CN111841456B - Extremely-tolerant carbon nanotube hydrogel as well as preparation method and application thereof - Google Patents
Extremely-tolerant carbon nanotube hydrogel as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an extremely-tolerant carbon nanotube hydrogel as well as a preparation method and application thereof. The preparation method comprises the following steps: providing carbon nanotube aerogel, infiltrating the surface of the carbon nanotube aerogel with a first aqueous solution containing micromolecules and/or macromolecules, and then drying to obtain micromolecule and/or macromolecule modified carbon nanotube xerogel; and fully soaking the carbon nanotube xerogel into a second aqueous solution to obtain the extremely-tolerant carbon nanotube hydrogel. The carbon nanotube hydrogel disclosed by the invention has an ultra-fast water transmission characteristic and higher conductivity, shows excellent tolerance to acid, alkali, salt, organic and other environments, and can be recovered reversibly under the condition of large-degree compression, so that the carbon nanotube hydrogel has a better application prospect in the fields of traumatic wound healing, emergency tourniquets, biological medicine carrying, water environment treatment, seawater desalination, new energy devices, wearable, underwater sensing, detection and the like.
Description
Technical Field
The invention relates to preparation of nano-carbon hydrogel, in particular to rapid water transfer hydrogel and environment-tolerant carbon nanotube hydrogel as well as a preparation method and application thereof, belonging to the technical field of carbon nanotube hydrogel synthesis and nanomaterial science.
Background
The hydrogel serving as a three-dimensional porous material has the advantages of being widely researched in the fields of energy sources, biological medicine carrying, intelligent devices, environmental water treatment and the like. At present, the hydrogel is classified according to the material, and can be classified into synthetic polymer-based hydrogel, carbon-based hydrogel and natural-based hydrogel.
The water swell, water absorption and water absorption rate of the hydrogel may be indicative of the water transport properties of the hydrogel. The gel with the porous structure has the performance of rapid water transmission, and meanwhile, the water transmission performance of the hydrogel is influenced by the environments of acid, alkali and salt.
The superporous hydrogel prepared by monomer polymerization foaming has a micron-sized pore structure, and can realize a rapid water transmission effect through the capillary action of micropores. The superporous hydrogels prepared by this method are a type of hydrogels known to have a faster water transport rate. However, the superporous hydrogel can realize rapid water transmission by adopting a drying technology of ethanol dehydration, and the production process is complex. The porous gel film is coated with super-absorbent polyacrylamide hydrogel and polyacrylic acid particles to realize rapid water absorption expansion, but the transmission rate of expanded water of the porous film is reduced after water absorption by the structure, and finally saturated water absorption cannot be realized. In the carbon-based hydrogel, such as graphene hydrogel, carbon nanotube hydrogel and biological carbohydrate hydrogel, the carbon-based hydrogel has a three-dimensional carbon network structure, and has a large specific surface area and abundant pores. However, although the carbon-based hydrogel prepared at present has abundant micro-nano pores, most of the micro-nano pores are closed pores, and the formation of larger capillary force and the realization of rapid water transmission are difficult. Kuang, J et al prepare polysaccharide-based superporous hydrogel (carbohydrate. Polymer.2011, 83(1), 284-290) by copolymerization foaming of polysaccharide-based monomer and acrylic acid monomer, and realize rapid water transmission.
In acid and alkali environments, natural-based hydrogels (such as chitosan and sodium alginate) and polymer hydrogels are difficult to realize water absorption swelling in acid and alkali environments because functional groups on a macromolecular chain segment undergo protonation reaction to cause the swelling or shrinkage of the macromolecular chain. The carbon-based hydrogel part is prepared by hydrothermal carbonization, the surface of the carbon-based hydrogel contains more hydroxyl and carboxyl, and protonation easily occurs in an acid-base environment. In addition, the water transport performance of the hydrogel is also affected by the salt concentration, and the water transport performance of the hydrogel is obviously reduced by the low-concentration salt solution. Ma, Y et al copolymerized lignin with bisacrylamide and acrylic acid to obtain lignin-based polyacrylic acid nanocomposite hydrogel (Polymer 2017,128, 12-23). The hydrogel can absorb water and swell under acid and alkali, but the water transmission performance in acid-alkali environment is unstable and changes along with the change of pH value.
