CN111592050A - Biomass-based porous carbon in-situ growth nano Fe3O4Wave-absorbing material and preparation method thereof - Google Patents
Biomass-based porous carbon in-situ growth nano Fe3O4Wave-absorbing material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002028 Biomass Substances 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 239000011358 absorbing material Substances 0.000 title claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229920001661 Chitosan Polymers 0.000 claims abstract description 92
- 239000002904 solvent Substances 0.000 claims abstract description 69
- -1 aldehyde sodium alginate Chemical class 0.000 claims abstract description 68
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000661 sodium alginate Substances 0.000 claims abstract description 55
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 53
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 53
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 49
- 239000004698 Polyethylene Substances 0.000 claims abstract description 48
- 229920000573 polyethylene Polymers 0.000 claims abstract description 48
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 47
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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 abstract description 33
- 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 claims abstract description 28
- 229940072056 alginate Drugs 0.000 claims abstract description 28
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 28
- 229920000615 alginic acid Polymers 0.000 claims abstract description 28
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 239000012153 distilled water Substances 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 11
- 229940014800 succinic anhydride Drugs 0.000 claims description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 8
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 3
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 3
- RGHNJXZEOKUKBD-QTBDOELSSA-N L-gulonic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-QTBDOELSSA-N 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 230000002427 irreversible effect Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 2
- 238000004227 thermal cracking Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention relates to the technical field of wave absorption, and discloses biomass-based porous carbon in-situ growth nano Fe3O4The wave-absorbing material is prepared by carrying out condensation reaction on carboxyl-terminated polyethylene glycol grafted chitosan with different chain lengths and aldehyde sodium alginate to obtain polyethylene glycol-chitosan crosslinked sodium alginate, and reacting the polyethylene glycol-chitosan crosslinked sodium alginate with Fe3+In the system, sodium ions and Fe of gulonic acid in sodium alginate3+Irreversible ion exchange occursAnd then cross-linking sodium alginate to form polyethylene glycol-chitosan cross-linked ferric alginate composite gel, and reducing Fe in high-temperature hot solvent reduction system of ethylene glycol and diethylene glycol3+In-situ generation of nano Fe3O4Uniformly distributed in a composite gel matrix, and subjected to high-temperature thermal cracking, wherein chitosan-ferric alginate is used as a biomass carbon source, polyethylene glycols with different chain lengths are used as pore-forming agents, and nano Fe is used3O4The nano-particles are uniformly dispersed in a porous carbon structure with light weight and low density, and the interface polarization effect and the impedance matching performance are improved.
Description
Technical Field
The invention relates to the technical field of wave absorption, in particular to nano Fe grown in situ by biomass-based porous carbon3O4The wave-absorbing material and the preparation method thereof.
Background
Along with the rapid increase of electronic information and communication frequency, serious electromagnetic interference, electromagnetic radiation and other pollution are caused, and the microwave absorbing material has important application in the aspects of environment, medical treatment, national defense safety and the like.
The ferroferric oxide is a traditional ferrite wave-absorbing material, has the advantages of rich natural resources, small environmental pollution and high wave-absorbing strength, the porous carbon material is a microwave absorbing material with excellent conductivity, light weight and strong loss, the ferroferric oxide can be combined with the porous carbon material, the dielectric loss and the impedance matching performance of the composite material are improved, the specific surface area of the ferroferric oxide is improved at present, the contact area with the porous carbon material is increased, and the interface polarization effect between the ferroferric oxide and the porous carbon material is enhanced, so that the wave-absorbing performance of the composite material can be improved.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a biomass-based porous carbon in-situ growth method for nano Fe3O4The wave-absorbing material and the preparation method thereof solve the problem of the traditional Fe3O4The impedance matching performance of the material is poor, and the wave-absorbing performance is not high.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: biomass-based porous carbon in-situ growth nano Fe3O4The preparation method of the wave-absorbing material comprises the following steps:
(1) adding distilled water, sodium alginate and sodium periodate into a reaction bottle, stirring at a constant speed for reaction for 4-10h, adding excessive glycol to neutralize the sodium periodate, dialyzing and purifying to obtain the aldehyde sodium alginate.
