CN107051382B - Porous carbon nanofiber material for carbon dioxide adsorption and preparation method thereof - Google Patents
Porous carbon nanofiber material for carbon dioxide adsorption and preparation method thereof Download PDFInfo
- Publication number
- CN107051382B CN107051382B CN201710266028.3A CN201710266028A CN107051382B CN 107051382 B CN107051382 B CN 107051382B CN 201710266028 A CN201710266028 A CN 201710266028A CN 107051382 B CN107051382 B CN 107051382B
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- adsorption
- carbon
- porous carbon
- nanofiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon dioxide (CO)2) A porous carbon nanofiber material for adsorption and a preparation method thereof belong to the field of nanomaterials and environmental management. The preparation method comprises the following steps: screening a carbon precursor and an organic pore-forming agent by a thermogravimetric method; preparing a spinning solution; obtaining a composite nanofiber membrane by an electrostatic spinning method; and (3) obtaining the porous carbon nanofiber material with ultrahigh specific surface area through low-temperature preoxidation and high-temperature carbonization treatment. The method can avoid the activation step of the traditional carbon material preparation, has low cost and simple preparation process, and can selectively regulate and control the pore structure. The invention provides a high-efficiency carbon dioxide adsorbent, which has ultrahigh specific surface area and ultrahigh porosity; the carbon dioxide adsorbent has a large number of micropores and ultramicropores, and is very beneficial to carbon dioxide adsorption, so that the carbon dioxide adsorption capacity is large; meanwhile, the material has the advantages of mild desorption conditions, reusability and the like, and has good application prospect and environmental improvement benefit in the field of carbon dioxide capture.
Description
Technical Field
The invention discloses a porous carbon nanofiber material for carbon dioxide adsorption and a preparation method thereof, and belongs to the field of nanomaterials and environmental management.
Background
In recent years, the greenhouse effect is a hot issue of concern in the environmental field, mainly caused by the enrichment of greenhouse gases in the atmosphere. Carbon dioxide is an important component of greenhouse gas, and with the increasing frequency of human economic activities and the large consumption of fossil fuels, the concentration of carbon dioxide in the atmosphere increases year by year; the influence of greenhouse effect on global climate is more and more serious, which causes abnormal phenomena such as global climate warming and extreme climate frequent occurrence; therefore, reducing carbon dioxide emissions and having an extremely important significance for carbon dioxide capture.
The carbon material is used as a common solid adsorbent, has the characteristics of high specific surface, high porosity, good thermal stability, good chemical stability and the like, and has a wide application prospect in the field of carbon dioxide adsorption; a large number of scholars have engaged in relevant research at home and abroad, and reports the application of various carbon materials including activated carbon, carbon nanofiber, carbon nanotube, graphene and the like in the field of carbon dioxide adsorption, and good adsorption effects are obtained, such as: james M. Tour et al (ACS appl. mater. Interfaces, 2015, 7, 1376-A preparation method and application of Carbon dioxide adsorbent material, namely, preparing an activated Carbon material by activating a Carbon precursor to adsorb Carbon dioxide, and preparing Carbon nanofibers by Ki Bong Lee and the like (Carbon, 99, 2016, 354 and 360) and Jun Liu and the like (Chemical Engineering Journal, 276, 2015 and 44-50) through an electrostatic spinning technology to adsorb Carbon dioxide; although these materials are on CO2The carbon dioxide adsorbent has remarkable adsorption effect, but most of the carbon dioxide adsorbents developed at the present stage need to be prepared by a physical activation method or a chemical activation method. The activation process related to the preparation method has complex process and difficult control of conditions; the activating reagent has strong corrosivity and high equipment maintenance cost; and secondary pollution is easy to generate after activation, which causes a new environmental management problem.
The hybrid electrostatic spinning method is a method for preparing a composite nanofiber membrane by performing hybrid electrostatic spinning on two or more immiscible macromolecules; the method mainly draws polymer solution into filaments through high-voltage electrostatic acting force to form a nanofiber membrane; the prepared nano-fibers have uniform size and the diameter is in the range of dozens of nanometers to several micrometers; as is well known, the electrostatic spinning nanofiber membrane can be used for preparing a carbon nanofiber material with high specific surface area through low-temperature pre-oxidation, high-temperature carbonization, high-temperature activation and other treatments; for the carbon nanofiber material prepared by adopting the composite electrostatic spinning nanofiber membrane, due to the fact that the physical properties of two or more mixed polymers are different, one or more of the two or more polymers can be easily decomposed and removed in the subsequent heat treatment process (pre-oxidation and carbonization), and therefore a large number of pores are formed in the generated carbon nanofiber framework, and the specific surface area and the porosity of the material are greatly improved. Therefore, the carbon nanofiber material with high specific surface area and high porosity can be obtained without activating treatment.
The method for preparing the porous carbon nanofiber material by adopting the hybrid electrostatic spinning method and the heat treatment method is widely concerned and becomes a research hotspot in academia and industry; numerous researchers have published relevant research results at home and abroad, such as Jae-Wook Lee and the like (Small, 2007, 91-95), Young Hee Lee and the like (chem. Commun, 2010, 1320-; generally, the method has the problems that the thermally unstable macromolecule is not completely decomposed after heat treatment to generate mass residue, the structure is collapsed to form closed pores and the like, so that the carbon nanofiber material has the problems of low specific surface area, low porosity and the like; meanwhile, the composite electrostatic spinning carbon nanofiber material is mainly applied to electrode materials, and is generally prepared by a coaxial electrostatic spinning method or by adding a doping material so as to improve the mesoporous content and increase the electrochemical activity; however, what plays a key role in the carbon dioxide adsorption performance is the content of micropores and ultramicropores of the material, so that the adsorption capacity of the composite electrostatic spinning carbon nanofiber material containing a large number of mesopores to carbon dioxide is low in the past; therefore, how to prepare the porous carbon nanofiber material with high specific surface area, high micropore and ultramicropore content and good carbon dioxide adsorption performance by using a hybrid electrostatic spinning method and a heat treatment method while avoiding activation treatment is a hotspot and difficulty of current research.
