CN114456279B - Preparation method of chitosan hydroxynaphthalene aldehyde Schiff base and chitosan hydroxynaphthalene aldehyde Schiff base copper complex, and product and application thereof - Google Patents
Preparation method of chitosan hydroxynaphthalene aldehyde Schiff base and chitosan hydroxynaphthalene aldehyde Schiff base copper complex, and product and application thereof Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 80
- -1 hydroxynaphthalene aldehyde Schiff base Chemical class 0.000 title claims abstract description 60
- 239000002262 Schiff base Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 17
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 9
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- 239000000126 substance Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
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- 239000000975 dye Substances 0.000 abstract description 11
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- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The invention discloses a preparation method of chitosan hydroxynaphthalene aldehyde Schiff base and a chitosan hydroxynaphthalene aldehyde Schiff base copper complex, and a product and application thereof, and belongs to the technical field of photocatalysts. A preparation method of chitosan hydroxyl naphthalene aldehyde Schiff base is characterized in that: the preparation method comprises the following steps: s1, dissolving chitosan in absolute ethyl alcohol to obtain an absolute ethyl alcohol solution of chitosan; s2, heating the absolute ethyl alcohol solution of the chitosan to 60-100 ℃, uniformly stirring, and then adding 2-hydroxynaphthalene-1-formaldehyde into the absolute ethyl alcohol solution of the chitosan; reacting chitosan with 2-hydroxynaphthalene-1-formaldehyde at 60-100 ℃ to obtain yellow precipitate; s3: and cooling the reaction solution to room temperature, performing reduced pressure suction filtration, and performing reduced pressure drying to obtain the chitosan hydroxynaphthalene aldehyde Schiff base. The photocatalyst has the advantages of high recycling rate, low cost and simple preparation process, is used for degrading organic dyes such as methylene blue, and the like, and the preparation method and the application of the photocatalyst in degrading the methylene blue.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a preparation method of chitosan hydroxynaphthalene aldehyde Schiff base and a chitosan hydroxynaphthalene aldehyde Schiff base copper complex, and a product and application thereof.
Background
Currently, water resource pollution is one of the problems generally facing urgent needs to be solved in countries around the world. Today, people are advocated about meeting the natural harmony. While economies are rapidly evolving, many countries face different levels of environmental problems, and water pollution is a challenge that people have to pay attention to.
Industrial wastewater is a large pollution source of water pollution, and with the development of textile, leather, papermaking, rubber and food processing industries in China, a large amount of wastewater containing dye is discharged into water body, so that serious water body pollution is caused. It has been shown that dye methylene blue damages eyes and skin, and may cause vomiting, arrhythmia and even death, so elimination of methylene blue in wastewater is critical to the current society.
Methylene blue is a widely used organic dye which is difficult to degrade, toxic and has relatively large damage to the environment.
The photocatalysis principle is based on the oxidation-reduction capability of the photocatalyst under the condition of illumination, so that the purposes of purifying pollutants, synthesizing substances, converting substances and the like can be achieved. In general, photocatalytic oxidation reactions degrade organic matter into carbon dioxide and water using a semiconductor as a catalyst and light as energy. Therefore, the photocatalysis technology is used as an efficient and safe environment-friendly environment purification technology, and the improvement of indoor air quality is accepted by the international academy.
The search for degradation catalysts with high reuse rate, low cost and simple preparation process for degrading organic matters is an intense research field of large researchers.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of chitosan hydroxynaphthalene aldehyde Schiff base and chitosan hydroxynaphthalene aldehyde Schiff base copper complex, and a product and application thereof, and provides a photocatalyst which has high recycling rate, low cost and simple preparation process and is used for degrading organic dyes such as methylene blue, a preparation method of the photocatalyst and application of the photocatalyst in degrading the methylene blue.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
The preparation method of the chitosan hydroxyl naphthalene aldehyde Schiff base comprises the following steps:
s1, dissolving chitosan in absolute ethyl alcohol to obtain an absolute ethyl alcohol solution of chitosan;
s2, heating the absolute ethyl alcohol solution of the chitosan to 60-100 ℃, uniformly stirring, and then adding 2-hydroxynaphthalene-1-formaldehyde into the absolute ethyl alcohol solution of the chitosan; reacting chitosan with 2-hydroxynaphthalene-1-formaldehyde at 60-100 ℃ to obtain yellow precipitate;
s3: and cooling the reaction solution to room temperature, performing reduced pressure suction filtration, and performing reduced pressure drying to obtain the chitosan hydroxynaphthalene aldehyde Schiff base.
Preferably, the chitosan has a degree of deacetylation of 75%;
the chemical structural formulas of the chitosan, the 2-hydroxynaphthalene-1-formaldehyde and the chitosan condensed hydroxynaphthalene aldehyde Schiff base are respectively shown as a formula (I), a formula (II) and a formula (III);
preferably, the mass ratio of chitosan to 2-hydroxynaphthalene-1-formaldehyde is 1:0.304.
