CN115386337B - Chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and preparation method thereof - Google Patents
Chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof. The preparation method disclosed by the invention is simple in synthesis process, rich in material resources, environment-friendly, wide in application prospect, and excellent in performance, and the prepared chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material is used for electromagnetic wave absorption.
Description
Technical Field
The invention relates to the technical field of nanocomposite and electromagnetic wave absorption, in particular to a chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof.
Background
Based on the high-speed development and wide application of information technology, electromagnetic radiation pollution becomes the fourth environmental pollution after water, air and noise, and the electromagnetic pollution problem seriously threatens human health and information safety, and becomes one of the important problems to be solved in the development of the current society. Electromagnetic absorption is the most effective method for truly solving electromagnetic radiation pollution, and research and development of high-performance electromagnetic wave absorbers with thin, light, wide and strong characteristics are urgent. The wave-absorbing material in the prior art has the problems of high density, narrow wave-absorbing frequency band, complex synthesis process, expensive raw materials, single loss mechanism and the like.
Compared with traditional polyaniline, chiral polyaniline can show special optical rotation and circular dichroism due to the unique supercoiled structure, and generates cross polarization coupling effect under the action of alternating electromagnetic field, so that chiral polyaniline has multiple electromagnetic wave loss mechanism, and meanwhile, chiral polyaniline has lower sensitivity to frequency, can effectively widen absorption frequency band, and is one of the conductive polymers with the most application prospect.
Carbon black, graphene, carbon fiber, carbon nanotube and the like are important carbon-based wave absorbing materials, but the preparation cost is high, the energy consumption is high, and the industrial application scale is restricted. Therefore, it is important to find a green, environment-friendly, low-cost and high-efficiency carbon material. The biomass-derived porous carbon material has the advantages of rich resources, environmental protection, low cost, excellent conductivity, adjustable pore channel structure, large specific surface area and the like, and is a candidate with great potential value for synthesizing the carbon-based composite wave-absorbing material. The channel structure can effectively regulate and control dielectric constant, optimize impedance matching, simultaneously make incident electromagnetic waves generate multiple reflection and scattering, extend the propagation path of electromagnetic waves, and provide more opportunities for absorbing and attenuating electromagnetic wave energy. The high specific surface area provides rich sites for the growth of chiral polyaniline, and is favorable for heterogeneous interface construction and improvement of interface polarization. Thus, optimizing microstructure and material composition is a potential approach to solve the increasing electromagnetic interference problem.
Chinese patent CN201210005404.0 discloses an expanded graphite/polyaniline/cobalt ferrite wave absorbing material and preparation process, comprising the following steps: (1) preparing expanded graphite; (2) preparing absolute ethanol containing expanded graphite; (3) preparing an expanded graphite/polyaniline binary compound; (4) Preparing an expanded graphite/polyaniline/cobalt ferrite ternary complex; (5) And (3) weighing the ternary complex of the expanded graphite/polyaniline/cobalt ferrite and the paraffin, uniformly mixing, and performing ball milling to obtain the expanded graphite/polyaniline/cobalt ferrite wave-absorbing material. The polyaniline wave-absorbing material has the advantages of medium electromagnetic wave absorbing capacity through a double mechanism of dielectric loss and magnetic loss and poor overall performance.
Chinese patent CN201210034964.9 discloses a method for preparing neodymium doped manganese zinc ferrite-polyaniline composite wave-absorbing material, according to the stoichiometric proportion of mn0.4zn0.6ndxfe2-xO4 (x=0.025-0.1), using chemical co-deposition method to prepare neodymium doped manganese zinc ferrite with different doping amounts; then preparing the neodymium-doped manganese-zinc ferrite-polyaniline composite wave-absorbing material (5% -20%) by adopting an in-situ composite method according to the mass ratio of the neodymium-doped manganese-zinc ferrite to the aniline monomer of 1-4:20. The preparation process is complex, the preparation time is long, and the production cost of the polyaniline wave-absorbing material is high.
