CN114570358A - Preparation of nano-fiber woven carbonized chitin microsphere loaded nano-metal catalyst and application of nano-fiber woven carbonized chitin microsphere loaded nano-metal catalyst in dye degradation - Google Patents
Preparation of nano-fiber woven carbonized chitin microsphere loaded nano-metal catalyst and application of nano-fiber woven carbonized chitin microsphere loaded nano-metal catalyst in dye degradation Download PDFInfo
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- CN114570358A CN114570358A CN202210162325.4A CN202210162325A CN114570358A CN 114570358 A CN114570358 A CN 114570358A CN 202210162325 A CN202210162325 A CN 202210162325A CN 114570358 A CN114570358 A CN 114570358A
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- 229920002101 Chitin Polymers 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 239000004005 microsphere Substances 0.000 title claims abstract description 43
- 239000002121 nanofiber Substances 0.000 title claims abstract description 42
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 29
- 230000015556 catabolic process Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
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- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 claims description 8
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 8
- 229940012189 methyl orange Drugs 0.000 claims description 8
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 claims description 8
- 229960003531 phenolsulfonphthalein Drugs 0.000 claims description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 8
- 229940043267 rhodamine b Drugs 0.000 claims description 8
- 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 description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
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- 229920000136 polysorbate Polymers 0.000 claims description 3
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- 239000002253 acid Substances 0.000 claims description 2
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a nano-metal catalyst loaded by carbonized chitin microspheres woven by nano-fibers and application of the nano-metal catalyst in dye degradation, relates to the technical field of catalytic degradation, and aims to solve the problems that the existing chitin material is difficult to dissolve and the structure of a fiber spherical 3D microsphere is damaged by high-temperature treatment and the application of the catalyst in high activity and stability of dye degradation. Comprises the steps of firstly, using shrimp shells and crab shells bought from the market to carry out chitin pretreatment; step two, preparing a chitin solution by using a chitin precursor; step three, preparing chitin microspheres from the chitin solution by an emulsification method; step four, carbonizing the chitin nano-fiber microspheres at high temperature to obtain chitin nano-fiber carbon spheres; and step five, dropwise adding the palladium acetate solution into the chitin nanofiber carbon sphere acetone solution, and performing activation reduction reaction by using a reducing agent sodium borohydride to obtain the chitin-based Pd/NCM catalyst.
Description
Technical Field
The invention relates to the technical field of catalytic degradation, in particular to a preparation method of a nano-metal catalyst loaded by carbonized chitin microspheres woven by nano-fibers and application of the nano-metal catalyst in dye degradation.
Background
With the development of society, the improvement of economy and the acceleration of urbanization process, the problem of water pollution worldwide becomes more serious. The random discharge of industrial wastewater is the most serious source of water quality deterioration, such as papermaking wastewater, textile printing and dyeing wastewater, dye wastewater, fertilizer wastewater and the like, are deposited at the bottom of a water body, and part of the wastewater forms toxic slurry, so that the water body is in an anaerobic state, and the living environment of aquatic animals and plants is damaged. More importantly, most dyes are toxic, chemically stable and difficult-to-degrade organic matters, and finally pose a great threat to human health.
The metal reduction method is to add a metal element with strong reducibility into the wastewater and reduce the oxidative metal ions into elemental metal. This method is commonly used for treating wastewater containing heavy metal ions. A typical example is the reduction of mercury-containing waste water by iron filings. It is noted that the conventional dye wastewater treatment method Fenton oxidation method also adds metallic iron. However, the reaction conditions have certain requirements on the pH value of the environment, and the reaction conditions are difficult to recycle and are not favorable for popularization of environmental protection. In recent years, metal and metal oxide Nanoparticles (NPs) in inorganic reagents have been the focus of research. The supported metal catalyst not only contains metal particles, but also has a large specific surface area and a developed pore structure, so that the reaction space can be effectively increased, and the reaction rate can be improved.
