CN115557494B - Conductive cellulose nano-alkene, preparation method and application thereof - Google Patents
Conductive cellulose nano-alkene, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of conductive cellulose, and particularly relates to conductive cellulose nano-alkene, a preparation method and application thereof. The preparation method of the conductive cellulose nano-alkene comprises the following steps: adding plant cellulose into sulfuric acid solution, and introducing nitrogen at the temperature of not higher than 25 ℃ to isolate air; and then stirring and reacting for 2-6 hours in a water bath at 80-95 ℃ under the nitrogen atmosphere, and centrifugally washing and freeze-drying the obtained suspension after the reaction is finished to obtain the conductive cellulose nanometer alkene. According to the invention, the conductive cellulose nanometer alkene is prepared by a one-step sulfuric acid method at low temperature and normal pressure, the cellulose surface is dehydrated and carbonized by instantaneously releasing high heat when the sulfuric acid is hydrated to generate a covalent bond, and then a highly graphitized carbon layer is self-assembled, so that the conductive cellulose nanometer alkene has more excellent conductivity and more uniform and controllable size compared with the previous two-step sulfuric acid method, and is an ideal conductive support framework material.
Description
Technical Field
The invention belongs to the technical field of conductive cellulose, and particularly relates to conductive cellulose nano-alkene, a preparation method and application thereof.
Background
Cellulose is the most abundant biopolymer on earth, can be extracted from natural plants, algae and microorganisms, and is an important renewable material. Cellulose has flexibility, hydrophilicity, degradability and abundant surface chemical properties, and can form three-dimensional hierarchical structures such as films, aerogel, hydrogel and the like. However, cellulose has been challenging in the fields of energy, electronics, solar cells, catalysis, etc., because it is inherently non-conductive and its inherent insulating properties can block the transport of electrons in the material, increase internal resistance, and reduce conductivity.
The most typical strategy for imparting conductivity to cellulose is to convert cellulose into conductive carbon material by carbonization treatment, and two methods commonly used are a high-pressure hydrothermal method and a pyrolysis method, respectively. For example, patent document publication No. CN113683088A discloses that cellulose and an activator are uniformly mixed using sodium bicarbonate as an activator, and then carbonized at 600 ℃ for 2 hours in a nitrogen atmosphere to obtain cellulose-based activated carbon; for another example, as disclosed in patent document CN106283273a, a cellulose fiber is first heat-treated in a pre-oxidation furnace, and treated at 250 ℃ for 10min; placing the pre-oxidized fiber in a carbonization furnace, carbonizing for 4 hours at 400 ℃ in a nitrogen atmosphere, and carbonizing for 1 hour at a high temperature of 1400 ℃ to obtain cellulose-based carbon fiber; however, the existing carbonization method does not meet the safety requirement, the preparation process is complex and complicated, toxic gas is discharged in the preparation process, and the defects of low carbon yield, uncontrollable morphological structure, unavoidable high energy consumption and the like are also present.
In the earlier study, ginger fiber was added to a sulfuric acid solution, followed by two steps: the first step is to stir at 40 ℃ for 30min for hydrolysis, and the second step is to stir at 90 ℃ for reaction; the conductive cellulose nano-alkene prepared by the method mainly presents a granular structure and is agglomerated. Therefore, on the basis of safety, sustainability and low cost, developing an effective way to controllably convert cellulose into high quality graphite carbon materials has important application value.
Disclosure of Invention
Based on the above-mentioned drawbacks and deficiencies of the prior art, it is an object of the present invention to at least solve one or more of the above-mentioned problems of the prior art, in other words, to provide a conductive cellulose nano-alkene satisfying one or more of the aforementioned needs, and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation method of the conductive cellulose nano-alkene comprises the following steps:
adding plant cellulose into sulfuric acid solution, and introducing nitrogen at the temperature of not higher than 25 ℃ to isolate air; and then stirring and reacting for 2-6 hours in a water bath at 80-95 ℃ under the nitrogen atmosphere, and centrifugally washing and freeze-drying the obtained suspension after the reaction is finished to obtain the conductive cellulose nanometer alkene.