Disclosure of Invention
The invention aims to provide an extremely-tolerant carbon nanotube hydrogel, a preparation method and application thereof, so that the defects of the prior art are overcome.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an extremely tolerant carbon nanotube hydrogel, which comprises the following steps:
providing a carbon nanotube aerogel;
infiltrating the surface of the carbon nanotube aerogel with a first aqueous solution containing small molecules and/or macromolecules, and then drying to obtain a small molecule and/or macromolecule modified carbon nanotube xerogel;
and fully soaking the carbon nanotube xerogel into a second aqueous solution to obtain the extremely-tolerant carbon nanotube hydrogel.
In some preferred embodiments, the small molecule includes any one or a combination of two or more of ethanol, ethylene glycol, glycerol, n-butanol, erythritol, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and the like, but is not limited thereto.
In some preferred embodiments, the polymer includes any one or a combination of two or more of polyvinyl alcohol, polyethylene glycol, polyglycerol, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyisopropylacrylamide, polyvinylpyrrolidone, hydroxymethyl cellulose, carboxymethyl cellulose, chitosan, sodium alginate, and the like, but is not limited thereto.
The embodiment of the invention also provides the carbon nano tube hydrogel prepared by the method, the carbon nano tube hydrogel has a reversible double-network structure, the porosity of the carbon nano tube hydrogel is 90-99%, and the water transmission rate is 2-30 g g-1s-1The conductivity is 2-80S/m, the saturated water absorption capacity in strong acid, strong base, strong salt and high temperature environment is at least 300 times of the self weight, and the carbon nano tube hydrogel has the characteristics of super elasticity and compression resistance and can realize reversible recovery under compression deformation of more than 90%.
The embodiment of the invention also provides application of the carbon nanotube hydrogel in the fields of water environment treatment, seawater desalination, traumatic wound healing, emergency tourniquets, biological medicine carrying, new energy devices, underwater sensing devices, flexible wearable devices or detection.
Compared with the prior art, the invention has the beneficial effects that:
compared with the hydrogel researched in the prior art, the carbon nanotube hydrogel prepared by the method disclosed by the invention has an ultra-fast water transmission characteristic, and the hydrogel has excellent tolerance to acid, alkali, salt, organic and other environments. The carbon nanotube hydrogel can still be reversibly recovered under the condition of large-degree compression, and the characteristics enable the carbon nanotube hydrogel to have wide application prospects in the fields of traumatic wound healing, emergency tourniquets, biological medicine carrying, water environment treatment, seawater desalination and the like. In addition, compared with the common hydrogel, the carbon nanotube hydrogel prepared by the method has higher conductivity, so that the hydrogel has better application prospects in the electronic fields of new energy devices, wearability, underwater sensing, detection and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1A is an SEM image of an extremely tolerant carbon nanotube hydrogel in an exemplary embodiment of the invention;
FIG. 1B is a pictorial representation of an extremely durable carbon nanotube hydrogel in accordance with an exemplary embodiment of the present invention;
FIG. 2 is a graph comparing the electrical conductivity of an extremely durable carbon nanotube hydrogel and a carbon nanotube aerogel in an exemplary embodiment of the invention.
FIG. 3 is a graph of the results of rheological testing of an extremely durable carbon nanotube hydrogel in an exemplary embodiment of the invention;
FIG. 4 is a graph illustrating the results of a compression testing of an extremely durable carbon nanotube hydrogel in an exemplary embodiment of the invention;
FIG. 5 is a graph showing the results of a cyclic compression performance test of an extremely durable carbon nanotube hydrogel in an exemplary embodiment of the invention.