Disclosure of Invention
The invention aims to solve the problems that the composite electrostatic spinning carbon nanofiber material serving as a carbon dioxide adsorbent has low specific surface area, low porosity, low content of micropores and ultramicropores, small carbon dioxide adsorption capacity and the like, and provides a porous carbon nanofiber material for adsorbing carbon dioxide and a preparation method thereof.
The invention provides a high-efficiency carbon dioxide adsorbent which has the characteristics of ultrahigh specific surface area, ultrahigh porosity, controllable pore structure and the like; in particular, the material has a porous structure in which mesopores favor CO2The gas is transported in the material, so that the material has quick adsorptionDynamics; a large number of micropores and ultramicropores are beneficial to carbon dioxide adsorption, so that the carbon dioxide adsorption capacity is large; meanwhile, the adsorption acting force of the material is intermolecular electrostatic acting force, is a typical physical adsorption type material, has the advantages of mild desorption condition, material reutilization and the like, and has good application prospect and environmental management benefit in the field of carbon dioxide capture.
The technical scheme of the invention is as follows: screening out proper macromolecules as a carbon precursor and an organic pore-forming agent reasonably by a thermogravimetric analysis method, preparing composite electrostatic spinning nanofiber by a mixed electrostatic spinning technology, reasonably obtaining and controlling pre-oxidation and carbonization treatment parameters according to thermogravimetric analysis data, and completely removing thermally unstable macromolecules to prepare a high-efficiency carbon dioxide adsorbent with high specific surface area, high porosity, high micropore content and ultramicropore content; the method can avoid activation treatment, has low cost and simple preparation process, and avoids the problem of secondary pollution in the activation process; meanwhile, the pore structure of the prepared material can be reasonably regulated, a large number of micropores and ultramicropores are formed, and the adsorption of carbon dioxide is facilitated; the method specifically comprises the following steps.
(1) Taking a small amount of macromolecules, and analyzing the thermal stability of the target macromolecules at a certain temperature in an analysis gas atmosphere by a thermogravimetric analyzer; the polymer with good thermal stability (mass residue after thermogravimetric analysis) is used as a carbon precursor, and the polymer with poor thermal stability (no mass residue after thermogravimetric analysis) is used as an organic pore-forming agent.
(2) Mixing and dissolving a carbon precursor and an organic pore-forming agent in a certain proportion in an organic solvent to prepare a mixed spinning solution with a certain mass fraction.
(3) And (3) transferring the mixed spinning solution in the step (2) to an injector, and preparing the composite electrostatic spinning nanofiber membrane by using an electrostatic spinning technology.
(4) And (4) placing the composite electrostatic spinning nanofiber membrane obtained in the step (3) in a blast oven, and pre-oxidizing at low temperature in an air atmosphere to obtain pre-oxidized porous nanofibers.
(5) And (4) placing the pre-oxidized porous nanofiber membrane obtained in the step (4) in a carbonization furnace, and carbonizing at high temperature to obtain the porous carbon nanofiber.
The analysis gas atmosphere in the step (1) is N2、O2Or both according to the following weight ratio of 9:1-1:9 proportion of mixed gas; the certain temperature in the step (1) is 200-1000 ℃.
The carbon precursor in the step (2) is one or more of Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), phenolic resin and pitch (pitch).
The organic pore-forming agent in the step (2) is one or more of polymethyl methacrylate (PMMA), Cellulose Acetate (CA), polypropylene pyrrolidone (PVP), polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinyl butyral (PVB) and nylon 6.
The organic solvent in the step (2) is one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), Tetrahydrofuran (THF) and ethanol.
The mass fraction of the mixed spinning solution in the step (2) is 10-30%, wherein the ratio of the carbon precursor to the organic pore-forming agent is 9:1-1: 9.
The electrostatic spinning process conditions in the step (3) are as follows: the static spinning voltage is 10-25kv, the receiving distance is 10-30cm, the flow rate of the spinning solution is 0.5-2ml/min, and the spinning time is 10-30 h.
The pre-oxidation process conditions in the step (4) are as follows: the temperature is 200-300 ℃, the heating rate is 1-10 ℃/min, the processing time is 1-6h, wherein the pre-oxidation temperature and the processing time are determined by thermogravimetric analysis data of the carbon precursor and the organic pore-forming agent.
The carbonization process conditions in the step (5) are as follows: the temperature is 600-1000 ℃, the heating rate is 1-10 ℃, and the processing time is 1-6h, wherein the carbonization temperature and the processing time are determined by thermogravimetric analysis data of the carbon precursor and the organic pore-forming agent.
