CN113880073A - Lignin-based carbon nanotube and preparation method thereof - Google Patents
Lignin-based carbon nanotube and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lignin-based carbon nanotube and a preparation method thereof. According to the invention, the surface charge of lignin is regulated, the electropositive lignin and electronegative lignin with good water solubility are utilized to carry out layer-by-layer self-assembly through a porous alumina template to obtain the lignin nanotube, and the lignin nanotube is obtained through calcination carbonization, template dissolution, washing and drying. Electrostatic acting force between positive charges and negative charges, and acting force such as pi-pi interaction and hydrogen bond between aromatic rings unique to lignin are important for layer-by-layer self-assembly. The semi-rigid aromatic skeleton of the lignin also plays a good role in stabilizing and supporting in the self-assembly process. The preparation process of the lignin-based carbon nanotube is green and environment-friendly, and the process is simple and easy to master. The prepared carbon nano tube has controllable pipe diameter, wall thickness and the like, and a straight pipe body, so that the high-value application range of lignin is expanded, and the development and application of biomass resources are promoted.
Description
Technical Field
The invention belongs to the field of lignin carbon materials, and particularly relates to a lignin-based carbon nanotube and a preparation method thereof.
Background
The carbon nano tube as a one-dimensional nano material has extremely high aspect ratio, light weight and small thickness, so that the carbon nano tube has high specific surface area, has unique optical, electric, thermal, mechanical and other characteristics, has attracted wide attention since the formal discovery in 1991, and has great potential in the fields of energy, catalysis, materials and the like.
The methods commonly used for preparing carbon nanotubes include arc discharge, laser ablation, chemical vapor deposition, and the like. The arc discharge method and the laser ablation method input high energy through physical means, consume solid carbon sources such as graphite, carbon black and the like, and induce carbon atoms to self-assemble into the carbon nano tube, so that the prepared carbon nano tube has a complete structure, high graphitization degree and few defects. However, the arc discharge method and the laser ablation method require vacuum conditions and continuous replacement of graphite targets, are expensive, and are difficult to perform large-scale continuous production. The chemical vapor deposition method uses gas such as methane, ethylene, acetylene, benzene, etc. as a carbon source, and the carbon source is decomposed into carbon atoms on a catalyst, and carbon nanotubes are formed on the catalyst. The chemical vapor deposition method has the advantages of mild operation conditions, low cost, controllable synthesis and the like, and is a suitable method for producing the carbon nano tube on a large scale. However, the chemical vapor deposition method has high requirements on equipment, poor product graphitization degree, high catalyst manufacturing cost and complex post-treatment.
Lignin is the most abundant natural aromatic polymer in nature and is also a major byproduct in the paper industry. Due to the advantages of being renewable, rich in functional groups, high in carbon content, high in aromaticity and the like, the lignin becomes a potential precursor for preparing advanced carbon-based materials. At present, lignin-based carbon materials such as carbon fibers, porous carbon, carbon microspheres and the like are developed, and the lignin-based carbon materials have application potential in the fields of adsorption, catalysis, energy storage and the like. At present, few research reports on lignin-based carbon nanotubes are reported, and the research reports mainly focus on pyrolysis, in particular on the preparation of carbon nanotubes by cracking lignin into carbon source gas and then catalyzing. Luo Weihua and the like pyrolyze lignin @ catalyst nano micelle (Chinese patent application CN112265981A) and catalyst/lignin micro-nano fiber (Chinese patent application CN112342642A) prepared by electrostatic spinning in a protective atmosphere, and obtain the lignin-based carbon nano tube after acid treatment. Shao gift books and the like, the transition metal oxide/SBA-15 supported catalyst and lignin liquid are mixed, frozen, dried and calcined at high temperature, and then acid-base treatment is carried out to obtain the lignin-based carbon nano tube with hierarchical pore structure (Chinese patent CN 112973625A). On one hand, pyrolysis and calcination often require higher temperature and longer time, and the energy consumption of the process is high; the synthesis of the catalyst and the subsequent catalytic conversion reaction conditions need to be strictly controlled and are harsh; on the other hand, the carbon nanotubes prepared by the two methods are difficult to control in morphology and difficult to utilize at a high value.