Disclosure of Invention
The invention aims to provide a chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof. The prepared chiral polyaniline/biomass derived porous carbon composite wave-absorbing material is used for electromagnetic wave absorption and has excellent performance.
In order to solve the technical problems, the specific scheme adopted by the invention is a preparation method of chiral polyaniline/biomass derived porous carbon composite wave-absorbing material: the biomass material is carbonized at high temperature to prepare biomass-derived porous carbon, and the biomass-derived porous carbon is polymerized to form chiral polyaniline on the surface of the biomass-derived porous carbon under the combined action of a chiral compound inducer and an initiator, so that the composite wave-absorbing material is prepared.
As a preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material, the preparation method is further optimized: the method specifically comprises the following steps:
s1: removing impurities from biomass materials, crushing, immersing the biomass materials into KOH solution, and filtering and drying to obtain biomass powder for later use;
s2: calcining the biomass powder obtained in the step S1 under inert atmosphere, naturally cooling to room temperature after calcining, grinding, washing, and freeze-drying to obtain biomass-derived porous carbon powder for later use;
s3: immersing the biomass-derived porous carbon powder prepared in the step S2 into an aqueous solution of an aniline monomer and a chiral compound inducer to prepare a suspension pre-solution, and cooling to 0-5 ℃;
s4: and (3) dissolving an initiator in deionized water, then dropwise adding the solution into the suspension pre-solution prepared in the step (S3), and filtering, washing, centrifuging and freeze-drying to prepare the chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material.
As a preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material, the preparation method is further optimized: in the step S1, the biomass material refers to crop straw or shell waste, wherein the crop straw is straw of corn, sorghum, sunflower or wheat, and the shell waste is shell of nuts.
As a preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material, the preparation method is further optimized: in the step S1, the biomass material is crushed and then passes through a 20-300-mesh sieve, the concentration of KOH solution is 0.5-3mol/L, and after the biomass material is immersed in the KOH solution, the biomass material is subjected to ultrasonic vibration for 10-30min and then is kept stand for 3-12h.
As a preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material, the preparation method is further optimized: the biomass powder in the step S2 is calcined in a tube furnace, the temperature rising rate in the calcining process is 2-15 ℃/min, the calcining temperature is 500-800 ℃, and the heat preservation time is 1-5h.
As a preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material, the preparation method is further optimized: the chiral compound inducer consists of a chiral compound inducer main body and a compound additive, wherein the mass ratio of the inducer main body to the compound additive is 10:1-10:3, the chiral compound inducer main body is camphorsulfonic acid, and the compound additive is one or any mixture of mandelic acid, p-methyl dibenzoyl tartaric acid, dibenzoyl tartaric acid or chloropropionic acid.
As a preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material, the preparation method is further optimized: in the step S3, the ratio of the aniline monomer to the chiral compound inducer is 1:1-1:4.
As a preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material, the preparation method is further optimized: in the step S4, the initiator is ammonium persulfate, ferric trichloride, potassium permanganate or hydrogen peroxide, and the ratio of the initiator to the mass of the aniline monomer in the suspension pre-solution is 1:1-1:1.5.
As a preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material, the preparation method is further optimized: in the step S4, the dripping speed of the aqueous solution of the initiator is 1-10ml/min, the dripping is carried out at the stirring speed of 50-300r/min, and the reaction is carried out for 10-24h after the dripping is finished.
A chiral polyaniline/biomass derived porous carbon composite wave-absorbing material is prepared by any one of the preparation methods.