(2) Adding a pyridine solvent, polyethylene glycol and succinic anhydride into a reaction bottle, reacting for 5-10h at a constant speed in a constant temperature reaction device at 30-50 ℃, distilling under reduced pressure to remove pyridine, and dialyzing and purifying by using distilled water to obtain carboxyl-terminated polyethylene glycol.
(3) Adding a mixed solvent of distilled water and acetonitrile and chitosan into a reaction bottle, slowly dropwise adding glacial acetic acid until the chitosan is dissolved, uniformly dispersing by ultrasonic, reacting for 6-12h at 30-60 ℃, distilling the solution under reduced pressure to remove the solvent, dialyzing and purifying by using distilled water, and thus obtaining the carboxyl-terminated polyethylene glycol grafted chitosan.
(4) Adding a distilled water solvent and carboxyl-terminated polyethylene glycol grafted chitosan into a reaction bottle, uniformly dispersing by ultrasonic, adding aldehyde sodium alginate, uniformly stirring for reaction for 12-24h, filtering to remove the solvent, dialyzing and purifying to prepare the polyethylene glycol-chitosan crosslinked sodium alginate.
(5) Adding distilled water solvent, polyethylene glycol-chitosan cross-linked sodium alginate and ferric chloride into a reaction bottle, performing ultrasonic dispersion uniformly, standing and aging for 48-72h, filtering to remove the solvent, dialyzing and purifying to obtain the polyethylene glycol-chitosan cross-linked ferric alginate.
(6) Adding a glycol solvent and polyethylene glycol-chitosan cross-linked ferric alginate into a reaction bottle, adding diethylene glycol after ultrasonic dispersion is uniform, stirring uniformly, pouring into a reaction kettle, heating to 180-class temperature of 200 ℃, reacting for 24-48h, filtering the solvent, dialyzing, purifying, placing a solid mixed product into an atmosphere resistance furnace, heating to 450-class temperature of 500 ℃ in a nitrogen atmosphere, and carrying out heat preservation and calcination for 2-3h to prepare the biomass porous carbon in-situ growth nano Fe3O4The wave-absorbing material.
Preferably, the molecular weight of the polyethylene glycol in the step (2) is 1000-4000, and the mass ratio of the polyethylene glycol to the succinic anhydride is 12-50: 1.
Preferably, the constant temperature reaction unit in step (2) includes constant temperature heating device, and the constant temperature heating device top is provided with the water bath, and the water bath outside is provided with the heat preservation, and the water bath top is provided with the slide rail, and slide rail active link has the pulley, and pulley active link has the heated board, the inside fixedly connected with support frame of heated board, support frame swing joint reaction bottle.
Preferably, the mass ratio of the chitosan, the carboxyl-terminated polyethylene glycol, the N-hydroxysuccinimide and the dicyclohexylcarbodiimide in the step (3) is 100:400-1600:200-250: 100-130.
Preferably, the mass ratio of aldehyde group sodium alginate of the carboxyl-terminated polyethylene glycol grafted chitosan in the step (4) is 40-80: 100.
Preferably, the mass ratio of the polyethylene glycol-chitosan crosslinked sodium alginate to the ferric chloride in the step (5) is 10-30: 100.
Preferably, the mass ratio of the polyethylene glycol-chitosan crosslinked iron alginate to the diethylene glycol in the step (6) is 10: 3-8.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the biomass-based porous carbon in-situ growth nano Fe3O4The wave absorbing material is prepared by the steps of activating carboxyl groups of carboxyl-terminated polyethylene glycol, condensing with partial amino groups of chitosan to obtain carboxyl-terminated polyethylene glycol grafted chitosan with different chain lengths, then carrying out condensation reaction on the residual amino groups of the chitosan and aldehyde sodium alginate to obtain polyethylene glycol-chitosan crosslinked sodium alginate, and reacting in the presence of Fe3+In the system, sodium ions and Fe of gulonic acid in sodium alginate3+Irreversible ion exchange occurs, sodium alginate is crosslinked to form polyethylene glycol-chitosan crosslinked ferric alginate composite gel, and then Fe is added into a high-temperature hot solvent reduction system of ethylene glycol and diethylene glycol3+In-situ generation of nano Fe in polyethylene glycol-chitosan cross-linked iron alginate3O4Of nano Fe3O4Uniformly distributed in a composite gel matrix, and subjected to high-temperature thermal cracking, wherein chitosan-ferric alginate is used as a biomass carbon source, polyethylene glycols with different chain lengths are used as pore-forming agents, so that the biomass-based porous carbon in-situ growth nano Fe is obtained3O4The wave-absorbing material.