A preparation method of a chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex comprises the following steps:
s1: adding the chitosan hydroxynaphthalene aldehyde Schiff base obtained by the preparation method of the chitosan hydroxynaphthalene aldehyde Schiff base in any one of claims 1-3 into an organic solvent to obtain a mixed solution;
s2: heating and stirring the mixed solution in a water bath at 70 ℃, and completely dissolving chitosan hydroxynaphthalene aldehyde Schiff base into an organic solvent;
s3: to the mixed solution, cu (NO) was added 3 ·3H 2 O, chitosan hydroxyl naphthalene aldehyde Schiff base and Cu (NO) 3 ·3H 2 O fully reacts to generate green precipitate;
s4: vacuum filtering and drying are carried out to obtain the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex.
Preferably, the organic solvent is a mixed solution of absolute ethyl alcohol and acetone, and the volume ratio of the absolute ethyl alcohol to the acetone is 1-2.
Preferably, the chitosan is condensed with hydroxyl naphthalene aldehyde Schiff base and Cu (NO) 3 ·3H 2 The mass ratio of O is 0.5:0.46.
Preferably, the chitosan is condensed with hydroxyl naphthalene aldehyde Schiff base and Cu (NO) 3 ·3H 2 The reaction temperature of O is 60-100 ℃.
A chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex is prepared by a preparation method of the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex.
The application of chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex as photocatalyst.
The application of chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex as a photocatalyst in catalytic degradation of methylene blue.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) The preparation process of the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex is simple and easy to operate.
(2) The chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex prepared by the preparation method of the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex can be used as a photocatalyst for degrading organic dyes such as methylene blue, and the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex has the advantages of high recycling rate, low cost and simple preparation process.
Drawings
FIG. 1 is a scanning electron micrograph of a copper complex of a chitosan hydroxynaphthalene aldehyde schiff base of the invention;
FIG. 2 is an infrared spectrum of the chitosan hydroxynaphthalene aldehyde Schiff base and the copper complex thereof;
FIG. 3 is a graph showing the ultraviolet-visible absorption spectrum of methylene blue of experimental group 1 of the present invention;
FIG. 4 is a graph showing the degradation rate of methylene blue solution under various experimental conditions according to the present invention.
Detailed Description
The technique of the present invention is further explained by the following specific experiments:
synthetic examples of chitosan hydroxynaphthalene aldehyde schiff base:
1g of chitosan (degree of deacetylation: 75%) was added to 100mL of a three-necked round bottom, and 50mL of absolute ethanol was further added as a solvent; heating to 60 ℃, stirring for 30 minutes, then dripping 0.304g of 2-hydroxynaphthalene-1-formaldehyde, and reacting for 2 hours at 60 ℃ to obtain yellow precipitate; after the reaction mixture was cooled to room temperature, vacuum filtration was performed, and the yellow precipitate was dried at 50℃under reduced pressure to obtain 0.85g of chitosan hydroxynaphthalene aldehyde Schiff base.
Examples of synthesis of chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complexes:
adding 0.5g of chitosan hydroxynaphthalene aldehyde Schiff base into 100mL of three-port round bottom, adding 20mL of absolute ethyl alcohol and 10mL of acetone as solvents, heating and stirring in a water bath at 70 ℃ for 30min, and adding 0.46g of Cu (NO) after the naphthalene aldehyde Schiff base is completely dissolved 3 ·3H 2 After the addition of O, keeping the temperature at 70 ℃ for heating reaction for 2 hours to generate green precipitate; after the reaction is finished, carrying out vacuum filtration, and drying the green precipitate at 50 ℃ under reduced pressure to obtain 0.48g of chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex.
Verification example: and (3) performing a degradation experiment on methylene blue by using a chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex as a photocatalyst, and setting an experimental group 1, a control group 1 and a control group 2.
Experiment group 1: 50mL of methylene blue solution (MB) is added into a 100mL beaker, the concentration of the methylene blue solution is 10mg/L, 0.2g of chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex is added into the beaker as a photocatalyst, and the mixture is stirred for 15min in a light-shielding environment and then is kept stand for 45min, so that the system reaches adsorption balance; then 0.2mL H was added 2 0 2 The solution acts as an oxidizing agent.
Control group 1: 50mL of methylene blue solution (MB) with the concentration of 10mg/L is added into a 100mL beaker, 0.2g of chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex serving as a photocatalyst is added into the beaker, and the mixture is stirred for 15min under a light-shielding environment and then is kept stand for 45min, so that the system reaches adsorption equilibrium.
Control group 2: 50mL of methylene blue solution (MB) is added into a 100mL beaker, the concentration of the methylene blue solution is 10mg/L, and the mixture is stirred for 15min in a light-proof environment and then is kept stand for 45min, so that the system reaches adsorption equilibrium; then 0.2mL H was added 2 0 2 The solution acts as an oxidizing agent.
The supernatants of experimental group 1, control group 1 and control group 2 were placed on an ultraviolet-visible spectrophotometer, respectively, and the absorption spectrum of the methylene blue solution was scanned (spectral curve recorded as t=0).