In conclusion, the methods of arc discharge, laser ablation, chemical vapor deposition and the like for preparing the carbon nanotubes all use fossil energy as a carbon source, the equipment requirement is high, the preparation conditions are severe, and the post-treatment purification process is complex; the preparation of the carbon nano tube by taking the lignin as the carbon source needs high-temperature heat treatment and uses expensive catalyst for catalytic conversion. Therefore, a method for preparing the lignin-based carbon nanotube with simpler process, greenness, high efficiency and controllable appearance needs to be developed.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a preparation method of a lignin-based carbon nanotube.
The invention utilizes lignin with electropositive molecules and lignin with electronegative molecules to carry out layer-by-layer self-assembly in tiny pore channels of an alumina template to form lignin nano-tubes, and then the lignin-based carbon nano-tubes are prepared by high-temperature calcination. Except electrostatic force between positive charges and negative charges, action forces such as pi-pi interaction and hydrogen bonds between aromatic rings peculiar to lignin are important for layer-by-layer self-assembly, and the semi-rigid aromatic skeleton support of the lignin is assisted, so that a layer-by-layer self-assembly tubular structure of the lignin and a calcined carbon nanotube structure can be stabilized. The method takes renewable resource biomass as a carbon source, does not use toxic reagents and expensive catalysts, has simple operation process, low requirement on equipment conditions, more environment-friendly and green preparation process, controllable pipe diameter, wall thickness and the like of the prepared carbon nano-tube, straight tube body and good application potential.
The invention also aims to provide the lignin-based carbon nanotube prepared by the method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of lignin-based carbon nanotubes comprises the following steps:
(1) alternately soaking a porous alumina template with the pore diameter of 30-300 nm in an electropositive lignin aqueous solution and an electronegative lignin aqueous solution with the concentration of 2-10 g/L, performing lignin electrostatic layer-by-layer self-assembly at room temperature, and washing with water after each soaking self-assembly is finished to obtain the porous alumina template with the number of lignin self-assembly layers of 5-30;
(2) calcining and carbonizing the self-assembled porous alumina template in an inert or nitrogen gas atmosphere, then dissolving the porous alumina template by using an alkaline solution, and centrifugally washing the obtained product to obtain the lignin-based carbon nanotube.
Preferably, the pore diameter of the porous alumina template in the step (1) is 60-110 nm.
Preferably, the concentration of the electropositive lignin aqueous solution and the concentration of the electronegative lignin aqueous solution in the step (1) are both 2-5 g/L.
Preferably, the electropositive lignin in step (1) is at least one of quaternized lignin and aminated lignin; the electronegative lignin is at least one of sulfonated lignin, carboxymethylated lignin and lignosulfonate.
Preferably, in the step (1), the time for soaking the porous alumina template in the electropositive lignin aqueous solution and the electronegative lignin aqueous solution for one time is 4-12 hours.
Preferably, the number of the lignin self-assembly layers in the step (1) is 5-15. Soaking the electropositive lignin once is a self-assembled layer, and soaking the electronegative lignin once is a self-assembled layer.
Preferably, in the step (1), ultrasonic cleaning is carried out for 0.5-2 min after the porous alumina template is immersed in the lignin solution every time to assist lignin molecules to enter micro channels of the alumina template, and after immersion self-assembly is finished, ultrasonic cleaning is carried out for 2-3 times by using deionized water every time for 30-60 s.
Preferably, the temperature of the calcination carbonization in the step (2) is 500-1500 ℃, and more preferably 600-800 ℃; the time is 30-60 min.
Preferably, the alkaline solution in the step (2) is a NaOH solution with the concentration of 4-8 mol/L.
Preferably, the centrifugal washing in step (2) means: and (3) centrifugally washing a product dissolved in the alkaline solution for several times by using deionized water until the pH value is 7, and centrifuging for 10-60 min under the single centrifugation condition of 5000-15000 r/min.
The invention provides a lignin-based carbon nanotube prepared by the method.
The lignin-based carbon nanotube has controllable pipe diameter, controllable wall thickness, regular shape, straight pipe body and natural defects, and has wide application prospect in the fields of adsorption, catalysis and energy materials.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention takes the lignin as the raw material, has wide source and is environment-friendly, and the application range of the industrial lignin is enlarged, thereby promoting the development and the application of the biomass.
(2) The preparation process is green and environment-friendly, the whole reaction process is carried out in aqueous solution, no organic solvent is used, the reaction flow is simple, the equipment requirement is low, and the preparation process is easy to master.