The biomass-based porous carbon in-situ growth nano Fe3O4Nano Fe3O4Uniformly dispersed in a porous carbon structure with light weight and low density, and improves the nano Fe3O4The interfacial polarization effect with the porous carbon,and nano Fe3O4The method is favorable for improving the impedance matching performance of the porous carbon material, simultaneously improving the chain length of the polyethylene glycol, controllably adjusting the pore structure and the pore diameter of the porous carbon, and further optimizing the electromagnetic performance and the wave-absorbing performance of the composite material.
Drawings
FIG. 1 is a schematic view of an isothermal reaction apparatus;
FIG. 2 is a schematic view of the front of the insulation board;
fig. 3 is a schematic top view of an insulation board adjustment.
1-constant temperature heating device; 2-water bath; 3, insulating layer; 4-a slide rail; 5-a pulley; 6-heat insulation board; 7-a support frame; 8-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: biomass-based porous carbon in-situ growth nano Fe3O4The wave-absorbing material is characterized in that: the biomass-based porous carbon in-situ growth nano Fe3O4The preparation method of the wave-absorbing material comprises the following steps:
(1) adding distilled water, sodium alginate and sodium periodate into a reaction bottle, stirring at a constant speed for reaction for 4-10h, adding excessive glycol to neutralize the sodium periodate, dialyzing and purifying to obtain the aldehyde sodium alginate.
(2) Adding a pyridine solvent, polyethylene glycol with the molecular weight of 1000-4000 and succinic anhydride into a reaction bottle, wherein the mass ratio of the two is 12-50:1, in a constant-temperature reaction device, the constant-temperature reaction device comprises a constant-temperature heating device, a water bath is arranged above the constant-temperature heating device, a heat insulation layer is arranged outside the water bath, a slide rail is arranged above the water bath, the slide rail is movably connected with a pulley, the pulley is movably connected with a heat insulation plate, a support frame is fixedly connected inside the heat insulation plate, the support frame is movably connected with the reaction bottle, stirring reaction is carried out at a constant speed for 5-10h at 30-50 ℃, pyridine is removed through reduced pressure distillation, and distilled water is used for dialysis and purification to.
(3) Adding a mixed solvent of distilled water and acetonitrile and chitosan into a reaction bottle, slowly dripping glacial acetic acid until the chitosan is dissolved, uniformly dispersing by ultrasonic waves, then carrying out reaction on terminal carboxyl polyethylene glycol, N-hydroxysuccinimide and dicyclohexylcarbodiimide at the mass ratio of 100:400-1600:200-250:100-130, reacting at 30-60 ℃ for 6-12h, carrying out reduced pressure distillation on the solution to remove the solvent, and carrying out dialysis purification by using distilled water to prepare the terminal carboxyl polyethylene glycol grafted chitosan.
(4) Adding distilled water solvent and carboxyl-terminated polyethylene glycol grafted chitosan into a reaction bottle, uniformly dispersing by ultrasonic, adding aldehyde sodium alginate in a mass ratio of 40-80:100, uniformly stirring for reaction for 12-24h, filtering to remove the solvent, dialyzing and purifying to obtain the polyethylene glycol-chitosan crosslinked sodium alginate.
(5) Adding distilled water solvent, polyethylene glycol-chitosan cross-linked sodium alginate and ferric chloride with the mass ratio of 10-30:100 into a reaction bottle, standing and aging for 48-72h after uniform ultrasonic dispersion, filtering to remove the solvent, dialyzing and purifying to prepare the polyethylene glycol-chitosan cross-linked ferric alginate.
(6) Adding a glycol solvent and polyethylene glycol-chitosan cross-linked ferric alginate into a reaction bottle, adding diethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the ethylene glycol solvent to the polyethylene glycol-chitosan cross-linked ferric alginate is 10:3-8, stirring uniformly, pouring into a reaction kettle, heating to 180 degrees centigrade and 200 degrees centigrade, reacting for 24-48h, filtering the solvent, dialyzing and purifying, placing a solid mixed product into an atmosphere resistance furnace, heating to 450 degrees centigrade and 500 degrees centigrade in nitrogen atmosphere, and performing heat preservation and calcination for 2-3h to prepare the biomass porous carbon in-situ growth nano Fe3O4The wave-absorbing material.
