CN114277576B - Preparation method of multifunctional cotton fabric loaded with Cu-MOFs - Google Patents
Preparation method of multifunctional cotton fabric loaded with Cu-MOFs Download PDFInfo
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Abstract
The invention relates to the technical field of functional textile preparation, in particular to a preparation method of a multifunctional cotton fabric loaded with Cu-MOFs, which comprises the following steps: step one, modifying cotton fabric by polycarboxylic acid; and secondly, loading Cu-MOFs on the cotton fabric by adopting a layer-by-layer assembly method at room temperature, and endowing the cotton fabric with various functions such as antibiosis, adsorption, photocatalysis and the like. According to the invention, carboxyl is introduced into cotton fabric to adsorb copper ions, then a layer-by-layer assembly method is adopted, copper ions are combined with ZnO nano particles to form a (Zn, cu) hydroxyl double-salt intermediate, so that the anion exchange rate is improved, and Cu-MOFs are rapidly loaded on the cotton fabric at room temperature. The invention has the characteristics of low energy consumption, simple equipment, convenient operation and the like. The prepared multifunctional cotton fabric loaded with Cu-MOFs has wide application prospect.
Description
Technical Field
The invention relates to the technical field of functional textile preparation, in particular to a preparation method of a multifunctional cotton fabric loaded with Cu-MOFs.
Background
Metal organic framework Materials (MOFs) are a novel class of porous materials formed by the coordinated assembly of organic ligands and inorganic structural units (metal ions or metal clusters) and have microporous, mesoporous and macroporous structures. The method has wide application in the fields of gas phase adsorption and separation, liquid phase adsorption and separation, medicine release, photocatalysis, antibiosis and the like. Copper is used as one of microelements necessary for human body, and although the copper has good biocompatibility, the traditional copper nano particles are difficult to control the release speed of metal ions during antibiosis, and can cause certain damage to normal tissues of the human body. Compared with copper nano particles, the Cu-MOFs have the characteristics of high specific surface area, controllable ion release speed, flexible chemical structure and the like, and have larger application potential.
A common method for preparing Cu-MOFs is solvothermal method. As in patent No. cn202111084845.X, a method for preparing a copper metal organic framework material is disclosed, which promotes the growth of crystal nuclei through high temperature conditions, and consumes a lot of energy. Since the powdery Cu-MOFs have some defects in application, such as the resistance among particles is overcome by the external force of a fluidized bed during gas adsorption, the reduction of the contact area between solids and gas caused by particle deposition is prevented; powder particles are difficult to collect during liquid adsorption, and the recycling rate is low; poor water stability in the catalytic process, and the like, researchers aim to combine Cu-MOFs with fiber materials to improve the performance and widen the application. The common methods mainly comprise in-situ growth, electrostatic spinning, self-assembly and the like. In-situ growth is to attach metal ions or organic ligands in the precursor solution to the fiber, and to use the metal ions or organic ligands as nucleation sites to grow crystals continuously to induce Cu-MOFs to be generated on the surface of the fiber. However, the nucleation speed is high, the particle size of the final particles is generally large, the final particles are difficult to firmly adhere to the fibers, the water stability of the Cu-MOFs is poor, the structure is easy to collapse, and certain limitation exists. In the electrostatic spinning method, cu-MOFs and a polymer solution are mixed, and spray spinning is performed in a strong electric field to form nanofibers. Compared with the traditional in-situ growth method, the Cu-MOFs can be more uniformly dispersed on the fiber, have higher specific surface area and porosity, but part of the Cu-MOFs are encapsulated by the hydrophobic polymer, and the service performance is limited. The layer-by-layer assembly method is to alternately immerse the fiber base material into the metal ion solution and the ligand solution at normal temperature, and circularly react for multiple times to increase the number of nucleation sites for Cu-MOFs crystal growth, and synthesize Cu-MOFs on the fiber surface layer by layer. The method is simple to operate, the generated particles are uniformly distributed, but the process is long in time.