The supernatants of the experiment group 1, the control group 1 and the control group 2 are all placed under an ultraviolet lamp, a light source is turned on for starting timing, and absorption spectra of the methylene blue solution at t=10min, t=20min, t=40min, t=60min and t=80min are scanned respectively (as shown in fig. 3).
The degradation rate of the dye can be calculated through the absorbance of the dye solution at the maximum absorption wavelength at different moments, and the degradation rate is used for representing the degradation degree of the dye, and the degradation rate is calculated according to the following formula:
D＝(A 0 －A t )/A 0 ×100％
wherein A is 0 For the initial absorbance value of the dye at t=0, a t Is the absorbance value of the dye after the light irradiation t time.
Experimental results of degradation of methylene blue by chitosan hydroxynaphthalene aldehyde schiff base Cu (II) complex as photocatalyst are analyzed:
verifying the photocatalytic activity of the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex by measuring the decomposition condition of a Methylene Blue (MB) solution under ultraviolet irradiation; in the presence of chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex, the characteristic absorption peak of the Methylene Blue (MB) solution gradually decreases along with the extension of the irradiation time, and the degradation rate (D%) of the Methylene Blue (MB) is calculated according to the absorbance of the Methylene Blue (MB) solution at 664nm of the characteristic absorption peak in the ultraviolet light region.
Referring to fig. 4, it can be found from experiment group 1 that the Methylene Blue (MB) degradation rate after 20 and 60min of illumination is 27.9% and 83.5%, respectively, and the Methylene Blue (MB) degradation rate after 80min of illumination reaches 93.1%, and the TOC removal rate reaches 90.2%, respectively, in the presence of hydrogen oxide and catalyst.
Referring to fig. 4, it can be found by comparing the control group 1 that the degradation rate of Methylene Blue (MB) reaches 65.5% after the solution of Methyl Blue (MB) is irradiated for 80min under the condition that only the catalyst is added without hydrogen peroxide, and observing fig. 4 shows that the degradation rate of Methylene Blue (MB) can degrade Methylene Blue (MB) better than that of chitosan hydroxynaphthalene aldehyde schiff base Cu (II) complex without hydrogen peroxide.
Referring to FIG. 4, it can be seen from control group 2 that the degradation rate of Methylene Blue (MB) was low after 80min of the illumination reaction of Methylene Blue (MB) with hydrogen peroxide alone.
In addition, through experiments, the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex is repeatedly used as a photocatalyst, the catalytic activity of the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex is unchanged, the original catalyst activity is still maintained, and further, the conclusion can be inferred that the reuse rate of the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex is high.
Claims (1)
1. The application of a chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex as a photocatalyst in catalytic degradation of methylene blue is characterized in that: the preparation method of the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex for catalyzing and degrading methylene blue comprises the following steps of:
s1, dissolving chitosan in absolute ethyl alcohol to obtain an absolute ethyl alcohol solution of chitosan;
s2, heating the absolute ethyl alcohol solution of the chitosan to 60-100 ℃, uniformly stirring, and then adding 2-hydroxynaphthalene-1-formaldehyde into the absolute ethyl alcohol solution of the chitosan; reacting chitosan with 2-hydroxynaphthalene-1-formaldehyde at 60-100 ℃ to obtain yellow precipitate, wherein the mass ratio of the chitosan to the 2-hydroxynaphthalene-1-formaldehyde is 1:0.304;
s3: cooling the reaction solution to room temperature, performing reduced pressure suction filtration, and performing reduced pressure drying to obtain chitosan hydroxynaphthalene aldehyde Schiff base;
the deacetylation degree of the chitosan is 75%;
the chemical structural formulas of the chitosan, the 2-hydroxynaphthalene-1-formaldehyde and the chitosan condensed hydroxynaphthalene aldehyde Schiff base are respectively shown as a formula (I), a formula (II) and a formula (III);
adding the chitosan hydroxynaphthalene aldehyde Schiff base obtained in the step S3 into an organic solvent to obtain a mixed solution;
s4: heating and stirring the mixed solution in a water bath at 70 ℃, and completely dissolving chitosan hydroxynaphthalene aldehyde Schiff base into an organic solvent, wherein the organic solvent is a mixed solvent of absolute ethyl alcohol and acetone, and the volume ratio of the absolute ethyl alcohol to the acetone is 1-2;
s5: to the mixed solution, cu (NO) was added 3 ·3H 2 O, chitosan hydroxyl naphthalene aldehyde Schiff base and Cu (NO) 3 ·3H 2 O fully reacts to generate green precipitate, and the chitosan hydroxyl naphthalene aldehyde Schiff base and Cu (NO) 3 ·3H 2 O is 0.5:0.46, and the mass ratio of the chitosan hydroxyl naphthalene aldehyde Schiff base to Cu (NO) 3 ·3H 2 The reaction temperature of O is 60-100 ℃;
s6: vacuum filtering and drying are carried out to obtain the chitosan hydroxynaphthalene aldehyde Schiff base Cu (II) complex.
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