Detailed Description
In view of the defects of hydrogel in water transmission and environmental tolerance in the prior art, the inventor of the present invention has made a long-term study and a great deal of practice to provide the technical scheme of the present invention, which is mainly to prepare the carbon nanotube aerogel through the chemical vapor deposition technology, and the carbon nanotube aerogel is compounded with the micromolecule hydrogel and the high molecular hydrogel to prepare the carbon nanotube hydrogel with the reversible double-network structure and the extreme tolerance. The technical solution, the implementation process and the principle thereof will be further explained with reference to the attached drawings, but it should not be understood as the limitation of the scope of the present invention, and the insubstantial modifications and adjustments made by those skilled in the art according to the above disclosure still belong to the scope of the present invention.
As one aspect of the technical solution of the present invention, it relates to a method for preparing an extremely tolerant carbon nanotube hydrogel, comprising:
providing a carbon nanotube aerogel;
infiltrating the surface of the carbon nanotube aerogel with a first aqueous solution containing small molecules and/or macromolecules, and then drying to obtain a small molecule and/or macromolecule modified carbon nanotube xerogel;
and fully soaking the carbon nanotube xerogel into a second aqueous solution to obtain the extremely-tolerant carbon nanotube hydrogel.
In some preferred embodiments, the small molecule may include any one or a combination of two or more of ethanol, ethylene glycol, glycerol, n-butanol, erythritol, Sodium Dodecylbenzenesulfonate (SDBS), Sodium Dodecylsulfate (SDS), and the like, but is not limited thereto.
In some preferred embodiments, the polymer may include any one or a combination of two or more of polyvinyl alcohol, polyethylene glycol, polyglycerol, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyisopropylacrylamide, polyvinylpyrrolidone, hydroxymethylcellulose, carboxymethylcellulose, chitosan, sodium alginate, and the like, but is not limited thereto.
In some preferred embodiments, the concentration of the first aqueous solution is 0.05 to 15.0 wt%.
In some preferred embodiments, the soaking time is 0.5-3 h.
In some preferred embodiments, the preparation method comprises: and taking the carbon nanotube aerogel out of the first aqueous solution, and drying at 30-120 ℃ for 0.5-5 h to obtain the carbon nanotube xerogel.
In some preferred embodiments, the second aqueous solution includes any one or a combination of two or more of water, an acidic solution, a basic solution, a salt solution, and the like, but is not limited thereto.
Further, the acidic substance contained in the acidic solution includes any one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like, but is not limited thereto.
Further, the alkaline substance contained in the alkaline solution includes any one or a combination of two or more of ammonia, sodium hydroxide, potassium hydroxide, and the like, but is not limited thereto.
Further, the salt solution contains salts including any one or a combination of two or more of sulfate, chloride, nitrate, phosphate, and the like, but is not limited thereto.
In some preferred embodiments, the temperature of the second aqueous solution is 0 to 100 ℃.
Further, the pH value of the second aqueous solution is 0-14.
Further, the concentration of the salt solution is 0.01-25.50 wt%.
In some preferred embodiments, the preparation method comprises: and preparing the carbon nano tube aerogel by adopting a floating catalytic chemical vapor deposition method and a secondary deposition method.
In some more specific embodiments, the extremely tolerant carbon nanotube hydrogels are prepared by the following steps:
preparing carbon nano tube aerogel in a protective atmosphere in a tubular furnace by adopting a floating catalysis technology and secondary deposition;
soaking the carbon nano tube aerogel in micromolecule and macromolecule aqueous solution with certain concentration for 0.5-3 h, taking out and drying at 30-120 ℃ to obtain the carbon nano tube xerogel. And (3) soaking the carbon nanotube xerogel in water with the temperature of 0-100 ℃ and the pH value of 0-14 to prepare the carbon nanotube hydrogel.
In some preferred embodiments, the carbon nanotube aerogel may be a single-walled carbon nanotube aerogel, a multi-walled carbon nanotube aerogel, or the like, but is not limited thereto.