Compared with the prior carbon dioxide adsorbent, the carbon dioxide adsorbent has the following beneficial effects: (1) the carbon nanofiber prepared by the method is an ultrafine nanofiber (the outer diameter is 100nm-2 mu m) and has an ultra-high specific surfaceVolume (specific surface area 200-2Per g), developed pore structure (pore diameter of 0.1-100nm, pore volume of 0.2-2 cm)3Per g), more micropores (micropore volume of 0.1-1.5 cm)3(iv)/g); (2) the material has a very good adsorption effect on carbon dioxide, a developed porous structure is formed in the pre-oxidation process and the carbonization process, external carbon dioxide gas is favorably diffused in the material, meanwhile, a large number of micropores show a very good adsorption effect on the carbon dioxide, the material shows a good adsorption performance under the condition of low pressure (1 bar), and the adsorption capacity on the carbon dioxide is 1.5-10 mmol/g; (3) the process of adsorbing carbon dioxide by the material is physical adsorption, the adsorption rate is high, the material has small adsorption heat to carbon dioxide, can be desorbed at room temperature, and is favorable for recycling of the material.
Compared with the existing preparation method of the carbon dioxide adsorbent for carbon materials, the preparation method of the invention has the following effective effects: the pore-forming performance is obvious, the complex activation step in the traditional carbon material preparation can be avoided, the cost is low, the preparation process is simple, and the problem of secondary pollution in the activation process is avoided; regulating and controlling pre-oxidation and carbonization treatment parameters reasonably according to thermogravimetric analysis data, and selectively regulating and controlling the pore structure of the prepared material to form a large number of micropores and ultramicropores, which is beneficial to the adsorption of carbon dioxide; the method has the advantages of simple process, low energy consumption, small damage to equipment, contribution to expanded production and high efficiency, energy conservation and environmental friendliness.
Drawings
FIG. 1 is the thermogravimetric plot of PAN and PMMA in example 1.
FIGS. 2-4 are SEM images of PAN/PMMA porous carbon nanofibers from example 1.
FIG. 5 is N of PAN/PMMA porous carbon nanofiber in example 12Adsorption and desorption curve chart.
FIG. 6 is a pore size distribution diagram of the PAN/PMMA porous carbon nanofibers of example 1.
FIG. 7 is CO of PAN/PMMA porous carbon nanofiber in example 12Adsorption profile.
Detailed Description
The following describes a porous carbon nanofiber material for carbon dioxide adsorption and a method for preparing the same according to the present invention in terms of several specific embodiments, it being understood that the following specific embodiments are illustrative and not limiting to the scope of the invention, which is defined by the claims; it will be apparent to those skilled in the art that various changes in the materials selected and in the control parameters of the preparation of these embodiments can be made without departing from the spirit and scope of the invention.
Example 1.
The porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and PMMA as raw materials.
(1) Weighing 20mg of PAN and PMMA polymer powder respectively, placing the PAN and PMMA polymer powder into a crucible respectively, placing the crucible into a thermogravimetric analyzer, and introducing N at the flow rate of 60ml/min2And heating the gas to 1000 ℃ at the heating rate of 5 ℃/min, and automatically recording the weight loss conditions of the two macromolecules by a thermogravimetric analyzer. Its thermogravimetric plot, as shown in FIG. 1; thus, PAN is a carbon precursor and PMMA is an organic pore former.
(2) Weighing PAN and PMMA in a mass ratio of 1:1, adding the mixture into DMF, and continuously stirring the mixture at room temperature until the high polymer is completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 15%.
(3) Transferring the spinning solution prepared in the step (2) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/PMMA composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(4) And (4) placing the electrostatic spinning composite nanofiber membrane obtained in the step (3) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(5) And (3) placing the dried nanofiber membrane obtained in the step (4) in a forced air drying box for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 280 ℃ in air atmosphere, raising the temperature at the rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/PMMA pre-oxidized nanofiber membrane.
(6) Placing the pre-oxidized nano fiber membrane obtained in the step (5) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 1000 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/PMMA porous carbon nanofiber material; the SEM of the obtained sample is shown in figures 2-4, and the outer diameter of the carbon nanofiber is 450 nm; by N2The absorption and desorption tests showed that the specific surface area of the material was 1100.74m according to the BET method analysis shown in FIG. 52The volume of pores of the material is 0.577cm by adopting DFT method analysis3(ii)/g, micropore volume of 0.376 cm3The pore size distribution is shown in FIG. 6.
(7) Weighing 100mg of the porous carbon nanofiber material prepared in example 1, transferring the porous carbon nanofiber material into an adsorption tube, and reacting the porous carbon nanofiber material with high-purity N2Activating for 6 hours at 200 ℃; after activation, the adsorption tube is transferred to a carbon dioxide high-pressure adsorption instrument, the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃ is respectively measured, and the adsorption curve of the porous carbon nanofiber material on carbon dioxide at 0 ℃ and 1bar is shown in fig. 7; the material prepared in example 1 had an adsorption capacity for carbon dioxide of 4.21mmol/g at 0 ℃ and a pressure of 1 bar; the adsorption capacity of the material prepared in example 1 for carbon dioxide at 25 ℃ and 1bar pressure was 3.02 mmol/g.
Example 2.
The porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and PMMA as raw materials.
(1) Weighing PAN and PMMA in a mass ratio of 1:1, adding the mixture into DMF, and continuously stirring the mixture at room temperature until the high polymer is completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 15%.
(2) Transferring the spinning solution prepared in the step (1) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/PMMA composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(3) And (3) placing the electrostatic spinning composite nanofiber membrane obtained in the step (2) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(4) And (3) placing the dried nanofiber membrane obtained in the step (3) in a forced air drying box for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 280 ℃ in air atmosphere, raising the temperature at the rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/PMMA pre-oxidized nanofiber membrane.