Preferably, the temperature of the water bath is 88-92 ℃.
As a preferable scheme, the plant cellulose is one of microcrystalline cellulose, aspen fiber, wheat straw, cotton fiber, bamboo pulp fiber and fibrilia.
Preferably, the sulfuric acid solution has a mass fraction of 50-80 wt%.
As a preferable scheme, the solid-to-liquid ratio of the plant cellulose to the sulfuric acid solution is 1g: (50-100) mL.
Preferably, the ventilation time period for introducing nitrogen in the environment of not higher than 25 ℃ to isolate air is 30min.
The invention also provides the conductive cellulose nano-alkene prepared by the preparation method according to the scheme, and the conductive cellulose nano-alkene is of a rod-shaped structure.
Preferably, the resistance of the conductive cellulose nano-alkene is less than 5 omega.
The invention also provides application of the conductive cellulose nano-alkene, which is characterized by being used as a conductive material of an electronic device.
Preferably, the electronic device is a one-dimensional, two-dimensional or three-dimensional electronic device.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the conductive cellulose nanometer alkene is prepared by a one-step sulfuric acid method at low temperature and normal pressure, the cellulose surface is dehydrated and carbonized by instantaneously releasing high heat when sulfuric acid is hydrated to generate a covalent bond, and then a highly graphitized carbon layer is self-assembled, so that the conductive cellulose nanometer alkene has more excellent conductivity compared with the previous two-step sulfuric acid method, and is an ideal conductive support framework material;
(2) The preparation method adopts a one-step method, and has the advantages of simple process, safety and low energy consumption;
(3) The conductive cellulose nano-alkene has higher yield, the structure is bar-shaped, the cellulose characteristic is kept good, and the solution dispersibility is excellent;
(4) The raw material of the invention is natural plant cellulose, which has wide sources, low price, environmental protection, sustainability and reproducibility;
(5) The conductive cellulose nano-alkene provided by the invention is used as a novel conductive cellulose, solves the inherent insulation problem while maintaining the cellulose characteristic, and has huge application potential in the aspects of energy storage, catalysis and sensing.
Drawings
FIG. 1 is a scanning electron microscope image of a conductive cellulose nano-alkene prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of the conductive cellulose nano-alkene prepared in example 1 of the present invention;
FIG. 3 is an electrochemical impedance spectrum of the conductive cellulose nano-alkene prepared in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the conductive cellulose nano-alkene prepared in comparative example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the following specific examples.
Example 1:
the preparation method of the conductive cellulose nano-alkene of the embodiment comprises the following steps:
1) Diluting 40mL of sulfuric acid in 40mL of water, and performing ultrasonic treatment at 20 ℃ for 5 minutes to obtain a 64wt% sulfuric acid solution;
2) 1g of microcrystalline cellulose was added to 80mL of 64wt% sulfuric acid solution, and nitrogen was purged at 20℃for 30 minutes to remove air; and then stirring and reacting for 4 hours in a water bath kettle at 90 ℃ under the nitrogen atmosphere, centrifuging and washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nanometer alkene.
The conductive cellulose nanoenes of this example were characterized as follows:
as shown in fig. 1, the conductive cellulose nano-alkene of the present embodiment has a uniform morphology, and maintains a rod-shaped structure of cellulose nano-crystals (abbreviated as CNC) with a high aspect ratio.
As shown in fig. 2, the lattice fringes of the conductive cellulose nano-alkene of the present embodiment have a spacing of 0.315nm, that is, a highly ordered graphitized carbon layer is formed.
As shown in fig. 3, the conductive cellulose nano-olefin of the present embodiment has low resistance, i.e., excellent conductivity.
