CN105923622A - Polyacrylonitrile nanofiber/polyimide-based carbon aerogel adsorption material and preparation method thereof - Google Patents
Polyacrylonitrile nanofiber/polyimide-based carbon aerogel adsorption material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of carbon adsorption materials, and particularly relates to a polyacrylonitrile nanofiber/polyimide-based carbon aerogel adsorption material and a preparation method thereof. According to the polyacrylonitrile nanofiber/polyimide-based carbon aerogel adsorption material, electrostatic spinning polyacrylonitrile nanofibers and water-soluble polyamide acid serve as raw materials. The preparation process of the polyacrylonitrile nanofiber/polyimide-based carbon aerogel adsorption material includes the steps that firstly, polyacrylonitrile nanofibers are prepared through the electrospinning technology; then, pre-oxidized polyacrylonitrile fibers are obtained through further pre-oxidation; then, electrospun polyacrylonitrile nanofibers and water-soluble polyamide acid are uniformly dispersed through high-speed stirring; composite carbon aerogel is prepared through the freeze-drying technology, the thermal imidization technology and the high-temperature carbonization technology. The obtained carbon aerogel adsorption material is uniform in pore size distribution, large in specific area, high in strength, small in density and excellent in performance and can be widely applied to the fields of sewage treatment, air cleaning and the like.
Description
Technical field
The invention belongs to carbon adsorbing material technical field, it is specifically related to a kind of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material and preparation method thereof, described carbon aerogels adsorbing material pore-size distribution is homogeneous, specific surface area is big, intensity is high, density is little, it is the adsorbing material of a class excellent performance, the field such as sewage disposal, air cleaning can be widely used in.
Background technology
In recent years; the air pollution, the water that increasingly sharpen pollute, soil pollution makes the environmental protection consciousness of people constantly strengthen; especially after the universalness of PM2.5 concept, material development person puts into searching one after another, prepares the on of the new material for environmental conservation and improvement.Wherein, adsorbing material has the advantages such as high-specific surface area, high porosity, structure-controllable, has quite varied application in the field such as sewage disposal, air cleaning.Activated carbon is one of commercially available adsorbing material currently mainly, but owing to its internal structure is fine and close, adsorbance is relatively low.Therefore, the internal material with carbon element more loose porous, that porosity is bigger of exploitation is focus and the difficult point of current research.
Carbon aerogels is the carbon adsorbing material of the class excellent combination property that developed recently gets up.Research finds, the performance of carbon aerogels is closely related with its internal loose structure, how by the microstructure of material carrying out appropriate design and regulating and controlling the key being to promote carbon aerogels combination property further.But, the microstructure of current most of carbon aerogels is the most single, such as: the carbon fiber aeroge that is made up of one-dimensional carbon fiber merely, the graphene carbon aeroge etc. being made up of two-dimensional graphene.Therefore, how the nano material (such as one-dimensional carbon fiber, two-dimensional sheet carbon) of different dimensions being carried out high efficiency composition is one of important development direction preparing high performance carbon aeroge.
Therefore, the present invention is with Static Spinning polyacrylonitrile 1-dimention nano fiber and water miscible polyamic acid macromolecule as presoma, by technical processs such as pre-oxidation, high-speed stirred, lyophilization, hot imidization, carbonizations, it is successfully prepared a kind of carbon aerogels material being made up of one-dimensional carbon nano-fiber and two-dimensional sheet carbon.This polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material mainly has the advantage that primary solvent used in (1) this carbon aerogels adsorbing material preparation process is water, and therefore this technique does not the most produce pollution to environment；(2) this carbon aerogels adsorbing material is made up of two-dimensional sheet carbon and one-dimensional carbon nano-fiber, and carbon nano-fiber crosses between two-dimensional sheet carbon, serve the effect of mutually support, this not only substantially increases the mechanical property that material is overall, and the existence of this special construction also improves material overall " siphonic effect ", be greatly improved for absorption property more most of one-component carbon aerogels material of making this carbon aerogels.
Summary of the invention
It is an object of the invention to provide polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material of a kind of preparation process environmental friendliness, excellent performance and preparation method thereof.