(5) Placing the pre-oxidized nano fiber membrane obtained in the step (4) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 800 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/PMMA carbon nanofiber material; the outer diameter of the obtained carbon nanofiber is 450 nm; by N2Adsorption and desorption tests, and the specific surface area of the material is 711.39m by adopting the BET method for analysis2The volume of pores of the material is 0.401cm by adopting DFT method analysis3(ii)/g, micropore volume of 0.206 cm3/g。
(6) Weighing 100mg of the porous carbon nanofiber material prepared in example 2, transferring the porous carbon nanofiber material into an adsorption tube, and reacting the porous carbon nanofiber material with high-purity N2Activating for 6 hours at 200 ℃; after activation, transferring the adsorption tube into a carbon dioxide high-pressure adsorption instrument, and respectively measuring the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃; the adsorption capacity of the material prepared in example 2 for carbon dioxide at 0 ℃ and 1bar pressure was 3.41 mmol/g; the adsorption capacity of the material prepared in example 2 for carbon dioxide at 25 ℃ and a pressure of 1bar was 2.47 mmol/g.
Example 3.
The porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and PMMA as raw materials.
(1) Weighing PAN and PMMA in a mass ratio of 1:1, adding the mixture into DMF, and continuously stirring the mixture at room temperature until the high polymer is completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 15%.
(2) Transferring the spinning solution prepared in the step (1) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/PMMA composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(3) And (3) placing the electrostatic spinning composite nanofiber membrane obtained in the step (2) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(4) And (3) placing the dried nanofiber membrane obtained in the step (3) in a forced air drying box for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 280 ℃ in air atmosphere, raising the temperature at the rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/PMMA pre-oxidized nanofiber membrane.
(5) Placing the pre-oxidized nano fiber membrane obtained in the step (4) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 600 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/PMMA carbon nanofiber material; the outer diameter of the obtained carbon nanofiber is 400 nm; by N2The adsorption and desorption test shows that the specific surface area of the material is 417.55m by adopting a BET method2The volume of the pores of the material is 0.266cm by adopting DFT method analysis3In terms of a volume of micropores, 0.138 cm3/g。
(6) Weighing 100mg of the porous carbon nanofiber material prepared in example 3, transferring the porous carbon nanofiber material into an adsorption tube, and reacting the porous carbon nanofiber material with high-purity N2Activating for 6 hours at 200 ℃; after activation, transferring the adsorption tube into a carbon dioxide high-pressure adsorption instrument, and respectively measuring the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃; the adsorption capacity of the material prepared in example 3 for carbon dioxide at 0 ℃ and 1bar pressure was 2.64 mmol/g; the material prepared in example 3 was at 25 ℃, 1bThe adsorption capacity for carbon dioxide under ar pressure was 2.17 mmol/g.
Example 4.
The porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and PMMA as raw materials.
(1) Weighing PAN and PMMA in a mass ratio of 1:1, adding the mixture into DMF, and continuously stirring the mixture at room temperature until the high polymer is completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 15%.
(2) Transferring the spinning solution prepared in the step (1) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/PMMA composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(3) And (3) placing the electrostatic spinning composite nanofiber membrane obtained in the step (2) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(4) And (3) placing the dried nanofiber membrane obtained in the step (3) in a forced air drying oven for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 240 ℃ in air atmosphere, raising the temperature at a rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/PMMA pre-oxidized nanofiber membrane.
(5) Placing the pre-oxidized nano fiber membrane obtained in the step (4) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 1000 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/PMMA carbon nanofiber material; the outer diameter of the obtained carbon nanofiber is 450 nm; by N2The adsorption and desorption test shows that the specific surface area of the material is 395.12m by adopting a BET method2The volume of pores of the material is 0.203cm by adopting DFT method analysis3In terms of a volume of micropores of 0.156 cm3/g。
(6) Weighing 100mg of the porous carbon nanofiber material prepared in example 4, transferring the porous carbon nanofiber material to an adsorption tube, and purifying the porous carbon nanofiber materialHigh purity N2Activating for 6 hours at 200 ℃; after activation, transferring the adsorption tube into a carbon dioxide high-pressure adsorption instrument, and respectively measuring the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃; the material prepared in example 4 had an adsorption capacity for carbon dioxide of 3.14 mmol/g at 0 ℃ and a pressure of 1 bar; the adsorption capacity of the material prepared in example 4 for carbon dioxide at 25 ℃ and a pressure of 1bar was 2.30 mmol/g.
Example 5.
The porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and PMMA as raw materials.
(1) Weighing PAN and PMMA in a mass ratio of 1:1, adding the mixture into DMF, and continuously stirring the mixture at room temperature until the high polymer is completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 15%.
(2) Transferring the spinning solution prepared in the step (1) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/PMMA composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(3) And (3) placing the electrostatic spinning composite nanofiber membrane obtained in the step (2) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(4) And (3) placing the dried nanofiber membrane obtained in the step (3) in a forced air drying oven for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 300 ℃ in air atmosphere, raising the temperature at the rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/PMMA pre-oxidized nanofiber membrane.
(5) Placing the pre-oxidized nano fiber membrane obtained in the step (4) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 1000 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/PMMA carbon nanofiber material; the outer diameter of the obtained carbon nanofiber is 450 nm; by N2The adsorption and desorption test shows that the specific surface area of the material is 853.17m by adopting a BET method2The volume of the pores of the material is 0.596cm by adopting DFT method analysis3(ii)/g, micropore volume of 0.279cm3/g。
(6) Weighing 100mg of the porous carbon nanofiber material prepared in example 5, transferring the porous carbon nanofiber material into an adsorption tube, and reacting the porous carbon nanofiber material with high-purity N2Activating for 6 hours at 200 ℃; after activation, transferring the adsorption tube into a carbon dioxide high-pressure adsorption instrument, and respectively measuring the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃; the material prepared in example 5 had an adsorption capacity for carbon dioxide of 3.74mmol/g at 0 ℃ and a pressure of 1 bar; the adsorption capacity of the material prepared in example 5 for carbon dioxide at 25 ℃ and a pressure of 1bar was 2.57 mmol/g.