Example 1
(1) Adding distilled water, sodium alginate and sodium periodate into a reaction bottle, stirring at a constant speed for reaction for 4 hours, adding excessive glycol to neutralize the sodium periodate, dialyzing and purifying to prepare the aldehyde sodium alginate.
(2) Adding a pyridine solvent, polyethylene glycol with the molecular weight of 1000 and succinic anhydride into a reaction bottle, wherein the mass ratio of the two is 12:1, in a constant-temperature reaction device, the constant-temperature reaction device comprises a constant-temperature heating device, a water bath is arranged above the constant-temperature heating device, a heat insulation layer is arranged on the outer side of the water bath, a slide rail is arranged above the water bath, a pulley is movably connected with the slide rail, a heat insulation plate is movably connected with the pulley, a support frame is fixedly connected inside the heat insulation plate, the support frame is movably connected with the reaction bottle, stirring and reacting for 5 hours at a constant speed at 30 ℃, removing pyridine through reduced pressure distillation, and dialyzing and purifying by using distilled.
(3) Adding a mixed solvent of distilled water and acetonitrile and chitosan into a reaction bottle, slowly dropwise adding glacial acetic acid until the chitosan is dissolved, uniformly dispersing by ultrasonic waves, reacting for 6 hours at 30 ℃ with terminal carboxyl polyethylene glycol, N-hydroxysuccinimide and dicyclohexylcarbodiimide in a mass ratio of 100:400:200:100, distilling the solution under reduced pressure to remove the solvent, dialyzing and purifying by using distilled water, and thus obtaining the terminal carboxyl polyethylene glycol grafted chitosan.
(4) Adding distilled water solvent and carboxyl-terminated polyethylene glycol grafted chitosan into a reaction bottle, adding aldehyde sodium alginate after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 12 hours, filtering to remove the solvent, dialyzing and purifying to prepare the polyethylene glycol-chitosan crosslinked sodium alginate, wherein the mass ratio of the aldehyde sodium alginate to the distilled water solvent to the carboxyl-terminated polyethylene glycol grafted chitosan is 40: 100.
(5) Adding a distilled water solvent, polyethylene glycol-chitosan cross-linked sodium alginate and ferric chloride in a mass ratio of 10:100 into a reaction bottle, performing ultrasonic dispersion uniformly, standing and aging for 48h, filtering to remove the solvent, and performing dialysis and purification to obtain the polyethylene glycol-chitosan cross-linked ferric alginate.
(6) Adding a glycol solvent and polyethylene glycol-chitosan cross-linked ferric alginate into a reaction bottle, adding diethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the ethylene glycol solvent to the polyethylene glycol-chitosan cross-linked ferric alginate is 10:3, stirring uniformly, pouring into a reaction kettle, heating to 180 ℃, reacting for 24h, filtering the solvent, dialyzing and purifying, placing a solid mixed product into an atmosphere resistance furnace, heating to 450 ℃ in a nitrogen atmosphere, preserving heat and calcining for 2h, and preparing to obtain the biomass-based porous carbon in-situ growth nano Fe3O4The wave-absorbing material 1.
Example 2
(1) Adding distilled water, sodium alginate and sodium periodate into a reaction bottle, stirring at a constant speed for reaction for 4 hours, adding excessive glycol to neutralize the sodium periodate, dialyzing and purifying to prepare the aldehyde sodium alginate.
(2) Adding a pyridine solvent, polyethylene glycol with the molecular weight of 1500 and succinic anhydride into a reaction bottle, wherein the mass ratio of the two is 18:1, in a constant-temperature reaction device, the constant-temperature reaction device comprises a constant-temperature heating device, a water bath is arranged above the constant-temperature heating device, a heat insulation layer is arranged on the outer side of the water bath, a slide rail is arranged above the water bath, a pulley is movably connected with the slide rail, a heat insulation plate is movably connected with the pulley, a support frame is fixedly connected inside the heat insulation plate, the support frame is movably connected with the reaction bottle, stirring and reacting for 5 hours at a constant speed at 40 ℃, removing pyridine through reduced pressure distillation, and dialyzing and purifying by using distilled.