Advantageous effects
The preparation method of the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material takes biomass derived porous carbon prepared by high-temperature carbonization and activation as a substrate, and has adjustable unique pore channel structure, high specific surface and a large number of surface functional groups, so that sufficient adhesion and growth sites are provided for chiral polyaniline. Under the unique induction of the chiral compound inducer, the chiral compound inducer and the initiator are synergistic, the polyaniline main chain preferentially adopts a spiral configuration to obtain chiral polyaniline and is attached to the surface of the biomass-derived porous carbon, so that the chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material is obtained. The chiral polyaniline can show special optical rotation and circular dichroism due to the unique supercoiled structure, and generates cross polarization coupling effect under the action of alternating electromagnetic field, so that the chiral polyaniline has multiple electromagnetic wave loss mechanism, the wave absorbing performance can be effectively regulated and controlled by adjusting chiral parameters, compared with the electromagnetic parameters, the impedance matching can be realized more easily, and meanwhile, based on the biomass-derived porous carbon matrix, the chiral composite material has a unique three-dimensional pore structure, is favorable for establishing a three-dimensional conductive network, prolonging an electromagnetic wave transmission channel, enhancing multiple reflection and scattering, and further shows excellent electromagnetic wave absorption and attenuation characteristics. The method has the advantages of simple synthesis process, rich material resources, environmental friendliness and wide application prospect.
Drawings
FIG. 1 is an SEM image of a composite wave-absorbing material prepared in example 1;
Detailed Description
The technical solution of the present invention will be clearly and completely described in the following with reference to specific embodiments, but the scope of the present invention is not limited to the embodiments, and changes made to the technical solution of the present invention by those skilled in the art should fall within the scope of the present invention.
Example 1
A chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof comprise the following steps:
1) Repeatedly cleaning peanut shells to remove surface impurities, drying, crushing, sieving with a 50-mesh sieve, immersing in KOH solution with the concentration of 1mol/L, carrying out ultrasonic vibration for 30min, standing for 12h, and then filtering and drying.
2) Placing the obtained biomass powder into a tube furnace, and adding the biomass powder into N 2 Calcining under the protection of atmosphere, wherein the temperature rising rate is 5 ℃/min, the calcining temperature is 750 ℃, the heat preservation time is 2h, grinding after naturally cooling to room temperature, and freeze-drying after hydrochloric acid washing and multiple times of water washing to obtain the biomass-derived porous carbon powder.
3) 0.5ml of aniline monomer, 1.16g of camphorsulfonic acid and 0.17g of mandelic acid are fully dissolved in 50ml of deionized water, then 0.5g of biomass-derived porous carbon powder is weighed and immersed into the solution, and after uniform and stable suspension pre-solution is obtained through ultrasonic and stirring, the ice water bath is cooled to 0-5 ℃.
4) 1.25g of ammonium persulfate is weighed and fully dissolved in 20ml of deionized water, after being cooled to constant temperature by an ice water bath, the mixture is dropwise added into suspension of aniline monomer, camphorsulfonic acid, mandelic acid and biomass-derived porous carbon powder at a constant speed of 3ml/min by a constant pressure dropping funnel, the mixture is slowly stirred at 100r/min in the dropping process, stirring is stopped after the dropping is finished, the mixture is placed in the ice water bath for standing reaction for 24 hours, and then the mixture is filtered, washed, centrifuged and freeze-dried to prepare the chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material (SEM image of the wave-absorbing material is shown in figure 1).
Wave absorbing performance: based on the coaxial reflection/transmission method, a vector network analyzer is adopted to test the wave absorbing performance of the polyaniline/biomass derived porous carbon composite material at the frequency of 2-18 GHz. The sample size was: the outer diameter is 7.00mm, the inner diameter is 3.00mm, and the thickness is 2.00mm. The paraffin matrix and the polyaniline/biomass derived porous carbon composite wave-absorbing material are uniformly mixed according to the mass ratio of 4:1, and then pressed into a coaxial circular ring shape by using a specific die for testing. When the thickness of the material is 1.8mm, the minimum reflection loss value can reach-42.58 dB, and the effective absorption bandwidth can reach 4.5GHz.
Example 2
A chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof comprise the following steps:
1) Repeatedly cleaning walnut shell to remove surface impurities, drying, pulverizing, sieving with 20 mesh sieve, soaking in KOH solution with concentration of 2mol/L, ultrasonic oscillating for 30min, standing for 8 hr, filtering, and drying.
2) Placing the obtained biomass powder into a tube furnace, and adding N into the biomass powder 2 Calcining under the protection of atmosphere, wherein the temperature rising rate is 5 ℃/min, the calcining temperature is 800 ℃, the heat preservation time is 3h, grinding after naturally cooling to room temperature, and freeze-drying after hydrochloric acid washing and water washing to obtain the biomass-derived porous carbon powder.