Example 6.
The porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and PVP as raw materials.
(1) Weighing 20mg of PAN and PVP polymer powder respectively, placing the PAN and PVP polymer powder into a crucible respectively, placing the crucible into a thermogravimetric analyzer, and introducing N at the flow rate of 60ml/min2And heating the gas to 1000 ℃ at the heating rate of 5 ℃/min, and automatically recording the weight loss conditions of the two macromolecules by a thermogravimetric analyzer. PAN has mass residue, PVP has no mass residue; thus, PAN acts as a carbon precursor and PVP is an organic pore former.
(2) Weighing PAN and PVP with the mass ratio of 1:1, adding the PAN and the PVP into DMF, and continuously stirring at room temperature until macromolecules are completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 15%.
(3) Transferring the spinning solution prepared in the step (2) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/PVP composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(4) And (4) placing the electrostatic spinning composite nanofiber membrane obtained in the step (3) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(5) And (3) placing the dried nanofiber membrane obtained in the step (4) in a blast drying oven for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 280 ℃ in an air atmosphere, raising the temperature at a rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/PVP pre-oxidized nanofiber membrane.
(6) Placing the pre-oxidized nano fiber membrane obtained in the step (5) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 1000 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/PVP carbon nanofiber material; by N2The adsorption and desorption test shows that the specific surface area of the material is 354.67m by adopting a BET method2The volume of pores of the material is 0.176cm by DFT method analysis3A micropore volume of 0.143 cm/g3/g。
(7) Weighing 100mg of the porous carbon nanofiber material prepared in example 6, transferring the porous carbon nanofiber material into an adsorption tube, and reacting the porous carbon nanofiber material with high-purity N2Activating for 6 hours at 200 ℃; after activation, transferring the adsorption tube into a carbon dioxide high-pressure adsorption instrument, and respectively measuring the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃; the material prepared in example 6 had an adsorption capacity for carbon dioxide of 3.21mmol/g at 0 ℃ and a pressure of 1 bar; the adsorption capacity of the material prepared in example 6 for carbon dioxide at 25 ℃ and a pressure of 1bar was 2.45 mmol/g.
Example 7.
The porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and PVP as raw materials.
(1) Weighing PAN and PVP with the mass ratio of 1:1, adding the PAN and the PVP into DMF, and continuously stirring at room temperature until macromolecules are completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 15%.
(2) Transferring the spinning solution prepared in the step (1) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/PVP composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(3) And (3) placing the electrostatic spinning composite nanofiber membrane obtained in the step (2) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(4) And (3) placing the dried nanofiber membrane obtained in the step (3) in a forced air drying oven for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 280 ℃ in air atmosphere, raising the temperature at the rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/PVP pre-oxidized nanofiber membrane.
(5) Placing the pre-oxidized nano fiber membrane obtained in the step (4) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 800 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/PVP carbon nanofiber material; by N2The adsorption and desorption test shows that the specific surface area of the material is 267.22m by adopting a BET method2The volume of pores of the material is 0.135cm by adopting DFT method analysis3In terms of a volume of micropores, 0.107cm3/g。
(6) Weighing 100mg of the porous carbon nanofiber material prepared in example 7, transferring the porous carbon nanofiber material to an adsorption tube, and reacting the porous carbon nanofiber material with high-purity N2Activating for 6 hours at 200 ℃; after activation, transferring the adsorption tube into a carbon dioxide high-pressure adsorption instrument, and respectively measuring the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃; the material prepared in example 7 had an adsorption capacity for carbon dioxide of 2.54 mmol/g at 0 ℃ and a pressure of 1 bar; the adsorption capacity of the material prepared in example 7 for carbon dioxide at 25 ℃ and a pressure of 1bar was 2.10 mmol/g.
Example 8.
The porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and PVP as raw materials.
(1) Weighing PAN and PVP with the mass ratio of 1:1, adding the PAN and the PVP into DMF, and continuously stirring at room temperature until macromolecules are completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 15%.
(2) Transferring the spinning solution prepared in the step (1) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/PVP composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(3) And (3) placing the electrostatic spinning composite nanofiber membrane obtained in the step (2) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(4) And (3) placing the dried nanofiber membrane obtained in the step (3) in a forced air drying oven for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 280 ℃ in air atmosphere, raising the temperature at the rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/PVP pre-oxidized nanofiber membrane.
(5) Placing the pre-oxidized nano fiber membrane obtained in the step (4) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 600 ℃, the temperature rise rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/PVP carbon nanofiber material; by N2Adsorption and desorption tests, wherein the specific surface area of the material is 157.44m by adopting a BET method2The volume of the pores of the material is 0.0788cm by adopting DFT method analysis3Per g, micropore volume of 0.064cm3/g。
(6) Weighing 100mg of the porous carbon nanofiber material prepared in example 8, transferring the porous carbon nanofiber material to an adsorption tube, and reacting the porous carbon nanofiber material with high-purity N2Activating for 6 hours at 200 ℃; after activation, transferring the adsorption tube into a carbon dioxide high-pressure adsorption instrument, and respectively measuring the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃; the adsorption capacity of the material prepared in example 8 for carbon dioxide at 0 ℃ and 1bar pressure was 2.34 mmol/g; the adsorption capacity of the material prepared in example 8 for carbon dioxide at 25 ℃ and a pressure of 1bar was 2.05 mmol/g.
