphene aerogel is prepared using the method high temperature reduction of high annealing, so not only to equipment requirement
The hydrophobic performance for the graphene aerogel that height can be such that aeroge shrinks, and be prepared is also not good enough.
CN106517160A discloses a kind of preparation method of isotropic super-elasticity graphene aerogel: (1) restoring
In the presence of agent, graphene oxide aqueous dispersions are stirred at low speed with lauryl sodium sulfate aqueous solution after mixing, then high-speed stirred
Foaming, graphene oxide layer is restored to form tridimensional network；(2) freezing reinforcing graphene sheet layer is formed by hole wall,
Last normal heating is dry, obtains the graphene aerogel of isotropic.The graphene aerogel that this method is prepared is hydrophobic
Performance is bad.
CN109232013A discloses a kind of preparation method of big size graphene cystosepiment: (1) to graphene oxide water
Reducing agent is added in solution and adds surfactant after to be restored dose is completely dissolved, stirs the gas into graphene oxide solution
Bubble, obtains the foaming graphene oxide solution with micron order uniform liquid crystal phase；(2) by the foaming oxygen of micron order uniform liquid crystal phase
Graphite alkene solution, which is transferred in mold, heats reduction, obtains big size graphene hydrogel；(3) large scale hydrogel is cold
Freeze, then melt, obtains the big size graphene hydrogel of freeze thaw processing；(4) by the large scale stone of freeze thaw processing
Black alkene hydrogel naturally dry or the drying at 30~60 DEG C, obtain big size graphene cystosepiment.What this method was prepared
Grapheme foam plate hydrophobic performance is bad.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of modified graphene aeroge, it is prepared by this method
Modified graphene aeroge has good hydrophobicity.
The present invention provides a kind of preparation method of modified graphene aeroge, includes the following steps:
(1) mixed solution containing graphene oxide, surfactant and reducing agent is made；
(2) mixed solution is foamed, obtains graphene hydrogel；
(3) graphene hydrogel is reacted in the presence of monohydric alcohol and alkalescent catalyst, obtains modified graphene water
Gel；
(4) modified graphene hydrogel is freezed and is thawed, obtain modified graphene aeroge.
Preparation method according to the present invention, it is preferable that the purity of graphene oxide is 95% or more, piece diameter≤50 μm, piece
Thickness degree≤30nm, oxygen carbon molar ratio are 0.15~0.65.
Preparation method according to the present invention, it is preferable that reducing agent is selected from acidic reduction agent, alkaline reducer, microorganism also
One of former agent is a variety of.
Preparation method according to the present invention, it is preferable that the mass ratio of graphene oxide and reducing agent is 1:1~5.
Preparation method according to the present invention, it is preferable that surfactant is selected from natural surfactant or artificial synthesized table
One of face activating agent is a variety of.
Preparation method according to the present invention, it is preferable that the mass ratio of graphene oxide and surfactant be 1:0.05~
2。
Preparation method according to the present invention, it is preferable that in step (2), make mixed solution foam by way of stirring, turn
Speed is 5000~20000rpm, and mixing time is 5~60min.
Preparation method according to the present invention, it is preferable that monohydric alcohol is selected from the unitary fat with 2~10 carbon atom chains
Alcohol.
Preparation method according to the present invention, it is preferable that alkalescent catalyst is selected from ammonium hydroxide, triethylamine, diethylamine, cyclohexylamine
Or one of aniline.
Preparation method according to the present invention, it is preferable that the volume ratio of monohydric alcohol and alkalescent catalyst is 1:4~10.
The present invention, which first passes through reducing agent, restores graphene oxide, after addition monohydric alcohol and alkalescent catalyst make reduction
Graphene oxide be further modified, obtain hydrophobic performance raising modified graphene aeroge.In currently preferred technology
In scheme, alkalescent catalyst is ammonium hydroxide, the modified graphene aeroge being prepared can in this way had preferably hydrophobic
Property.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to
This.
Production method of the invention includes the following steps: the step of (1) prepares mixed solution；(2) the step of foaming；(3)
Modified step；(4) the step of aeroge is made is freezed.It is further explained below.
<the step of preparing mixed solution>
The mixed solution containing graphene oxide, surfactant and reducing agent is made.It can be by graphene oxide, surface
Activating agent and reducing agent co-dissolve Yu Shuizhong form mixed solution.It can also first prepare to obtain graphene oxide water solution, so
Surfactant and reducing agent are mixed with graphene oxide water solution afterwards, form mixed solution.Mixed solution can be by super
The mode of sound is prepared, and the ultrasonic time is 5~60min.Preferably, the ultrasonic time is 5~30min.It is highly preferred that super
The time of sound is 8~20min.
