CN115160652B - Magnetic nanocellulose-carbon composite aerogel and preparation method and application thereof - Google Patents
Magnetic nanocellulose-carbon composite aerogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnetic nanocellulose-carbon composite aerogel, and a preparation method and application thereof. The composition of the magnetic nanocellulose-carbon composite aerogel comprises matrix graphene aerogel and doped magnetic nanocellulose, the composition of the magnetic nanocellulose comprises carrier nanocellulose and loaded magnetic nanoparticles, and the preparation method comprises the following steps: the preparation method comprises the steps of firstly loading magnetic nanoparticles on the surface of nanocellulose to prepare magnetic nanocellulose, then dispersing graphene oxide and the magnetic nanocellulose with water, adding a reducing agent to carry out heating reduction, and then freezing, unfreezing, cleaning and drying to obtain the magnetic nanocellulose-carbon composite aerogel. The magnetic nano cellulose-carbon composite aerogel disclosed by the invention has the advantages of high compression strength, good impedance matching property, excellent wave-absorbing property and the like, is simple in preparation process and mild in preparation conditions, and can be widely applied to the fields of electromagnetic wave absorption, electromagnetic shielding, flame retardation, heat insulation, strain sensing and the like.
Description
Technical Field
The invention relates to the technical field of carbon aerogel materials, in particular to magnetic nanocellulose-carbon composite aerogel and a preparation method and application thereof.
Background
In recent years, various electronic communication products are widely popularized, which bring convenience to life of people and bring an increasingly serious problem of electromagnetic wave pollution. Electromagnetic waves of various frequency bands not only affect the normal operation of electronic communication products, but also may harm human health, and the development of high-performance electromagnetic wave absorbing materials becomes one of the current research hotspots. The carbon aerogel (such as graphene aerogel) is a porous carbon material constructed by carbon nano materials in a three-dimensional space, has the advantages of low density, high porosity, large specific surface area and the like, and has wide application prospects in wave absorption, energy storage, adsorption, catalysis, sensing and other aspects. However, pure carbon aerogel is relatively brittle, and the carbon skeleton is easily damaged under the action of external force, and carbon aerogel has relatively high dielectric property, so that the impedance mismatch problem is easily caused, and the good wave-absorbing performance is difficult to obtain.
Therefore, the development of the carbon aerogel with high compression strength, good impedance matching property and excellent wave-absorbing performance has very important significance.
Disclosure of Invention
The invention aims to provide a magnetic nanocellulose-carbon composite aerogel, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a magnetic nanocellulose-carbon composite aerogel comprises matrix graphene aerogel and doped magnetic nanocellulose; the magnetic nano-cellulose comprises carrier nano-cellulose and loaded magnetic nano-particles.
Preferably, the magnetic nanocellulose-carbon composite aerogel is prepared from graphene oxide, nanocellulose and magnetic nanoparticles in a mass ratio of 1-10.
Preferably, the graphene oxide is in a sheet shape, and the sheet diameter is 10 to 50 μm.
Preferably, the graphene oxide has a single-layer or few-layer structure.
Preferably, the length of the nano-cellulose is 0.1-20 μm, and the diameter is 4-500 nm.
Preferably, the nanocellulose is at least one of bacterial cellulose nanofibers, cellulose nanowhiskers and microfibrillated nanocellulose.
Preferably, the length of the bacterial cellulose nanofiber is 10-20 microns, and the diameter of the bacterial cellulose nanofiber is 50-100 nm.
Preferably, the cellulose nanowhiskers have a length of 0.1 to 0.5 μm and a diameter of 4 to 10nm.
Preferably, the microfibrillated nanocellulose has a length of 5 to 10 μm and a diameter of 50 to 500nm.
Preferably, the magnetic nanoparticles are Fe 3 O 4 At least one of nanoparticles and zinc-cobalt-nickel ferrite nanoparticles.
