CN111617747A - Chitosan/nano-metal composite hydrogel and preparation method and application thereof - Google Patents

Chitosan/nano-metal composite hydrogel and preparation method and application thereof Download PDF

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CN111617747A
CN111617747A CN202010394620.3A CN202010394620A CN111617747A CN 111617747 A CN111617747 A CN 111617747A CN 202010394620 A CN202010394620 A CN 202010394620A CN 111617747 A CN111617747 A CN 111617747A
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张丽华
谢海波
黄富荣
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Guizhou University
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Abstract

The invention discloses a chitosan/nano metal composite hydrogel and a preparation method and application thereof. The chitosan hydrogel containing sulfhydryl or thioether is used as a matrix, and metal nano-particles with the particle size of 0.1-100nm are uniformly dispersed in the matrix. Can be used in the fields of catalysis, water treatment, pharmacy and antibiosis. The invention has the characteristics of good metal nanoparticle loading stability and high dispersibility, and also has the characteristics of simple preparation process, convenient operation, low cost and wide application range.

Description

Chitosan/nano-metal composite hydrogel and preparation method and application thereof
Technical Field
The invention relates to a hydrogel and a preparation method and application thereof, in particular to a chitosan/nano metal composite hydrogel and a preparation method and application thereof.
Background
Polymeric hydrogels are materials with a three-dimensional network structure. Two conditions must be met for the polymer to become a hydrogel material: the main chain or the side chain of the macromolecule has a large number of hydrophilic groups and has a proper cross-linked network structure. The starting material for preparing the polymer hydrogel can be a monomer (water-soluble or oil-soluble monomer), a polymer (natural or synthetic polymer) or a mixture of a monomer and a polymer (functional material, 2003(4): 382-385). The hydrogel can generate obvious swelling behavior in water, can keep a certain shape and cannot be dissolved. The water absorption capacity and water retention capacity of hydrogels generally depend on a three-dimensional network structure composed by covalent bonds, hydrogen bonds, ionic bonds, physical entanglement, etc. (Soft Matter,2010,6(11), 2364-. Hydrogels exist in a variety of physical forms, including membranes, spheres, microgels and nanogels, among others.
The hydrogel taking marine biomass as the raw material is beneficial to relieving the shortage of petroleum resources and preventing global warming, and has attracted extensive attention at home and abroad. Chitosan, as a typical marine biomass material, is the only basic polysaccharide existing in large quantities in nature, has good hygroscopicity, moisture retention, biodegradability, biocompatibility, antibacterial property and the like, and has important significance for sustainable development of the whole human society by fully utilizing cellulose resources (Progress in polymer science,2011,36(8), 981-. The chitosan is insoluble in water and alkaline solution, and can be dissolved in organic acid solution such as formic acid, acetic acid and the like and inorganic acid such as diluted phosphoric acid, diluted hydrochloric acid and the like; the amino group on the molecular structure of the chitosan can be protonated to form-NH 3+ in an acid solution, and the carboxyl group of the dilute acid is deprotonated to form-COO-. The addition of the dibasic acid can introduce a cross-linking structure among molecular chains of the chitosan.
The nano metal with the size less than 100nm has surface effect and quantum size effect, shows different characteristics of Catalysis, optics, electricity and the like from the macroscopic bulk metal, and has potential application in the fields of Catalysis, sensors, photoelectric devices, biomedicine and the like (Applied Catalysis B-Environmental, 241, 415-423). Generally, the production of nanometals requires the reduction of the high-valence metal ions to zero-valence. However, pure nano-metal has high surface energy, and is easily aggregated to form large-sized metal particles, and meanwhile, the unique properties of nano-metal are lost. Therefore, immobilization of nanometals on a suitable support is an effective approach to solve this problem.
Although the research of loading metal nanoparticles by using hydrogel, graphene, silica microspheres and the like as carriers has been carried out at present, the current loading modes have the defects of poor loading stability and low dispersibility.
Disclosure of Invention
The invention aims to provide chitosan/nano metal composite hydrogel and a preparation method and application thereof. The invention has the characteristics of good metal nanoparticle loading stability and high dispersibility, and also has the characteristics of simple preparation process, convenient operation, low cost and wide application range.