Example 9.
A porous carbon nanofiber material for carbon dioxide is prepared by taking PAN and CA as raw materials.
(1) Weighing 20mg of PAN and CA polymer powder respectively, placing the PAN and CA polymer powder into a crucible, placing the crucible into a thermogravimetric analyzer, and introducing N at the flow rate of 60ml/min2And heating the gas to 1000 ℃ at the heating rate of 5 ℃/min, and automatically recording the weight loss conditions of the two macromolecules by a thermogravimetric analyzer. PAN has mass residuals, CA has no mass residuals; thus, PAN is a carbon precursor and CA is an organic pore former.
(2) Weighing PAN and CA with the mass ratio of 1:1, adding the PAN and CA into DMF, and continuously stirring the mixture at room temperature until macromolecules are completely dissolved to form a uniform and transparent solution, wherein the mass fraction of the spinning solution is 30%.
(3) Transferring the spinning solution prepared in the step (2) into an injector, connecting the injector with an automatic sample injector, connecting a needle with a high-voltage power supply for electrostatic spinning, and receiving by using a receiving device to obtain a PAN/CA composite electrostatic spinning nanofiber membrane; the flow rate was 1ml/min, the spinning voltage was 17kv and the distance of the needle from the receiver was 15 cm.
(4) And (4) placing the electrostatic spinning composite nanofiber membrane obtained in the step (3) in a vacuum drying oven, and performing vacuum drying for 12 hours at the temperature of 90 ℃ to remove residual organic solvent.
(5) And (3) placing the dried nanofiber membrane obtained in the step (4) in a forced air drying oven for pre-oxidation, vertically placing the nanofiber membrane, fixing two ends of the nanofiber membrane by using iron clamps to prevent the nanofiber membrane from being heated and shrunk, adjusting the temperature to 280 ℃ in air atmosphere, raising the temperature at the rate of 10 ℃/min, and carrying out pre-oxidation treatment for 1h to obtain the PAN/CA pre-oxidized nanofiber membrane.
(6) Placing the pre-oxidized nano fiber membrane obtained in the step (5) in a vacuum tube furnace for carbonization treatment; the tube furnace was evacuated 3 times to remove the residual air in the tube, and then N was introduced2Setting the flow rate at 200ml/min, the carbonization temperature at 800 ℃, the heating rate at 5 ℃/min and the carbonization time at 1h to obtain the PAN/CA carbon nanofiber material; by N2The adsorption and desorption test shows that the specific surface area of the material is 380.34m by adopting a BET method2Per g, using DFT methodThe material is separated to obtain the material with the pore volume of 0.258cm3Per g, micropore volume of 0.146cm3/g。
(7) Weighing 100mg of the porous carbon nanofiber material prepared in example 9, transferring the porous carbon nanofiber material to an adsorption tube, and reacting the porous carbon nanofiber material with high-purity N2Activating for 6 hours at 200 ℃; after activation, transferring the adsorption tube into a carbon dioxide high-pressure adsorption instrument, and respectively measuring the adsorption effect on carbon dioxide within the pressure range of 1bar at 0 ℃ and 25 ℃; the material prepared in example 9 had an adsorption capacity for carbon dioxide of 3.59 mmol/g at 0 ℃ and a pressure of 1 bar; the material prepared in example 9 had an adsorption capacity for carbon dioxide of 2.57mmol/g at 25 ℃ and a pressure of 1 bar.
Claims (10)
1. A porous carbon nanofiber material for carbon dioxide adsorption is applied to carbon dioxide adsorption and is characterized in that the preparation method of the porous carbon nanofiber material is characterized in that a thermogravimetric analyzer is utilized to reasonably screen out macromolecules as a proper carbon precursor and an organic pore-forming agent, and a porous carbon nanofiber membrane is prepared through a mixed electrostatic spinning technology and one-step high-temperature carbonization treatment; the porous carbon nanofiber membrane has an obvious porous structure, a large number of mesopores and micropores coexist, and the specific surface area and the porosity are ultrahigh; the carbon nanofiber of the porous carbon nanofiber membrane is superfine nanofiber, and the outer diameter of the carbon nanofiber is 100nm-2 mu m; the specific surface area of the porous carbon nanofiber membrane is 200-1600m2Per g, pore diameter of 0.1-100nm and pore volume of 0.2-2cm3Per g, more micropores with a micropore volume of 0.1-1.5cm3(ii)/g; the preparation method specifically comprises the following steps:
(1) taking a small amount of macromolecules, and analyzing the thermal stability of the target macromolecules at a certain temperature in an analysis gas atmosphere by a thermogravimetric analyzer; the thermal stability is good, the high molecules with mass left after thermogravimetric analysis are used as carbon precursors, the thermal stability is poor, and the high molecules without mass left after thermogravimetric analysis are used as organic pore-forming agents; the carbon precursor is at least one of polyacrylonitrile PAN, polyvinylidene fluoride (PVDF), phenolic resin and pitch; the organic pore-forming agent is at least one of polymethyl methacrylate (PMMA), Cellulose Acetate (CA), polypropylene pyrrolidone (PVP), polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinyl butyral (PVB) and nylon 6;
(2) mixing a carbon precursor and an organic pore-forming agent according to a certain proportion, dissolving the mixture in an organic solvent, and preparing a mixed spinning solution with a certain mass fraction; the mass fraction of the mixed spinning solution is 10-30%, wherein the ratio of the carbon precursor to the organic pore-forming agent is 9:1-1: 9;
(3) transferring the mixed spinning solution in the step (2) into an injector, and preparing a composite electrostatic spinning nanofiber membrane by an electrostatic spinning technology;
(4) placing the composite electrostatic spinning nanofiber membrane obtained in the step (3) in a blast oven, and pre-oxidizing at low temperature in an air atmosphere to obtain pre-oxidized porous nanofibers; the preoxidation process conditions are as follows: the temperature is 200 ℃ and 300 ℃, the heating rate is 1-10 ℃/min, and the processing time is 1-6 h;
(5) placing the pre-oxidized porous nanofiber membrane obtained in the step (4) in a carbonization furnace, and carbonizing at high temperature to obtain porous carbon nanofibers; the carbonization process conditions are as follows: the temperature is 600-1000 ℃, the heating rate is 1-10 ℃, and the treatment time is 1-6 h.