The preparation method of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material that the present invention proposes, specifically comprises the following steps that
(1) certain density polyacrylonitrile (PAN) spinning liquid under agitation, is prepared；
(2) by method of electrostatic spinning, PAN nanofiber is prepared；
(3) temperature programming under air conditions, the PAN nanofiber preparing step (2) pre-oxidizes, and must arrive surface and have hydrophilic preoxidised polyacrylonitrile (the being designated as o-PAN) nanofiber of oxygen-containing functional group；
(4) by the o-PAN nanofiber dispersion of step (3) in deionized water, homodisperse dispersion liquid after high-speed stirred, is obtained；
(5) water-soluble polyamic acid (PAA) is dissolved in deionized water, after stirring, obtain polyamic acid solution；
(6), after being mixed by the solution of step (4) and step (5), further high-speed stirred obtains the blended dispersion liquid of homodisperse o-PAN nanofiber and PAA；
(7) it is solid by the freezing in refrigerator or liquid nitrogen of the dispersion liquid of step (6) gained, lyophilization in freezer dryer subsequently, obtain polyacrylonitrile nanofiber/polyamic acid aeroge, be designated as o-PAN/PAA；
(8) utilize Temperature Programmed Processes, the polyacrylonitrile nanofiber/polyamic acid aeroge of step (7) gained is carried out hot imidization and carbonization, obtains polyacrylonitrile nanofiber/polyimide-based carbon aerogels, be designated as oP.
In step of the present invention (1), the solvent used by polyacryl-nitrile spinning fluid isN,N-dimethylformamide, concentration (mass fraction) is 10% ~ 15%.
In step of the present invention (2), described electrostatic spinning process parameter is: voltage is 15 ~ 20 kV, spinning vessel used be pinhole diameter be the 5 mL plastic injectors of 0.5 mm, flow velocity is 0.2 ~ 0.3 mm/min, and receiving range is 10 ~ 20 cm.
In step of the present invention (3), described programmed rate is 1 ~ 2 DEG C/min, keeps 1.5-2.5 h(preferably to keep 2 h) after rising to platform temperature 230 ~ 280 DEG C.
In step of the present invention (4), realizing the high-speed stirred of the polyacrylonitrile nanofiber of pre-oxidation by the refiner that model is IKA T25, mixing speed 15000 ~ 21000 r/min, preferably mixing speed are 18000 r/min, mixing time be 20 ~ 40 min, preferably mixing time be 30 min.
In step of the present invention (5), the preparation method of described water-soluble polyamic acid is with patent CN104355302A.
In step of the present invention (5), the diamine monomer of described synthesis of polyimides include p-phenylenediamine (PPDA), 4,4 ' diaminodiphenyl ethers (ODA), binary anhydride monomer includes pyromellitic acid anhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA) or diphenyl ether tetracarboxylic dianhydride (ODPA).
In step of the present invention (5), the polar solvent of described synthesis of polyimides includesN,N-dimethyl acetylamide,N-methyl pyrrolidone,N,N-dimethylformamide.
In step of the present invention (6), described dispersion liquid total solid content is 2 ~ 4%, and the mass fraction of PAA is 35 ~ 100%(preferably 35 ~ 95%).
In step of the present invention (8), described hot imidization process is: heated up at nitrogen atmosphere Program by the polyacrylonitrile nanofiber/polyamic acid aeroge obtained, design parameter is as follows: rise to 300 DEG C with the heating rate (the preferably heating rate of 2 DEG C/min) of 1.5-2.5 DEG C/min from room temperature, and respectively at 100 DEG C, 200 DEG C, 300 DEG C keep 0.5 h, 0.5 h, are naturally down to room temperature after 1 h.
In step of the present invention (8), described carbonisation is: heated up at nitrogen atmosphere Program by the polyacrylonitrile nanofiber after hot imidization/polyamic acid aeroge, design parameter is as follows: with the heating rate (the preferably heating rate of 5 DEG C/min) of 4-6 DEG C/min from room temperature to 800 ~ 1400 DEG C, keep 0.5 ~ 2h, be the most naturally down to room temperature.
Accompanying drawing 1 is the preparation process schematic diagram of polyacrylonitrile nanofiber/polyimide-based carbon aerogels.
Polyacrylonitrile nanofiber prepared by the present invention/polyimide-based carbon aerogels material, pore-size distribution is homogeneous, specific surface area is big, intensity is high, density is little, is the adsorbing material of a class excellent performance, can be widely used in the field such as sewage disposal, air cleaning.