Chitin is the second most abundant natural polymer biomass material next to cellulose. It has the characteristics of biodegradation and regeneration. The chitin is widely existed in shrimp and crab shells, and is the best way to solve the problem of shrimp and crab shell wastes. Chitin is used as a raw material, an alkali/urea aqueous solution is used as a solvent, and a physical mixing method is adopted to prepare the chitin solution. Then, the chitin microspheres with the nano-fiber-shaped structures are prepared by an emulsion method. The material has rich nano-porous structure and high specific surface area, and provides good attachment sites for the metal catalyst. Palladium metal has strong hydrogen absorption and permeation capabilities. It is reported that 1 volume of metallic palladium can absorb nearly 3000 volumes of hydrogen at room temperature. Palladium is very suitable for the preparation of catalysts for catalytic reactions due to its special properties.
However, macromolecular protein and calcium salt existing in crushed shrimp shells and crab shells in the preparation process can cause difficulty in dissolution, development and utilization, and then the fiber spherical structure of the chitin microspheres can be damaged in the carbonization process, and in addition, the catalytic efficiency, applicability and stability of the Pd/NCM catalyst can not be ensured, so that the economic cost is reduced, and therefore the existing requirements are not met.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-metal catalyst loaded on carbonized chitin microspheres woven by nano-fibers and an application of the nano-metal catalyst in dye degradation, so as to solve the problems that how to reduce the molecular weight of chitin in the background technology is proposed, the chitin can be utilized, the fibrous spherical structure of the chitin microspheres can be damaged in the carbonization process, and the catalytic efficiency, the applicability and the stability of Pd/NCM are researched.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a nano-metal catalyst loaded by carbonized chitin microspheres woven by nano fibers and an application of the nano-metal catalyst in dye degradation comprise the following steps: pulverizing commercially available shrimp shell and crab shell to obtain powder, treating with acid and alkali for 2-3 times, and adding 4wt% of H2O2Stirring at 80 ℃ for 20min, and drying in an oven at 60 ℃ for later use to obtain a chitin precursor;
step two, preparation of chitin solution: dispersing the chitin precursor obtained in the step one in an alkali/urea mixed aqueous solution, putting the obtained mixed solution into a low-temperature bath at-40 ℃, and repeatedly freezing and thawing to obtain a chitin solution;
step three, preparing the chitin nano-fiber microspheres: pouring the chitin solution obtained in the step two into a mixed solution of 250g of isooctane and 16.5g of span 85 which are uniformly stirred in an ice-water bath, stirring for 1 hour, adding 9g of Tween 85, continuously stirring for 1 hour, removing ice water, continuously spraying hot water at 100 ℃ onto a reaction bottle, keeping the interior of the reaction bottle in a high-temperature state for 7 minutes, stopping stirring, adjusting the pH value to 7-8, cleaning a microsphere surface solvent and a surfactant, and freeze-drying to obtain chitin nanofiber microspheres;
step four, preparing chitin nano fiber carbon spheres: placing the chitin nano-fiber microspheres in the third step into a tube furnace, introducing inert gas, heating to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, keeping the temperature in a ventilating state after carbonization, naturally cooling to room temperature, and taking out to obtain chitin nano-fiber carbon spheres;
step five, preparing the Pd/NCM catalyst: and (2) dropwise adding a palladium acetate solution with the concentration of 3wt% of [ Pd ] into a chitin nanofiber carbon sphere acetone solution, magnetically stirring for 3 hours, washing off the unsupported Pd particles in the obtained solution by using the acetone solution, then putting the solution into a sodium borohydride aqueous solution, activating and reducing for 30min, washing redundant sodium borohydride by using water, and freeze-drying to obtain the chitin-based Pd/NCM catalyst.
Preferably, the pretreatment of the chitin in the first step is carried out under the acid-base treatment condition of a solution of 5% NaOH and 7% HCl.