In order to solve the above problems, the present application needs to propose a method for preparing a multifunctional cotton fabric loaded with Cu-MOFs.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a multifunctional cotton fabric loaded with Cu-MOFs, which is characterized in that carboxyl is firstly introduced into the cotton fabric to adsorb copper ions, then a layer-by-layer assembly method is adopted, copper ions are combined with ZnO nano particles to form a (Zn, cu) hydroxyl double-salt intermediate, so that the anion exchange rate is improved, the Cu-MOFs are rapidly loaded onto the cotton fabric with wide application and low cost at room temperature, the problems that powdery Cu-MOFs are easy to agglomerate, difficult to recycle, low in reuse rate and the like are solved, and meanwhile, the method can endow the cotton fabric with various functions such as antibiosis, adsorption and photocatalysis and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a preparation method of a multifunctional cotton fabric loaded with Cu-MOFs comprises the following specific steps:
step one, adopting polycarboxylic acid to modify cotton fabric: soaking cotton fabric in an aqueous solution containing 4wt% of polycarboxylic acid and 4wt% of sodium hypophosphite for 5min, and then rolling by using a padder, and performing double soaking and double padding; pre-baking the padded cotton fabric at 100 ℃ for 3min, and finally baking at 180 ℃ for 3min to obtain a modified cotton fabric;
step two, loading Cu-MOFs on the cotton fabric by adopting a layer-by-layer assembly method: preparing 0.02-0.1M copper salt aqueous solution A, and soaking the modified cotton fabric obtained in the step one in the solution A for 10min; then adding 0.02-0.1M nano ZnO dispersion liquid into the solution A, rapidly stirring to form a hydroxyl double-salt solution B, continuously soaking the modified cotton fabric in the solution B for 10-20min, and then taking out; preparing a trimesic acid solution C with the volume ratio of ethanol to N, N-dimethylformamide being 1:1, and soaking the taken-out modified cotton fabric in the solution C for 10-20min, and taking out; and (3) circularly and alternately soaking the modified cotton fabric in the solution B and the solution C, taking out the fabric after layer-by-layer assembly, washing with water, and drying to obtain the multifunctional cotton fabric.
Preferably, in the first step, the cotton fabric may be a cotton fabric or a knitted fabric; the polycarboxylic acid is one of citric acid, butane tetracarboxylic acid and polymaleic acid.
Preferably, in the second step, the copper salt is one of copper nitrate, copper sulfate and copper chloride.
Preferably, in the second step, nano ZnO is added to have a particle size of 30-50nm.
Preferably, in the second step, the layer-by-layer assembly method is performed at room temperature.
Preferably, in the second step, the dipping bath ratio of the modified cotton fabric is 1:10-1:30.
Preferably, in the second step, the number of times of cyclic alternating impregnation is 1-10 times.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the carboxyl is introduced into the cotton fabric to adsorb copper ions, so that the binding fastness of Cu-MOFs and the cotton fabric can be improved.
2. The invention utilizes the combination of copper ions and ZnO nano particles to form (Zn, cu) hydroxyl double-salt intermediate, improves the anion exchange rate, and can rapidly load Cu-MOFs on cotton fabrics only under the condition of room temperature.
3. The invention uniformly distributes Cu-MOFs on cotton fabrics with wide application and low cost, can solve the problems of easy agglomeration, difficult recovery, low repeated use rate and the like of powdery Cu-MOFs, can endow the cotton fabrics with various functions such as antibiosis, adsorption, photocatalysis and the like, and has wide application prospect.
4. The invention has the advantages of low energy consumption, simple equipment, convenient operation and the like, and is convenient for industrial production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a product according to example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the product of example 2 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the product of example 3 of the present invention.
Detailed Description
The following technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the protection scope of the present invention is more clearly defined. The described embodiments of the present invention are intended to be only a few, but not all embodiments of the present invention, and all other embodiments that may be made by one of ordinary skill in the art without inventive faculty are intended to be within the scope of the present invention.
Example 1:
referring to fig. 1, a method for preparing a multifunctional cotton fabric loaded with Cu-MOFs comprises the following specific steps:
step one, adopting butane tetracarboxylic acid to modify cotton fabrics: after immersing the cotton fabric in an aqueous solution containing 4wt% of butane tetracarboxylic acid and 4wt% of sodium hypophosphite for 5min, padding with a padder, and double padding. Pre-baking the padded cotton fabric for 3min at 100 ℃, and finally baking for 3min at 180 ℃ to obtain the modified cotton fabric.
Step two, loading Cu-MOFs on the cotton fabric by adopting a layer-by-layer assembly method: a 0.02M aqueous solution a of copper nitrate trihydrate was prepared and the modified cotton fabric was immersed in the solution a for 10min. Then adding 0.02M nano ZnO dispersion liquid into the solution A, rapidly stirring to form a hydroxyl double-salt solution B, and taking out the modified cotton fabric after the modified cotton fabric is immersed in the solution B for 10min. Ethanol and N, N-dimethylformamide with the volume ratio of 1:1 are used as solvents to prepare a trimesic acid solution C with the concentration of 0.05M, and the taken-out modified cotton fabric is taken out after being immersed in the solution C for 10min. And (3) circularly and alternately soaking the modified cotton fabric in the solution B and the solution C for 3 times, taking out the fabric, washing with water, and drying to obtain the multifunctional cotton fabric.
Example 2:
referring to fig. 2, a method for preparing a multifunctional cotton fabric loaded with Cu-MOFs comprises the following specific steps:
step one, modifying cotton fabric by citric acid: after immersing the cotton fabric in an aqueous solution containing 4wt% of citric acid and 4wt% of sodium hypophosphite for 5min, rolling with a padder, and double-dipping and double-padding. Pre-baking the padded cotton fabric for 3min at 100 ℃, and finally baking for 3min at 180 ℃ to obtain the modified cotton fabric.