(3) Adding a mixed solvent of distilled water and acetonitrile and chitosan into a reaction bottle, slowly dropwise adding glacial acetic acid until the chitosan is dissolved, uniformly dispersing by ultrasonic waves, reacting for 12 hours at 60 ℃ for 12 hours, distilling the solution under reduced pressure to remove the solvent, dialyzing and purifying by using distilled water, and thus obtaining the carboxyl-terminated polyethylene glycol grafted chitosan.
(4) Adding a distilled water solvent and carboxyl-terminated polyethylene glycol grafted chitosan into a reaction bottle, uniformly dispersing by ultrasonic, adding aldehyde sodium alginate, stirring at a constant speed for 24 hours, reacting for 24 hours, filtering to remove the solvent, dialyzing and purifying to obtain the polyethylene glycol-chitosan crosslinked sodium alginate.
(5) Adding a distilled water solvent, polyethylene glycol-chitosan cross-linked sodium alginate and ferric chloride in a mass ratio of 15:100 into a reaction bottle, performing ultrasonic dispersion uniformly, standing and aging for 72h, filtering to remove the solvent, and performing dialysis and purification to obtain the polyethylene glycol-chitosan cross-linked ferric alginate.
(6) Adding glycol solvent and polyethylene glycol-chitosan cross-linked ferric alginate into a reaction bottle, adding diethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the ethylene glycol solvent to the polyethylene glycol-chitosan cross-linked ferric alginate is 10:4, stirring uniformly, pouring into a reaction kettle, and heating to a temperature ofReacting at 190 ℃ for 36h, filtering the solvent, dialyzing and purifying, placing the solid mixed product in an atmosphere resistance furnace, heating to 460 ℃ in the nitrogen atmosphere, and carrying out heat preservation and calcination for 2.5h to obtain the biomass-based porous carbon in-situ growth nano Fe3O4The wave-absorbing material 2.
Example 3
(1) Adding distilled water, sodium alginate and sodium periodate into a reaction bottle, stirring at a constant speed for reaction for 8 hours, adding excessive glycol to neutralize the sodium periodate, dialyzing and purifying to prepare the aldehyde sodium alginate.
(2) Adding a pyridine solvent, polyethylene glycol with the molecular weight of 2000 and succinic anhydride into a reaction bottle, wherein the mass ratio of the two is 25:1, in a constant-temperature reaction device, the constant-temperature reaction device comprises a constant-temperature heating device, a water bath is arranged above the constant-temperature heating device, a heat insulation layer is arranged on the outer side of the water bath, a slide rail is arranged above the water bath, a pulley is movably connected with the slide rail, a heat insulation plate is movably connected with the pulley, a support frame is fixedly connected inside the heat insulation plate, the support frame is movably connected with the reaction bottle, stirring and reacting for 8 hours at a constant speed at 40 ℃, removing pyridine through reduced pressure distillation, and dialyzing and purifying by using distilled.
(3) Adding a mixed solvent of distilled water and acetonitrile and chitosan into a reaction bottle, slowly dropwise adding glacial acetic acid until the chitosan is dissolved, uniformly dispersing by ultrasonic waves, then reacting for 8 hours at 40 ℃, distilling the solution under reduced pressure to remove the solvent, and dialyzing and purifying by using distilled water to prepare the carboxyl-terminated polyethylene glycol grafted chitosan, wherein the mass ratio of the chitosan to the carboxyl-terminated polyethylene glycol to the N-hydroxysuccinimide to the dicyclohexylcarbodiimide is 100:800:180: 120.
(4) Adding distilled water solvent and carboxyl-terminated polyethylene glycol grafted chitosan into a reaction bottle, adding aldehyde sodium alginate after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 18h, filtering to remove the solvent, dialyzing and purifying to prepare the polyethylene glycol-chitosan crosslinked sodium alginate, wherein the mass ratio of the aldehyde sodium alginate to the distilled water solvent to the carboxyl-terminated polyethylene glycol grafted chitosan is 65: 100.
(5) Adding distilled water solvent, polyethylene glycol-chitosan cross-linked sodium alginate and ferric chloride with the mass ratio of 25:100 into a reaction bottle, standing and aging for 60h after uniform ultrasonic dispersion, filtering to remove the solvent, dialyzing and purifying to prepare the polyethylene glycol-chitosan cross-linked ferric alginate.