Preferably, the structural formula of the zinc-cobalt-nickel ferrite which is the composition of the zinc-cobalt-nickel ferrite nano particles is Zn x Co y Ni z Fe 2 O 4 In the formula, x is not less than 0,y not less than 0,z not less than 0, x + y + z =1.
The preparation method of the magnetic nanocellulose-carbon composite aerogel comprises the following steps: the preparation method comprises the steps of firstly loading magnetic nanoparticles on the surface of nanocellulose to prepare magnetic nanocellulose, then dispersing graphene oxide and the magnetic nanocellulose with water, adding a reducing agent to carry out heating reduction, and then freezing, unfreezing, cleaning and drying to obtain the magnetic nanocellulose-carbon composite aerogel.
Preferably, the preparation method of the magnetic nanocellulose-carbon composite aerogel comprises the following steps:
1) Dispersing ferric salt or a mixture of ferric salt and at least one of cobalt salt, nickel salt and zinc salt in ethylene glycol, adding sodium acetate, polyvinylpyrrolidone and nanocellulose, uniformly mixing, adding the obtained dispersion liquid into a reaction kettle, and carrying out solvent thermal reaction to obtain magnetic nanocellulose;
2) Dispersing graphene oxide and magnetic nanocellulose with water, adding a reducing agent, and heating and reducing to obtain magnetic nanocellulose-reduced graphene oxide composite hydrogel;
3) Freezing and unfreezing the magnetic nanocellulose-reduced graphene oxide composite hydrogel, then washing with water, then dialyzing with water, and then drying to obtain the magnetic nanocellulose-carbon composite aerogel.
Preferably, the amount of the substance of sodium acetate is 3 to 10 times of the amount of the substance of iron salt, or 3 to 10 times of the amount of the substance of metal atoms in a mixture of iron salt and at least one of cobalt salt, nickel salt and zinc salt.
Preferably, the mass ratio of the polyvinylpyrrolidone to the ferrite generated by the solvothermal reaction theory is 0.5-2:1.
Preferably, the iron salt is FeCl 3 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、Fe 2 (SO 4 ) 3 At least one of (1).
Preferably, the cobalt salt is CoCl 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 At least one of O.
Preferably, the nickel salt is NiCl 2 ·6H 2 O、NiSO 4 ·6H 2 At least one of O.
Preferably, the zinc salt is ZnCl 2 、ZnSO 4 ·7H 2 At least one of O.
Preferably, the solvothermal reaction is carried out at 140-200 ℃, and the reaction time is 12-24 h.
Preferably, the mass ratio of the graphene oxide to the reducing agent is 1:1-5.
Preferably, the reducing agent is at least one of ascorbic acid (LAA), ethylenediamine (EDA) and hydrazine hydrate.
Preferably, the heating reduction is carried out at 75-95 ℃, and the heating reduction time is 20-90 min.
Preferably, the freezing time is 6 to 12 hours.
Preferably, the thawing time is 2h to 12h.
Preferably, the drying is carried out at 60-100 ℃, and the drying time is 12-48 h.
An electromagnetic wave absorbing material comprises the magnetic nanocellulose-carbon composite aerogel.
The invention has the beneficial effects that: the magnetic nano cellulose-carbon composite aerogel disclosed by the invention has the advantages of high compression strength, good impedance matching property, excellent wave-absorbing property and the like, is simple in preparation process and mild in preparation conditions, and can be widely applied to the fields of electromagnetic wave absorption, electromagnetic shielding, flame retardation, heat insulation, strain sensing and the like.
Specifically, the method comprises the following steps:
1) The magnetic nanocellulose-carbon composite aerogel is doped with the magnetic nanocellulose, so that the dielectric constant of the carbon aerogel can be reduced, the impedance matching performance can be adjusted, and the magnetic loss can be increased by introducing the magnetic nanoparticles, so that the minimum reflection loss of the composite aerogel is obviously reduced, the effective absorption bandwidth is increased, and the wave-absorbing performance of the composite aerogel is improved;
2) The magnetic nanocellulose-carbon composite aerogel is doped with the magnetic nanocellulose, a large number of hydroxyl groups on the nanocellulose can be subjected to condensation reaction with carboxyl groups on graphene oxide to form cross-linked bonds, so that the structural stability and the compressive strength of the composite aerogel can be improved, meanwhile, the flexible nanocellulose can also improve the brittleness of the carbon aerogel and improve the toughness of the composite aerogel;
3) Compared with a freeze drying method commonly used for preparing carbon aerogel, the preparation method disclosed by the invention has the advantages of milder preparation conditions, simpler operation, energy conservation and environmental friendliness.