(3) The pipe diameter of the lignin-based carbon nano-tube can be determined by the aperture of the alumina template, and the pipe wall thickness can be determined by the number of self-assembled layers, so that the controllable preparation of the lignin-based carbon nano-tube is realized.
Drawings
FIG. 1 is a picture of a sample object obtained after lyophilization in example 1. The sample was a fluffy black solid.
Fig. 2 is a graph of laser confocal measurements (fluorescence signal on the left, optical signal in the middle, and superimposed signal on the right) of the lignin tube obtained in example 1, step (2), after the alumina template is dissolved out after the lignin self-assembly in the pores of the porous alumina template (i.e., without carbonization in step 3). The aromatic skeleton (phenylpropane unit) peculiar to lignin can emit blue-green fluorescence under the excitation of ultraviolet light.
FIG. 3 is a transmission electron micrograph of the samples obtained in examples 1 to 4. 1a-b corresponds to example 1, the pipe diameter of the sample is observed to be 100nm, and the pipe wall of the self-assembly 5 layers is very thin. 2a-b correspond to example 2, the sample tube diameter is 180nm, and the self-assembly 5-layer tube wall is very thin. 3a-b corresponding to example 3, the diameter of the sample tube was 240nm, and the thickness of the self-assembled 10-layer carbon nanotube was 8 nm. 4a-b corresponding to example 4, the diameter of the sample tube is 240nm, and the wall thickness of the self-assembled 15-layer carbon nanotube is 14 nm. 5a-b corresponding to example 5, the sample tube diameter was 350nm, and the wall thickness of the self-assembled 20-layer carbon nanotube was 30 nm. The prepared carbon nanotube wall is thickened along with the increase of the number of self-assembly layers.
FIG. 4 is a transmission electron micrograph of the sample obtained in comparative examples 1 to 3. 4-1 corresponds to comparative example 1, the selected porous alumina template has too large aperture, the prepared lignin-based carbon nanotube has too large tube diameter, good support cannot be formed inside, and the part except the port cannot maintain a tubular shape. 4-2 corresponds to comparative example 2, because the lignin concentration is too low, lead to the self-assembly efficiency too low, through the carbonization lignin-based carbon nanotube wall too thin after the self-assembly of longer time, can't maintain the spatial structure of carbon tube, through freeze-drying already take the form of staggered lamellar. 4-3 corresponds to comparative example 3, because ultrasonic cleaning is not carried out after each layer of self-assembly, and no cotton swab is used to wipe off the redundant lignin on the surface of the alumina before carbonization, the thick carbon shell exists at the end port after carbonization, and because the redundant lignin on the surface exists in the self-assembly process, the new lignin molecules are prevented from entering the tiny pore canal, and the wall of the prepared carbon tube is very thin.
FIG. 5 is a scanning electron micrograph of a sample obtained in example 3 (the left and right images are the same and different in view angle). The tube diameter was observed to be 260nm, comparable to transmission electron microscopy data. And the hollow structure can be seen from the tearing gap, thus confirming that the sample is a hollow carbon tube.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Dissolving 200mg of quaternized lignin in 100ml of deionized water, performing ultrasonic treatment for 30min to fully dissolve the lignin, centrifuging at 4000r/min for 10min, and taking supernatant to obtain a quaternized lignin aqueous solution. 200mg of sodium lignosulfonate is dissolved in 100ml of deionized water, and the lignin is fully dissolved by ultrasonic treatment for 30min to obtain a sodium lignosulfonate aqueous solution.
(2) Immersing a porous alumina template with the aperture of 60nm into a quaternized lignin aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after standing, and ultrasonically cleaning the porous alumina template twice by using deionized water for 30s each time, wherein the self-assembly of the first layer is finished. And then immersing the porous alumina template into sodium lignosulfonate aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after the standing is finished, and ultrasonically cleaning the porous alumina template twice by using deionized water for 30s each time, wherein the self-assembly of the second layer is finished. And sequentially putting the second layer of self-assembled porous alumina template into the used positive and negative electro-lignin aqueous solution according to the method, performing ultrasonic treatment, standing, washing, and circularly repeating the operation until 5 layers are self-assembled. After the self-assembly, the excess lignin attached to the upper and lower surfaces of the porous alumina template is wiped off by a cotton swab.