(6) Adding a glycol solvent and polyethylene glycol-chitosan cross-linked ferric alginate into a reaction bottle, adding diethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the ethylene glycol solvent to the polyethylene glycol-chitosan cross-linked ferric alginate is 10:6, stirring uniformly, pouring into a reaction kettle, heating to 190 ℃, reacting for 36h, filtering the solvent, dialyzing and purifying, placing a solid mixed product into an atmosphere resistance furnace, heating to 480 ℃ in a nitrogen atmosphere, preserving heat and calcining for 2.5h, and preparing to obtain the biomass-based porous carbon in-situ growth nano Fe3O4And (3) a wave-absorbing material.
Example 4
(1) Adding distilled water, sodium alginate and sodium periodate into a reaction bottle, stirring at a constant speed for reaction for 10 hours, adding excessive glycol to neutralize the sodium periodate, dialyzing and purifying to prepare the aldehyde sodium alginate.
(2) Adding a pyridine solvent, polyethylene glycol with the molecular weight of 4000 and succinic anhydride into a reaction bottle, wherein the mass ratio of the pyridine solvent to the polyethylene glycol to the succinic anhydride is 50:1, in a constant-temperature reaction device, the constant-temperature reaction device comprises a constant-temperature heating device, a water bath is arranged above the constant-temperature heating device, a heat insulation layer is arranged on the outer side of the water bath, a slide rail is arranged above the water bath, a pulley is movably connected with the slide rail, a heat insulation plate is movably connected with the pulley, a support frame is fixedly connected inside the heat insulation plate, the support frame is movably connected with the reaction bottle, stirring reaction is carried out at a constant speed for 10 hours at 50 ℃, pyridine is removed through.
(3) Adding a mixed solvent of distilled water and acetonitrile and chitosan into a reaction bottle, slowly dropwise adding glacial acetic acid until the chitosan is dissolved, uniformly dispersing by ultrasonic waves, reacting for 12 hours at 60 ℃ for 12 hours, distilling the solution under reduced pressure to remove the solvent, and dialyzing and purifying by using distilled water to prepare the carboxyl-terminated polyethylene glycol grafted chitosan, wherein the mass ratio of the chitosan to the carboxyl-terminated polyethylene glycol to the N-hydroxysuccinimide to the dicyclohexylcarbodiimide is 100:1600:250: 130.
(4) Adding a distilled water solvent and carboxyl-terminated polyethylene glycol grafted chitosan into a reaction bottle, uniformly dispersing by ultrasonic, adding aldehyde sodium alginate, stirring at a constant speed for 24 hours, reacting for 24 hours, filtering to remove the solvent, dialyzing and purifying to obtain the polyethylene glycol-chitosan crosslinked sodium alginate.
(5) Adding a distilled water solvent, polyethylene glycol-chitosan cross-linked sodium alginate and ferric chloride in a mass ratio of 30:100 into a reaction bottle, performing ultrasonic dispersion uniformly, standing and aging for 72h, filtering to remove the solvent, and performing dialysis and purification to obtain the polyethylene glycol-chitosan cross-linked ferric alginate.
(6) Adding a glycol solvent and polyethylene glycol-chitosan cross-linked ferric alginate into a reaction bottle, adding diethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the ethylene glycol solvent to the polyethylene glycol-chitosan cross-linked ferric alginate is 10:8, stirring uniformly, pouring into a reaction kettle, heating to 200 ℃, reacting for 48 hours, filtering the solvent, dialyzing and purifying, placing a solid mixed product into an atmosphere resistance furnace, heating to 500 ℃ in a nitrogen atmosphere, preserving heat and calcining for 3 hours, and preparing to obtain the biomass-based porous carbon in-situ growth nano Fe3O4And (4) a wave-absorbing material.
Comparative example 1
(1) Adding distilled water, sodium alginate and sodium periodate into a reaction bottle, stirring at a constant speed for reaction for 10 hours, adding excessive glycol to neutralize the sodium periodate, dialyzing and purifying to prepare the aldehyde sodium alginate.
