CN109180991A - A kind of N doping HCNFs/SA-Men+The preparation method of plural gel - Google Patents
A kind of N doping HCNFs/SA-Men+The preparation method of plural gel Download PDFInfo
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- CN109180991A CN109180991A CN201810981416.4A CN201810981416A CN109180991A CN 109180991 A CN109180991 A CN 109180991A CN 201810981416 A CN201810981416 A CN 201810981416A CN 109180991 A CN109180991 A CN 109180991A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 55
- 239000000661 sodium alginate Substances 0.000 claims description 54
- 235000010413 sodium alginate Nutrition 0.000 claims description 54
- 229940005550 sodium alginate Drugs 0.000 claims description 54
- 239000000499 gel Substances 0.000 claims description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 49
- 239000002131 composite material Substances 0.000 claims description 46
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 43
- 239000004917 carbon fiber Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000017 hydrogel Substances 0.000 claims description 26
- 239000004964 aerogel Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000000746 purification Methods 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 19
- -1 cation chloride Chemical class 0.000 claims description 18
- 238000010907 mechanical stirring Methods 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002134 carbon nanofiber Substances 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 230000000802 nitrating effect Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000005121 nitriding Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 54
- 239000007789 gas Substances 0.000 description 28
- 229910052786 argon Inorganic materials 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 18
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 18
- 238000002156 mixing Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000006424 Flood reaction Methods 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000006835 compression Effects 0.000 description 9
- RSJOBNMOMQFPKQ-ZVGUSBNCSA-L copper;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O RSJOBNMOMQFPKQ-ZVGUSBNCSA-L 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 5
- 235000015110 jellies Nutrition 0.000 description 5
- 239000008274 jelly Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 241000446313 Lamella Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of N doping HCNFs/SA-Men+The preparation method of plural gel has the N doping HCNFs/SA-Me of three-dimensional net structure by ammonia source pyrolysismethod or step hydro-thermal nitriding preparation using ammonia or ammonium hydroxide as nitrogen sourcen+Plural gel.N doping HCNFs/SA-Me prepared by the present inventionn+Plural gel has pore structure abundant, high-specific surface area and three-dimensional net structure, and preparation method simple process, at low cost, high production efficiency, N doping amount are controllable, can industrialized production, have very big application potential and practical significance in terms of absorption, the energy.
Description
Technical field
The invention belongs to functional polymer composites technical fields, and in particular to a kind of N doping HCNFs/SA-Men+It is multiple
Close the preparation method of gel.
Background technique
Hydrogel is that one kind is formed by by chemical bond, hydrogen bond, Van der Waals force or physical entanglement with three-dimensional cross-linked net
Network structure, simultaneously containing hydrophilic radicals such as hydroxyl, amide groups, sulfonic group, carboxyls, but new function high score not soluble in water itself
Sub- material.Hydrogel can be swollen in water, tens times to thousands of times up to gel dry weight of water absorption.Due to three-dimensional network
Hydrogel has specific response and higher water absorbing properties, has been widely used in industry, agricultural, forestry, garden in recent years
The every field such as skill, health, medicine.It is moreover, specific using its high-adsorption-capacity, the fast rate of adsorption and reproducibility etc.,
It is used for adsorption treatment heavy metal ion, fuel waste water etc. and receives the extensive concern of people.And it by copolymerization, hands over
The modes such as connection, grafting, doping make electric active molecule form composite material in high-hydrophilic gel internal networking structure, have gathered solidifying
Glue characteristic and electroactive characteristic.Gel component assigns composite material high-hydrophilic, swellability, good biocompatibility and small
High diffusibility of the molecule in three-dimensional net structure.Electric active molecule makes composite material possess high conductivity, electrochemical oxidation
Reproducibility, electromechanical transformational etc. can obtain certain application in fields in terms of adsorbing separation, the energy etc..However, existing skill
The various types of gel complex material in art, usually using gel rubber material as substrate, conducting polymer, carbon nanotube, graphene,
Graphene oxide, metal nanoparticle etc. are by the methods of blending, doping preparation, therefore specific surface area is small, mechanical performance, conduction
Performance and stability are bad, the application in fields such as cause in terms of adsorbing separation, the energy to be restricted.
Alginate is odorless, nontoxic, and solution viscosity is high, and has good biocompatibility and biodegradable characteristics
Natural polysaccharide high polymer, abundant raw material is easy to get and cheap, there is it emphatically in fields such as medicine, weaving, organizational projects
The purposes wanted.Wherein, containing a large amount of-COO- group in sodium alginate structure, in the presence of metal cation, easily
Ionomer occurs with it and forms network structure, so that hydrogel is formed, but the hydrogel quality is crisp, mechanical strength and processing
Performance is poor.
One-dimensional carbon material of the diameter of carbon nano-fiber between carbon nanotube and common carbon fibers, growth course
More complicated, using different technological parameters, its pattern has biggish difference, such as crystal whisker-shaped, forked, two-way shape, multidirectional
Shape, helical form etc..Carbon nano-fiber has high intensity, high-modulus, preferable thermal conductivity and good surface size effect etc.