Drawings
FIG. 1 is RGO/BC/Fe of example 1 3 O 4 And (5) an appearance diagram of the composite aerogel.
FIG. 2 is RGO/BC/Fe of example 1 3 O 4 SEM image of composite aerogel.
FIG. 3 is a test chart of the wave absorbing properties of the RGO aerogel of comparative example 1.
FIG. 4 is a test chart of the wave-absorbing performance of the RGO/BC composite aerogel of the comparative example 2.
FIG. 5 is RGO/BC/Fe of example 1 3 O 4 And (3) a test chart of the wave-absorbing performance of the composite aerogel.
FIG. 6 is RGO/BC/Fe of example 2 3 O 4 And (3) a test chart of the wave-absorbing performance of the composite aerogel.
FIG. 7 is RGO/BC/Fe of example 3 3 O 4 And (3) a test chart of the wave-absorbing performance of the composite aerogel.
FIG. 8 is RGO/BC/Fe of example 4 3 O 4 Test chart of wave-absorbing property of composite aerogel.
FIG. 9 is the RGO/BC/CoFe of example 5 2 O 4 Test chart of wave-absorbing property of composite aerogel.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a magnetic nanocellulose-carbon composite aerogel is prepared from graphene oxide (GO, a sheet-shaped, single-layer or few-layer structure with the sheet diameter of 10-50 μm), bacterial cellulose nanofibers (BC, the length of 10-20 μm and the diameter of 50-100 nm) and Fe in a mass ratio of 4 3 O 4 The preparation method of the nano-particle comprises the following steps:
1) Adding 400mg of GO into 40mL of deionized water, stirring for 30min at 600rpm, and performing ultrasonic treatment at 250W for 40min to obtain GO dispersion liquid with the concentration of 10 mg/mL;
2) 0.7g of FeCl 3 ·6H 2 Adding O into 60mL of glycol, adding 1.87g of sodium acetate (NaAC) and 250mg of polyvinylpyrrolidone (PVP), uniformly stirring, dropwise adding 25g of BC dispersion liquid with the solid content of 0.8%, stirring at 600rpm for 1h, pouring the obtained dispersion liquid into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an aging oven, reacting at 200 ℃ for 12h, centrifuging and washing the obtained reaction liquid at 3500rpm for 5 times, freeze-drying the product for 24h, and keeping the temperature of a cold trap at-60 ℃ to obtain the magnetic nanocellulose (marked as BC/Fe) 3 O 4 )；
3) 400mg of BC/Fe 3 O 4 Adding into 36mL deionized water, adding 4mL Sodium Dodecyl Benzene Sulfonate (SDBS) dispersion solution with concentration of 50mg/mL, stirring at 400rpm for 30min, and performing ultrasonic treatment at 250W for 20min to obtain BC/Fe with concentration of 10mg/mL 3 O 4 A dispersion liquid;
4) 40mL of GO dispersion, 20mL of BC/Fe 3 O 4 Mixing the dispersion with 20mL deionized water, adding 800mg ascorbic acid (LAA), stirring at 400rpm for 20min to obtain GO/BC/Fe 3 O 4 Dispersing GO/BC/Fe 3 O 4 Subpackaging the dispersion into glass bottles with wood stoppers, and placing into an aging oven for reduction at 75 deg.C for 30min to obtain magnetic nanofiberPlain-reduced graphene oxide composite hydrogel (marked as RGO/BC/Fe) 3 O 4 Composite hydrogels);
5) Mixing RGO/BC/Fe 3 O 4 The composite hydrogel is placed in a refrigerator, frozen at-18 ℃ for 6h, thawed at room temperature for 2h, then the surface of the composite hydrogel is washed with deionized water, then dialysis is carried out with deionized water, the volume ratio of the hydrogel to the deionized water is 1 3 O 4 Composite aerogel).