Example 2:
the preparation method of the conductive cellulose nano-alkene of the embodiment comprises the following steps:
1) Diluting 40mL of sulfuric acid in 40mL of water, and performing ultrasonic treatment at 25 ℃ for 5 minutes to obtain a 64wt% sulfuric acid solution;
2) 1g of cotton was added to 100mL of 64wt% sulfuric acid solution, and nitrogen was purged at 25℃for 30 minutes to remove air; and then stirring and reacting for 3 hours in a water bath kettle at 95 ℃ under the nitrogen atmosphere, centrifuging and washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nanometer alkene.
Example 3:
the preparation method of the conductive cellulose nano-alkene of the embodiment comprises the following steps:
1) 50mL of sulfuric acid is diluted in 30mL of water, and ultrasonic treatment is carried out for 5 minutes at the temperature of 23 ℃ to obtain 75wt% sulfuric acid solution;
2) 1g of bamboo pulp fiber is added into 75mL of 75wt% sulfuric acid solution, and nitrogen is introduced for 30min at the temperature of 23 ℃; and then stirring and reacting for 4 hours in a water bath kettle at 92 ℃ under the nitrogen atmosphere, centrifuging and washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nanometer alkene.
Example 4:
the preparation method of the conductive cellulose nano-alkene of the embodiment comprises the following steps:
1) Diluting 40mL of sulfuric acid in 40mL of water, and performing ultrasonic treatment at 18 ℃ for 5 minutes to obtain a 64wt% sulfuric acid solution;
2) 1g of poplar fiber is added into 80mL of 64wt% sulfuric acid solution, and nitrogen is introduced for 30min at 18 ℃; and then stirring and reacting for 5 hours in a water bath kettle at 88 ℃ under the nitrogen atmosphere, centrifuging and washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nanometer alkene.
Example 5:
the preparation method of the conductive cellulose nano-alkene of the embodiment comprises the following steps:
1) 50mL of sulfuric acid is diluted in 30mL of water, and ultrasonic treatment is carried out for 5 minutes at room temperature, so as to obtain 75wt% sulfuric acid solution;
2) 1g of wheat straw is added into 50mL of 75wt% sulfuric acid solution, and nitrogen is introduced for 30min at room temperature; and then stirring and reacting for 6 hours in a water bath kettle at 80 ℃ under the nitrogen atmosphere, centrifuging and washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nanometer alkene.
Comparative example 1:
the preparation method of the conductive cellulose nano-alkene of the comparative example comprises the following steps:
1) Diluting 40mL of sulfuric acid in 40mL of water, and performing ultrasonic treatment at 20 ℃ for 5 minutes to obtain 64wt% sulfuric acid solution;
2) 1g of microcrystalline cellulose is added to 80mL of 64wt% sulfuric acid solution, and nitrogen is introduced at 20 ℃ for 30min; then stirring and reacting for 0.5 hour in a water bath kettle at 40 ℃ under the nitrogen atmosphere, then heating to 90 ℃ and reacting for 4 hours, centrifuging and washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nanometer alkene.
As shown in fig. 4, the conductive cellulose nano-alkene prepared in comparative example 1 mainly has a granular structure, and also has a part of the conductive cellulose nano-alkene maintains a rod-shaped structure but is continuously wrapped by the granular nano-alkene, so that the agglomeration phenomenon is obvious; this is because, during the reaction at 40 ℃, the high concentration protons from the sulfuric acid first attack the disordered region of the microcrystalline cellulose, undergo sufficient hydrolysis, hydrolyzing the microcrystalline cellulose first into cellulose nanocrystalline CNC; and then heating to 90 ℃, and simultaneously dehydrating and carbonizing the CNC outer layer molecular chain and hydrolyzed cellulose molecules in the disordered region by sulfuric acid. The graphitization of the crystalline region requires more energy than the graphitization of the cellulose disordered region. Therefore, the time required for forming the carbon layer is longer, and under the barrier effect of the carbon layer which is absent in the early stage, sulfuric acid can enter a molecular chain segment of a deeper layer of CNC, so that a part of a crystallization area is also damaged; finally, the obtained conductive cellulose nano-alkene is mainly of a granular structure.