It is greatly paid close attention to by people.Wherein, helical form carbon nano-fiber is that a kind of novel carbon fiber of vapor phase growth is straight in addition to having
Heat resistance, the chemical stability of carbon fiber have on hot hydrogen storage material, conducing composite material, elastic material and absorbing material
Have it is far-reaching using swollen property and low-density, because its special helical structure has typical Chiral properties and good elasticity,
But it is easy to reunite, electric conductivity, stability, adsorbing metal ions, hydrophily and chemical active sites are poor.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of N doping HCNFs/SA-Men+
The preparation method of plural gel, solution sodium alginate gel texture material is crisp, mechanical strength is bad, electric conductivity is bad, leads
Cause the problem of application in fields is restricted in terms of adsorbing separation and the energy etc..
To achieve the above object, the present invention adopts the following technical scheme: a kind of N doping HCNFs/SA-Men+Plural gel
Preparation method, include the following steps:
1) N doping HCNFs/ SA-Men+The preparation of composite hydrogel
Under the atmosphere containing ammonia, spiral nanometer carbon fiber is placed at 800 ~ 1000 DEG C and is reacted, obtains N doping spiral
Then ultrasonic disperse 30 in deionized water is added in the N doping spiral nanometer carbon fiber and surfactant by carbon nano-fiber
~ 60 min obtain the first dispersion liquid, then sodium alginate emulsion is added into first dispersion liquid, and 1 ~ 2h of mechanical stirring must be mixed
Liquid is closed, metal cation chloride solution is finally added into the mixed liquor, after standing 5 ~ 12h, impregnates, wash through deionized water
It washs, obtains N doping HCNFs/ SA-Men+Composite hydrogel；
2) N doping HCNFs/ SA-Men+The preparation of composite aerogel
30 ~ 60 min of ultrasonic disperse in deionized water is added in spiral nanometer carbon fiber and surfactant and obtains the second dispersion liquid；
Ammonium hydroxide is added into second dispersion liquid again and 30 ~ 60min of sodium alginate emulsion ultrasonic disperse obtains mixed liquor, then to institute
It states addition metal cation chloride solution, 1 ~ 2h of mechanical stirring in mixed liquor and obtains Men+Mixed liquor, finally by the Men+It is mixed
Conjunction liquid, which is fitted into reaction kettle, carries out hydro-thermal reaction, impregnates, washing, frozen drying, obtains through deionized water after being cooled to room temperature
To N doping HCNFs/ SA-Men+Composite aerogel.
In this way, the active sites of adsorption metallic can be increased in the middle introducing nitrogen atom structure of HCNFs, from
And enhance HCNFs and Men+Interaction, adjustable conduction type changes the electronic structure of spiral nanometer carbon fiber, improves
Free carrier density, to improve electric conductivity and stability；The active sites for increasing adsorption metallic, to enhance
The interaction of spiral nanometer carbon fiber and metallic；In addition, the middle introducing nitrogen atom of spiral nanometer carbon fiber can part
Replace carbon, changes the surface nature of material, its cellular structure of modulation enhances its hydrophily, and influences the acid of material surface
Alkalinity provides a large amount of chemical activity positions.
Further, the HCNFs/ SA-Me of the N dopingn+The preparation of composite hydrogel can also use following methods: will
Spiral nanometer carbon fiber and surfactant are added in deionized water, and 10 ~ 30min of ultrasonic disperse obtains third dispersion liquid, then to
Sodium alginate emulsion is added in the dispersion liquid and ammonium hydroxide, 1 ~ 2h of ultrasonic disperse obtain mixed liquor, the mixed liquor is put into
Hydro-thermal reaction is carried out in reaction kettle and obtains nitrating mixed liquor, and it is molten that metal cation chloride is finally added into above-mentioned nitrating mixed liquor
Liquid, 1 ~ 2h of mechanical stirring impregnate, washing through deionized water, obtain N doping HCNFs/SA-Men+Composite hydrogel.
In this way, sodium alginate and spiral nanometer carbon fiber are after mixing, metal cation, sodium alginate and gold are added
Gel can be cross-linked to form by belonging to cation contact, and spiral nanometer carbon fiber is enable to be uniformly distributed in gel.
Further, the spiral nanometer carbon fiber purifies with the following method is made: using the nitric acid of mass fraction 50 ~ 70%
Solution floods spiral nanometer carbon fiber crude product, and in 120 ~ 140 DEG C of 1 ~ 2h of purifying, centrifuge washing to supernatant liquor is in neutrality, sets
After 8 ~ 10h dry in 60 ~ 80 DEG C of vacuum ovens, product is pulverized, the sieving of 325 mesh is to get the spiral arrived after purification
Carbon nano-fiber.
Further, the mass fraction of surfactant is 1% ~ 3% in the dispersion liquid, spiral nanometer carbon in the dispersion liquid
The concentration of fiber or N doping spiral nanometer carbon fiber is 0.01 ~ 0.5mg/L, and the dispersion liquid is the first dispersion liquid, second point
Dispersion liquid or third dispersion liquid.
Further, the surfactant is cetyl trimethylammonium bromide, polyvinylpyrrolidone and cetyl
One or more of trimethyl ammonium chloride.
Further, the metal cation chloride in the metal cation chloride solution is FeCl3、CaCl2、
CuCl2、BaCl2Or ZnCl2Deng；The concentration of the metal cation chloride solution is 0.01 ~ 0.05mol/L.
Further, the mass fraction of sodium alginate is 1 ~ 5% in the sodium alginate emulsion.
Further, the dispersion liquid, sodium alginate emulsion and belong to cation chloride solution volume ratio be 1 ~ 3:1 ~
2:0.2 ~ 1, the dispersion liquid are the first dispersion liquid, the second dispersion liquid or third dispersion liquid.