In the present invention, the concentration of graphene oxide can be 0.5~20mg/ml in mixed solution.Preferably, stone is aoxidized
The concentration of black alkene is 1~15mg/ml.It is highly preferred that the concentration of graphene oxide is 2~7mg/ml.
Graphene oxide in the present invention can be obtained using conventional method.Including but not limited to pass through Hummers method, change
Into Hummers method, liquid phase method, Mechanical Method, the methods of electrochemical oxidation process be prepared.One according to the present invention specific
Embodiment, graphene oxide are prepared by improved Hummers method.
In the present invention, the purity of graphene oxide is 95% or more, piece diameter≤50 μm, lamellar spacing≤30nm, oxygen carbon
Molar ratio is 0.15~0.65.Preferably, the purity of graphene oxide is 96% or more.It is highly preferred that graphene oxide is pure
Degree is 98% or more.For example, can be 99%.Preferably, the piece diameter of graphene oxide is 2~45 μm.It is highly preferred that oxidation ink
The piece diameter of alkene is 20~30 μm.Preferably, the lamellar spacing of graphene oxide is 1~10nm.It is highly preferred that graphene oxide
Lamellar spacing is 5~10nm.Preferably, the oxygen carbon molar ratio of graphene oxide is 0.2~0.5.It is highly preferred that graphene oxide
Oxygen carbon molar ratio be 0.3~0.5.It can make the modified graphene aeroge being prepared that there is superior hydrophobicity in this way
Energy.
In the present invention, reducing agent can selected from one of acidic reduction agent, alkaline reducer, reducing microorganisms or
It is a variety of.Alkaline reducer can be selected from ethylenediamine, sodium ascorbate, ammonium hydroxide, hydrazine hydrate, sodium borohydride, vulcanized sodium, even two sulfurous
One of sour sodium, potassium borohydride, sodium tetraborate are a variety of.Preferably, alkaline reducer be selected from ethylenediamine, sodium ascorbate or
One of ammonium hydroxide is a variety of.It is highly preferred that alkaline reducer is ethylenediamine.Acidic reduction agent can be selected from gallic acid, sulphur
One of sour ferrous iron, ascorbic acid, citric acid, oxalic acid or hydroiodic acid are a variety of.Preferably, acidic reduction agent is selected from galla turcica
One of acid, ascorbic acid or oxalic acid are a variety of.It is highly preferred that acidic reduction agent is gallic acid.Reducing microorganisms can
Think activated sludge.
In the present invention, the mass ratio of graphene oxide and reducing agent is 1:1~5.Preferably, graphene oxide and reduction
The mass ratio of agent is 1:2~5.It is highly preferred that the mass ratio of graphene oxide and reducing agent is 1:2~3.It can make to prepare in this way
Obtained modified graphene aeroge has superior hydrophobic performance.
In the present invention, surfactant be selected from one of natural surfactant or artificially synthesised surfactant or
It is a variety of.Natural surfactant can be protide surfactant.Preferably, protide surfactant is selected from animal protein
Or one of vegetable protein or a variety of.It is highly preferred that protide surfactant is vegetable protein.Artificial synthesized surface-active
Agent can be cationic surfactant, anionic surfactant or nonionic surfactant.Cationic surfactant
It can be quaternary ammonium compound.Preferably, cationic surfactant is selected from cetyl trimethylammonium bromide, benzalkonium chloride or benzene
Prick one of bromine ammonium or a variety of.It is highly preferred that cationic surfactant is cetyl trimethylammonium bromide.Anion table
Face activating agent can be hydrosulphate surfactant or sulphonic acid compound surfactant.Preferably, hydrosulphate surface-active
Agent is selected from one or both of sulfated castor oil, lauryl sodium sulfate.It is highly preferred that hydrosulphate surfactant is
Lauryl sodium sulfate.Preferably, sulphonic acid compound surfactant is selected from dioctyl succinate disulfonate acid, dodecyl benzene sulfonic acid
One of sodium, sodium glycocholate or kayexalate are a variety of.It is highly preferred that sulphonic acid compound surfactant is dodecane
One of base benzene sulfonic acid sodium salt or kayexalate are a variety of.A specific embodiment according to the present invention, it is sulfonated
Object surfactant is neopelex.Nonionic surfactant can be N vinylamide polymer class table
Face activating agent.Preferably, nonionic surfactant can be polyvinylpyrrolidone.