(2) Adding a pyridine solvent, polyethylene glycol with the molecular weight of 600 and succinic anhydride into a reaction bottle, wherein the mass ratio of the two is 8:1, in a constant-temperature reaction device, the constant-temperature reaction device comprises a constant-temperature heating device, a water bath is arranged above the constant-temperature heating device, a heat insulation layer is arranged on the outer side of the water bath, a slide rail is arranged above the water bath, a pulley is movably connected with the slide rail, a heat insulation plate is movably connected with the pulley, a support frame is fixedly connected inside the heat insulation plate, the support frame is movably connected with the reaction bottle, stirring and reacting for 5 hours at a constant speed at 50 ℃, removing pyridine through reduced pressure distillation, and dialyzing and purifying by using distilled.
(3) Adding a mixed solvent of distilled water and acetonitrile and chitosan into a reaction bottle, slowly dropwise adding glacial acetic acid until the chitosan is dissolved, uniformly dispersing by ultrasonic waves, reacting for 10 hours at 60 ℃ with terminal carboxyl polyethylene glycol, N-hydroxysuccinimide and dicyclohexylcarbodiimide in a mass ratio of 100:250:180:80, distilling the solution under reduced pressure to remove the solvent, dialyzing and purifying by using distilled water, and thus obtaining the terminal carboxyl polyethylene glycol grafted chitosan.
(4) Adding a distilled water solvent and carboxyl-terminated polyethylene glycol grafted chitosan into a reaction bottle, uniformly dispersing by ultrasonic, adding aldehyde sodium alginate, stirring at a constant speed for 18 hours, reacting for 18 hours, filtering to remove the solvent, dialyzing and purifying to obtain the polyethylene glycol-chitosan crosslinked sodium alginate.
(5) Adding a distilled water solvent, polyethylene glycol-chitosan cross-linked sodium alginate and ferric chloride in a mass ratio of 6:100 into a reaction bottle, performing ultrasonic dispersion uniformly, standing and aging for 72h, filtering to remove the solvent, and performing dialysis and purification to obtain the polyethylene glycol-chitosan cross-linked ferric alginate.
(6) Adding a glycol solvent and polyethylene glycol-chitosan cross-linked ferric alginate into a reaction bottle, adding diethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the ethylene glycol solvent to the polyethylene glycol-chitosan cross-linked ferric alginate is 10:2, stirring uniformly, pouring into a reaction kettle, heating to 200 ℃, reacting for 24h, filtering the solvent, dialyzing and purifying, placing a solid mixed product into an atmosphere resistance furnace, heating to 460 ℃ in a nitrogen atmosphere, preserving heat and calcining for 3h, and preparing to obtain the biomass porous carbon in-situ growth nano Fe3O4Comparison 1.
Respectively growing nano Fe in situ by using the biomass-based porous carbon in the examples and the comparative examples3O4The wave-absorbing material and paraffin are uniformly mixed, the mass ratio is 3:10, the mixture is pressed into a sheet with the thickness of 2mm, a vector network analyzer of AV36 3629D is used for testing the electromagnetic and wave-absorbing properties, and the test standard is GB/T32596-.
Claims (7)
1. Biomass-based porous carbon in-situ growth nano Fe3O4The wave-absorbing material is characterized in that: the biomass-based porous carbon in-situ growth nano Fe3O4The preparation method of the wave-absorbing material comprises the following steps:
(1) adding sodium alginate and sodium periodate into a distilled aqueous solvent, stirring for reaction for 4-10h, adding excessive glycol to neutralize the sodium periodate, and dialyzing and purifying to prepare aldehyde sodium alginate;
(2) adding polyethylene glycol and succinic anhydride into a pyridine solvent, stirring and reacting for 5-10h in a constant-temperature reaction device at 30-50 ℃, and carrying out reduced pressure distillation, dialysis and purification to obtain carboxyl-terminated polyethylene glycol;
(3) adding chitosan into a mixed solvent of distilled water and acetonitrile, slowly dropwise adding glacial acetic acid until the chitosan is dissolved, uniformly dispersing by ultrasonic, reacting terminal carboxyl polyethylene glycol, N-hydroxysuccinimide and dicyclohexylcarbodiimide at 30-60 ℃ for 6-12h, distilling under reduced pressure, dialyzing and purifying to prepare the terminal carboxyl polyethylene glycol grafted chitosan;
(4) adding terminal carboxyl polyethylene glycol grafted chitosan into a distilled aqueous solvent, adding aldehyde sodium alginate after uniform ultrasonic dispersion, stirring for reaction for 12-24h, filtering, dialyzing and purifying to prepare polyethylene glycol-chitosan crosslinked sodium alginate;
(5) adding polyethylene glycol-chitosan cross-linked sodium alginate and ferric chloride into a distilled aqueous solvent, performing ultrasonic dispersion uniformly, standing and aging for 48-72h, filtering, dialyzing and purifying to prepare polyethylene glycol-chitosan cross-linked ferric alginate;
(6) adding polyethylene glycol-chitosan cross-linked ferric alginate into an ethylene glycol solvent, adding diethylene glycol after ultrasonic dispersion is uniform, stirring uniformly, pouring into a reaction kettle, heating to 180 ℃ for 200 ℃, reacting for 24-48h, filtering, dialyzing, purifying, placing a solid mixed product into an atmosphere resistance furnace, heating to 450 ℃ for 500 ℃ in a nitrogen atmosphere, and carrying out heat preservation and calcination for 2-3h to prepare the biomass porous carbonIn-situ growth of nano Fe3O4The wave-absorbing material.