Further, reaction temperature is 80 ~ 140 DEG C in the hydro-thermal reaction, and the reaction time is 6 ~ 10 h.
Further, in the freeze-drying reaction temperature be -55 ~ -70 DEG C, the reaction time be 12 ~ for 24 hours.
Compared with prior art, the invention has the following beneficial effects:
1, N doping HCNFs/SA-Me prepared by the present inventionn+Plural gel is in porous three-dimensional net structure, wherein alginic acid
Sodium (SA) and metal cation (Men+) it is cross-linked to form gel, and it is aided with spiral nanometer carbon fiber.Wherein in suitable pH and temperature
Under the conditions of, the Na in sodium alginate molecular structure G unit+Ion exchange reaction can occur with some high valent cationics, lead
In the cavity body structure for causing metal cation to be located at (negatively charged G unit is surrounded and formed), a large amount of G units are gradually accumulated,
Three-dimensional net structure is formed, the mobility of the structural controllability hydrone makes gel internal structure to generate gelling
It is even closer.Spiral and curved shape characteristic because of spiral nanometer carbon fiber, greatly increase the specific surface of composite material
Product, so the introducing of spiral nanometer carbon fiber makes its internal structure become loose, interior gap space is big, between gel molecular
Active force is uneven, greatly improved the water storage performance of plural gel.In addition, the incorporation of spiral nanometer carbon fiber can be obvious
The compression strength for improving plural gel is primarily due to HCNFs with large specific surface area, low-density, high intensity and high-modulus
Characteristic, with sodium alginate (SA) it is compound after, the 3 D complex network structure of formation can effectively enhance the mechanical performance of gel,
Solves the poor disadvantage of sodium alginate material processing performance, to enhance the compressive property of plural gel.
2, the HCNFs/SA-Me of N doping prepared by the present inventionn+Plural gel has pore structure abundant, high-ratio surface
Product, electric conductivity is good and three-dimensional net structure, preparation method simple process, at low cost, and high production efficiency, N doping amount are controllable,
Can industrialized production, in absorption, have very big application potential and practical significance in terms of the energy.
Detailed description of the invention
Fig. 1 is Ca2+Influence diagram of the concentration to HCNFs/SA hydrogel Equilibrium swelling ratio；
Fig. 2 is HCNFs/SA- Ca made from embodiment 72+Composite hydrogel SEM figure；
Fig. 3 is HCNFs/SA- Fe made from embodiment 83+Composite hydrogel SEM figure；
Fig. 4 is plural gel XRD spectra；
Fig. 5 is Ca2+The compression strength figure of cross-linked hydrogel；
Fig. 6 is that different cationic crosslinked composite aerogels try hard to the adsorption energy of acetone；
In figure 1 be comparative example 2,2 be 1,3 comparative example 5,4 of embodiment be embodiment 4,5 be comparative example 3,6 be embodiment 2,7 compare
It is comparative example 4,10 be embodiment 3,11 be comparative example 7,12 is embodiment 6 that example 6,8, which is embodiment 5,9,；
Fig. 7 is the compression strength figure of different cationic crosslinked composite aerogels；
In figure 1 be comparative example 2,2 be 1,3 comparative example 5,4 of embodiment be embodiment 4,5 be comparative example 3,6 be embodiment 2,7 compare
It is comparative example 4,10 be embodiment 3,11 be comparative example 7,12 is embodiment 6 that example 6,8, which is embodiment 5,9,.
Specific embodiment
Invention is further described in detail with attached drawing combined with specific embodiments below.Not to experiment in following embodiment
What method was illustrated, be routine operation, and agents useful for same is common commercially available.
One, the concentration optimization of metal cation chloride solution
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, under protection of argon gas, with 5 DEG C/min liter
Temperature closes argon gas and leads to acetylene 1h to 580 DEG C, closes the logical argon gas of acetylene and is cooled to room temperature, is made spiral nanometer carbon fiber (HCNFs)
Crude product；
2) HCNFs made from 1.0 g step 1) is weighed in three-necked flask, and appropriate mass fraction is added will for 68 % nitric acid
HCNFs floods, and then places it in 140 DEG C of water-baths and purifies 2 h, after centrifuge washing to supernatant liquor is in neutrality (pH=7),
After being placed in 80 DEG C of vacuum ovens dry 10h again, is ground and product is pulverized to get arriving after purification with agate mortar
HCNFs, it is spare；
3) HCNFs the and 0.03g cetyl trimethylammonium bromide (CTAB) made from 0.5 g step 2 of precise after purification
In 500 ml beakers, then 100 ml deionized waters are added into above-mentioned beaker, 60 min of ultrasonic disperse, obtaining concentration is
The HCNFs solution of 0.5mg/ml, then sodium alginate (SA) cream that 100ml mass fraction is 2 % is added into the HCNFs solution
The ammonium hydroxide of turbid and 15ml, ultrasonic disperse 30 min are spare；
4) it is fitted into 80 ml ptfe autoclaves to mixing turbid made from step 3), and places it in 100 DEG C of air blast
In drying box after hydro-thermal reaction 8h, then the CaCl of 100ml various concentration is added thereto2Solution (0,0.03mol/L,
0.06mol/L, 0.09mol/L, 0.16mol/L, 0.24mol/L, 0.36mol/L and 0.48mol/L), mechanical stirring 2h is stood
12 h, then place the product in washing by soaking multiple in deionized water to remove impurity, and N doping HCNFs/SA-Ca is made2+Compound Water
Gel.