In some preferred embodiments, the carbon nanotube aerogel may be a three-dimensional disordered carbon nanotube aggregate, a three-dimensional ordered carbon nanotube array, or the like, but is not limited thereto.
Further, the three-dimensional carbon nanotube aggregate is subjected to mechanical strength enhancement by using a CVD method and nano carbon to obtain the compression-resistant carbon nanotube aerogel.
Further, the carbon nanotube hydrogel has a super-hydrophobic interface, and the contact angle with water is more than 150 degrees.
Furthermore, the carbon nanotube aerogel is modified by small molecules and macromolecules to form a double-network structure.
Among them, in some more preferred embodiments, a method for preparing a porous compression-resistant carbon nanotube aerogel comprises:
(1) heating a reaction chamber of chemical vapor deposition equipment to 800-1400 ℃ in a protective atmosphere, then at least introducing a first carbon source, a reducing gas and a catalyst into the reaction chamber, and reacting for 2-10 hours to obtain a cage-shaped carbon nanotube assembly;
(2) and in a protective atmosphere, heating the reaction chamber of the chemical vapor deposition equipment to 800-1400 ℃ again, then at least introducing a second carbon source into the reaction chamber, and reacting for 10-120 min to obtain the carbon nanotube aerogel.
Further, the specific steps of the preparation method of the carbon nanotube aerogel are detailed as follows:
(1) and (3) heating a Chemical Vapor Deposition (CVD) system to 800-1400 ℃ at the speed of 5-15 ℃/min in a protective gas of nitrogen or argon, introducing a hydrogen/protective gas mixed gas, injecting the hydrogen/protective gas mixed gas into the CVD system by using ethanol, dichlorobenzene and the like as carbon sources and ferrocene as a catalyst, and generating a cage-shaped carbon nanotube assembly at the tail part.
(2) And (3) placing the generated carbon nanotube assembly in a CVD (chemical vapor deposition) tube furnace, heating to 800-1400 ℃ at the speed of 5-15 ℃/min under the protective gas of nitrogen or argon, introducing carbon sources such as ethanol, ethylene, methane, acetylene and the like, preserving heat for 10-120 min, and cooling to obtain the porous compression-resistant carbon nanotube aerogel.
In some preferred embodiments, the preparation method comprises: and heating the temperature in the reaction chamber to 800-1400 ℃ at a heating rate of 2-25 ℃/min, preferably 5-15 ℃/min.
Further, the floating catalysis temperature of the carbon nano tube aerogel in the step (1) is 800-1400 ℃, and the heating rate is 2-25 ℃/min; the temperature adopted by the secondary deposition technology in the step (2) is 800-1400 ℃, and the heating rate is 2-25 ℃/min.
In some preferred embodiments, the first carbon source used in the floating catalytic technology of step (1) may include any one or a combination of two or more of ethanol, toluene, dichlorobenzene, xylene, and the like, but is not limited thereto.
In some preferred embodiments, the second carbon source in the step (2) secondary deposition technique may include any one or a combination of two or more of ethanol, toluene, xylene, methane, ethylene, acetylene, and the like, but is not limited thereto.
Further, the catalyst used in the floating catalyst technology of step (1) may include any one or a combination of two or more of ferric chloride, cobalt chloride, nickel chloride, titanium dioxide, ferrocene, etc., but is not limited thereto.
Further, the step (1) further comprises: introducing an auxiliary agent into the reaction chamber, wherein the auxiliary agent may include one or any combination of thiophene, carbon disulfide and the like, but is not limited thereto.
Further, the introduction rate (i.e. injection rate) of the first carbon source, the second carbon source and the catalyst is 10-100 ml/h.
Further, the reducing gas includes hydrogen.
Further, the gas used in the floating catalysis technology of the carbon nanotube aerogel is a mixed gas of hydrogen and an inert gas, and the inert gas may be argon, nitrogen, and the like, but is not limited thereto.