Preferably, in the step two, the chitin solution is prepared, and the mixed aqueous solution of alkali and urea is an aqueous solution of sodium hydroxide and urea, wherein the ratio of sodium hydroxide: urea: the mass ratio of water is 11 wt%: 4 wt%: 85wt% and the mass concentration of the chitin solution is 6 wt%.
Preferably, in the third step, the chitin nano-fiber microspheres are prepared, and the pH is adjusted by using 5: 1H2And O is realized by HCl.
Preferably, the inert gas in the fourth step is argon.
The application of the nano metal catalyst loaded by the carbonized chitin microsphere woven by the nano fibers in dye degradation is characterized in that 1mgPd/NCM catalyst is dispersed in 3ml of water, mixed with 1ml of organic dye, and added with 0.4ml of sodium borohydride to realize degradation reaction.
Preferably, the organic dyes include methylene blue, rhodamine B, phenol red, methyl orange, methyl red and congo red.
Preferably, the concentration of methylene blue is 640ppm, the concentration of rhodamine B is 920ppm, the concentration of phenol red is 700ppm, the concentration of methyl orange is 640ppm, the concentration of methyl red is 520ppm, and the concentration of Congo red is 1380 ppm.
Preferably, the degradation condition is reaction under the conditions of normal temperature and stirring at the rotating speed of 600 rpm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention firstly represents a nano metal catalytic material loaded by carbonized chitin microspheres woven by nano fibers by a preparation method, the material is formed by compounding carbonized chitin microspheres and metal palladium, metal palladium particles are successfully anchored on the chitin microspheres in the loading process, different from a simple physical load, a catalyst containing chemical bonds is more stable, and metal is not easy to drop or form metal clusters, so that the continuation of metal active centers is facilitated. The recycling performance of the supported catalyst is better than that of the traditional homogeneous catalyst, and the excellent catalyst is further provided for the catalytic degradation of organic dyes.
2. The invention has the characteristics of simple process, low price, wide application and the like, the chitin as the degradable material can not cause secondary pollution to the environment, and the supported catalyst is beneficial to recycling and is suitable for industrial catalytic degradation of organic dyes. And when the organic pollutants are catalytically degraded, the method is efficient and rapid, high in cyclicity and strong in applicability, and the most breakthrough is that the organic pollutants can be efficiently degraded even after 20 cycles.
3. The chitin carbide supported metal palladium catalyst provided by the invention can be used for efficiently degrading organic dyes with different structures, and has tolerance to high-concentration dyes. And the reaction condition is mild. Provides development potential for industrial treatment of dye wastewater and provides research basis for recovery and reuse of catalyst after dye degradation.
4. The chitin used in the invention is the second largest renewable resource next to cellulose on earth, and chitin molecules contain abundant functional groups (hydroxyl and acetamido), and have good biocompatibility, degradability, chemical stability and thermal stability. So that the chitin material has good advantages when being used as a catalyst carrier.
Drawings
FIG. 1 shows electron microscope, Raman, XRD and XPS images of the chitin material before and after carbonization and loading;
FIG. 2 is a graph of the degraded methylene blue UV absorption spectrum and C/C0 of the present invention;
FIG. 3 is a diagram of the ultraviolet absorption spectra, C/C0 diagram and structure diagram of rhodamine B, phenol red, methyl orange, methyl red and Congo red of the present invention;
FIG. 4 is a flow chart of the preparation of the chitin-based Pd/NCM catalyst of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1, an embodiment of the present invention: a preparation method of a nano-metal catalyst loaded by carbonized chitin microspheres woven by nano-fibers and an application of the nano-metal catalyst in dye degradation comprise the following steps:
pretreatment of chitin: putting crushed shrimp shells and crab shells purchased from the market into a 5% NaOH aqueous solution, stirring and filtering at the rotating speed of 800 rpm, washing macromolecular proteins in the shells, adjusting the pH to 7-8 by using HCl, washing by using water and filtering; adding into 7% HCl aqueous solution, stirring at 800 rpm, filtering, removing calcium salt in shell, adjusting pH to 7-8 with NaOH, washing with water, filtering, repeating the above steps for 2 times, adding 4% H2O2 aqueous solution, stirring at 80 deg.C for 20min, and washing excess H with water2O2Filtering, and drying in an oven at 60 ℃ for later use to obtain the chitin material.