HCNFs/SA-Ca made from metal cation chloride solution by various concentration2+Composite hydrogel carries out water-setting
The measurement of glue Equilibrium swelling ratio:
Hydrogel after drying is denoted as W in electronic analytical balance weighing1, put known weight W into2Tea bag in, room temperature is underlying
6 h in deionized water takes out gel and tea bag, wipes the extra water of gel surface with paper handkerchief after its complete swelling, weighs
Gel and tea bag weight W after swelling3, ESD is calculated according to the following formula:
ESD= ( W3-W2) / W1
As a result it as shown in Figure 1, can be clearly seen when the concentration of metal cation chloride solution is 0.03 mol/L, is made
HCNFs/SA-Ca2+The Equilibrium swelling ratio of composite hydrogel can reach best.
Two, N doping HCNFs/SA-Men+The preparation method of plural gel
Embodiment 1
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, under protection of argon gas, with 5 DEG C/min
580 DEG C are warming up to, argon gas is closed and leads to 1 h of acetylene, the logical argon gas of acetylene is closed and is cooled to room temperature, spiral nanometer carbon fiber is made
(HCNFs) crude product；
2) HCNFs made from 0.1 g step 1) at room temperature, is weighed in three-necked flask, and it is 68 % nitre that appropriate mass fraction, which is added,
Acid floods HCNFs, then places it in 140 DEG C of water-baths and purifies 2h, and centrifuge washing to supernatant liquor is in neutrality (PH=7)
Afterwards, it then is placed in 80 DEG C of vacuum ovens after 10 h of drying, is ground and product is pulverized to get arriving after purification with agate mortar
HCNFs, it is spare；
3) HCNFs the and 0.03g cetyl trimethylammonium bromide (CTAB) made from 0.5 g step 2 of precise after purification
In 500 ml beakers, then 100 ml deionized waters are added into above-mentioned beaker, 60 min of ultrasonic disperse, obtaining concentration is
The HCNFs solution of 0.5mg/ml, then sodium alginate (SA) cream that 100ml mass fraction is 2 % is added into the HCNFs solution
After 30 min of ultrasonic disperse, then the FeCl that 100ml concentration is 0.03 mol/L is added in the ammonium hydroxide of turbid and 15ml thereto3It is molten
Liquid, mechanical stirring 2h must mix turbid after standing 12h.
4) it is fitted into 80 ml ptfe autoclaves to mixing turbid made from step 3), and places it in 100 DEG C
In air dry oven after 8 h of hydro-thermal reaction, then place the product in after washing by soaking multiple in deionized water removing impurity, it is placed in jelly
- 55 DEG C of 24 h of freeze-drying, obtain N doping HCNFs/SA- Fe in drying box3+Composite aerogel.
Embodiment 2
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, under protection of argon gas, with 5 DEG C/min
580 DEG C are warming up to, argon gas is closed and leads to 1 h of acetylene, the logical argon gas of acetylene is closed and is cooled to room temperature, spiral nanometer carbon fiber is made
(HCNFs) crude product；
2) HCNFs made from 1.0 g step 1) is weighed in three-necked flask, and appropriate mass fraction is added will for 68 % nitric acid
HCNFs floods, and then places it in 140 DEG C of water-baths and purifies 2 h, after centrifuge washing to supernatant liquor is in neutrality (pH=7),
After being placed in 80 DEG C of vacuum ovens dry 10 h again, is ground and product is pulverized to get arriving after purification with agate mortar
HCNFs, it is spare；
3) HCNFs and 0.03 g cetyl trimethylammonium bromide made from 0.5 g step 2 of precise after purification
(CTAB) in 500 ml beakers, then 100 ml deionized waters are added into above-mentioned beaker, 60 min of ultrasonic disperse obtains concentration
For the HCNFs solution of 0.5 mg/ml, then the sodium alginate that 100 ml mass fractions are 2 % is added into the HCNFs solution
(SA) ammonium hydroxide of emulsion and 15 ml, after 30 min of ultrasonic disperse, then it is 0.03 mol/L's that 100 ml concentration are added thereto
CaCl2Mixing turbid is made in solution, 2 h of mechanical stirring.
4) it is fitted into 80 ml ptfe autoclaves to mixing turbid made from step 3), and places it in 100 DEG C
In air dry oven after 8 h of hydro-thermal reaction, then place the product in after washing by soaking multiple in deionized water removing impurity, it is placed in jelly
For 24 hours, N doping HCNFs/SA-Ca is made in -55 DEG C of freeze-dryings in drying box2+Composite aerogel.
N doping HCNFs/SA-Ca obtained2+Composite aerogel, with Ca2+The HCNFs/ SA plural gel journey block of crosslinking
Shape, clearance space is big, illustrates that the active force between gel molecular is uneven, so more hydrones can be stored.