Using scanning electron microscope (SEM), transmission electron microscope (TEM), electronic balance to characterize structure and morphology and the absorption property of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material that the present invention is obtained, its result is as follows:
(1) SEM test result shows: polyacrylonitrile nanofiber/polyimide-based carbon aerogels prepared in the present invention is made up of one-dimensional carbon nano-fiber and two-dimensional sheet carbon, present loose structure, and be interconnected between hole, inside has carbon nano-fiber to intert, thus forms specific ordered 3 D structure.This special construction construct the specific surface area substantially increasing material with carbon element, the absorption for organic pollution provides more storage space, and the raising to polyacrylonitrile nanofiber/polyimide-based carbon aerogels performance plays a key effect, and sees accompanying drawing 2；
(2) TEM test result shows: the internal structure of polyacrylonitrile nanofiber/polyimide-based carbon aerogels prepared in the present invention can be embodied from TEM more fully, find that one-dimensional carbon nano-fiber interts and mistake from two-dimensional sheet carbon inside, obtain the polyacrylonitrile nanofiber/polyimide-based carbon aerogels of height hydridization, see accompanying drawing 3；
(3) absorption test result shows, prepared polyacrylonitrile nanofiber/polyimide-based carbon aerogels all has preferable adsorption to common organic solvents and oily matter.Result of study shows, polyacrylonitrile nanofiber/polyimide-based carbon aerogels has reached 20-62 times of own wt to the adsorbance of different material, pump oil wherein shows the most excellent absorption property (reaching 62 times of own wt), sees accompanying drawing 4.This mainly can give the credit to " siphonic effect " of the loose structure within carbon aerogels and carbon nano-fiber.Additionally, the cycle performance of polyacrylonitrile nanofiber/polyimide-based carbon aerogels is detected, find that it all shows the stable circulation performance of excellence to ethanol and acetone.After 5 circulation absorptions, its adsorbance is held in more than the 90% of initial adsorbance；
(4) rate of adsorption test result shows, prepared polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material has all shown the characteristic of quick adsorption to heptane and chloroform, find its will be able to bubble through the water column in 9 s on heptane all adsorb totally, also quickly demersal chloroform solution can be dripped off in 1.5 s full absorption.This all illustrates the absorption property that polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material is excellent, sees accompanying drawing 5；
(5) polyacrylonitrile nanofiber prepared by/polyimide-based carbon aerogels adsorbing material is met fire after absorption ethanol and can be burnt immediately, and along with the consumption flame of ethanol constantly weakens until extinguishing.After fray-out of flame, polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material, not by any destruction, this also illustrates this adsorbing material and has the most excellent stable circulation performance, participate in accompanying drawing 6.
Compared with prior art, its remarkable advantage is as follows for the present invention:
(1) use electrostatic spinning technique to prepare the presoma of carbon nano-fiber, substantially increase yardstick controllability prepared by material；
(2) preparation process is simple, easily operated, and carries out under the conditions of water system, is a kind of Green Chemistry preparation method；
(3) it is connected with each other by running through structure between one-dimensional carbon nano-fiber and two-dimensional sheet carbon, not only increases integrally-built stability, its mechanical property is greatly improved, and increases the specific surface area of material so that it is show more excellent absorption property.
Accompanying drawing explanation
Fig. 1 is polyacrylonitrile nanofiber in the present invention/polyimide-based carbon aerogels preparation process schematic diagram.
Fig. 2 is the SEM photograph of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material prepared in the present invention.
Fig. 3 is the TEM photo of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material prepared in the present invention.
Fig. 4 is the absorption property test result of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material prepared in the present invention: the adsorbance to different solvents.
Fig. 5 is polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material test result to the different solvents rate of adsorption prepared in the present invention.Wherein, (a) is polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material rate of adsorption photo to heptane；B () is polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material rate of adsorption photo to chloroform.
Fig. 6 is the polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material prepared in present invention combustion experiment photo after absorption ethanol.
Detailed description of the invention
Below in conjunction with instantiation, the present invention is expanded on further, it should be appreciated that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various change or amendment by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1 ,The present embodiment comprises the following steps:
Weigh 3 g polyacrylonitrile (PAN) powder to be mixed in 30 mL DMF, stir 6 h at room temperature and obtain the polyacrylonitrile spinning solution of face light yellow complexion.By electrostatic spinning technique, above-mentioned solution being spun into nanofiber, design parameter is: voltage is 18 kV, spinning vessel used be pinhole diameter be the 5 mL plastic injectors of 0.5 mm, flow velocity is 0.2 mm/min, and receiving range is 15 cm, and the spinning time is 1 h.Deposition polyacrylonitrile nanofiber film on the collector is carried out pre-oxidation treatment under temperature programming control, obtain the polyacrylonitrile nanofiber (o-PAN) of pre-oxidation, design parameter is: heating rate is 2 DEG C/min, keeps 2 h after rising to platform temperature 250 DEG C.