3) 0.4ml of aniline monomer, 1g of camphorsulfonic acid, 0.05g of mandelic acid and 0.25g of p-methyl dibenzoyl tartaric acid are fully dissolved in 30ml of deionized water, then 0.4g of biomass-derived porous carbon powder is weighed and immersed in the solution, and after uniform and stable suspension pre-liquid is obtained through ultrasonic and stirring, the ice water bath is cooled to 0-5 ℃.
4) Weighing 0.8g of ferric trichloride, fully dissolving in 15ml of deionized water, cooling to constant temperature in an ice water bath, dripping into suspension of aniline monomer, camphorsulfonic acid, mandelic acid, p-methyl dibenzoyl tartaric acid and biomass-derived porous carbon powder at a constant speed of 3ml/min through a constant pressure dripping funnel, slowly stirring at 80r/min in the dripping process, stopping stirring after dripping, standing in an ice water bath for reaction for 24 hours, filtering, washing, centrifuging, and freeze-drying to obtain the chiral polyaniline/biomass-derived porous carbon composite wave absorbing material.
Wave absorbing performance: based on the coaxial reflection/transmission method, a vector network analyzer is adopted to test the wave absorbing performance of the polyaniline/biomass derived porous carbon composite material at the frequency of 2-18 GHz. The sample size was: the outer diameter is 7.00mm, the inner diameter is 3.00mm, and the thickness is 2.00mm. The paraffin matrix and the polyaniline/biomass derived porous carbon composite wave-absorbing material are uniformly mixed according to the mass ratio of 4:1, and then pressed into a coaxial circular ring shape by using a specific die for testing. When the thickness of the material is 2.1mm, the minimum reflection loss value can reach-39.64 dB, and the effective absorption bandwidth can reach 4.32GHz.
Example 3
A chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof comprise the following steps:
1) Repeatedly cleaning sorghum straw to remove surface impurities, drying, crushing, sieving with a 20-mesh sieve, immersing in KOH solution with the concentration of 1.5mol/L, carrying out ultrasonic vibration for 30min, standing for 8h, and filtering and drying.
2) Placing the obtained biomass powder into a tube furnace, and adding the biomass powder into N 2 Calcining under the protection of atmosphere, wherein the temperature rising rate is 5 ℃/min, the calcining temperature is 750 ℃, the heat preservation time is 1h, grinding after naturally cooling to room temperature, and freeze-drying after hydrochloric acid washing and water washing to obtain the biomass-derived porous carbon powder.
3) 0.5ml of aniline monomer, 1.2g of camphorsulfonic acid, 0.3g of p-methyl dibenzoyl tartaric acid and 0.01ml of chloropropionic acid are fully dissolved in 30ml of deionized water, 0.5g of biomass-derived porous carbon powder is weighed and immersed in the solution, and after uniform and stable suspension pre-liquid is obtained through ultrasonic and stirring, the ice water bath is cooled to 0-5 ℃.
4) 1.2g of ammonium persulfate is weighed and fully dissolved in deionized water, after being cooled to constant temperature by an ice water bath, the ammonium persulfate is dropwise added into suspension of aniline monomer, camphorsulfonic acid, p-methyl dibenzoyl tartaric acid, chloropropionic acid and biomass-derived porous carbon powder at a constant speed of 3ml/min by a constant pressure dropping funnel, the slow stirring is carried out at 150r/min in the dropping process, the stirring is stopped after the dropping is finished, the mixture is placed in an ice water bath for standing reaction for 24 hours, and then the mixture is filtered, washed, centrifuged and freeze-dried to obtain the chiral polyaniline/biomass-derived porous carbon composite wave absorbing material.