Embodiment 3
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, under protection of argon gas, with 5 DEG C/min
580 DEG C are warming up to, argon gas is closed and leads to 1 h of acetylene, the logical argon gas of acetylene is closed and is cooled to room temperature, spiral nanometer carbon fiber is made
(HCNFs) crude product；
2) HCNFs made from 1.0 g step 1) is weighed in three-necked flask, and appropriate mass fraction is added will for 68 % nitric acid
HCNFs floods, and then places it in 140 DEG C of water-baths and purifies 2 h, after centrifuge washing to supernatant liquor is in neutrality (pH=7),
After being placed in 80 DEG C of vacuum ovens dry 10 h again, is ground and product is pulverized to get arriving after purification with agate mortar
HCNFs, it is spare；
3) HCNFs and 0.03 g cetyl trimethylammonium bromide made from 0.5 g step 2 of precise after purification
(CTAB) in 500 ml beakers, then 100 ml deionized waters are added into above-mentioned beaker, 60 min of ultrasonic disperse obtains concentration
For the HCNFs solution of 0.5 mg/ml, then the sodium alginate (SA) that addition 100ml mass fraction is 2% into the HCNFs solution
After 30 min of ultrasonic disperse, then the CuCl that 100 ml concentration are 0.03mol/L is added in the ammonium hydroxide of emulsion and 15 ml thereto2
Mixing turbid is made in solution, 2 h of mechanical stirring.
4) it is fitted into 80 ml ptfe autoclaves to mixing turbid made from step 3), and places it in 100 DEG C
In air dry oven after 8 h of hydro-thermal reaction, then place the product in after washing by soaking multiple in deionized water removing impurity, it is placed in jelly
N doping HCNFs/SA- Cu is made in -55 DEG C of 24 h of freeze-drying in drying box2+Composite aerogel.
Embodiment 4
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, under protection of argon gas, with 5 DEG C/min
580 DEG C are warming up to, argon gas is closed and leads to 1 h of acetylene, the logical argon gas of acetylene is closed and is cooled to room temperature, spiral nanometer carbon fiber is made
(HCNFs) crude product；
2) HCNFs made from 1.0 g step 1) is weighed in three-necked flask, and appropriate mass fraction is added will for 68 % nitric acid
HCNFs floods, and then places it in 140 DEG C of water-baths and purifies 2 h, after centrifuge washing to supernatant liquor is in neutrality (pH=7),
After being placed in 80 DEG C of vacuum ovens dry 10 h again, is ground and product is pulverized to get arriving after purification with agate mortar
HCNFs, it is spare；
3) HCNFs and 0.03 g cetyl trimethylammonium bromide made from 0.5 g step 2 of precise after purification
(CTAB) in 500 ml beakers, then 100 ml deionized waters are added into above-mentioned beaker, 60 min of ultrasonic disperse obtains concentration
For the HCNFs solution of 0.5 mg/ml, then the sodium alginate that 100 ml mass fractions are 3 % is added into the HCNFs solution
(SA) ammonium hydroxide of emulsion and 15 ml, after 30 min of ultrasonic disperse, then it is 0.03 mol/L's that 100 ml concentration are added thereto
FeCl3Mixing turbid is made in solution, 2 h of mechanical stirring.
4) it is fitted into 80 ml ptfe autoclaves to mixing turbid made from step 3), and places it in 100 DEG C
In air dry oven after 8 h of hydro-thermal reaction, then place the product in after washing by soaking multiple in deionized water removing impurity, it is placed in jelly
For 24 hours, N doping HCNFs/SA-Fe is made in -55 DEG C of freeze-dryings in drying box3+Composite aerogel.
Embodiment 5
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, is write in argon gas protection, with 5 DEG C/min liter
Temperature closes argon gas and leads to acetylene 1h to 580 DEG C, closes the logical argon gas of acetylene and is cooled to room temperature, is made spiral nanometer carbon fiber (HCNFs)
Crude product；
2) HCNFs made from 1.0 g step 1) is weighed in three-necked flask, and appropriate mass fraction is added will for 68 % nitric acid
HCNFs floods, and then places it in 140 DEG C of water-baths and purifies 2 h, after centrifuge washing to supernatant liquor is in neutrality (pH=7),
After being placed in 80 DEG C of vacuum ovens dry 10h again, is ground and product is pulverized to get arriving after purification with agate mortar
HCNFs, it is spare；
3) HCNFs the and 0.03g cetyl trimethylammonium bromide (CTAB) made from 0.5 g step 2 of precise after purification
In 500 ml beakers, then 100 ml deionized waters are added into above-mentioned beaker, 60 min of ultrasonic disperse, obtaining concentration is 0.5
The HCNFs solution of mg/ml, then sodium alginate (SA) milkiness that 100 ml mass fractions are 3 % is added into the HCNFs solution
After 30 min of ultrasonic disperse, then the CaCl that 100 ml concentration are 0.03 mol/L is added in the ammonium hydroxide of liquid and 15ml thereto2It is molten
Mixing turbid is made in liquid, 2 h of mechanical stirring.
4) it is fitted into 80 ml ptfe autoclaves to mixing turbid made from step 3), and places it in 100 DEG C
In air dry oven after hydro-thermal reaction 8h, then place the product in washing by soaking multiple in deionized water to remove impurity, is placed in freeze-drying
- 55 DEG C of freeze-dryings for 24 hours, obtain N doping HCNFs/SA- Ca in dry case2+Composite aerogel.