By 1.95 g above-mentioned o-PAN nanofiber dispersion in 50 mL deionized waters, high-speed stirred 30 min under the mixing speed of 18000 r/min, obtain homodisperse suspension (1).1.05 g water-soluble polyamic acids are dissolved in 50 mL deionized waters, under standard machinery stirs, obtain polyamic acid solution.Being mixed with polyamic acid solution by suspension (1) subsequently, under the mixing speed of 18000 r/min, further high-speed stirred 10 min obtains the mixing suspension of polyacrylonitrile nanofiber and polyamic acid.It is solid by the freezing in refrigerator or liquid nitrogen of this mixing suspension, lyophilization 48 h in freezer dryer subsequently, obtain polyacrylonitrile nanofiber/polyamic acid aeroge, be designated as o-PAN/PAA-35.
Subsequently, above-mentioned polyacrylonitrile nanofiber/polyamic acid aeroge is carried out hot imidization and carbonization, obtain polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material, be designated as oP-35.The specific procedure of hot imidization is: rise to 300 DEG C with the heating rate of 2 DEG C/min from room temperature, and respectively at 100 DEG C, 200 DEG C, 300 DEG C keep 0.5 h, 0.5 h, are naturally down to room temperature after 1 h.The specific procedure of carbonization is: be naturally down to room temperature with the heating rate of 5 DEG C/min after room temperature to 800 DEG C, holding 1h.
Embodiment 2 ,The present embodiment comprises the following steps:
Weigh 3 g polyacrylonitrile (PAN) powder to be mixed in 30 mL DMF, stir 6 h at room temperature and obtain the polyacrylonitrile spinning solution of face light yellow complexion.By electrostatic spinning technique, above-mentioned solution being spun into nanofiber, design parameter is as follows: voltage is 18 kV, spinning vessel used be pinhole diameter be the 5 mL plastic injectors of 0.5 mm, flow velocity is 0.2 mm/min, and receiving range is 15 cm, and the spinning time is 1 h.Deposition polyacrylonitrile nanofiber film on the collector is carried out pre-oxidation treatment to above-mentioned fibrous membrane under temperature programming control, obtain the polyacrylonitrile nanofiber (o-PAN) of pre-oxidation, design parameter is: heating rate is 2 DEG C/min, keeps 2 h after rising to platform temperature 250 DEG C.
By 1.5 g above-mentioned o-PAN nanofiber dispersion in 50 mL deionized waters, high-speed stirred 30 min under the mixing speed of 18000 r/min, obtain homodisperse suspension (1).1.5 g water-soluble polyamic acids are dissolved in 50 mL deionized waters, under standard machinery stirring, obtain polyamic acid solution.Being mixed with polyamic acid solution by suspension (1) subsequently, under the mixing speed of 18000 r/min, further high-speed stirred 10 min obtains the mixing suspension of polyacrylonitrile nanofiber and polyamic acid.It is solid by the freezing in refrigerator or liquid nitrogen of this mixing suspension, lyophilization 48 h in freezer dryer subsequently, obtain polyacrylonitrile nanofiber/polyamic acid aeroge, be designated as o-PAN/PAA-50.
Subsequently, above-mentioned polyacrylonitrile nanofiber/polyamic acid aeroge is carried out hot imidization and carbonization, obtain polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material, be designated as oP-50.The specific procedure of hot imidization is: rise to 300 DEG C with the heating rate of 2 DEG C/min from room temperature, and respectively at 100 DEG C, 200 DEG C, 300 DEG C keep 0.5 h, 0.5 h, are naturally down to room temperature after 1 h.The specific procedure of carbonization is: be naturally down to room temperature with the heating rate of 5 DEG C/min after room temperature to 800 DEG C, holding 1h.
Embodiment 3 ,The present embodiment comprises the following steps:
3 g water-soluble polyamic acids are dissolved in 100 mL deionized waters, under standard machinery stirs, obtain polyamic acid solution.Being solid by polyamic acid solution freezing in refrigerator or liquid nitrogen, lyophilization 48 h in freezer dryer, obtains polyamic acid aeroge, is designated as PAA subsequently.