Wave absorbing performance: based on the coaxial reflection/transmission method, the polyaniline/biomass derived porous carbon composite material is tested by adopting a vector network analyzer under the wave absorbing performance of 2-18 GHz. The sample size was: the outer diameter is 7.00mm, the inner diameter is 3.00mm, and the thickness is 2.00mm. The paraffin matrix and the polyaniline/biomass derived porous carbon composite wave-absorbing material are uniformly mixed according to the mass ratio of 4:1, and then pressed into a coaxial circular ring shape by using a specific die for testing. When the thickness of the material is 2.4mm, the minimum reflection loss value can reach 40.54dB, and the effective absorption bandwidth can reach 4.28GHz.
Example 4
A chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof comprise the following steps:
1) Repeatedly cleaning sunflower straw to remove surface impurities, drying, pulverizing, sieving with 80 mesh sieve, soaking in KOH solution with concentration of 1.5mol/L, ultrasonic oscillating for 30min, standing for 12 hr, filtering, and drying.
Placing the obtained biomass powder into a tube furnace, and adding the biomass powder into N 2 Calcining under the protection of atmosphere, wherein the temperature rising rate is 5 ℃/min, the calcining temperature is 750 ℃, the heat preservation time is 2h, grinding after naturally cooling to room temperature, and freeze-drying after hydrochloric acid washing and water washing to obtain the biomass-derived porous carbon powder.
2) 0.45ml of aniline monomer, 1.1g of camphorsulfonic acid, 0.25g of p-methyl dibenzoyl tartaric acid and 0.01ml of chloropropionic acid are fully dissolved in 30ml of deionized water, then 0.4g of biomass-derived porous carbon powder is weighed and immersed into the solution, and after uniform and stable suspension pre-liquid is obtained through ultrasonic and stirring, the ice water bath is cooled to 0-5 ℃.
3) Weighing 0.75g of ferric trichloride, fully dissolving in deionized water, cooling to constant temperature in an ice water bath, dripping into suspension of aniline monomer, camphorsulfonic acid, p-methyl dibenzoyl tartaric acid, chloropropionic acid and biomass-derived porous carbon powder at a constant speed of 3ml/min through a constant pressure dripping funnel, stirring at a slow speed of 100r/min in the dripping process, stopping stirring after dripping, standing in an ice water bath for reaction for 24 hours, filtering, washing, centrifuging, and freeze-drying to obtain the chiral polyaniline/biomass-derived porous carbon composite wave absorbing material.
Wave absorbing performance: based on the coaxial reflection/transmission method, a vector network analyzer is adopted to test the wave absorbing performance of the polyaniline/biomass derived porous carbon composite material at the frequency of 2-18 GHz. The sample size was: the outer diameter is 7.00mm, the inner diameter is 3.00mm, and the thickness is 2.00mm. The paraffin matrix and the polyaniline/biomass derived porous carbon composite wave-absorbing material are uniformly mixed according to the mass ratio of 4:1, and then pressed into a coaxial circular ring shape by using a specific die for testing. When the thickness of the material is 2mm, the minimum reflection loss value can reach-41.92 dB, and the effective absorption bandwidth can reach 4.06GHz.
Comparative example 1
A chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof comprise the following steps:
1) Repeatedly cleaning peanut shells to remove surface impurities, drying, crushing, sieving with a 50-mesh sieve, immersing in KOH solution with the concentration of 1mol/L, carrying out ultrasonic vibration for 30min, standing for 12h, and then filtering and drying.
2) Placing the obtained biomass powder into a tube furnace, and adding the biomass powder into N 2 Calcining under atmosphere protection, wherein the temperature rising rate is 5 ℃/min, the calcining temperature is 750 ℃, the heat preservation time is 2h, naturally cooling to room temperature, grinding, and hydrochloric acidWashing with water for multiple times, and freeze-drying to obtain biomass-derived porous carbon powder.
3) 0.5ml of aniline monomer is fully dissolved in 50ml of deionized water, then 0.5g of biomass-derived porous carbon powder is weighed and immersed into the solution, and after uniform and stable suspension pre-liquid is obtained through ultrasonic and stirring, the ice water bath is cooled to 0-5 ℃.