Further, the gas of the protective atmosphere used in the secondary deposition technique is a mixed gas of hydrogen and an inert gas, and the inert gas may be argon, nitrogen, or the like, but is not limited thereto.
In one aspect, the present invention relates to a carbon nanotube hydrogel prepared by the method described above.
Further, the carbon nanotube hydrogel has a reversible double-network structure, and the porous structure of the carbon nanotube aerogel is maintained by the carbon nanotube hydrogel, so that the hydrogel has an ultra-fast water transmission rate and saturated water absorption capacity.
Further, the porosity of the carbon nanotube hydrogel reaches 90-99%.
Further, the water transmission rate of the carbon nano tube hydrogel reaches 2-30 g g-1s-1。
Further, the electric conductivity of the carbon nano tube hydrogel reaches 2-80S/m.
Furthermore, the carbon nanotube hydrogel can be reversibly reused, has excellent environmental tolerance, can be reused in extreme environments such as strong acid (the concentration is more than 1mol/L), strong base (the concentration is more than 1mol/L), strong salt (the content of salt is more than 20 wt%), high temperature (such as boiling water) and the like, and can realize rapid water transmission and large saturated water absorption capacity, wherein the saturated water absorption capacity can reach 300 times of the weight of the hydrogel.
Further, the temperature of the high-temperature environment is 60-100 ℃.
Furthermore, the carbon nanotube hydrogel has a rapid water transmission channel, and can realize rapid water transmission and large adsorption capacity in acid, alkali, salt and other environments, and has very wide application prospects in water treatment, seawater desalination, emergency tourniquets, underwater sensing and the like.
Further, the carbon nanotube hydrogel has the characteristics of super elasticity and compression resistance, and can realize reversible recovery under the compression deformation of more than 90%.
As one aspect of the technical scheme of the invention, the carbon nanotube hydrogel is applied to the fields of water environment treatment, seawater desalination, traumatic wound healing, emergency tourniquets, biological medicine carrying, biological medicine, new energy devices, underwater sensing devices, flexible wearable devices or detection.
By the preparation process, the carbon nano tube hydrogel prepared by the invention has ultra-fast water transmission characteristics, and the hydrogel has excellent tolerance to acid, alkali, salt, organic and other environments. The carbon nanotube hydrogel can still recover reversibly under the condition of large-degree compression. The characteristics enable the carbon nanotube hydrogel to have wide application prospects in the fields of traumatic wound healing, tourniquets, biological drug loading, water environment treatment and the like. In addition, compared with the common hydrogel, the carbon nanotube hydrogel prepared by the method has higher conductivity, so that the hydrogel has better application prospect in the electronic fields of wearable, underwater sensing, detection and the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described in further detail below with reference to the accompanying drawings and several preferred embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples are carried out under conventional conditions without specifying the specific conditions. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The carbon nanotube aerogels in the following examples were prepared using this protocol:
(1) and (3) heating a Chemical Vapor Deposition (CVD) system to 800-1400 ℃ at the speed of 5-15 ℃/min in a protective gas of nitrogen or argon, introducing a hydrogen/protective gas mixed gas, injecting the hydrogen/protective gas mixed gas into the CVD system by using ethanol, dichlorobenzene and the like as carbon sources and ferrocene as a catalyst, and generating a cage-shaped carbon nanotube assembly at the tail part.
(2) And (3) placing the generated carbon nanotube assembly in a CVD (chemical vapor deposition) tube furnace, heating to 800-1400 ℃ at the speed of 5-15 ℃/min under the protective gas of nitrogen or argon, introducing carbon sources such as ethanol, ethylene, methane, acetylene and the like, preserving heat for 10-120 min, and cooling to obtain the porous compression-resistant carbon nanotube aerogel.