The technical scheme of the invention is as follows: a chitosan/nano metal composite hydrogel takes chitosan hydrogel containing sulfydryl or thioether as a matrix, and metal nano particles with the particle size of 0.1-100nm are uniformly dispersed in the matrix.
A preparation method of the chitosan/nano metal composite hydrogel comprises the following steps:
(1) selecting chitosan as a raw material;
(2) mixing chitosan, mercaptoacid or thioether acid and water;
(3) reacting the mixture at 20-80 ℃ for 1-8h to obtain homogeneous chitosan solution;
(4) centrifuging and defoaming the homogeneous chitosan solution, and then dripping ethanol into the homogeneous chitosan solution to form spherical chitosan gel;
(5) placing the spherical chitosan gel in a solution containing target metal ions, and oscillating for 1-48h at normal temperature to adsorb the target metal ions;
(6) and placing the gel adsorbed with the target metal ions in a sodium borohydride solution, and oscillating for 1-48h at normal temperature to obtain the chitosan/nano metal composite hydrogel.
In the preparation method of the chitosan/nano metal composite hydrogel, the chitosan in the step (1) is one or a combination of any more of chitosan extracted from crab shells, shrimp shells, insects or microorganisms and other biomass resources; the deacetylation degree of the chitosan is 50% -100%.
In the preparation method of the chitosan/nano metal composite hydrogel, the mercapto acid or the thioether acid in the step (2) has water solubility, and the mercapto acid or the thioether acid has the following structural characteristics:
Figure RE-GDA0002601207610000031
wherein:
a series is monoacid containing sulfydryl;
b series dibasic acid containing sulfhydryl or thioether.
In the preparation method of the chitosan/nano metal composite hydrogel, in the mixed system in the step (2), the mass concentration of the chitosan is 0.1-10%, and the mass concentration of the mercapto acid or the thioether acid is 0.1-30%.
In the preparation method of the chitosan/nano metal composite hydrogel, the volume ratio of the ethanol to the chitosan solution in the step (4) is 5-10: 1.
In the preparation method of the chitosan/nano metal composite hydrogel, the chitosan has the following structure:
Figure RE-GDA0002601207610000032
therein, 50<n<1000, parts by weight; r is-NH2Or protonated amino-NH3 +(ii) a Wherein, when the amino group is protonated, the mercapto acid or the thioether acid is deprotonated to form one or more than one mixture of the following structures:
Figure RE-GDA0002601207610000041
wherein:
a series is monoacid containing sulfydryl;
b series dibasic acid containing sulfhydryl or thioether.
In the preparation method of the chitosan/nano-metal composite hydrogel, the metal ion concentration in the solution containing the target metal ions in the step (5) is 0.01-100mg/mL, and the volume ratio of the spherical chitosan gel to the solution containing the target metal ions is 1: 10-100.
In the preparation method of the chitosan/nano-metal composite hydrogel, the concentration of the sodium borohydride solution in the step (6) is 0.01-10mol/L, and the volume ratio of the gel adsorbed with the target metal ions to the sodium borohydride solution is 1: 10-100.
The chitosan/nano metal composite hydrogel is applied to the fields of catalysis, water treatment, pharmacy and antibiosis.
The invention has the advantages of
According to the invention, chitosan is dissolved in aqueous solution of mono-carboxylic acid and dicarboxylic acid containing sulfydryl or thioether, the amino group of a chitosan molecular chain is protonated to destroy the hydrogen bond network structure of the chitosan to promote the dissolution of the chitosan molecular chain, the dicarboxylic acid has a crosslinking effect on the chitosan molecular chain, chitosan hydrogel containing sulfydryl or thioether is prepared through the regeneration of an anti-solvent, and then nano metal particles are loaded on the gel, so that the chitosan/nano metal composite hydrogel material is prepared.
The invention has the obvious advantages that the prepared composite hydrogel material takes the chitosan hydrogel containing sulfydryl or thioether as a matrix, nano metal is uniformly dispersed in the matrix, the particle size is about 0.1-100nm, and the composite hydrogel material has unique structural advantages; the chitosan hydrogel is convenient and rapid to prepare, controllable in size and shape, has a sulfur-containing sulfydryl or thioether group, an amino group and a hydroxyl group on a molecular structure, can stably load a large amount of nano metal, and can effectively avoid the problem of agglomeration in the preparation process of the nano metal.