4) 1.25g of ammonium persulfate is weighed and fully dissolved in 20ml of deionized water, after being cooled to constant temperature by an ice water bath, the ammonium persulfate is dropwise added into suspension of aniline monomer and biomass derived porous carbon powder at a constant speed of 3ml/min through a constant pressure dropping funnel, the slow stirring is carried out at a speed of 100r/min in the dropping process, after the dropping is finished, the stirring is stopped, the mixture is placed in the ice water bath for standing reaction for 24 hours, and then the mixture is filtered, washed, centrifuged and freeze-dried to prepare the chiral polyaniline/biomass derived porous carbon composite wave absorbing material.
Wave absorbing performance: based on the coaxial reflection/transmission method, a vector network analyzer is adopted to test the wave absorbing performance of the polyaniline/biomass derived porous carbon composite material at the frequency of 2-18 GHz. The sample size was: the outer diameter is 7.00mm, the inner diameter is 3.00mm, and the thickness is 2.00mm. The paraffin matrix and the polyaniline/biomass derived porous carbon composite wave-absorbing material are uniformly mixed according to the mass ratio of 4:1, and then pressed into a coaxial circular ring shape by using a specific die for testing. When the thickness of the material is 1.6mm, the minimum reflection loss value can reach-21.36 dB, and the effective absorption bandwidth can reach 2.88GHz.
Comparative example 2
A chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and a preparation method thereof comprise the following steps:
1) Repeatedly cleaning peanut shells to remove surface impurities, drying, crushing, sieving with a 50-mesh sieve, immersing in KOH solution with the concentration of 1mol/L, carrying out ultrasonic vibration for 30min, standing for 12h, and then filtering and drying.
2) Placing the obtained biomass powder into a tube furnace, and adding the biomass powder into N 2 Calcining under atmosphere protection, wherein the temperature rising rate is 5 ℃/min, the calcining temperature is 750 ℃, the heat preservation time is 2h, grinding after naturally cooling to room temperature, and freeze-drying after hydrochloric acid washing and multiple water washing to obtain biomassAnd (3) derivatizing the porous carbon powder.
3) 0.5ml of aniline monomer and 1.16g of camphorsulfonic acid are fully dissolved in 50ml of deionized water to prepare the biomass-derived porous carbon powder, then 0.5g of biomass-derived porous carbon powder is weighed and immersed into the solution, and after uniform and stable suspension pre-liquid is obtained through ultrasonic and stirring, the solution is cooled to 0-5 ℃ through ice water bath.
4) 1.25g of ammonium persulfate is weighed and fully dissolved in 20ml of deionized water, after being cooled to constant temperature by an ice water bath, the ammonium persulfate is dropwise added into suspension of aniline monomer, camphorsulfonic acid and biomass-derived porous carbon powder at a constant speed of 3ml/min by a constant pressure dropping funnel, the suspension is slowly stirred at a speed of 100r/min in the dropping process, stirring is stopped after the dropping is finished, the mixture is placed in the ice water bath for standing reaction for 24 hours, and then the mixture is filtered, washed, centrifuged and freeze-dried to prepare the chiral polyaniline/biomass-derived porous carbon composite wave absorbing material.
Wave absorbing performance: based on the coaxial reflection/transmission method, a vector network analyzer is adopted to test the wave absorbing performance of the polyaniline/biomass derived porous carbon composite material at the frequency of 2-18 GHz. The sample size was: the outer diameter is 7.00mm, the inner diameter is 3.00mm, and the thickness is 2.00mm. The paraffin matrix and the polyaniline/biomass derived porous carbon composite wave-absorbing material are uniformly mixed according to the mass ratio of 4:1, and then pressed into a coaxial circular ring shape by using a specific die for testing. When the thickness of the material is 1.7mm, the minimum reflection loss value can reach-33.68 dB, and the effective absorption bandwidth can reach 3.8GHz.