Example 1
And cutting the prepared carbon nanotube aerogel into a proper size by using a laser cutting machine. Preparing a Sodium Dodecyl Sulfate (SDS) water solution with the concentration of 1%, taking a proper amount of the Sodium Dodecyl Sulfate (SDS) solution, and soaking the carbon nanotube aerogel in the solution for 1h to prepare the Sodium Dodecyl Sulfate (SDS) -modified carbon nanotube hydrogel. The hydrogel was placed in a forced air oven and dried at 80 ℃ for 8h to give a carbon nanotube xerogel (labeled as CNT/SDS). The obtained carbon nanotube xerogel is placed in deionized water with the temperature of 25 ℃ and the pH value of 7 to obtain the carbon nanotube hydrogel, and the SEM picture can be seen in figure 1A, and the object picture can be seen in figure 1B. The hydrogel was investigated for water transport rate and water absorption capacity, and the test results are shown in table 1.
Example 2
And cutting the prepared carbon nanotube aerogel into a proper size by using a laser cutting machine. Preparing 1% polyvinylpyrrolidone (PVP) aqueous solution, taking a proper amount of the PVP solution, and soaking the carbon nano tube aerogel in the solution for 1h to prepare the polyvinylpyrrolidone (PVP) modified carbon nano tube hydrogel. The hydrogel was placed in a forced air oven and dried at 80 ℃ for 8h to give a carbon nanotube xerogel (labeled as CNT/PVP). The obtained carbon nanotube xerogel was placed in deionized water at 25 ℃ and pH 7 to obtain a carbon nanotube hydrogel, and the water transmission rate and water absorption capacity of the hydrogel were investigated, and the test results are shown in Table 1.
Example 3
And cutting the prepared carbon nanotube aerogel into a proper size by using a laser cutting machine. Preparing a polyvinyl alcohol (PVA) aqueous solution with the concentration of 1%, taking a proper amount of the PVA solution, and soaking the carbon nano tube aerogel in the solution for 1h to prepare the PVA (PVA) -modified carbon nano tube hydrogel. The hydrogel was placed in a forced air oven and dried at 80 ℃ for 8h to give a carbon nanotube xerogel (labeled as CNT/PVA). The obtained carbon nanotube xerogel was placed in deionized water at 25 ℃ and pH 7 to obtain a carbon nanotube hydrogel, and the water transport rate and water absorption capacity of the hydrogel were investigated, and the test results are shown in table 1.
Example 4
Cutting the prepared carbon nano tube aerogel into a proper size by using a laser cutting machine. Preparing a polyethylene glycol (PEG) aqueous solution with the concentration of 1%, taking a proper amount of polyethylene glycol (PEG) solution, and soaking the carbon nano tube aerogel in the solution for 1h to prepare the polyethylene glycol (PEG) -modified carbon nano tube hydrogel. The hydrogel was placed in a forced air oven and dried at 80 ℃ for 8h to give a carbon nanotube xerogel (labeled as CNT/PEG). The obtained carbon nanotube xerogel was placed in deionized water at 25 ℃ and pH 7 to obtain a carbon nanotube hydrogel, and the water transport rate and water absorption capacity of the hydrogel were investigated, and the test results are shown in table 1.
The results of the water transport rate and water absorption test of the carbon nanotube hydrogels obtained in examples 1 to 4 are shown in table 1 below:
table 1 results of water transport rate and water absorption capacity test of the carbon nanotube hydrogels obtained in examples 1 to 4
Example 5
The CNT/PVA xerogels prepared in example 3 above were placed in 1M hydrochloric acid (pH 0), pH 5, pH 7, pH 9, 1mol/L sodium hydroxide (pH 14) solutions, respectively, to obtain carbon nanotube hydrogels, and the water transport rate and water absorption capacity of the hydrogels were investigated at different pH values.
The results of the water transport rate and water absorption test of the carbon nanotube hydrogel obtained in example 5 are shown in the following table 2:
table 2 test results of water transport rate and water absorption amount of the carbon nanotube hydrogel obtained in example 5
Example 6
The CNT/PVA xerogels prepared in example 3 above were placed in salt solutions (NaCl) of different concentrations, 0.01 wt%, 0.5 wt%, 1 wt%, 10 wt%, 25.5 wt%, respectively, to obtain carbon nanotube hydrogels, and the water transport rates and water absorption amounts of the hydrogels in different salt concentrations were investigated.