The chitosan/nano metal composite hydrogel material prepared by the invention can be applied to the fields of catalysis, water treatment, pharmacy, antibiosis and the like, for example, can be used for catalyzing and degrading nitrobenzene derivatives, can be used for adsorbing mercury ions in water, and can be used for producing medical intermediates such as 4-aminophenol and the like.
The invention also has the advantages of simple process, convenient operation, low cost and the like.
Drawings
FIG. 1: the invention discloses a flow chart of patent steps;
FIG. 2: scanning Electron Microscope (SEM) photographs of the chitosan/nanogold composite hydrogel;
FIG. 3: a Transmission Electron Microscope (TEM) picture and an XRD spectrogram of the chitosan/nano-gold composite hydrogel;
FIG. 4: the ultraviolet-visible spectrophotometer monitored the 4-nitrophenol reduction process.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1
The preparation method comprises the following steps:
(1) selecting chitosan with deacetylation degree of 50% as a raw material;
(2) mixing 0.1 wt% of chitosan, 0.1 wt% of mercaptoacid or thioether acid and the balance of water;
(3) placing the mixture at 20 ℃ for reacting for 8h to obtain homogeneous chitosan solution;
(4) centrifuging and defoaming homogeneous chitosan solution, and then mixing the solution according to the volume ratio of 1: 5, dripping ethanol to form spherical chitosan gel;
(5) placing the spherical chitosan gel in a solution containing target metal ions, wherein the concentration of the metal ions is 0.01mg/mL, oscillating for 48 hours at normal temperature, and adsorbing the target metal ions;
(6) placing the gel adsorbed with the target metal ions in a sodium borohydride solution with the concentration of 0.01mol/L according to the volume ratio of 1:10, and oscillating for 48 hours at normal temperature to obtain the chitosan/nano metal composite hydrogel.
Example 2
The preparation method comprises the following steps:
(1) selecting chitosan with deacetylation degree of 100% as a raw material;
(2) mixing 10 wt% of chitosan, 30 wt% of mercaptoacid or thioether acid and the balance of water;
(3) placing the mixture at 80 ℃ for reaction for 1h to obtain homogeneous chitosan solution;
(4) centrifuging and defoaming homogeneous chitosan solution, and then mixing the solution according to the volume ratio of 1:10, dripping ethanol to form spherical chitosan gel;
(5) placing the spherical chitosan gel in a solution containing target metal ions, wherein the concentration of the metal ions is 100mg/mL, oscillating for 1h at normal temperature, and adsorbing the target metal ions;
(6) placing the gel adsorbed with the target metal ions in a sodium borohydride solution with the concentration of 10mol/L according to the volume ratio of 1:100, and oscillating for 1h at normal temperature to obtain the chitosan/nano metal composite hydrogel.
Example 3
Crab chitosan 1.25 g, 3-mercaptopropionic acid 0.394 g, thiomalic acid 0.279 g and deionized water 20mL were weighed according to the procedure of example 1, and added together into a round bottom flask at 80 ℃ with mechanical stirring for 6h to obtain a homogeneous solution of chitosan. The chitosan solution was subjected to centrifugal deaeration at 10,000rpm, and was dropped dropwise into 3 times the amount of absolute ethanol using a disposable syringe to form chitosan gel beads having a diameter of 3 mm. Soaking the hydrogel beads in anhydrous ethanol for 2 hr for aging. Transferring 300 chitosan gel beads to 50mL of 1.5mM sodium chloroaurate aqueous solution, oscillating for 24h at 25 ℃, transferring the chitosan gel column to 30mL of 0.1M sodium borohydride aqueous solution, oscillating for 2h at 25 ℃, and reducing the loaded Au (III) into the nano-gold to obtain the chitosan/nano-gold composite hydrogel.