(3) And putting the self-assembled porous alumina template into a tubular furnace, carbonizing in an inert gas atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping for 30 min. And placing the obtained carbonized porous alumina template into 6mol/L NaOH aqueous solution for stirring and dissolving. After complete dissolution, the sample is centrifugally washed for 30min by using 10000r/min of deionized water, the washing times are 4 times, and finally the pH value is 7. And (3) freezing the obtained suspension in a refrigerator overnight, and then carrying out freeze drying for 2 days by using a freeze dryer at the temperature of-60 ℃ and under the condition of 10Pa to obtain the lignin-based carbon nanotube.
Example 2
(1) 200mg of aminated lignin is dissolved in 100ml of deionized water, and the lignin is fully dissolved by ultrasonic treatment for 30min to obtain an aminated lignin aqueous solution. 200mg of carboxymethylated lignin is dissolved in 100ml of deionized water, and the lignin is fully dissolved by ultrasonic treatment for 30min to obtain the carboxymethylated lignin aqueous solution.
(2) Immersing a porous alumina template with the aperture of 90nm into the aminated lignin aqueous solution, carrying out ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after standing, and ultrasonically cleaning the porous alumina template twice by deionized water for 30s each time, wherein the self-assembly of the first layer is finished. And then immersing the porous alumina template into a carboxymethylated lignin aqueous solution, carrying out ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after the standing is finished, and ultrasonically cleaning the porous alumina template twice by using deionized water for 30s each time, wherein the self-assembly of the second layer is finished. And sequentially putting the second layer of self-assembled porous alumina template into the used positive and negative electro-lignin aqueous solution according to the method, performing ultrasonic treatment, standing, washing, and circularly repeating the operation until 5 layers are self-assembled. After the self-assembly, the excess lignin attached to the upper and lower surfaces of the porous alumina template is wiped off by a cotton swab.
(3) And putting the self-assembled porous alumina template into a tubular furnace, carbonizing in an inert gas atmosphere, heating to 700 ℃ at a heating rate of 5 ℃/min, and keeping for 30 min. And putting the obtained carbonized porous alumina template into 6mol/L NaOH solution for stirring and dissolving. After complete dissolution, the sample is centrifugally washed for 30min by using 10000r/min of deionized water, the washing times are 4 times, and finally the pH value is 7. And (3) freezing the obtained suspension in a refrigerator overnight, and then carrying out freeze drying for 2 days by using a freeze dryer at the temperature of-60 ℃ and under the condition of 10Pa to obtain the lignin-based carbon nanotube.
Example 3
(1) Dissolving 200mg of quaternized lignin in 100ml of deionized water, performing ultrasonic treatment for 30min to fully dissolve the lignin, centrifuging at 4000r/min for 10min, and taking supernatant to obtain a quaternized lignin aqueous solution. 200mg of sodium lignosulfonate is dissolved in 100ml of deionized water, and the lignin is fully dissolved by ultrasonic treatment for 30min to obtain a sodium lignosulfonate aqueous solution.
(2) Immersing a porous alumina template with the aperture of 110nm into a quaternized lignin aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after standing, and ultrasonically cleaning the porous alumina template twice by deionized water for 30s each time, wherein the self-assembly of the first layer is finished. And then immersing the porous alumina template into sodium lignosulfonate aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after the standing is finished, and ultrasonically cleaning the porous alumina template twice by using deionized water for 30s each time, wherein the self-assembly of the second layer is finished. And sequentially putting the second layer of self-assembled porous alumina template into the used positive and negative electro-lignin aqueous solution according to the method, performing ultrasonic treatment, standing, washing, and circularly repeating the operation until 10 layers are self-assembled. After the self-assembly, the excess lignin attached to the upper and lower surfaces of the porous alumina template is wiped off by a cotton swab.
(3) And putting the self-assembled porous alumina template into a tubular furnace, carbonizing in an inert gas atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping for 30 min. And putting the obtained carbonized porous alumina template into 6mol/L NaOH solution for stirring and dissolving. After complete dissolution, the sample is centrifugally washed for 30min by using 10000r/min of deionized water, the washing times are 4 times, and finally the pH value is 7. And (3) freezing the obtained suspension in a refrigerator overnight, and then carrying out freeze drying for 2 days by using a freeze dryer at the temperature of-60 ℃ and under the condition of 10Pa to obtain the lignin-based carbon nanotube.