2. The use of the porous carbon nanofiber material for carbon dioxide adsorption according to claim 1, wherein the carbon precursor in step (1) is Polyacrylonitrile (PAN).
3. The use of the porous carbon nanofiber material for adsorbing carbon dioxide as claimed in claim 1, wherein the organic pore-forming agent in step (1) is polymethyl methacrylate (PMMA).
4. The application of the porous carbon nanofiber material for adsorbing carbon dioxide as claimed in claim 1, wherein the mass fraction of the mixed spinning solution in the step (2) is 15%, and the ratio of the carbon precursor to the organic pore-forming agent is 1: 1.
5. The application of the porous carbon nanofiber material for adsorbing carbon dioxide as claimed in claim 1, wherein the pre-oxidation process in the step (4) is carried out at a temperature of 280 ℃ and a temperature rise rate of 10 ℃/min for 1 h.
6. The use of the porous carbon nanofiber material for carbon dioxide adsorption according to claim 1, wherein the carbonization process in the step (5) is performed at a carbonization temperature of 1000 ℃, a temperature rise rate of 5 ℃/min, and a carbonization time of 1 h.
7. The use of a porous carbon nanofiber material for carbon dioxide adsorption as claimed in claim 1, wherein the analysis gas atmosphere in step (1) is N2、O2Or both according to the following weight ratio of 9:1-1:9 proportion of mixed gas; the certain temperature in the step (1) is 200-1000 ℃.
8. The use of the porous carbon nanofiber material for carbon dioxide adsorption according to claim 1, wherein the organic solvent in step (2) is one or more of N, N-dimethylformamide DMF, N-dimethylacetamide DMAC, tetrahydrofuran THF and ethanol.
9. The application of the porous carbon nanofiber material for adsorbing carbon dioxide as claimed in claim 1, wherein the electrospinning process conditions in the step (3) are as follows: the static spinning voltage is 10-25kv, the receiving distance is 10-30cm, the flow rate of the spinning solution is 0.5-2ml/min, and the spinning time is 10-30 h.
10. The application of the porous carbon nanofiber material for adsorbing carbon dioxide as claimed in claim 1, wherein the porous carbon nanofiber material shows good adsorption performance under the condition of low pressure of 1bar, and the adsorption capacity to carbon dioxide is 1.5-10 mmol/g; the carbon dioxide adsorption process is physical adsorption, the adsorption rate is high, the material has small adsorption heat to the carbon dioxide, can be desorbed at room temperature, and is favorable for recycling of the material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710266028.3A CN107051382B (en) | 2017-04-21 | 2017-04-21 | Porous carbon nanofiber material for carbon dioxide adsorption and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710266028.3A CN107051382B (en) | 2017-04-21 | 2017-04-21 | Porous carbon nanofiber material for carbon dioxide adsorption and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107051382A CN107051382A (en) | 2017-08-18 |
| CN107051382B true CN107051382B (en) | 2020-12-18 |
Family
ID=59600940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710266028.3A Active CN107051382B (en) | 2017-04-21 | 2017-04-21 | Porous carbon nanofiber material for carbon dioxide adsorption and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107051382B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110389156A (en) * | 2018-04-19 | 2019-10-29 | 北京化工大学 | A kind of preparation method and application of functionalization graphene sensing membrane is in wireless sensing |
| CN108774810B (en) * | 2018-06-25 | 2021-09-24 | 上海交通大学 | Preparation method of nitrogen and fluorine double-doped microporous carbon nanofiber |
| CN109868528A (en) * | 2019-01-30 | 2019-06-11 | 西南大学 | A kind of one-dimensional porous carbon nanofiber material and its preparation method and application |
| CN110136991A (en) * | 2019-05-21 | 2019-08-16 | 天津工业大学 | A kind of preparation method and application of carbon nano-fiber |
| CN113993617A (en) * | 2019-06-13 | 2022-01-28 | 于利希研究中心有限公司 | For separating CO from gas mixtures2Or NH3Preparation method of carbon fiber material, carbon fiber material and application thereof |
| CN111472056B (en) * | 2020-04-30 | 2021-05-07 | 上海凯矜新材料科技有限公司 | Purifying CO in waste gas2Adsorption film, preparation method and regeneration method |
| CN113754020B (en) * | 2020-06-02 | 2023-05-30 | 中国科学院城市环境研究所 | Adsorption-enhanced electric Fenton cathode material and preparation method thereof |
| CN113351259B (en) * | 2021-07-16 | 2023-08-25 | 河南科技大学 | Method for synthesizing disulfide by catalyzing oxidization of sulfhydryl compound by cobalt nanoparticle/carbon fiber composite mesoporous material |
| CN114505050B (en) * | 2022-02-28 | 2024-06-21 | 江苏惠尔船舶技术有限公司 | Preparation method of zirconium doped mesoporous molecular sieve fiber based on electrostatic spinning technology |
| CN115739021B (en) * | 2022-11-25 | 2024-09-20 | 扬州工业职业技术学院 | Phosphorus doped ZIF-8 based porous carbon fiber adsorption material, and preparation method and application thereof |