However. In the above example 1, the one-step method directly reacts at 90 ℃, sulfuric acid rapidly dehydrates and carbonizes on the surface of cellulose to self-assemble into a carbon layer, and the cellulose is protected from entering the deep chain segment; meanwhile, the disordered region of the microcrystalline cellulose is also attacked, so that the microcrystalline cellulose chain segment is broken, and finally the conductive cellulose nano-alkene with a rod-shaped structure, uniform morphology and a highly oriented graphitized carbon layer on the surface is obtained.
The resistance of the conductive cellulose nano-olefins of example 1 and comparative example 1 was subjected to comparative test as shown in table 1 below.
| Sample of | Resistor (omega) |
| Example 1 | 4.91 |
| Comparative example 1 | 9.68 |
Therefore, the conductive cellulose nano-graphene of the embodiment of the invention is more beneficial to the rapid transfer of electrons/ions due to the highly oriented graphite carbon layer, and can be used as a conductive material of an electronic device, for example: one-, two-or three-dimensional electronic devices.
In the above embodiments and alternatives thereof, the mass fraction of the sulfuric acid solution may also be 50wt%, 60wt%, 70wt%, 80wt%, etc.
In the above embodiments and alternatives thereof, the plant cellulose may also be fibrilia.
In the above embodiment and the alternatives thereof, the ventilation duration for isolating the air is not limited to 30min, and is specifically determined according to the actual application requirements.
In view of the numerous embodiments of the present invention, each embodiment can be determined within a limited range of parameters according to practical application requirements, and experimental data are huge and numerous, which are not suitable for one-by-one enumeration and explanation herein, but the content of verification required by each embodiment and the obtained final conclusion are close, and the resistance of the conductive cellulose nano-alkene is less than 5Ω.
The foregoing is only illustrative of the preferred embodiments and principles of the present invention, and changes in specific embodiments will occur to those skilled in the art upon consideration of the teachings provided herein, and such changes are intended to be included within the scope of the invention as defined by the claims.
Claims (10)
1. The preparation method of the conductive cellulose nano-alkene is characterized by comprising the following steps:
adding plant cellulose into sulfuric acid solution, and introducing nitrogen at the temperature of not higher than 25 ℃ to isolate air; and then stirring and reacting for 2-6 hours in a water bath at 80-95 ℃ under the nitrogen atmosphere, and centrifugally washing and freeze-drying the obtained suspension after the reaction is finished to obtain the conductive cellulose nanometer alkene.
2. The method of claim 1, wherein the water bath is at a temperature of 88 to 92 ℃.
3. The method according to claim 1, wherein the plant cellulose is one of microcrystalline cellulose, poplar fiber, wheat straw, cotton fiber, bamboo pulp fiber, and hemp fiber.
4. The preparation method according to claim 1, wherein the mass fraction of the sulfuric acid solution is 50-80 wt%.
5. The method according to claim 1, wherein the solid-to-liquid ratio of the plant cellulose to sulfuric acid solution is 1g: (50-100) mL.
6. The method according to claim 1, wherein the aeration period in which nitrogen is introduced at not higher than 25 ℃ to isolate air is 30 minutes.
7. The conductive cellulose nano-alkene according to any one of claims 1 to 6, wherein the conductive cellulose nano-alkene has a rod-like structure.
8. The conductive cellulose nanoene of claim 7, wherein the conductive cellulose nanoene has a resistance of less than 5 Ω.
9. Use of a conductive cellulose nanoene according to claim 7 or 8 as a conductive material for electronic devices.
10. The use of claim 9, wherein the electronic device is a one-, two-or three-dimensional electronic device.
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