Example 4
The application of the chitosan/nano-gold composite hydrogel comprises the following experimental steps of catalyzing the reduction reaction of 4-nitrophenol to prepare 4-aminophenol:
1) preparing 0.1mM 4-nitrophenol aqueous solution;
2) preparing 0.1M aqueous solution of sodium borohydride;
3) 3ml of NaBH4 solution and 3ml of 4-nitrophenol solution were added into a beaker, 30 chitosan/nanogold composite hydrogel materials prepared in example 2 were added, a reaction was carried out at room temperature, and an ultraviolet-visible spectrophotometer was used to monitor the reaction process.
Example 5
According to the steps of example 1, 1.25 g of shrimp chitosan, 0.71 g of 3-mercaptopropionic acid, 0.5 g of thiomalic acid and 20mL of deionized water are weighed and added into a round-bottom flask together, the temperature is 60 ℃, and the mixture is mechanically stirred for 4 hours to obtain a homogeneous solution of chitosan. The chitosan solution was subjected to centrifugal deaeration at 10,000rpm, and was dropped dropwise into 3 times the amount of absolute ethanol using a disposable syringe to form chitosan gel beads having a diameter of 3 mm. Soaking the hydrogel beads in anhydrous ethanol for 4 hr for aging. Transferring 300 chitosan gel beads to 50mL of 1.5mM sodium chloroaurate aqueous solution, oscillating for 24h at 25 ℃, then transferring the chitosan gel beads to 30mL of 0.1M sodium borohydride aqueous solution, oscillating for 2h at 25 ℃, and reducing the loaded Au (III) into the nano-gold to obtain the chitosan/nano-gold composite hydrogel.
Example 6
According to the steps of example 1, 1.25 g of shrimp chitosan, 0.71 g of thioglycolic acid, 0.5 g of thiomalic acid and 20mL of deionized water are weighed and added into a round bottom flask together, the temperature is 60 ℃, and the mixture is mechanically stirred for 4 hours to obtain a homogeneous solution of chitosan. The chitosan solution was subjected to centrifugal deaeration at 10,000rpm, and was dropped dropwise into 3 times the amount of absolute ethanol using a disposable syringe to form chitosan gel beads having a diameter of 3 mm. Soaking the hydrogel beads in anhydrous ethanol for 4 hr for aging. Transferring 300 chitosan gel beads to 50mL of 1.5mM sodium chloroaurate aqueous solution, oscillating for 24h at 25 ℃, transferring the chitosan gel column to 30mL of 0.1M sodium borohydride aqueous solution, oscillating for 2h at 25 ℃, and reducing the loaded Au (III) into the nano-gold to obtain the chitosan/nano-gold composite hydrogel.
Example 7
According to the procedure of example 1, 1.25 g of chitosan extracted from oyster mushroom mycelia, 0.284 g of 4-mercaptobutyric acid, 0.803 g of thiomalic acid and 20mL of deionized water were weighed and added together into a round-bottomed flask at 40 ℃ with mechanical stirring for 4 hours to obtain a homogeneous solution of chitosan. The chitosan solution was subjected to centrifugal deaeration at 10,000rpm, and was dropped dropwise into 3 times the amount of absolute ethanol using a disposable syringe to form chitosan gel beads having a diameter of 3 mm. Soaking the hydrogel beads in anhydrous ethanol for 4 hr for aging. Transferring 300 chitosan gel beads to 50mL of 1.5mM sodium chloroaurate aqueous solution, oscillating for 24h at 25 ℃, transferring the chitosan gel column to 30mL of 0.1M sodium borohydride aqueous solution, oscillating for 2h at 25 ℃, and reducing the loaded Au (III) into the nano-gold to obtain the chitosan/nano-gold composite hydrogel.
Example 8
According to the procedure of example 1, 1.25 g of chitosan extracted from silkworm pupae, 0.284 g of 3-mercaptopropionic acid, 0.803 g of meso-2, 3-dimercaptosuccinic acid and 20mL of deionized water were weighed and added together into a round-bottomed flask at 40 ℃ with mechanical stirring for 4 hours to obtain a homogeneous solution of chitosan. The chitosan solution was subjected to centrifugal deaeration at 10,000rpm, and was dropped dropwise into 3 times the amount of absolute ethanol using a disposable syringe to form chitosan gel beads having a diameter of 3 mm. Soaking the hydrogel beads in anhydrous ethanol for 4 hr for aging. Transferring 300 chitosan gel beads to 50mL of 1.5mM sodium chloroaurate aqueous solution, oscillating for 24h at 25 ℃, transferring the chitosan gel column to 30mL of 0.1M sodium borohydride aqueous solution, oscillating for 2h at 25 ℃, and reducing the loaded Au (III) into the nano-gold to obtain the chitosan/nano-gold composite hydrogel.