The preparation method of the chitin carbonized microspheres comprises the following steps: dispersing chitin in a mixed aqueous solution of sodium hydroxide/urea, putting the obtained mixed solution into a low-temperature bath at minus 40 ℃, freezing the mixed solution into a frozen sand shape, physically stirring the frozen sand shape to be viscous, repeatedly freezing and thawing to obtain a chitin solution, pouring 100g of the chitin solution into a mixed solution of 250g of isooctane and 16.5g of span 85 which are uniformly stirred in an ice-water bath, stirring for 1 hour, adding 9g of Tween 85, stirring again, removing ice water, continuously spraying 100 ℃ hot water on a reaction bottle, keeping the interior in a high-temperature state for 7 minutes, stopping stirring, adjusting the pH value to 7-8, cleaning a microsphere surface solvent and a surfactant, freeze-drying for 24 hours to obtain chitin nanofiber microspheres, referring to figure 1a, putting the chitin nanofiber microspheres into a tubular furnace, introducing inert gas argon, heating to 800 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 2 hours. After the carbonization, the mixture is naturally cooled to room temperature in a ventilating state and taken out to obtain chitin nanofiber carbon spheres, and fig. 1b shows the structure.
The preparation method of the Pd/NCM catalyst comprises the following steps: and (2) dropwise adding a palladium acetate acetone solution with the concentration of 3wt% of [ Pd ] into a chitin nanofiber carbon sphere acetone solution, magnetically stirring for 3 hours, washing off unsupported Pd particles by using the acetone solution, filtering, then putting into a sodium borohydride aqueous solution, activating for 30min, washing redundant sodium borohydride by using water, and freeze-drying to obtain the chitin-based Pd/NCM catalyst.
Referring to fig. 2, in the application of the nano metal catalyst loaded on the nano chitin microsphere woven by nano fibers in dye degradation, 1mg of the catalyst and 640ppm of methylene blue are added into 3ml of aqueous solution under normal temperature and pressure, stirred uniformly, added with 0.4ml of sodium borohydride (0.1 mol/L) and stirred continuously, and 25 μ L of the solution is taken out at specific time intervals and diluted to 5 x 10- 4After centrifugation, measuring the absorbance of the solution of the supernatant at the wavelength of 664nm under an ultraviolet spectrophotometer, and establishing a methylene blue degradation degree and time curve and a C/C0 diagram, referring to FIG. 2 a; the catalyst was replaced by Pd (OAC) in the same manner2Pd/C, Initial Chitin, NCM, Pd/Chitin, Nano-Pd were measured at a wavelength of 664nm in an ultraviolet spectrophotometer, and a C/C0 graph was created, see FIG. 2 b.
The heterogeneous catalyst adopts a filtering and washing mode; the homogeneous catalyst is recovered by extraction, and the steps are repeated for 20 times. The degradation rate trend with rate is shown in fig. 2c, d.
And (3) catalyzing and degrading rhodamine B: under normal temperature and pressure, 1mg of catalyst and 920ppm of rhodamine B are added into 3ml of aqueous solution and stirred uniformly (stirring speed is 600 rpm), and then 0.4ml of sodium borohydride (0.1 mol/L) is added and stirred continuously. At specific time intervals, 25. mu.l of the solution was withdrawn and diluted to 5X 10-4And (5) after centrifugation, measuring the absorbance of the solution of the supernatant at the wavelength of 554nm under an ultraviolet spectrophotometer, and establishing an ultraviolet spectrum of rhodamine B and a C/C0 graph.