It is clear from comparative example 1 that the wave-absorbing performance of the finally produced material is significantly reduced without adding a composite inducer during the production of the wave-absorbing material, and that the wave-absorbing material is significantly improved by adding only the inducer main body and no additive during the production of the wave-absorbing material, but is still lower than that of examples 1 to 4. It can be seen from this: under the unique induction of the chiral compound inducer, the chiral compound inducer and the initiator are synergistic, the polyaniline main chain preferentially adopts a spiral configuration to obtain chiral polyaniline and is attached to the surface of the biomass-derived porous carbon, so that the chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material is obtained. The chiral polyaniline can show special optical rotation and circular dichroism due to the unique supercoiled structure, and generates cross polarization coupling effect under the action of alternating electromagnetic field, so that the chiral polyaniline has multiple electromagnetic wave loss mechanism, the effective regulation and control of wave absorbing performance can be realized by adjusting chiral parameters, and compared with the regulation of electromagnetic parameters, the impedance matching can be realized more easily.
Claims (6)
1. A preparation method of a chiral polyaniline/biomass derived porous carbon composite wave-absorbing material is characterized by comprising the following steps of: carbonizing a biomass material at high temperature to prepare biomass-derived porous carbon, and polymerizing the biomass-derived porous carbon under the combined action of a chiral compound inducer and an initiator to form chiral polyaniline on the surface of the biomass-derived porous carbon to prepare the composite wave-absorbing material; the method specifically comprises the following steps:
s1: removing impurities from biomass materials, crushing, immersing the biomass materials into KOH solution, and filtering and drying to obtain biomass powder for later use;
s2: calcining the biomass powder obtained in the step S1 under inert atmosphere, naturally cooling to room temperature after calcining, grinding, washing, and freeze-drying to obtain biomass-derived porous carbon powder for later use;
s3: immersing the biomass-derived porous carbon powder prepared in the step S2 into an aqueous solution of an aniline monomer and a chiral compound inducer to prepare a suspension pre-solution, and cooling to 0-5 ℃;
s4: dissolving an initiator in deionized water, then dropwise adding the solution into the suspension pre-solution prepared in the step S3, and obtaining the chiral polyaniline/biomass derived porous carbon composite wave-absorbing material through filtration, washing, centrifugation and freeze drying; the chiral compound inducer consists of a chiral compound inducer main body and a compound additive, wherein the mass ratio of the inducer main body to the compound additive is 10:1-10:3, the chiral compound inducer main body is camphorsulfonic acid, and the compound additive is one or any mixture of mandelic acid, p-methyl dibenzoyl tartaric acid, dibenzoyl tartaric acid or chloropropionic acid;
in the step S3, the mass ratio of the aniline monomer to the chiral compound inducer is 1:1-1:4;
in the step S4, the initiator is ammonium persulfate, ferric trichloride, potassium permanganate or hydrogen peroxide, and the ratio of the initiator to the mass of the aniline monomer in the suspension pre-solution is 1:1-1:1.5.
2. The method for preparing the chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material according to claim 1, wherein the method comprises the following steps: in the step S1, the biomass material refers to crop straw or shell waste, wherein the crop straw is straw of corn, sorghum, sunflower or wheat, and the shell waste is shell of nuts.
3. The method for preparing the chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material according to claim 1, wherein the method comprises the following steps: in the step S1, the biomass material is crushed and then passes through a 20-300 mesh sieve, the concentration of KOH solution is 0.5-3mol/L, and after the biomass material is immersed in the KOH solution, the biomass material is subjected to ultrasonic vibration for 10-30min and then is kept stand for 3-12h.
4. The method for preparing the chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material according to claim 1, wherein the method comprises the following steps: in the step S2, the biomass powder is calcined in a tube furnace, the temperature rising rate in the calcining process is 2-15 ℃/min, the calcining temperature is 500-800 ℃, and the heat preservation time is 1-5h.
5. The method for preparing the chiral polyaniline/biomass-derived porous carbon composite wave-absorbing material according to claim 1, wherein the method comprises the following steps: in the step S4, the dripping speed of the aqueous solution of the initiator is 1-10ml/min, the dripping is carried out at the stirring speed of 50-300r/min, and the reaction is carried out for 10-24h after the dripping is finished.
6. A chiral polyaniline/biomass derived porous carbon composite wave-absorbing material is characterized in that: a process according to any one of claims 1 to 5.
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