The above description is only for the purpose of illustrating the present invention and the appended claims, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.

Claims (10)

1. A chitosan/nano metal composite hydrogel is characterized in that: the chitosan hydrogel containing sulfhydryl or thioether is used as a matrix, and metal nano-particles with the particle size of 0.1-100nm are uniformly dispersed in the matrix.
2. The method for preparing the chitosan/nano-metal composite hydrogel according to claim 1, comprising the following steps:
(1) selecting chitosan as a raw material;
(2) mixing chitosan, mercaptoacid or thioether acid and water;
(3) reacting the mixture at 20-80 ℃ for 1-8h to obtain homogeneous chitosan solution;
(4) centrifuging and defoaming the homogeneous chitosan solution, and then dripping ethanol into the homogeneous chitosan solution to form spherical chitosan gel;
(5) placing the spherical chitosan gel in a solution containing target metal ions, and oscillating for 1-48h at normal temperature to adsorb the target metal ions;
(6) and placing the gel adsorbed with the target metal ions in a sodium borohydride solution, and oscillating for 1-48h at normal temperature to obtain the chitosan/nano metal composite hydrogel.
3. The method for preparing the chitosan/nano-metal composite hydrogel according to claim 2, wherein: the chitosan in the step (1) is one or the combination of any more of chitosan extracted from crab shells, shrimp shells, insects, microorganisms and other biomass resources; the deacetylation degree of the chitosan is 50-100%.
4. The method for preparing the chitosan/nano-metal composite hydrogel according to claim 2, wherein: the mercapto acid or the thioether acid in the step (2) has water solubility, and the mercapto acid or the thioether acid has the following structural characteristics:
Figure FDA0002487006680000021
wherein:
a series is monoacid containing sulfydryl;
b series dibasic acid containing sulfhydryl or thioether.
5. The method for preparing the chitosan/nano-metal composite hydrogel according to claim 2, wherein: in the mixed system in the step (2), the mass concentration of the chitosan is 0.1-10%, and the mass concentration of the mercapto acid or the thioether acid is 0.1-30%.
6. The method for preparing the chitosan/nano-metal composite hydrogel according to claim 2, wherein: the volume ratio of the ethanol to the chitosan solution in the step (4) is 5-10: 1.
7. The method for preparing the chitosan/nano-metal composite hydrogel according to claim 2, wherein: the chitosan has the following structure:
Figure FDA0002487006680000022
therein, 50<n<1000, parts by weight; r is-NH2Or protonated amino-NH3 +(ii) a Wherein, when the amino group is protonated, the mercapto acid or the thioether acid is deprotonated to form one or more than one mixture of the following structures:
Figure FDA0002487006680000023
wherein:
a series is monoacid containing sulfydryl;
b series dibasic acid containing sulfhydryl or thioether.
8. The method for preparing the chitosan/nano-metal composite hydrogel according to claim 2, wherein: the concentration of the metal ions in the solution containing the target metal ions in the step (5) is 0.01-100mg/mL, and the volume ratio of the spherical chitosan gel to the solution containing the target metal ions is 1: 10-100.
9. The method for preparing the chitosan/nano-metal composite hydrogel according to claim 2, wherein: the concentration of the sodium borohydride solution in the step (6) is 0.01-10mol/L, and the volume ratio of the gel absorbed with the target metal ions to the sodium borohydride solution is 1: 10-100.
10. Use of the chitosan/nanometal composite hydrogel of claim 1 in the fields of catalysis, water treatment, pharmaceuticals and antibacterials.
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CN116393102A (en) * 2023-03-16 2023-07-07 华南农业大学 Cadmium-arsenic synchronous removal composite material and preparation method and application thereof

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