In the present invention, the mass ratio of graphene oxide and surfactant is 1:0.5~3.Preferably, graphene oxide
Mass ratio with surfactant is 1:0.5~2.It is highly preferred that the mass ratio of graphene oxide and surfactant is 1:0.8
~1.5.It can make the modified graphene aeroge being prepared that there is superior hydrophobic performance in this way.
<the step of foaming>
Mixed solution is foamed, graphene hydrogel is obtained.In the present invention, mixed solution can be by way of stirring
Foaming.Revolving speed can be 5000~20000rpm.Preferably, revolving speed is 7000~15000rpm.It is highly preferred that revolving speed is 8000
~12000rpm.Mixing time is 5~60min.Preferably, mixing time is 8~40min.It is highly preferred that mixing time is 8
~20min.It can make the modified graphene aeroge being prepared that there is superior hydrophobic performance in this way.
Reduction reaction occurs in the presence of a reducing agent for graphene oxide.The temperature of reduction reaction can be 50~120 DEG C.It is excellent
Selection of land, the temperature of reduction reaction are 70~100 DEG C.It is highly preferred that the temperature of reduction reaction is 70~90 DEG C.Reduction reaction when
Between can be 5~20h.Preferably, the reaction time is 7~15h.It is highly preferred that the reaction time is 8~12h.
<modified step>
Graphene hydrogel is reacted in the presence of monohydric alcohol and alkalescent catalyst, obtains modified graphene water-setting
Glue.First monohydric alcohol can be mixed with alkalescent catalyst, then by the mixed liquor and graphene of monohydric alcohol and alkalescent catalyst
Hydrogel mixing.
In the present invention, monohydric alcohol can be selected from the unitary fatty alcohol with 2~10 carbon atom chains.Preferably, unitary
Alcohol can be selected from the unitary fatty alcohol with 2~8 carbon atom chains.It is highly preferred that monohydric alcohol can be selected from 2~5 carbon
The unitary fatty alcohol of atomic link.The unitary fatty alcohol can be unitary straight-chain fatty alcohol, or unitary Branched fatty
Alcohol；It preferably, is unitary straight-chain fatty alcohol.The unitary fatty alcohol can be unitary saturated fatty alcohol, or unitary
Unsaturated fatty alcohol；It preferably, is unitary saturated fatty alcohol；It is highly preferred that being unitary linear saturation fatty alcohol.For example, can be with
For ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol.Standby obtained modified graphene aeroge can in this way had more excellent
Hydrophobic performance.
In the present invention, alkalescent catalyst can be selected from one in ammonium hydroxide, triethylamine, diethylamine, cyclohexylamine or aniline
Kind is a variety of.Preferably, alkalescent catalyst can be selected from one of ammonium hydroxide, triethylamine or diethylamine or a variety of.More preferably
Ground, alkalescent catalyst can be ammonium hydroxide.
In the present invention, the volume ratio of monohydric alcohol and alkalescent catalyst is 1:4~10.Preferably, monohydric alcohol and weak base
Property catalyst volume ratio be 1:6~10.It is highly preferred that the volume ratio of monohydric alcohol and alkalescent catalyst is 1:7~9.In this way
It can make standby obtained modified graphene aeroge that there is superior hydrophobic performance.
In the presence of alkalescent catalyst, the reaction temperature of graphene hydrogel and monohydric alcohol can be 283~323K.It is excellent
Selection of land, reaction temperature can be 283~310K.It is highly preferred that reaction temperature can be 293~310K.Graphene hydrogel with
The reaction time of monohydric alcohol can be 0.5~10h.Preferably, the reaction time is 2~8 hours.It is highly preferred that the reaction time is 4
~7h.
It in the present invention, can also include the step of washing modified graphene hydrogel.Washing lotion used in washing step
It can be water or ethanol water.Preferably, washing lotion is ethanol water.It is highly preferred that in ethanol water ethyl alcohol content
For 0.5~20vol%, preferably 1~8vol%, more preferably 1~5vol%.
<freezing the step of aeroge is made>
Modified graphene hydrogel is freezed and thawed, modified graphene aeroge is obtained.
In the present invention, cooling time is 5~30h.Preferably, cooling time is 5~20h.It is highly preferred that cooling time
For 8~15h.