The results of the water transport rate and water absorption test of the carbon nanotube hydrogel obtained in example 6 are shown in table 3 below:
table 3 test results of water transport rate and water absorption amount of the carbon nanotube hydrogel obtained in example 6
Example 7
The CNT/PVA xerogels prepared in the above example 3 were placed in deionized water (pH 7) at different temperatures, 0 ℃, 20 ℃, 60 ℃ and 100 ℃ respectively, to obtain carbon nanotube hydrogels, and the water transport rate and water absorption capacity of the hydrogels in water at different temperatures were studied.
The results of the water transport rate and water absorption test of the carbon nanotube hydrogel obtained in example 7 are shown in Table 4 below:
table 4 test results of water transport rate and water absorption amount of the carbon nanotube hydrogel obtained in example 7
Further, the electrical conductivity of the carbon nanotube aerogel described above and the CNT/PVA hydrogel prepared in example 3 was measured and calculated using a two-wire method. The test result is shown in fig. 2, which indicates that the electrical conductivity of the prepared carbon nanotube hydrogel subjected to PVA modification treatment is equivalent to that of the carbon nanotube aerogel, and indicates that the carbon nanotube hydrogel has a very excellent conductive network structure inside.
Further, the CNT/PVA hydrogel prepared in example 3 was subjected to a rheological test at a temperature of 25 ℃ with a frequency change of 1 to 100 rad/s. The results of the tests are shown in FIG. 3, which shows that PVA and CNT form an elastic double-network structure through non-covalent crosslinking.
Further, the CNT/PVA hydrogel prepared in example 3 was subjected to a compression property test, and the change in the compressive stress at which the compressive strain of the carbon nanotube hydrogel was 10 to 90% was measured with a compression rate of 10 mm/min. The test results are shown in fig. 4, which shows that the carbon nanotube hydrogel has very excellent compression resistance, and the structural integrity can be maintained when the compression strain reaches 90%.
Further, the CNT/PVA hydrogel prepared in example 3 was subjected to a cyclic compression performance test, the compression rate was set to 10mm/min, the compression strain was 90%, and the CNT/PVA hydrogel cyclic compression stability was characterized by the cyclic compression test. The test results are shown in FIG. 5, which shows that the CNT/PVA hydrogel has very excellent cyclic compression stability, and the structural stability can be maintained after 50 cycles, and the hydrogel structure is not damaged.
Example 8
And cutting the prepared carbon nanotube aerogel into a proper size by using a laser cutting machine. Preparing a polyglycerol aqueous solution with the concentration of 0.05%, taking a proper amount of polyglycerol solution, and soaking the carbon nano tube aerogel in the solution for 0.5h to prepare the polyglycerol-modified carbon nano tube hydrogel. And (3) placing the hydrogel in a blast oven, and drying at 30 ℃ for 5h to obtain the carbon nanotube xerogel. The obtained carbon nanotube xerogel was placed in deionized water at 25 ℃ and pH 7 to obtain a carbon nanotube hydrogel, and the water transport rate and water absorption capacity of the hydrogel were investigated, and the test results were substantially the same as those of example 3.
In addition, the inventors of the present invention also performed experiments by replacing the polyvinyl alcohol in example 3 with polyacrylic acid, sodium polyacrylate, polyacrylamide, polyisopropylacrylamide, hydroxymethyl cellulose, carboxymethyl cellulose, chitosan, sodium alginate, and the like, respectively, and also obtained better results.