Example 4
(1) Dissolving 200mg of quaternized lignin in 100ml of deionized water, performing ultrasonic treatment for 30min to fully dissolve the lignin, centrifuging at 4000r/min for 10min, and taking supernatant to obtain a quaternized lignin aqueous solution. 200mg of sodium lignosulfonate is dissolved in 100ml of deionized water, and the lignin is fully dissolved by ultrasonic treatment for 30min to obtain a sodium lignosulfonate aqueous solution.
(2) Immersing a porous alumina template with the aperture of 110nm into a quaternized lignin aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after standing, and ultrasonically cleaning the porous alumina template twice by deionized water for 30s each time, wherein the self-assembly of the first layer is finished. And then immersing the porous alumina template into sodium lignosulfonate aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after the standing is finished, and ultrasonically cleaning the porous alumina template twice by using deionized water for 30s each time, wherein the self-assembly of the second layer is finished. And sequentially putting the second layer of self-assembled porous alumina template into the used positive and negative electro-lignin aqueous solution according to the method, performing ultrasonic treatment, standing, washing, and circularly repeating the operation until 15 layers are self-assembled. After the self-assembly, the excess lignin attached to the upper and lower surfaces of the porous alumina template is wiped off by a cotton swab.
(3) And putting the self-assembled porous alumina template into a tubular furnace, carbonizing in an inert gas atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping for 30 min. And putting the obtained carbonized porous alumina template into 6mol/L NaOH solution for stirring and dissolving. After complete dissolution, the sample is centrifugally washed for 30min by using 10000r/min of deionized water, the washing times are 4 times, and finally the pH value is 7. And (3) freezing the obtained suspension in a refrigerator overnight, and then carrying out freeze drying for 2 days by using a freeze dryer at the temperature of-60 ℃ and under the condition of 10Pa to obtain the lignin-based carbon nanotube.
Example 5
(1) Dissolving 200mg of quaternized lignin in 100ml of deionized water, performing ultrasonic treatment for 30min to fully dissolve the lignin, centrifuging at 4000r/min for 10min, and taking supernatant to obtain a quaternized lignin aqueous solution. 200mg of carboxymethylated lignin is dissolved in 100ml of deionized water, and the lignin is fully dissolved by ultrasonic treatment for 30min to obtain the carboxymethylated lignin aqueous solution.
(2) Immersing a porous alumina template with the aperture of 300nm into a quaternized lignin aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after standing, and ultrasonically cleaning the porous alumina template twice by deionized water for 30s each time, wherein the self-assembly of the first layer is finished. And then immersing the porous alumina template into a carboxymethylated lignin aqueous solution, carrying out ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after the standing is finished, and ultrasonically cleaning the porous alumina template twice by using deionized water for 30s each time, wherein the self-assembly of the second layer is finished. And sequentially putting the second layer of self-assembled porous alumina template into the used positive and negative electro-lignin aqueous solution according to the method, performing ultrasonic treatment, standing, washing, and circularly repeating the operation until 20 layers of self-assembly are achieved. After the self-assembly, the excess lignin attached to the upper and lower surfaces of the porous alumina template is wiped off by a cotton swab.
(3) And putting the self-assembled porous alumina template into a tubular furnace, carbonizing in an inert gas atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, and keeping for 30 min. And putting the obtained carbonized porous alumina template into 6mol/L NaOH solution for stirring and dissolving. After complete dissolution, the sample is centrifugally washed for 30min by using 10000r/min of deionized water, the washing times are 4 times, and finally the pH value is 7. And (3) freezing the obtained suspension in a refrigerator overnight, and then carrying out freeze drying for 2 days by using a freeze dryer at the temperature of-60 ℃ and under the condition of 10Pa to obtain the lignin-based carbon nanotube.
Comparative example 1
(1) Dissolving 200mg of quaternized lignin in 100ml of deionized water, performing ultrasonic treatment for 30min to fully dissolve the lignin, centrifuging at 4000r/min for 10min, and taking supernatant to obtain a quaternized lignin aqueous solution. 200mg of sodium lignosulfonate is dissolved in 100ml of deionized water, and the lignin is fully dissolved by ultrasonic treatment for 30min to obtain a sodium lignosulfonate aqueous solution.