Example 2:
a magnetic nanocellulose-carbon composite aerogel is prepared from GO (sheet, single-layer or few-layer structure, sheet diameter of 10-50 μm), BC (length of 10-20 μm, diameter of 50-100 nm) and Fe in a mass ratio of 5 3 O 4 The preparation method of the nano-particle comprises the following steps:
1) Adding 400mg of GO into 50mL of deionized water, stirring for 30min at 600rpm, and performing ultrasonic treatment at 250W for 40min to obtain GO dispersion liquid with the concentration of 8 mg/mL;
2) 1.4g of FeCl 3 ·6H 2 Adding O into 60mL of ethylene glycol, adding 3.74g of NaAC and 500mg of PVP, stirring uniformly, dropwise adding 25g of BC dispersion liquid with the solid content of 0.8%, stirring at 600rpm for 40min, pouring the obtained dispersion liquid into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an aging oven, reacting at 200 ℃ for 12h, centrifuging and washing the obtained reaction liquid at 3500rpm for 8 times, freeze-drying the product for 24h, and obtaining the magnetic nanocellulose (marked as BC/Fe) with the cold trap temperature of-60 DEG C 3 O 4 )；
3) 400mg of BC/Fe 3 O 4 Adding into 36mL deionized water, adding 4mL SDBS dispersion with concentration of 50mg/mL, stirring at 400rpm for 60min, performing ultrasonic treatment at 250W for 20min to obtain BC/Fe with concentration of 10mg/mL 3 O 4 A dispersion liquid;
4) 50mL of GO dispersion, 24mL of BC/Fe 3 O 4 Mixing the dispersion with 6mL of deionized water, adding 800mg of LAA, stirring at 400rpm for 20min to obtain GO/BC/Fe 3 O 4 Dispersing GO/BC/Fe 3 O 4 Subpackaging the dispersion into glass bottles with wood stoppers, and reducing in an aging oven at 75 deg.C for 30min to obtain magnetic nanocellulose-reduced graphene oxide composite hydrogel (RGO/BC/Fe) 3 O 4 Composite hydrogels);
5) Mixing RGO/BC/Fe 3 O 4 Freezing the composite hydrogel in a refrigerator at-18 ℃ for 8h, thawing at room temperature for 4h, washing the surface of the composite hydrogel with deionized water, dialyzing with deionized water, wherein the volume ratio of the hydrogel to the deionized water is 1:8, the dialysis time is 12h, replacing the deionized water every 4h, placing the composite hydrogel in a forced air drying oven, and drying at 65 ℃ for 24h to obtain the magnetic nanocellulose-carbon composite aerogel (marked as RGO/BC/Fe) 3 O 4 Composite aerogel).