2. The biomass-based porous carbon in-situ grown nano-Fe of claim 13O4The wave-absorbing material is characterized in that: the molecular weight of the polyethylene glycol in the step (2) is 1000-4000, and the mass ratio of the polyethylene glycol to the succinic anhydride is 12-50: 1.
3. The biomass-based porous carbon in-situ grown nano-Fe of claim 13O4The wave-absorbing material is characterized in that: the constant-temperature reaction device in the step (2) comprises a constant-temperature heating device, a water bath is arranged above the constant-temperature heating device, a heat preservation layer is arranged on the outer side of the water bath, a sliding rail is arranged above the water bath, a pulley is movably connected with the sliding rail, a heat preservation plate is movably connected with the pulley, a support frame is fixedly connected inside the heat preservation plate, and the support frame is movably connected with a reaction bottle.
4. The biomass-based porous carbon in-situ grown nano-Fe of claim 13O4The wave-absorbing material is characterized in that: the mass ratio of the chitosan, the carboxyl-terminated polyethylene glycol, the N-hydroxysuccinimide and the dicyclohexylcarbodiimide in the step (3) is 100:400-1600:200-250: 100-130.
5. The biomass-based porous carbon in-situ grown nano-Fe of claim 13O4The wave-absorbing material is characterized in that: the mass ratio of aldehyde group sodium alginate of the carboxyl-terminated polyethylene glycol grafted chitosan in the step (4) is 40-80: 100.
6. The biomass-based porous carbon in-situ grown nano-Fe of claim 13O4The wave-absorbing material is characterized in that: the mass ratio of the polyethylene glycol-chitosan cross-linked sodium alginate to the ferric chloride in the step (5) is 10-30: 100.
7. According to the rightThe biomass-based porous carbon in-situ grown nano Fe of claim 13O4The wave-absorbing material is characterized in that: the mass ratio of the polyethylene glycol-chitosan crosslinked ferric alginate to the diethylene glycol in the step (6) is 10: 3-8.
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| CN112591730A (en) * | 2020-12-16 | 2021-04-02 | 吕海燕 | Nitrogen-doped porous carbon cathode material with adjustable pore diameter and porosity and preparation method thereof |
| CN112745694A (en) * | 2020-12-29 | 2021-05-04 | 中国科学院兰州化学物理研究所 | Petroleum asphalt/ferroferric oxide composite wave absorbing agent, preparation method thereof and wave absorbing material |
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| CN112591730A (en) * | 2020-12-16 | 2021-04-02 | 吕海燕 | Nitrogen-doped porous carbon cathode material with adjustable pore diameter and porosity and preparation method thereof |
| CN112745694A (en) * | 2020-12-29 | 2021-05-04 | 中国科学院兰州化学物理研究所 | Petroleum asphalt/ferroferric oxide composite wave absorbing agent, preparation method thereof and wave absorbing material |
| WO2023029863A1 (en) * | 2021-09-01 | 2023-03-09 | 合肥水泥研究设计院有限公司 | Multifunctional biological drying conditioner and preparation method therefor |
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