Defrosting can carry out at room temperature.Dry step can also be included after the step of thawing.Drying can be normal
Pressure carries out.Drying temperature is 318~373K.Preferably, drying temperature is 325~350K.It is highly preferred that drying temperature is
325~340K.It can make the modified graphene aeroge being prepared that there is superior hydrophobic performance in this way.
Test method is described below.
Contact angle test: it is tested using contact angle tester.Deionized water drop is added in modified graphene aeroge
Sample surfaces form drop, are then taken pictures imaging with contact angle tester, are directly measured with protractor, obtain modified graphene
The contact angle of aeroge sample.
Embodiment 1
By 180mg graphene oxide, (purity 99%, piece diameter are 28 μm, lamellar spacing 8nm, and oxygen carbon molar ratio is
0.4) it is dissolved in aqueous solution, obtains the graphene oxide water solution that graphene oxide concentration is 3mg/ml.180mg ten is weighed respectively
Sodium dialkyl sulfate and 360mg sodium ascorbate, are added in graphene oxide water solution, and ultrasonic disperse 10min is mixed
Solution.
Mixed solution is stirred into 10min under the revolving speed of 10000rpm；Then at 80 DEG C, reduction reaction 10h is removed more
Remaining reaction solution obtains graphene hydrogel.
The volume ratio for preparing ethyl alcohol and ammonium hydroxide is the ammonium hydroxide alcohol mixed solution of 1:8, and ammonium hydroxide alcohol mixed solution is added
Into graphene hydrogel, under the conditions of 298K, 5h is reacted；Product after reaction is washed with the ethanol water of 1vol%,
Obtain modified graphene hydrogel.
Modified graphene hydrogel is freezed and 10h and is thawed, by the modified graphene hydrogel after defrosting in normal pressure and
It is dry under the conditions of 338K, obtain modified graphene aeroge.Experimental result is referring to table 1.
Embodiment 2
By 180mg graphene oxide, (purity 98%, piece diameter are 20 μm, lamellar spacing 5nm, and oxygen carbon molar ratio is
0.3) it is dissolved in aqueous solution, obtains the graphene oxide water solution that graphene oxide concentration is 3mg/ml.180mg ten is weighed respectively
Sodium dialkyl sulfate and 360mg sodium ascorbate, are added in graphene oxide water solution, and ultrasonic disperse 10min is mixed
Solution.
Mixed solution is stirred into 10min under the revolving speed of 10000rpm；Then at 80 DEG C, reduction reaction 10h is removed more
Remaining reaction solution obtains graphene hydrogel.
The volume ratio for preparing ethyl alcohol and ammonium hydroxide is the ammonium hydroxide alcohol mixed solution of 1:8, and ammonium hydroxide alcohol mixed solution is added
Into graphene hydrogel, under the conditions of 298K, 1h is reacted；Product after reaction is washed with the ethanol water of 1vol%,
Obtain modified graphene hydrogel.
Modified graphene hydrogel is freezed and 10h and is thawed, by the modified graphene hydrogel after defrosting in normal pressure and
It is dry under the conditions of 338K, obtain modified graphene aeroge.Experimental result is referring to table 1.
Embodiment 3
By 180mg graphene oxide, (purity 95%, piece diameter are 40 μm, lamellar spacing 3nm, and oxygen carbon molar ratio is
0.2) it is dissolved in aqueous solution, obtains the graphene oxide water solution that graphene oxide concentration is 3mg/ml.180mg ten is weighed respectively
Sodium dialkyl sulfate and 360mg sodium ascorbate, are added in graphene oxide water solution, and ultrasonic disperse 10min is mixed
Solution.
Mixed solution is stirred into 10min under the revolving speed of 10000rpm；Then at 80 DEG C, reduction reaction 10h is removed more
Remaining reaction solution obtains graphene hydrogel.
The volume ratio for preparing ethyl alcohol and ammonium hydroxide is the ammonium hydroxide alcohol mixed solution of 1:10, and ammonium hydroxide alcohol mixed solution is added
Into graphene hydrogel, under the conditions of 298K, 1h is reacted；Product after reaction is washed with the ethanol water of 1vol%,
Obtain modified graphene hydrogel.
Modified graphene hydrogel is freezed and 10h and is thawed, by the modified graphene hydrogel after defrosting in normal pressure and
It is dry under the conditions of 338K, obtain modified graphene aeroge.Experimental result is referring to table 1.