Example 3:
a magnetic nanocellulose-carbon composite aerogel is prepared from GO (sheet, single-layer or few-layer structure, sheet diameter of 10-50 μm), BC (length of 10-20 μm, diameter of 50-100 nm) and Fe at a mass ratio of 4 3 O 4 The preparation method of the nano-particle comprises the following steps:
1) Adding 400mg of GO into 40mL of deionized water, stirring for 30min at 600rpm, and performing ultrasonic treatment at 250W for 40min to obtain GO dispersion liquid with the concentration of 10 mg/mL;
2) 2.1g of FeCl 3 ·6H 2 Adding O into 60mL of ethylene glycol, adding 5.61g of NaAC and 750mg of PVP, stirring uniformly, dropwise adding 25g of BC dispersion liquid with the solid content of 0.8%, stirring at 600rpm for 40min, pouring the obtained dispersion liquid into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an ageing oven, reacting at 200 ℃ for 12h, centrifuging and washing the obtained reaction liquid at 3500rpm for 6 times, freeze-drying the product for 24h, and obtaining the magnetic nanocellulose (marked as BC/Fe) with the cold trap temperature of-60 DEG C 3 O 4 )；
3) 400mg of BC/Fe 3 O 4 Adding into 36mL deionized water, adding 4mL SDBS dispersion with concentration of 50mg/mL, stirring at 400rpm for 60min, performing ultrasonic treatment at 250W for 20min to obtain BC/Fe with concentration of 10mg/mL 3 O 4 Dispersion liquid；
4) 40mL of GO dispersion and 40mL of BC/Fe 3 O 4 Mixing the dispersion with water, adding 800mg LAA, stirring at 400rpm for 20min to obtain GO/BC/Fe 3 O 4 Dispersing GO/BC/Fe 3 O 4 Subpackaging the dispersion into glass bottles with wood stoppers, and reducing in an aging oven at 75 deg.C for 30min to obtain magnetic nanocellulose-reduced graphene oxide composite hydrogel (RGO/BC/Fe) 3 O 4 Composite hydrogels);
5) Mixing RGO/BC/Fe 3 O 4 Freezing the composite hydrogel in a refrigerator at-18 ℃ for 12h, thawing at room temperature for 6h, washing the surface of the composite hydrogel with deionized water, dialyzing with deionized water, wherein the volume ratio of the hydrogel to the deionized water is 1:6, the dialysis time is 12h, replacing the deionized water every 4h, placing the composite hydrogel in a forced air drying oven, and drying at 80 ℃ for 12h to obtain the magnetic nanocellulose-carbon composite aerogel (marked as RGO/BC/Fe) 3 O 4 Composite aerogel).
Example 4:
a magnetic nanocellulose-carbon composite aerogel is prepared from GO (sheet, single-layer or few-layer structure, sheet diameter of 10-50 μm), BC (length of 10-20 μm, diameter of 50-100 nm) and Fe at a mass ratio of 5 3 O 4 The preparation method of the nano-particle comprises the following steps:
1) Adding 400mg of GO into 40mL of deionized water, stirring for 30min at 600rpm, and performing ultrasonic treatment for 40min at 250W to obtain GO dispersion liquid with the concentration of 10 mg/mL;
2) 2.8g of FeCl 3 ·6H 2 Adding O into 60mL of glycol, adding 7.48g of NaAC and 1000mg of PVP, stirring uniformly, dropwise adding 25g of BC dispersion liquid with the solid content of 0.8%, stirring at 600rpm for 40min, pouring the obtained dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an aging oven, reacting at 200 ℃ for 12h, centrifuging and washing the obtained reaction liquid at 3500rpm for 6 times, freeze-drying the product for 24h, and obtaining the magnetic nanocellulose (marked as BC/Fe) with the cold trap temperature of-60 DEG C 3 O 4 )；
3) 400mg of BC/Fe 3 O 4 Addition of 3Adding 4mL SDBS dispersion liquid with the concentration of 50mg/mL into 6mL deionized water, stirring for 60min at 400rpm, performing ultrasonic treatment at 250W for 20min to obtain BC/Fe with the concentration of 10mg/mL 3 O 4 A dispersion liquid;
4) 40mL of GO dispersion and 40mL of BC/Fe 3 O 4 Mixing the dispersion, adding 800mg LAA, stirring at 400rpm for 20min to obtain GO/BC/Fe 3 O 4 Dispersing GO/BC/Fe 3 O 4 Subpackaging the dispersion into glass bottles with wood stoppers, and reducing in an aging oven at 75 deg.C for 30min to obtain magnetic nanocellulose-reduced graphene oxide composite hydrogel (RGO/BC/Fe) 3 O 4 Composite hydrogels);
5) Mixing RGO/BC/Fe 3 O 4 And (2) freezing the composite hydrogel in a refrigerator at-18 ℃ for 12h, thawing at room temperature for 6h, washing the surface of the composite hydrogel with deionized water, dialyzing with deionized water, wherein the volume ratio of the hydrogel to the deionized water is 1 3 O 4 A composite aerogel).