(2) Immersing a porous alumina template with the aperture of 350nm into a quaternized lignin aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after standing, and ultrasonically cleaning the porous alumina template twice by deionized water for 30s each time, wherein the self-assembly of the first layer is finished. And then immersing the porous alumina template into sodium lignosulfonate solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after the standing is finished, and ultrasonically cleaning the porous alumina template twice by using deionized water for 30s each time, wherein the self-assembly of the second layer is finished. And sequentially putting the second layer of self-assembled porous alumina template into the used positive and negative electro-lignin aqueous solution according to the method, performing ultrasonic treatment, standing, washing, and circularly repeating the operation until 10 layers are self-assembled. After the self-assembly, the excess lignin attached to the upper and lower surfaces of the porous alumina template is wiped off by a cotton swab.
(3) And putting the self-assembled porous alumina template into a tubular furnace, carbonizing in an inert gas atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping for 30 min. And putting the obtained carbonized porous alumina template into 6mol/L NaOH solution for stirring and dissolving. After complete dissolution, the sample is centrifugally washed for 30min by using 10000r/min of deionized water, the washing times are 4 times, and finally the pH value is 7. And (3) freezing the obtained suspension in a refrigerator overnight, and then carrying out freeze drying for 2 days by using a freeze dryer at the temperature of-60 ℃ and under the condition of 10Pa to obtain the lignin-based carbon nanotube.
The lignin-based carbon nanotube prepared by the comparative example cannot maintain the tubular shape except the port part due to the overlarge tube diameter, which indicates that the lignin-based carbon nanotube cannot be prepared by the porous alumina template with the overlarge pore diameter.
Comparative example 2
(1) Dissolving 100mg of quaternized lignin in 100ml of deionized water, performing ultrasonic treatment for 30min to fully dissolve the lignin, centrifuging at 4000r/min for 10min, and taking supernatant to obtain a quaternized lignin aqueous solution. Dissolving 100mg of sodium lignosulfonate in 100ml of deionized water, and carrying out ultrasonic treatment for 30min to fully dissolve lignin to obtain a sodium lignosulfonate aqueous solution.
(2) Immersing a porous alumina template with the aperture of 60nm into a quaternized lignin aqueous solution, performing ultrasonic treatment for 1min, and standing for 12 h. And taking out the porous alumina template after standing, and ultrasonically cleaning the porous alumina template twice by deionized water for 30s each time, wherein the self-assembly of the first layer is finished. And then immersing the porous alumina template into a sodium lignosulfonate aqueous solution, performing ultrasonic treatment for 1min, and standing for 12 h. And taking out the porous alumina template after the standing is finished, and ultrasonically cleaning the porous alumina template twice by using deionized water for 30s each time, wherein the self-assembly of the second layer is finished. And sequentially putting the second layer of self-assembled porous alumina template into the used positive and negative electro-lignin aqueous solution according to the method, performing ultrasonic treatment, standing, washing, and circularly repeating the operation until 10 layers are self-assembled. After the self-assembly, the excess lignin attached to the upper and lower surfaces of the porous alumina template is wiped off by a cotton swab.
(3) And putting the self-assembled porous alumina template into a tubular furnace, carbonizing in an inert gas atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping for 30 min. And putting the obtained carbonized porous alumina template into 6mol/L NaOH solution for stirring and dissolving. After complete dissolution, the sample is centrifugally washed for 30min by using 10000r/min of deionized water, the washing times are 4 times, and finally the pH value is 7. And (3) freezing the obtained suspension in a refrigerator overnight, and then carrying out freeze drying for 2 days by using a freeze dryer at the temperature of-60 ℃ and under the condition of 10Pa to obtain the lignin-based carbon nanotube.
In the comparative example, the concentrations of the quaternized lignin solution and the sodium lignosulfonate aqueous solution are too low, the self-assembly efficiency is too low, and after each layer of self-assembly lasts for 12 hours, the wall of the carbonized lignin-based carbon nanotube is still too thin and is sheet after freeze-drying, so that the shape of the independent tube cannot be identified.
Comparative example 3
(1) Dissolving 200mg of quaternized lignin in 100ml of deionized water, performing ultrasonic treatment for 30min to fully dissolve the lignin, centrifuging at 4000r/min for 10min, and taking supernatant to obtain a quaternized lignin aqueous solution. 200mg of sodium lignosulfonate is dissolved in 100ml of deionized water, and the lignin is fully dissolved by ultrasonic treatment for 30min to obtain a sodium lignosulfonate aqueous solution.