Table 1
| Test sample | Contact angle (°) |
| Embodiment 1 | 155 |
| Embodiment 2 | 148 |
| Embodiment 3 | 140 |
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of preparation method of modified graphene aeroge, which comprises the steps of:
(1) mixed solution containing graphene oxide, surfactant and reducing agent is made；
(2) mixed solution is foamed, obtains graphene hydrogel；
(3) graphene hydrogel is reacted in the presence of monohydric alcohol and alkalescent catalyst, obtains modified graphene hydrogel；
(4) modified graphene hydrogel is freezed and is thawed, obtain modified graphene aeroge.
2. preparation method according to claim 1, which is characterized in that the purity of graphene oxide is 95% or more, piece diameter
≤ 50 μm, lamellar spacing≤30nm, oxygen carbon molar ratio is 0.15~0.65.
3. preparation method according to claim 1, which is characterized in that reducing agent be selected from acidic reduction agent, alkaline reducer,
One of reducing microorganisms are a variety of.
4. preparation method according to claim 1, which is characterized in that the mass ratio of graphene oxide and reducing agent is 1:1
~5.
5. preparation method according to claim 1, which is characterized in that surfactant is selected from natural surfactant or people
One of work synthetic surfactant is a variety of.
6. preparation method according to claim 1, which is characterized in that the mass ratio of graphene oxide and surfactant is
1:0.05~2.
7. preparation method according to claim 1, which is characterized in that in step (2), make to mix by way of stirring molten
Liquid foaming, revolving speed are 5000~20000rpm, and mixing time is 5~60min.
8. preparation method according to claim 1, which is characterized in that monohydric alcohol, which is selected from, has 2~10 carbon atom chains
Unitary fatty alcohol.
9. any preparation method according to claim 1~8, which is characterized in that the alkalescent catalyst is selected from ammonia
One of water, triethylamine, diethylamine, cyclohexylamine or aniline are a variety of.
10. any preparation method according to claim 1~8, which is characterized in that the body of monohydric alcohol and alkalescent catalyst
Product is than being 1:4~10.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423095A (en) * | 2020-03-05 | 2020-07-17 | 厦门大学 | Method for treating residual activated sludge |
| CN112536004A (en) * | 2020-12-03 | 2021-03-23 | 航天特种材料及工艺技术研究所 | High-temperature-resistant elastic graphene aerogel material and preparation method thereof |
| CN115367738A (en) * | 2022-08-05 | 2022-11-22 | 广东墨睿科技有限公司 | Graphene aerogel and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
| US20170229253A1 (en) * | 2015-09-25 | 2017-08-10 | Robert Bosch Gmbh | Hybrid Supercapacitor |
| CN107640760A (en) * | 2017-10-13 | 2018-01-30 | 上海理工大学 | A kind of preparation method of graphene aerogel block, graphene aerogel block and its application |
| CN107686107A (en) * | 2017-08-28 | 2018-02-13 | 中国石油大学(华东) | The preparation method of the hydrophobic CNT graphene composite aerogel of elasticity |
-
2019
- 2019-06-27 CN CN201910567860.6A patent/CN110203910B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170229253A1 (en) * | 2015-09-25 | 2017-08-10 | Robert Bosch Gmbh | Hybrid Supercapacitor |
| CN106517160A (en) * | 2016-11-22 | 2017-03-22 | 青岛科技大学 | Method for preparing isotropic superelastic graphene aerogel |
| CN107686107A (en) * | 2017-08-28 | 2018-02-13 | 中国石油大学(华东) | The preparation method of the hydrophobic CNT graphene composite aerogel of elasticity |
| CN107640760A (en) * | 2017-10-13 | 2018-01-30 | 上海理工大学 | A kind of preparation method of graphene aerogel block, graphene aerogel block and its application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423095A (en) * | 2020-03-05 | 2020-07-17 | 厦门大学 | Method for treating residual activated sludge |
| CN111423095B (en) * | 2020-03-05 | 2022-04-08 | 厦门大学 | Method for treating residual activated sludge |
| CN112536004A (en) * | 2020-12-03 | 2021-03-23 | 航天特种材料及工艺技术研究所 | High-temperature-resistant elastic graphene aerogel material and preparation method thereof |
| CN115367738A (en) * | 2022-08-05 | 2022-11-22 | 广东墨睿科技有限公司 | Graphene aerogel and preparation method thereof |
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Denomination of invention: Preparation of modified graphene aerogel Granted publication date: 20210115 Pledgee: China Construction Bank Corporation Hefei Binhu New Area sub branch Pledgor: Zhongsu New Technology Co.,Ltd. Registration number: Y2024980016703 |