Embodiment 6
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, is write in argon gas protection, with 5 DEG C/min liter
Temperature closes argon gas and leads to acetylene 1h to 580 DEG C, closes the logical argon gas of acetylene and is cooled to room temperature, is made spiral nanometer carbon fiber (HCNFs)
Crude product；
2) HCNFs made from 1.0 g step 1) is weighed in three-necked flask, and appropriate mass fraction is added will for 68 % nitric acid
HCNFs floods, and then places it in 140 DEG C of water-baths and purifies 2 h, after centrifuge washing to supernatant liquor is in neutrality (pH=7),
After being placed in 80 DEG C of vacuum ovens dry 10h again, is ground and product is pulverized to get arriving after purification with agate mortar
HCNFs, it is spare；
3) HCNFs the and 0.03g cetyl trimethylammonium bromide (CTAB) made from 0.5 g step 2 of precise after purification
In 500 ml beakers, then 100 ml deionized waters are added into above-mentioned beaker, 60 min of ultrasonic disperse, obtaining concentration is 0.5
The HCNFs solution of mg/ml, then sodium alginate (SA) milkiness that 100 ml mass fractions are 3% is added into the HCNFs solution
After 30 min of ultrasonic disperse, then the CuCl that 100 ml concentration are 0.03mol/L is added in the ammonium hydroxide of liquid and 15 ml thereto2It is molten
Mixing turbid is made in liquid, 2 h of mechanical stirring.
4) it is fitted into 80 ml ptfe autoclaves to mixing turbid made from step 3), and places it in 100 DEG C
In air dry oven after 8 h of hydro-thermal reaction, then place the product in after washing by soaking multiple in deionized water removing impurity, it is placed in jelly
- 55 DEG C of 24 h of freeze-drying, obtain N doping HCNFs/SA- Cu in drying box2+Composite aerogel.
Embodiment 7
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, is write in argon gas protection, with 5 DEG C/min liter
Temperature closes argon gas and leads to 1 h of acetylene to 580 DEG C, closes the logical argon gas of acetylene and is cooled to room temperature, spiral nanometer carbon fiber is made
(HCNFs) crude product；
2) HCNFs made from 1.0 g step 1) is weighed in three-necked flask, and appropriate mass fraction is added will for 68 % nitric acid
HCNFs floods, and then places it in 140 DEG C of water-baths and purifies 2 h, after centrifuge washing to supernatant liquor is in neutrality (pH=7),
After being placed in 80 DEG C of vacuum ovens dry 10 h again, is ground and product is pulverized to get arriving after purification with agate mortar
HCNFs, it is spare；
3) HCNFs the and 0.03g cetyl trimethylammonium bromide (CTAB) made from 0.5 g step 2 of precise after purification
In 500 ml beakers, then 100 ml deionized waters are added into above-mentioned beaker, 60 min of ultrasonic disperse, obtaining concentration is
The HCNFs solution of 0.5mg/ml, then sodium alginate (SA) cream that 100ml mass fraction is 1 % is added into the HCNFs solution
The ammonium hydroxide of turbid and 15ml after 30 min of ultrasonic disperse, obtains mixing turbid.
4) it is fitted into 80 ml ptfe autoclaves to mixing turbid made from step 3), and places it in 100 DEG C
In air dry oven after hydro-thermal reaction 8h, then the CaCl that 100ml concentration is 0.03mol/L is added thereto2Solution, mechanical stirring
After 2h stands 12h, then place the product in washing by soaking multiple in deionized water to remove impurity, and HCNFs/SA-Ca is made2+Compound Water
Gel.
The HCNFs/SA-Ca prepared using scanning electron microscopic observation2+Composite hydrogel, as a result as shown in Figure 2.
Figure it is seen that being with Ca2+The HCNFs/SA-Ca obtained for cross-linking agents2+Composite hydrogel, in gel
There is lamellar structure in portion, and the SA structure of part is covered by lamellar structure, since the active force between gel molecular is uneven
Causing has very big gap in gel, this structure can store a large amount of hydrone, in this three-dimensional structure, in gel
Molecule is by Ca2+It has been joined together to form the structure for inhibiting hydrone flowing.
Embodiment 8
1) 0.3 g cupric tartrate of precise is put into quartz boat, is placed in sliding rail furnace, under protection of argon gas, with 5 DEG C/min
580 DEG C are warming up to, argon gas is closed and leads to 1 h of acetylene, the logical argon gas of acetylene is closed and is cooled to room temperature, spiral nanometer carbon fiber is made
(HCNFs) crude product；
2) HCNFs made from 0.1 g step 1) at room temperature, is weighed in three-necked flask, and it is 68 % nitre that appropriate mass fraction, which is added,
Acid floods HCNFs, then places it in 140 DEG C of water-baths and purifies 2 h, centrifuge washing to supernatant liquor be in neutrality (PH=
7) it after, then is placed in 80 DEG C of vacuum ovens after 10 h of drying, is ground with agate mortar and product is pulverized to get to after purification
HCNFs, it is spare；
3) using the HCNFs made from step 2 after purification as carbon source, under the atmosphere containing ammonia, 800 DEG C in tube furnace
Lower 1 h of pyrolysis ammonia, obtains the porous spiral nanometer carbon fiber of N doping.
4) the porous spiral nanometer carbon fiber of N doping and 0.03 g cetyl three made from 0.5 g step 3) of precise
Methyl bromide ammonium (CTAB) is in 500 ml beakers, then 100 ml deionized waters, ultrasonic disperse 60 are added into above-mentioned beaker
Min obtains the HCNFs solution that concentration is 0.5 mg/ml, then it is 2% that 100 ml mass fractions, which are added, into the HCNFs solution
Sodium alginate (SA) emulsion, mechanical stirring 1h, be made mixing turbid.