Example 9
And cutting the prepared carbon nanotube aerogel into a proper size by using a laser cutting machine. Preparing a sodium dodecyl benzene sulfonate aqueous solution with the concentration of 15.0%, taking a proper amount of the sodium dodecyl benzene sulfonate solution, and soaking the carbon nano tube aerogel in the solution for 3 hours to prepare the sodium dodecyl benzene sulfonate modified carbon nano tube hydrogel. And (3) placing the hydrogel in a blast oven, and drying at 120 ℃ for 0.5h to obtain the carbon nanotube xerogel. Placing the obtained carbon nano tube xerogel in deionized water with the temperature of 25 ℃ and the pH value of 7 to obtain carbon nano tube hydrogel,
in addition, the inventors also obtained better results by carrying out experiments by replacing the sodium lauryl sulfate in example 1 with ethanol, ethylene glycol, glycerol, n-butanol, erythritol, etc.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (5)
1. A preparation method of an extremely tolerant carbon nanotube hydrogel is characterized by comprising the following steps:
providing a carbon nanotube aerogel, wherein the carbon nanotube aerogel is prepared by adopting the following method:
(1) heating the chemical vapor deposition system to 800-1400 ℃ at the speed of 5-15 ℃/min in a protective gas of nitrogen or argon, introducing a hydrogen/protective gas mixed gas, injecting ethanol or dichlorobenzene serving as a first carbon source and ferrocene serving as a catalyst into the chemical vapor deposition system, and generating a cage-shaped carbon nanotube assembly;
(2) placing the carbon nanotube assembly in a CVD (chemical vapor deposition) tube furnace, heating to 800-1400 ℃ at the speed of 5-15 ℃/min under the protective gas of nitrogen or argon, introducing ethanol, ethylene, methane or acetylene as a second carbon source, preserving heat for 10-120 min, and cooling to obtain the carbon nanotube aerogel;
infiltrating the surface of the carbon nanotube aerogel with a first aqueous solution containing micromolecules and/or macromolecules, taking the carbon nanotube aerogel out of the first aqueous solution, drying at 30-120 ℃ for 0.5-5 h to obtain micromolecule and/or macromolecule modified carbon nanotube xerogel, wherein the micromolecules are selected from any one or combination of more than two of ethanol, ethylene glycol, glycerol, n-butanol, erythritol, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, the macromolecules are selected from any one or combination of more than two of polyvinyl alcohol, polyethylene glycol, polyglycerol, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyisopropyl acrylamide, polyvinylpyrrolidone, hydroxymethyl cellulose, carboxymethyl cellulose, chitosan and sodium alginate, the concentration of the first aqueous solution is 0.05-15.0 wt%, the soaking time is 0.5-3 h;
fully immersing the carbon nanotube xerogel into a second aqueous solution to obtain an extremely tolerant carbon nanotube hydrogel, wherein the second aqueous solution is selected from water, an acidic solution, an alkaline solution or a salt solution, the temperature of the second aqueous solution is 0-100 ℃, and the pH value of the second aqueous solution is 0-14;
the carbon nanotube hydrogel has a reversible double-network structure, the porosity of the carbon nanotube hydrogel is 90-99%, and the water transmission rate is 2-30 g g-1s-1The conductivity is 2 to 80S/m.
2. The method of claim 1, wherein: the acidic substance contained in the acidic solution is selected from any one or the combination of more than two of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
3. The method of claim 1, wherein: the alkaline substance contained in the alkaline solution is selected from any one or the combination of more than two of ammonia water, sodium hydroxide and potassium hydroxide.
4. The method of claim 1, wherein: the salt solution contains one or more of sulfate, chloride, nitrate and phosphate.
5. The method of claim 4, wherein: the concentration of the salt solution is 0.01-25.50 wt%.
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| CN113350569B (en) * | 2021-06-18 | 2022-07-08 | 西北大学 | Preparation method of hydrogel based on carbon nanotube composite molybdenum disulfide nanosheet |
| CN113354433A (en) * | 2021-07-01 | 2021-09-07 | 江苏脒诺甫纳米材料有限公司 | High-temperature-resistant silicon-based ceramic-based aerogel and preparation method thereof |
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