| CN116219584A (en) * | 2023-03-07 | 2023-06-06 | 北华大学 | Method for preparing hollow carbon nanofiber by using uniaxial electrostatic spinning technology and application of hollow carbon nanofiber |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721972A (en) * | 2009-12-08 | 2010-06-09 | 华东理工大学 | Method for preparing spherical activated carbon with large CO2absorption capacity |
| CN104342852A (en) * | 2014-10-27 | 2015-02-11 | 东华大学 | Preparation methods of porous carbon nanofiber felt and porous carbon nanofiber electrode |
| CN104805535A (en) * | 2015-04-14 | 2015-07-29 | 华南理工大学 | Preparation method of porous carbon nanofiber |
| CN106283660A (en) * | 2016-08-12 | 2017-01-04 | 东华大学 | A kind of preparation method of carbon dioxide adsorption amino modified nano-fiber material |
| CN106362684A (en) * | 2016-09-12 | 2017-02-01 | 东华大学 | Nitrogenous carbon nanofiber material used for adsorption separation of carbon dioxide and preparing method thereof |
| CN106435841A (en) * | 2016-09-21 | 2017-02-22 | 天津工业大学 | Polyacrylonitrile porous carbon fiber preparation method |
| CN106480552A (en) * | 2016-09-28 | 2017-03-08 | 广州凯耀资产管理有限公司 | Graphene/carbon nano-porous fiber and preparation method and application |
-
2017
- 2017-04-21 CN CN201710266028.3A patent/CN107051382B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721972A (en) * | 2009-12-08 | 2010-06-09 | 华东理工大学 | Method for preparing spherical activated carbon with large CO2absorption capacity |
| CN104342852A (en) * | 2014-10-27 | 2015-02-11 | 东华大学 | Preparation methods of porous carbon nanofiber felt and porous carbon nanofiber electrode |
| CN104805535A (en) * | 2015-04-14 | 2015-07-29 | 华南理工大学 | Preparation method of porous carbon nanofiber |
| CN106283660A (en) * | 2016-08-12 | 2017-01-04 | 东华大学 | A kind of preparation method of carbon dioxide adsorption amino modified nano-fiber material |
| CN106362684A (en) * | 2016-09-12 | 2017-02-01 | 东华大学 | Nitrogenous carbon nanofiber material used for adsorption separation of carbon dioxide and preparing method thereof |
| CN106435841A (en) * | 2016-09-21 | 2017-02-22 | 天津工业大学 | Polyacrylonitrile porous carbon fiber preparation method |
| CN106480552A (en) * | 2016-09-28 | 2017-03-08 | 广州凯耀资产管理有限公司 | Graphene/carbon nano-porous fiber and preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107051382A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107051382B (en) | Porous carbon nanofiber material for carbon dioxide adsorption and preparation method thereof | |
| CN108057420B (en) | High-performance coconut shell activated carbon adsorbent for separating methane/nitrogen and preparation method thereof | |
| WO2015106720A1 (en) | Method for producing super activated charcoal from biomass power plant ash | |
| CN111939770B (en) | Bismuth-based functional material for adsorbing gaseous iodine and preparation method and application thereof | |
| CN108439400A (en) | A kind of N doping bagasse active carbon and preparation method thereof | |
| CN103882559A (en) | High-specific surface porous carbon fiber, preparation method and application of carbon fiber | |
| CN106521717A (en) | Preparation method of porous carbon fiber with high specific surface area | |
| CN109137263A (en) | A kind of high-specific surface area polyacrylonitrile carbon fiber non-woven fabrics and preparation method | |
| CN109987604A (en) | A kind of porous carbon materials and preparation method thereof | |
| CN105621389A (en) | Supported composite carbon molecular sieve membrane | |
| CN103252214A (en) | Active carbon fiber and graded porous Ni-Ni3P/active carbon fiber composite material as well as preparation and application of two | |
| Yusof et al. | Effects of the activation temperature on the polyacrylonitrile/acrylamide-based activated carbon fibers | |
| CN112028074A (en) | Hierarchical pore activated carbon adjustable preparation method and application | |
| KR101418868B1 (en) | Manufacturing method of microporous adsorbents for carbon dioxide capture | |
| CN102897746A (en) | Porous carbon material and method for preparing same | |
| Wang et al. | Study of CO2 adsorption on carbon aerogel fibers prepared by electrospinning | |
| CN108355629A (en) | A kind of carbon nano-fiber composite material of uniform load carbonaceous particle and its application | |
| CN108773841B (en) | Porous carbon material prepared from waste diatomite and preparation method and application thereof | |
| CN114561747B (en) | Polyimide-based porous carbon nanofiber membrane and preparation method and application thereof | |
| CN107879324B (en) | Method for preparing nitrogen-doped carbon aerogel | |
| CN107473218B (en) | Ordered graded porous carbon material with directionally distributed functional groups, preparation method thereof and application thereof in flue gas desulfurization | |
| Shuahua et al. | The comparison of different activation techniques to prepare activated carbon materials from waste cotton fabric | |
| WO2020249441A1 (en) | Production method for carbon fibre material for separating co2 or nh3 from gas mixtures, carbon fibre material, and use thereof | |
| CN107640768B (en) | Preparation method of nitrogen-rich modified desulfurization adsorption material | |
| Guo et al. | Catalytic oxidation of NO at low concentrations by carbon nanofibers near room temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |