CN115557494A - Conductive cellulose nano-alkene and preparation method and application thereof - Google Patents
Conductive cellulose nano-alkene and 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 and 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 in an environment at a temperature of not higher than 25 ℃ to isolate air; and then stirring and reacting in a water bath at the temperature of 80-95 ℃ for 2-6 hours in the nitrogen atmosphere, and after the reaction is finished, centrifugally washing and freeze-drying the obtained suspension to obtain the conductive cellulose nano-alkene. The invention utilizes a one-step sulfuric acid method to prepare the conductive cellulose nano-alkene at low temperature and normal pressure, high heat is instantaneously released to dehydrate and carbonize the surface of cellulose when covalent bonds are generated through sulfuric acid hydration, and then the cellulose nano-alkene is self-assembled into a highly graphitized carbon layer.
Description
Technical Field
The invention belongs to the technical field of conductive cellulose, and particularly relates to conductive cellulose nano-alkene and 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. The cellulose has flexibility, hydrophilicity, degradability and abundant surface chemical properties, and can form three-dimensional hierarchical structures such as films, aerogels, hydrogels and the like. Cellulose, however, has met challenges in the areas of energy, electronics, solar cells, and catalysis 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 electrical conductivity to cellulose is to convert the cellulose into an electrically conductive carbon material by a carbonization process, two methods commonly used being a high-pressure hydrothermal method and a high-temperature pyrolysis method, respectively. For example, patent document No. CN113683088a discloses a cellulose-based activated carbon obtained by uniformly mixing cellulose and an activator using sodium bicarbonate as the activator and then carbonizing the mixture at 600 ℃ for 2 hours in a nitrogen atmosphere; for another example, patent document CN106283273A discloses a method of treating cellulose fibers at 250 ℃ for 10min by heat treatment in a pre-oxidation furnace; placing the pre-oxidized fiber in a carbonization furnace, carbonizing for 4 hours at 400 ℃ in a nitrogen atmosphere, and then carbonizing for 1 hour at 1400 ℃ to obtain cellulose-based carbon fiber; however, the existing carbonization method does not meet the requirement of safety, the preparation process is complex and tedious, toxic gases can be discharged in the preparation process, and the defects of low carbon yield, uncontrollable morphological structure, inevitable high energy consumption and the like exist.
In earlier studies, ginger fiber was added to a sulfuric acid solution, followed by two steps: the first step is to stir for 30min at 40 ℃ for hydrolysis, and the second step is to stir for reaction at 90 ℃; the conductive cellulose nano-alkene prepared by the method mainly has a granular structure and is agglomerated. Therefore, on the basis of safety, sustainability and low cost, an effective way for controllably converting cellulose into a high-quality graphite carbon material is developed, and the method has important application value.
Disclosure of Invention
Based on the above disadvantages and shortcomings of the prior art, it is an object of the present invention to at least solve one or more of the above problems of the prior art, in other words, to provide conductive cellulose nano-olefins, and a method for preparing the same and applications thereof, which satisfy one or more of the above requirements.
In order to achieve the purpose, 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 in an environment at a temperature of not higher than 25 ℃ to isolate air; and then stirring and reacting in a water bath at the temperature of 80-95 ℃ for 2-6 hours in the nitrogen atmosphere, and after the reaction is finished, centrifugally washing and freeze-drying the obtained suspension to obtain the conductive cellulose nano-alkene.
Preferably, the temperature of the water bath is 88-92 ℃.
Preferably, the plant cellulose is one of microcrystalline cellulose, poplar fiber, wheat straw, cotton fiber, bamboo pulp fiber and hemp fiber.
Preferably, the mass fraction of the sulfuric acid solution is 50 to 80wt%.
Preferably, the solid-to-liquid ratio of the plant cellulose to the sulfuric acid solution is 1g: (50-100) mL.
Preferably, the time period of the aeration by introducing nitrogen gas to isolate air in the environment of not higher than 25 ℃ is 30min.
The invention also provides the conductive cellulose nano-alkene prepared by the preparation method in the scheme, wherein the conductive cellulose nano-alkene is in a rod-shaped structure.
Preferably, the resistance of the conductive cellulose nano-alkene is less than 5 omega.
The invention also provides the 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) The conductive cellulose nano-alkene is prepared by a one-step sulfuric acid method at low temperature and normal pressure, high heat is instantaneously released to dehydrate and carbonize the surface of cellulose when covalent bonds are generated by sulfuric acid hydration, and then the cellulose nano-alkene is self-assembled into a highly graphitized carbon layer, so that compared with the previous two-step sulfuric acid method, the conductive cellulose nano-alkene is endowed with more excellent conductivity and is an ideal conductive support framework material;
(2) The preparation method adopts a one-step method, and has simple process, safety and low energy consumption;
(3) The conductive cellulose nano-alkene has high yield, a rod-shaped structure, good cellulose characteristic retention and excellent solution dispersibility;
(4) The raw material of the invention is natural plant cellulose, has wide source and low price, is green, environment-friendly, sustainable and renewable;
(5) The conductive cellulose nano-alkene disclosed by the invention is used as a novel conductive cellulose, the inherent insulation problem of the conductive cellulose nano-alkene is solved while the cellulose characteristics are kept, and the conductive cellulose nano-alkene has great application potential in the aspects of energy storage, catalysis and sensing.
Drawings
FIG. 1 is a scanning electron micrograph of a conductive cellulose nano-alkene prepared in example 1 of the present invention;
FIG. 2 is a transmission electron micrograph 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 micrograph of the conductive cellulose nano-alkene prepared in comparative example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the specific examples below.
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) Adding 1g of microcrystalline cellulose into 80mL of 64wt% sulfuric acid solution, and introducing nitrogen for 30min at 20 ℃ to remove air completely; and then stirring and reacting for 4 hours in a water bath kettle at 90 ℃ in the nitrogen atmosphere, centrifugally washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nano-alkene.
The conductive cellulose nano-olefins 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 cellulose nano-crystalline (CNC) rod-like structure with a high aspect ratio.
As shown in fig. 2, the conductive cellulose nano-alkene of the present embodiment has a lattice stripe spacing of 0.315nm, i.e., a highly ordered graphitized carbon layer is formed.
As shown in fig. 3, the conductive cellulose nano-alkene 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) Adding 1g cotton into 100mL of 64wt% sulfuric acid solution, introducing nitrogen at 25 deg.C for 30min to remove air; and then stirring and reacting for 3 hours in a water bath kettle at the temperature of 95 ℃ in the nitrogen atmosphere, centrifugally washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nano-alkene.
Example 3:
the preparation method of the conductive cellulose nano-alkene of the embodiment comprises the following steps:
1) Diluting 50mL of sulfuric acid in 30mL of water, and performing ultrasonic treatment at 23 ℃ for 5 minutes to obtain a 75wt% sulfuric acid solution;
2) Adding 1g of bamboo pulp fiber into 75mL of 75wt% sulfuric acid solution, and introducing nitrogen for 30min at 23 ℃; and then stirring and reacting for 4 hours in a water bath kettle at the temperature of 92 ℃ in the nitrogen atmosphere, centrifugally washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nano-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) Adding 1g of poplar fiber into 80mL of 64wt% sulfuric acid solution, and introducing nitrogen for 30min at 18 ℃; and then stirring and reacting for 5 hours in a water bath kettle at 88 ℃ in the nitrogen atmosphere, centrifugally washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nano-alkene.
Example 5:
the preparation method of the conductive cellulose nano-alkene of the embodiment comprises the following steps:
1) Diluting 50mL of sulfuric acid in 30mL of water, and performing ultrasonic treatment at room temperature for 5 minutes to obtain a 75wt% sulfuric acid solution;
2) Adding 1g of wheat straw into 50mL of 75wt% sulfuric acid solution, and introducing nitrogen for 30min at room temperature; and then stirring and reacting for 6 hours in a water bath kettle at the temperature of 80 ℃ in the nitrogen atmosphere, centrifugally washing the obtained suspension after the reaction is finished, and freeze-drying to obtain the conductive cellulose nano-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 a 64wt% sulfuric acid solution;
2) Adding 1g of microcrystalline cellulose into 80mL of 64wt% sulfuric acid solution, and introducing nitrogen for 30min at 20 ℃; and then, in the nitrogen atmosphere, firstly stirring and reacting for 0.5 hour in a water bath kettle at 40 ℃, then heating to 90 ℃ and reacting for 4 hours, after the reaction is finished, centrifugally washing the obtained suspension, and freeze-drying to obtain the conductive cellulose nano-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 rod-like structure which is continuously wrapped by the granular nano-alkene, so that the agglomeration phenomenon is obvious; the reason is that in the reaction process of 40 ℃, high-concentration protons from sulfuric acid attack disordered regions of microcrystalline cellulose first, and are sufficiently hydrolyzed to hydrolyze the microcrystalline cellulose into cellulose nanocrystal CNC; and then heating to 90 ℃, and simultaneously dehydrating and carbonizing the molecular chain of the CNC outer layer and the hydrolyzed cellulose molecules in the disordered region by using sulfuric acid. The energy required for graphitization of crystalline regions is greater than for graphitization of cellulose disordered regions. Therefore, the time for forming the carbon layer is longer, and sulfuric acid enters molecular chain segments of CNC deeper layers in the absence of the blocking effect of the carbon layer in the former period, so that a part of crystalline regions of the CNC are also damaged; finally, the obtained conductive cellulose nano-alkene is mainly in a granular structure.
However. In the embodiment 1, the reaction is directly carried out at 90 ℃ by a one-step method, sulfuric acid is quickly dehydrated, carbonized and self-assembled on the surface of cellulose to form a carbon layer, and the cellulose is protected to prevent the sulfuric acid from entering a deep chain segment; meanwhile, the disordered region of the microcrystalline cellulose can be attacked, so that the microcrystalline cellulose chain segment is broken, and finally the conductive cellulose nano-alkene with a rod-shaped structure, uniform appearance and a highly-oriented graphitized carbon layer on the surface is obtained.
Comparative tests of the resistance of the conductive cellulose nano-olefins of example 1 and comparative example 1 were conducted as shown in table 1 below.
| Sample (I) | Resistor (omega) |
| Example 1 | 4.91 |
| Comparative example 1 | 9.68 |
Therefore, the conductive cellulose nano-alkene of the embodiment of the invention has the highly oriented graphitic carbon layer, so that the conductive cellulose nano-alkene is more favorable for the rapid transfer of electrons/ions, and can be used as a conductive material of an electronic device, for example: one-dimensional, two-dimensional 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, the plant cellulose may also be hemp fiber.
In the above embodiments and their alternatives, the duration of the ventilation to isolate the air is not limited to 30min, and is determined according to the actual application requirements.
In view of numerous embodiments of the scheme of the invention, each embodiment can be determined according to the actual application requirements within the limited range of parameters, the experimental data is huge and numerous, and the experimental data is not suitable for being enumerated and explained one by one here, but the contents to be verified and the final conclusion obtained by each embodiment are all close, and the resistance of the conductive cellulose nano-alkene is less than 5 omega.
The foregoing has outlined, rather broadly, the preferred embodiment and principles of the present invention in order that those skilled in the art may better understand the detailed description of the invention without departing from its broader aspects.
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 in an environment at a temperature of not higher than 25 ℃ to isolate air; and then stirring and reacting in a water bath at the temperature of 80-95 ℃ for 2-6 hours in the nitrogen atmosphere, and after the reaction is finished, centrifugally washing and freeze-drying the obtained suspension to obtain the conductive cellulose nano-alkene.
2. The method of claim 1, wherein the temperature of the water bath is 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 method according to claim 1, wherein the sulfuric acid solution is contained in an amount of 50 to 80wt%.
5. The method according to claim 1, wherein the solid-to-liquid ratio of the plant cellulose to the sulfuric acid solution is 1g: (50-100) mL.
6. The method according to claim 1, wherein the time period for introducing nitrogen gas to exclude air in an environment of not higher than 25 ℃ is 30min.
7. The conductive cellulose nano-alkene prepared by the method according to any one of claims 1 to 6, wherein the conductive cellulose nano-alkene has a rod-like structure.
8. The conductive cellulose nano-alkene of claim 7, wherein the conductive cellulose nano-alkene has an electrical resistance of less than 5 Ω.
9. Use of the conductive cellulose nano-alkene of claim 7 or 8 as a conductive material in an electronic device.
10. The use of claim 9, wherein the electronic device is a one-, two-or three-dimensional electronic device.
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| CN116589886A (en) * | 2023-06-01 | 2023-08-15 | 东北林业大学 | MXene/conductive cellulose/conductive polymer high-conductivity ink, preparation method thereof and application thereof in flexible micro supercapacitor |
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| US20200095342A1 (en) * | 2018-09-21 | 2020-03-26 | King Abdulaziz University | Method for converting micro- to nano-crystalline cellulose |
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| US20100286387A1 (en) * | 2009-05-06 | 2010-11-11 | Hashaikeh Raed | Crystalline sulphated cellulose ii and its production from sulphuric acid hydrolysis of cellulose |
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| CN116589886A (en) * | 2023-06-01 | 2023-08-15 | 东北林业大学 | MXene/conductive cellulose/conductive polymer high-conductivity ink, preparation method thereof and application thereof in flexible micro supercapacitor |
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