5) FeCl that 100 ml concentration are 0.03 mol/L is added into mixing turbid made from step 4)3Solution is stood
After 12h, then place the product in washing by soaking multiple in deionized water to remove impurity, and HCNFs/ SA-Fe is made3+Compound water congealing
Glue.
The HCNFs/SA-Fe prepared using scanning electron microscopic observation3+Composite hydrogel is as a result, as shown in Figure 3.
As can be seen from Figure 3, spiral nanometer carbon fiber is coated by sodium alginate, shows big sheet, has on lamella
A large amount of aperture；Additionally, due to Fe3+With 3 positive charges, so each Fe3+It can make gel internal junction in conjunction with three SA chains
Structure is even closer.But the introducing of spiral nanometer carbon fiber makes its internal structure become loose, improves the absorption property of the gel.
Using N doping HCNFs/SA-Fe made from X-ray diffraction analysis instrument analysis embodiment 13+Composite aerogel, implementation
N doping HCNFs/SA-Ca made from example 22+N doping HCNFs/SA-Cu made from composite aerogel, embodiment 32+Compound gas
Gel, as a result as shown in Figure 4.
It can be seen that HCNFs from the XRD spectra of Fig. 4 plural gel and obvious diffraction maximum occur at 26.4 ° or so of 2 θ value, say
It is bright with the presence of HCNFs crystal form；Nearby there is broader more scattering peak, explanation at 26.4 ° or so in SA/HCNFs after SA is added
HCNFs success is compound to introduce SA gel, and the introducing of SA destroys the original crystalline structure of HCNFs, increases its randomness
Add；When introducing Ca in plural gel2+、Fe3+And Cu2+After crosslinking agent, the intensity at peak is decreased obviously, it may be possible to which crosslinking makes randomness
Increase.
Comparative example 1
Difference with embodiment 7 is no HCNFs, and other test operation steps and parameter are all the same.
Hydrogel made from embodiment 7 and comparative example 1 is tested to the compression strength of gel using Texture instrument, test condition:
Room temperature.Testing result is as shown in Figure 5.
From fig. 5, it can be seen that the hydrogel after crosslinking HCNFs has very high compression strength, compression strength can reach
8KPa or more, therefore, composite hydrogel produced by the present invention have good mechanical strength.
Comparative example 2
The difference from embodiment 1 is that other test operation steps and parameter are all the same without HCNFs.
Comparative example 3
The difference from example 2 is that other test operation steps and parameter are all the same without HCNFs.
Comparative example 4
Difference with embodiment 3 is no HCNFs, and other test operation steps and parameter are all the same.
Comparative example 5
Difference with embodiment 4 is no HCNFs, and other test operation steps and parameter are all the same.
Comparative example 6
Difference with embodiment 5 is no HCNFs, and other test operation steps and parameter are all the same.
Comparative example 7
Difference with embodiment 6 is no HCNFs, and other test operation steps and parameter are all the same.
Plural gel prepared by embodiment 1 ~ 6 and comparative example 2 ~ 7 is subjected to absorption and compressive property test.
Aerogel composite tests organic solvent absorption property:
It cuts one piece of sodium alginate composite aerogel and claims its quality, be denoted as m1；Spiral carbon sodium alginate after above-mentioned weighing is answered
It closes aeroge and is immersed in 30 s in organic solvent, make its abundant absorbing organic solvent, then take out carbon aerogels, quickly carry out
Quality weighing claims its quality, is denoted as m to prevent organic agent volatilization2.The mass weight gain of composite aerogel absorption front and back is than being spiral
Absorption property of the carbon sodium alginate composite aerogel to organic solvent.
Mass weight gain ratio (%)=(m2-m1)/m1
The test of aerogel composite compressive property:
Since sodium alginate base aeroge belongs to fragile material, and the size of the sample used in test is smaller, is unsuitable for using
The test of general-purpose testing machine, therefore judged by the mechanical property to aeroge.First sample is cut into rectangular, measures and records length
Degree and width.Then sample is placed on a wide range balance, and in one sheet glass of sample surfaces lid.Balance is zeroed,
Then one by one increase weight, when rupturing for the first time occurs in sample, record the quality of institute's weighting material, calculated using following formula anti-
Compressive Strength:
Compression strength=mg/S
In formula: the quality of m expression sample burst when institute weighting material；G is acceleration of gravity；S is effective contact surface of sample
Product.
Test result, as shown in Figure 6 and Figure 7.