Example 5:
a magnetic nanocellulose-carbon composite aerogel is prepared from GO (sheet, single-layer or few-layer structure, sheet diameter of 10-50 μm), BC (length of 10-20 μm, diameter of 50-100 nm) and CoFe in a mass ratio of 4 2 O 4 The preparation method of the nano-particle comprises the following steps:
1) Adding 400mg of GO into 50mL of deionized water, stirring at 600rpm for 40min, and performing 250W ultrasonic treatment for 40min to obtain GO dispersion liquid with the concentration of 8 mg/mL;
2) 922mg of FeCl 3 ·6H 2 O to 60mL of ethylene glycol, 496mg of Co (NO) was added 3 ) 2 ·6H 2 O, 3.74g of NaAC and 500mg of PVP are stirred uniformly, 25g of BC dispersion liquid with the solid content of 0.8% is dripped, the mixture is stirred at 600rpm for 60min, the obtained dispersion liquid is poured into a hydrothermal reaction kettle and then is placed into an aging oven to react for 12h at 200 ℃, and the obtained reaction liquid reacts at 3500rpmCentrifuging and washing for 6 times, freeze-drying the product for 24h at-60 deg.C to obtain magnetic nanocellulose (BC/CoFe) 2 O 4 )；
3) 600mg of BC/CoFe 2 O 4 Adding into 54mL deionized water, adding 6mL SDBS dispersion with concentration of 50mg/mL, stirring at 400rpm for 40min, performing ultrasonic treatment at 250W for 30min to obtain BC/CoFe with concentration of 10mg/mL 2 O 4 A dispersion liquid;
4) 50mL of GO dispersion and 30mL of BC/CoFe 2 O 4 Mixing the dispersion, adding 800mg LAA, stirring at 400rpm for 20min to obtain GO/BC/CoFe 2 O 4 Dispersing GO/BC/CoFe 2 O 4 Subpackaging the dispersion liquid into glass bottles with wood stoppers, and reducing the glass bottles in an aging oven at 75 ℃ for 30min to obtain the magnetic nanocellulose-reduced graphene oxide composite hydrogel (marked as RGO/BC/CoFe) 2 O 4 Composite hydrogels);
5) Mixing RGO/BC/CoFe 2 O 4 And (2) freezing the composite hydrogel in a refrigerator at-18 ℃ for 12h, thawing at room temperature for 6h, washing the surface of the composite hydrogel with deionized water, dialyzing with deionized water, wherein the volume ratio of the hydrogel to the deionized water is 1 2 O 4 Composite aerogel).
Comparative example 1:
the preparation method of the carbon aerogel comprises the following steps:
1) Adding 400mg of GO (in a sheet shape, a single-layer or few-layer structure, the sheet diameter is 10-50 mu m) into 80mL of deionized water, stirring at 600rpm for 20min, performing 250W ultrasonic for 40min, adding 800mg of ascorbic acid, and stirring at 600rpm for 10min to obtain GO dispersion liquid with the concentration of 5 mg/mL;
2) Subpackaging the GO dispersion liquid into glass bottles with wood plugs, and then putting the glass bottles into an ageing oven to reduce the GO dispersion liquid for 45min at 75 ℃ to obtain reduced graphene oxide hydrogel (marked as RGO hydrogel);
3) Placing the RGO hydrogel into a refrigerator, freezing at-18 ℃ for 6h, thawing at room temperature for 2h, then washing the surface of the hydrogel with deionized water, dialyzing with deionized water, wherein the volume ratio of the hydrogel to the deionized water is 1.