(2) Immersing a porous alumina template with the aperture of 60nm into a quaternized lignin aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And (3) taking out the porous alumina template after standing, directly immersing the porous alumina template into sodium lignosulfonate aqueous solution, performing ultrasonic treatment for 1min, and standing for 6 h. And taking out the porous alumina template after the standing is finished, and finishing the self-assembly of the second layer. And sequentially putting the second layer of self-assembled porous alumina template into the used positive and negative electro-lignin aqueous solutions according to the method, performing ultrasonic treatment, standing, and circularly repeating the operation until 10 layers are self-assembled.
(3) And putting the self-assembled porous alumina template into a tubular furnace, carbonizing in an inert gas atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping for 30 min. And putting the obtained carbonized porous alumina template into 6mol/L NaOH solution for stirring and dissolving. After complete dissolution, the sample is centrifugally washed for 30min by using 10000r/min of deionized water, the washing times are 4 times, and finally the pH value is 7. And (3) freezing the obtained suspension in a refrigerator overnight, and then carrying out freeze drying for 2 days by using a freeze dryer at the temperature of-60 ℃ and under the condition of 10Pa to obtain the lignin-based carbon nanotube.
According to the comparative example, because each layer of the porous alumina has no cleaning step after self-assembly, the redundant lignin adsorbed on the surface of the porous alumina prevents new lignin molecules from entering a pore channel for self-assembly, so that the pipe wall of the comparative example is very thin, and most of the lignin becomes a carbon shell in the shape of the surface of the template after carbonization.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the lignin-based carbon nanotube is characterized by comprising the following steps of:
(1) alternately soaking a porous alumina template with the pore diameter of 30-300 nm in an electropositive lignin aqueous solution and an electronegative lignin aqueous solution with the concentration of 2-10 g/L, performing lignin electrostatic layer-by-layer self-assembly at room temperature, and washing with water after each soaking self-assembly is finished to obtain the porous alumina template with the number of lignin self-assembly layers of 5-30;
(2) calcining and carbonizing the self-assembled porous alumina template in an inert or nitrogen gas atmosphere, then dissolving the porous alumina template by using an alkaline solution, and centrifugally washing the obtained product to obtain the lignin-based carbon nanotube.
2. The method for preparing lignin-based carbon nanotubes according to claim 1, wherein the electropositive lignin in step (1) is at least one of quaternized lignin and aminated lignin; the electronegative lignin is at least one of sulfonated lignin, carboxymethylated lignin and lignosulfonate.
3. The method for preparing lignin-based carbon nanotubes according to claim 1, wherein the pore size of the porous alumina template in step (1) is 60-110 nm.
4. The method for preparing lignin-based carbon nanotubes according to claim 1, wherein the concentration of the aqueous solution of electropositive lignin and the concentration of the aqueous solution of electronegative lignin in step (1) are both 2-5 g/L.
5. The method for preparing the lignin-based carbon nanotube according to claim 1, wherein in the step (1), the time for soaking the porous alumina template in the electropositive lignin aqueous solution and the electronegative lignin aqueous solution for one time is 4-12 h.
6. The method for preparing lignin-based carbon nanotubes according to claim 1, wherein the number of the lignin self-assembled layers in the step (1) is 5-15.
7. The method for preparing the lignin-based carbon nanotube according to claim 1, wherein in the step (1), the porous alumina template is ultrasonically cleaned for 0.5-2 min after being immersed in the lignin solution each time to assist the lignin molecules to enter the tiny pore channels of the alumina template, and after the immersion self-assembly is completed, the porous alumina template is ultrasonically cleaned for 2-3 times with deionized water each time for 30-60 s.
8. The method for preparing lignin-based carbon nanotubes according to claim 1, wherein the temperature of the calcination and carbonization in the step (2) is 500-1500 ℃; the time is 30-60 min.
9. The method for preparing lignin-based carbon nanotubes according to claim 1, wherein the alkaline solution in step (2) is NaOH solution with concentration of 4-8 mol/L.
10. A lignin-based carbon nanotube produced by the method of any one of claims 1 to 9.
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