Subsequently, above-mentioned polyamic acid aeroge is carried out hot imidization and carbonization, obtain polyimide-based carbon aerogels adsorbing material, be designated as oP-100.The specific procedure of hot imidization is: rise to 300 DEG C with the heating rate of 2 DEG C/min from room temperature, and respectively at 100 DEG C, 200 DEG C, 300 DEG C keep 0.5 h, 0.5 h, are naturally down to room temperature after 1 h.The specific procedure of carbonization is: be naturally down to room temperature with the heating rate of 5 DEG C/min after room temperature to 800 DEG C, holding 1h.
Claims (8)
1. the preparation method of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material, it is characterised in that specifically comprise the following steps that
(1) under agitation, preparation polyacrylonitrile (PAN) spinning liquid；
(2) by method of electrostatic spinning, PAN nanofiber is prepared；
(3) by temperature programming under air conditions, the PAN nanofiber preparing step (2) pre-oxidizes, and must arrive surface and have hydrophilic preoxidised polyacrylonitrile (the being designated as o-PAN) nanofiber of oxygen-containing functional group；
(4) by the o-PAN nanofiber dispersion of step (3) in deionized water, homodisperse dispersion liquid after high-speed stirred, is obtained；
(5) water-soluble polyamic acid (PAA) is dissolved in deionized water, after stirring, obtain polyamic acid solution；
(6) being mixed by the solution of step (4) and step (5), then high-speed stirred obtains the blended dispersion liquid of homodisperse o-PAN nanofiber and PAA further；
(7) it is solid by the freezing in refrigerator or liquid nitrogen of the blended dispersion liquid of step (6) gained, lyophilization in freezer dryer subsequently, obtain polyacrylonitrile nanofiber/polyamic acid aeroge, be designated as o-PAN/PAA；
(8) utilize Temperature Programmed Processes, the polyacrylonitrile nanofiber/polyamic acid aeroge of step (7) gained is carried out hot imidization and carbonization, obtains polyacrylonitrile nanofiber/polyimide-based carbon aerogels, be designated as oP.
The preparation method of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material the most according to claim 1, it is characterised in that the solvent used by polyacryl-nitrile spinning fluid described in step (1) isN,N-dimethylformamide, the mass concentration of polyacryl-nitrile spinning fluid is 10% ~ 15%.
The preparation method of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material the most according to claim 1, it is characterized in that in step (2), electrostatic spinning process parameter is: voltage is 15 ~ 20 kV, spinning vessel used be pinhole diameter be the 5 mL plastic injectors of 0.5 mm, flow velocity is 0.2 ~ 0.3
Mm/min, receiving range is 10 ~ 20 cm.
The preparation method of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material the most according to claim 3, it is characterized in that the programmed rate described in step (3) is 1 ~ 2 DEG C/min, after rising to platform temperature 230 ~ 280 DEG C, keep 1.5-2.5 h.
5., according to the preparation method of polyacrylonitrile nanofiber described in claim 1,2 or 4/polyimide-based carbon aerogels adsorbing material, it is characterised in that in step (4), mixing speed is 15000 ~ 21000
R/min, mixing time is 20 ~ 40 min.
The preparation method of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material the most according to claim 5, it is characterised in that in step (6), described dispersion liquid total solid content is 2 ~ 4%, and the mass fraction of PAA is 35 ~ 100%.
The preparation method of polyacrylonitrile nanofiber/polyimide-based carbon aerogels adsorbing material the most according to claim 6, it is characterized in that in step (8), described hot imidization process is: heated up at nitrogen atmosphere Program by the polyacrylonitrile nanofiber/polyamic acid aeroge obtained, design parameter is as follows: rise to 300 DEG C with the heating rate of 1.5-2.5 DEG C/min from room temperature, and respectively at 100 DEG C, 200 DEG C, 300 DEG C of holding 0.5 h, 0.5
H, 1 h, be down to room temperature the most naturally；
Described carbonisation is: heated up at nitrogen atmosphere Program by the polyacrylonitrile nanofiber after hot imidization/polyamic acid aeroge, design parameter is as follows: with the heating rate of 4-6 DEG C/min from room temperature to 800 ~ 1400 DEG C, keep 0.5 ~ 2h, be the most naturally down to room temperature.
8. the polyacrylonitrile nanofiber obtained by the described preparation method of one of claim 1-7/polyimide-based carbon aerogels adsorbing material, its pore-size distribution is homogeneous, specific surface area is big, intensity is high, density is little.
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