Step two, loading Cu-MOFs on the cotton fabric by adopting a layer-by-layer assembly method: a 0.1M aqueous solution a of copper sulfate pentahydrate was prepared and the modified cotton fabric was immersed in the solution a for 10min. Then adding 0.1M nano ZnO dispersion liquid into the solution A, rapidly stirring to form a hydroxyl double-salt solution B, and taking out the modified cotton fabric after the modified cotton fabric is immersed in the solution B for 10min. Ethanol and N, N-dimethylformamide with the volume ratio of 1:1 are used as solvents to prepare a trimesic acid solution C with the concentration of 0.1M, and the taken-out modified cotton fabric is taken out after being immersed in the solution C for 10min. And (3) circularly and alternately dipping the modified cotton fabric in the solution B and the solution C for 10 times, taking out the fabric, washing with water, and drying to obtain the multifunctional cotton fabric.
Example 3:
referring to fig. 3, a method for preparing a multifunctional cotton fabric loaded with Cu-MOFs comprises the following specific steps:
step one, adopting butane tetracarboxylic acid to modify cotton fabrics: after immersing the cotton fabric in an aqueous solution containing 4wt% of butane tetracarboxylic acid and 4wt% of sodium hypophosphite for 5min, padding with a padder, and double padding. Pre-baking the padded cotton fabric for 3min at 100 ℃, and finally baking for 3min at 180 ℃ to obtain the modified cotton fabric.
Step two, loading Cu-MOFs on the cotton fabric by adopting a layer-by-layer assembly method: A0.05M aqueous solution of cupric chloride dihydrate was prepared and the modified cotton fabric was immersed in the solution A for 10min. Then adding 0.05M nano ZnO dispersion liquid into the solution A, rapidly stirring to form a hydroxyl double-salt solution B, and taking out the modified cotton fabric after the modified cotton fabric is immersed in the solution B for 10min. Ethanol and N, N-dimethylformamide with the volume ratio of 1:1 are used as solvents to prepare a trimesic acid solution C with the concentration of 0.05M, and the taken-out modified cotton fabric is taken out after being immersed in the solution C for 10min. And (3) circularly and alternately dipping the modified cotton fabric in the solution B and the solution C for 5 times, taking out the fabric, washing with water, and drying to obtain the multifunctional cotton fabric.
In summary, the cotton fabric with multiple functions of antibiosis, adsorption, photocatalysis and the like is prepared by introducing carboxyl on the cotton fabric, adsorbing copper ions, and then rapidly loading Cu-MOFs on the cotton fabric at room temperature by adopting a layer-by-layer assembly method. The method has the advantages of small energy consumption, simple equipment, convenient operation and the like, can solve the problems of easy agglomeration, difficult recovery, low repeated use rate and the like of the powdery Cu-MOFs, can endow the cotton fabric with various functions such as antibiosis, adsorption, photocatalysis and the like, and has wide application prospect.
The foregoing describes the embodiments of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (1)
1. A preparation method of a multifunctional cotton fabric loaded with Cu-MOFs is characterized by comprising the following specific steps:
step one, adopting polycarboxylic acid to modify cotton fabric: soaking cotton fabric in an aqueous solution containing 4wt% of polycarboxylic acid and 4wt% of sodium hypophosphite for 5min, and then rolling by using a padder, and performing double soaking and double padding; pre-baking the padded cotton fabric at 100 ℃ for 3min, and finally baking at 180 ℃ for 3min to obtain a modified cotton fabric;
step two, loading Cu-MOFs on the cotton fabric by adopting a layer-by-layer assembly method: preparing 0.02-0.1M copper salt aqueous solution A, and soaking the modified cotton fabric obtained in the step one in the solution A for 10min; then adding 0.02-0.1M nano ZnO dispersion liquid into the solution A, rapidly stirring to form a hydroxyl double-salt solution B, continuously soaking the modified cotton fabric in the solution B for 10-20min, and then taking out; preparing a trimesic acid solution C with the volume ratio of ethanol to N, N-dimethylformamide being 1:1, and soaking the taken-out modified cotton fabric in the solution C for 10-20min, and taking out; the modified cotton fabric is circularly and alternately immersed in the solution B and the solution C, the fabric is taken out after being assembled layer by layer, washed by water and dried, and the multifunctional cotton fabric is obtained;
in the first step, the cotton fabric may be a cotton fabric or a knitted fabric; the polycarboxylic acid is one of citric acid, butane tetracarboxylic acid and polymaleic acid;
in the second step, the copper salt is one of copper nitrate, copper sulfate and copper chloride;
in the second step, nano ZnO with the particle size of 30-50nm is added;
in the second step, the layer-by-layer assembly method is carried out at room temperature;
in the second step, the dipping bath ratio of the modified cotton fabric is 1:10-1:30;
in the second step, the times of circularly and alternately dipping are 1-10 times.
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