Comparative example 2:
a nano-cellulose-carbon composite aerogel is prepared from GO (sheet, single-layer or few-layer structure, sheet diameter of 10-50 μm) and BC (length of 10-20 μm and diameter of 50-100 nm) in a mass ratio of 5:1, and the preparation method comprises the following steps:
1) Adding 400mg of GO into 50mL of deionized water, stirring for 30min at 600rpm, and performing ultrasonic treatment at 250W for 40min to obtain GO dispersion liquid with the concentration of 8 mg/mL;
2) Adding 10g of BC dispersion liquid with solid content of 0.8% into 10mL of deionized water, and stirring at 1000rpm for 30min to obtain BC dispersion liquid with concentration of 4 mg/mL;
3) Pouring 10mL of deionized water into 20mL of BC dispersion liquid in a stirring state, then dropwise adding 50mL of GO dispersion liquid, stirring at 600rpm for 40min, performing 250W ultrasonic for 20min, then adding 800mg of LAA, stirring at 600rpm for 10min to prepare GO/BC dispersion liquid, then subpackaging the GO/BC dispersion liquid into glass bottles with wood plugs, and then putting the glass bottles into an aging box to reduce at 75 ℃ for 45min to obtain nano-cellulose-reduced graphene oxide composite hydrogel (marked as RGO/BC composite hydrogel);
4) The RGO/BC composite hydrogel is placed in a refrigerator, frozen at-18 ℃ for 6 hours, thawed at room temperature for 2 hours, then the surface of the composite hydrogel is washed by deionized water, and then dialyzed by the deionized water, wherein the volume ratio of the hydrogel to the deionized water is 1.
And (4) performance testing:
1) RGO/BC/Fe of example 1 3 O 4 The appearance of the composite aerogel is shown in fig. 1, and the Scanning Electron Microscope (SEM) image is shown in fig. 2.
From the figure1 and 2, it can be seen that: RGO/BC/Fe of example 1 3 O 4 The composite aerogel has a regular appearance, a wrinkled surface and a loose porous structure inside.
2) RGO aerogel of comparative example 1, RGO/BC composite aerogel of comparative example 2, RGO/BC/Fe of examples 1-4 3 O 4 Composite aerogel and RGO/BC/CoFe of example 5 2 O 4 The wave-absorbing performance test chart of the composite aerogel is shown in the figures 3-9 in sequence, and the specific wave-absorbing performance test result is shown in the following table:
table 1 wave-absorbing performance test results
Note:
the method for testing the wave absorbing performance comprises the following steps: immersing aerogel into molten paraffin, vacuumizing to completely infiltrate the aerogel, taking out the aerogel, preparing a coaxial ring sample with the outer diameter of 7.00mm and the inner diameter of 3.04mm by using a mould after the paraffin is completely solidified, testing the electromagnetic parameters of the sample by using a vector network analyzer (model ZNA43, germany Luo Desi Watts company), and obtaining the wave absorbing performance of the aerogel according to the transmission line theory.
As can be seen from fig. 3 to 9 and table 1:
a) The minimum reflection loss of the RGO aerogel of the comparative example 1 is only-14.03 dB, and the good wave-absorbing performance cannot be obtained;
b) The RGO/BC composite aerogel of the comparative example 2 is added with a proper amount of bacterial cellulose, so that the wave absorbing performance of the carbon aerogel can be improved, and the minimum reflection loss of-47.61 dB is realized;
c) The introduction of the magnetic cellulose remarkably increases the wave absorbing performance of the aerogel, the minimum reflection loss corresponding to the composite aerogel of examples 1-5 is-64.50 dB, -67.96dB, -59.58dB, -69.54dB and-55.24 dB respectively, and the effective absorption bandwidth is close to 7GHz, in addition, compared with the RGO aerogel of comparative example 1, the minimum reflection loss peak of the composite aerogel of examples 1-5 also moves to low frequency;