From fig. 6, it can be seen that the incorporation of spiral nanometer carbon fiber can significantly improve suction of the composite aerogel for acetone
Attached ability because HCNFs has large specific surface area, therefore composite aerogel can be significantly improved for the adsorption capacity of acetone and
Different metal is cationic crosslinked not to have a significant effect for the absorption of acetone, and the concentration of sodium alginate is for composite aerogel
Influence is very huge, and content is that the SA of 2 % is substantially better than 3 %, and 2 apertures % SA are moderate to be evenly distributed, and 3 apertures % SA become smaller,
Storing acetone ability reduces.From figure 7 it can be seen that the incorporation of spiral nanometer carbon fiber can significantly improve the anti-of composite aerogel
Compressive Strength, wherein with FeCl3The aerogel material compression strength of crosslinking is minimum, but the incorporation of spiral nanometer carbon fiber greatly improves
Its compression strength.Be primarily due to HCNFs have large specific surface area and low-density characteristic, with SA it is compound after so that
Internal structure becomes comparatively dense, can effectively enhance the mechanical performance of aeroge.CaCl2Compression strength it is optimal on year-on-year basis.To sum up,
When the mass fraction of SA solution is 2 %, the concentration of HCNFs solution introduces 0.03 mol/L CaCl when being 0.5mg/L2As friendship
It is best at adsorption effect of the aeroge to acetone to join dosage form.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (10)
1. a kind of N doping HCNFs/SA-Men+The preparation method of plural gel, which comprises the steps of:
1) N doping HCNFs/SA-Men+The preparation of composite hydrogel
Under the atmosphere containing ammonia, spiral nanometer carbon fiber is placed at 800~1000 DEG C and is reacted, obtains N doping spiral
Then ultrasonic disperse 30 in deionized water is added in the N doping spiral nanometer carbon fiber and surfactant by carbon nano-fiber
~60min obtains the first dispersion liquid, then sodium alginate emulsion is added into first dispersion liquid, and 1~2h of mechanical stirring is obtained
Metal cation chloride solution is finally added in mixed liquor into the mixed liquor, after standing 5~12h, through deionization water logging
Bubble, washing, obtain N doping HCNFs/SA-Men+Composite hydrogel；
2) N doping HCNFs/SA-Men+The preparation of composite aerogel
30~60min of ultrasonic disperse in deionized water is added in spiral nanometer carbon fiber and surfactant and obtains the second dispersion liquid；
Ammonium hydroxide and 30~60min of sodium alginate emulsion ultrasonic disperse are added into second dispersion liquid again and obtains mixed liquor, then to
Metal cation chloride solution is added in the mixed liquor, 1~2h of mechanical stirring obtains Men+Mixed liquor, finally by the Men+
Mixed liquor, which is fitted into reaction kettle, carries out hydro-thermal reaction, impregnates after being cooled to room temperature through deionized water, washing, frozen drying,
Obtain N doping HCNFs/SA-Men+Composite aerogel.
2. N doping HCNFs/SA-Me according to claim 1n+The preparation method of plural gel, which is characterized in that the nitrogen
The HCNFs/SA-Me of dopingn+The preparation of composite hydrogel can also use following methods: spiral nanometer carbon fiber and surface is living
Property agent be added deionized water in, 10~30min of ultrasonic disperse obtains third dispersion liquid, then into the third dispersion liquid be added sea
Mosanom emulsion and ammonium hydroxide, 1~2h of ultrasonic disperse obtain mixed liquor, and it is anti-that the mixed liquor is put into progress hydro-thermal in reaction kettle
Deserved nitrating mixed liquor, finally into the nitrating mixed liquor be added metal cation chloride solution, 1~2h of mechanical stirring,
It is impregnated through deionized water, washing, obtains N doping HCNFs/SA-Men+Composite hydrogel.
3. N doping HCNFs/SA-Me according to claim 1 or claim 2n+The preparation method of plural gel, which is characterized in that institute
State spiral nanometer carbon fiber purify with the following method be made: flood spiral nanometer with the nitric acid solution of mass fraction 50~70%
Carbon fiber crude product, in 120~140 DEG C of 1~2h of purifying, centrifuge washing to supernatant liquor is in neutrality, and is placed in 60~80 DEG C of vacuum
In drying box after dry 8~10h, product is pulverized to get spiral nanometer carbon fiber after purification is arrived.
4. N doping HCNFs/SA-Me according to claim 1 or claim 2n+The preparation method of plural gel, which is characterized in that institute
The mass fraction for stating surfactant in dispersion liquid is 1%~3%, spiral nanometer carbon fiber or N doping spiral shell in the dispersion liquid
The concentration for revolving carbon nano-fiber is 0.01~0.5mg/L, and the dispersion liquid is the first dispersion liquid, the second dispersion liquid or third dispersion
Liquid.
5. N doping HCNFs/SA-Me according to claim 1 or claim 2n+The preparation method of plural gel, which is characterized in that institute
Stating surfactant is one in cetyl trimethylammonium bromide, polyvinylpyrrolidone and hexadecyltrimethylammonium chloride
Kind is a variety of.
6. N doping HCNFs/SA-Me according to claim 1 or claim 2n+The preparation method of plural gel, which is characterized in that institute
Stating the metal cation chloride in metal cation chloride solution is FeCl3、CaCl2、CuCl2、MgCl2Or ZnCl2；It is described
The concentration of metal cation chloride solution is 0.01~0.05mol/L.
7. N doping HCNFs/SA-Me according to claim 1 or claim 2n+The preparation method of plural gel, which is characterized in that institute
The mass fraction for stating sodium alginate in sodium alginate emulsion is 1~5%.
8. N doping HCNFs/SA-Me according to claim 1 or claim 2n+The preparation method of plural gel, which is characterized in that institute
The volume ratio for stating dispersion liquid, sodium alginate emulsion and metal cation chloride solution is 1~3:1~2:0.2~1, described
Dispersion liquid is the first dispersion liquid, the second dispersion liquid or third dispersion liquid.
9. N doping HCNFs/SA-Me according to claim 1 or claim 2n+The preparation method of plural gel, which is characterized in that institute
Stating reaction temperature in hydro-thermal reaction is 80~140 DEG C, and the reaction time is 6~10h.
10. N doping HCNFs/SA-Me according to claim 1n+The preparation method of plural gel, which is characterized in that described
In freeze-drying temperature be -55~-70 DEG C, the time be 12~for 24 hours.
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