d) The composite aerogels of examples 1 to 5 have lower minimum reflection loss and wider effective absorption band while the wave-absorbing band is shifted toward lower frequency direction, compared to the RGO aerogel of comparative example 1 and the RGO/BC composite aerogel of comparative example 2. In addition, different types of modified carbon aerogels can be prepared by loading different types of magnetic metal particles on the nanocellulose, and different loading amounts of magnetic nanocellulose can be prepared by adjusting the ratio of the cellulose to the magnetic particles, so that modified carbon aerogels with different magnetism can be obtained, the magnetic conductivity of the composite aerogel can be flexibly adjusted, and the wave-absorbing performance of the composite carbon aerogel can be improved;
in conclusion, the magnetic nano cellulose-carbon composite aerogel disclosed by the invention can be used as a light broadband wave-absorbing material and has wide application prospects in the fields of 5G communication, national defense, military industry and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. The magnetic nanocellulose-carbon composite aerogel is characterized by comprising matrix graphene aerogel and doped magnetic nanocellulose; the magnetic nano-cellulose comprises carrier nano-cellulose and loaded magnetic nano-particles; the magnetic nanocellulose-carbon composite aerogel is prepared from graphene oxide, nanocellulose and magnetic nanoparticles in a mass ratio of 1-10; the graphene oxide is flaky, and the sheet diameter is 10-50 mu m; the length of the nano-cellulose is 0.1-20 mu m, and the diameter is 4-500 nm; the nano-cellulose is at least one of bacterial cellulose nano-fiber, cellulose nano-whisker and microfibrillated nano-cellulose; the magnetic nano-particles are Fe 3 O 4 At least one of nanoparticles and zinc-cobalt-nickel ferrite nanoparticles; the magnetic nanocellulose-carbon composite aerogel is prepared by a preparation method comprising the following steps of: first to receiveLoading magnetic nano-particles on the surface of the rice cellulose to prepare magnetic nano-cellulose, dispersing graphene oxide and the magnetic nano-cellulose with water, adding a reducing agent for heating reduction, freezing, thawing, cleaning and drying to obtain the magnetic nano-cellulose-carbon composite aerogel.
2. The magnetic nanocellulose-carbon composite aerogel of claim 1, characterized by: the structural formula of the zinc-cobalt-nickel ferrite as the composition component of the zinc-cobalt-nickel ferrite nano particles is Zn x Co y Ni z Fe 2 O 4 In the formula, x is not less than 0,y not less than 0,z not less than 0, x + y + z =1.
3. The magnetic nanocellulose-carbon composite aerogel of claim 1, wherein: the heating reduction is carried out at the temperature of 75-95 ℃, and the heating reduction time is 20-90 min.
4. An electromagnetic wave absorbing material, comprising the magnetic nanocellulose-carbon composite aerogel according to any one of claims 1 to 3.
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| CA2898513A1 (en) * | 2015-07-27 | 2017-01-27 | Stephan HEATH | Methods, products, and systems relating to making, providing, and using nanocrystalline (nc) products comprising nanocrystalline cellulose (ncc), nanocrystalline (nc) polymers and/or nanocrystalline (nc) plastics or other nanocrystals of cellulose composites or structures, in combination with other materials |
| US20190245155A1 (en) * | 2018-01-24 | 2019-08-08 | Stephan HEATH | Methods, products, and systems relating to making, providing, and using nanocrystalline cellulose superlattice solar cells to produce electricity |
| CN108690556B (en) * | 2018-06-29 | 2021-03-19 | 安徽理工大学 | Preparation method of reduced graphene oxide/multiwalled carbon nanotube/nickel ferrite ternary nano composite wave-absorbing material |
| CN113336999A (en) * | 2021-06-29 | 2021-09-03 | 吉林大学 | Method for preparing magnetic nano cellulose aerogel by using straws |
| CN113801368B (en) * | 2021-10-20 | 2022-11-15 | 陕西科技大学 | Reduced graphene oxide/aramid nanofiber composite aerogel for electromagnetic shielding and preparation method thereof |
| CN114210276B (en) * | 2021-11-18 | 2023-05-23 | 中国安全生产科学研究院 | Magnetic carbon-based composite aerogel with fire early warning and flame retarding functions and preparation method thereof |
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