Catalytic degradation of phenol red: 1mg of catalyst and 700ppm of phenol red are added to 3ml of the aqueous solution under normal temperature and pressure, stirred (stirring rate 600 rpm) uniformly, and then 0.4ml of sodium borohydride (0.1 mol/L) is added and stirring is continued. And (3) taking out 25 mu l of the solution at specific time intervals to dilute the solution to 5 x 10-4mol, centrifuging, measuring the absorbance of the solution of the supernatant at the wavelength of 557nm under an ultraviolet spectrophotometer, and establishing a phenol red ultraviolet spectrum and a C/C0 graph.
And (3) methyl orange catalytic degradation: after 1mg of catalyst and 640ppm methyl orange were added to 3ml of the aqueous solution under normal temperature and pressure and stirred (stirring rate 600 rpm) uniformly, 0.4ml of sodium borohydride (0.1 mol/L) was added and stirring was continued. At specific time intervals, 25 μ l of the solution is taken out and diluted to 5 x 10-4mol, after centrifugation, the supernatant is subjected to ultraviolet spectrophotometer at 466nm wavelength to measure the absorbance of the solution, and a methyl orange ultraviolet spectrum and a C/C0 graph are established.
And (3) catalytic degradation of methyl red: 1mg of catalyst and 520ppm of methyl red were added to 3ml of the aqueous solution under normal temperature and pressure, stirred (stirring rate 600 rpm) uniformly, and then 0.4ml of sodium borohydride (0.1 mol/L) was added thereto and the stirring was continued. At specific time intervals, 25 μ l of the solution is taken out and diluted to 5 x 10-4mol, after centrifugation, the supernatant is subjected to ultraviolet spectrophotometer at the wavelength of 430nm to measure the absorbance of the solution, and a methyl red ultraviolet spectrum and a C/C0 graph are established.
Catalytic degradation of Congo red: 1mg of catalyst and 1380ppm Congo red were added to 3ml of the aqueous solution under normal temperature and pressure, stirred (stirring rate 600 rpm) uniformly, and then 0.4ml of sodium borohydride (0.1 mol/L) was added thereto, and the stirring was continued. And (3) taking out 25 mu l of the solution at specific time intervals to dilute the solution to 5 x 10-4mol, centrifuging, measuring the absorbance of the solution of the supernatant at the 497nm wavelength under an ultraviolet spectrophotometer, and establishing a Congo red ultraviolet spectrum and a C/C0 graph.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. A preparation method of a nano metal catalyst loaded by carbonized chitin microspheres woven by nano fibers is characterized by comprising the following steps: the method comprises the following steps:
step one, chitin pretreatment: pulverizing commercially available shrimp shell and crab shell to obtain powder, treating with acid and alkali for 2-3 times, and adding 4wt% of H2O2Stirring at 80 ℃ for 20min, and drying in an oven at 60 ℃ for later use to obtain a chitin precursor;
step two, preparation of chitin solution: dispersing the chitin precursor obtained in the step one in an alkali/urea mixed aqueous solution, putting the obtained mixed solution into a low-temperature bath at-40 ℃, and repeatedly freezing and thawing to obtain a chitin solution;
step three, preparing the chitin nano-fiber microspheres: pouring the chitin solution in the step two into a mixed solution of 250g of isooctane and 16.5g of span 85 which are uniformly stirred in an ice-water bath, stirring for 1 hour, adding 9g of Tween 85, continuously stirring for 1 hour, removing ice water, continuously spraying hot water at 100 ℃ onto a reaction bottle, keeping the interior in a high-temperature state for 7 minutes, stopping stirring, adjusting the pH value to 7-8, cleaning a microsphere surface solvent and a surfactant, and freeze-drying to obtain chitin nano-fiber microspheres;
step four, preparing chitin nano fiber carbon spheres: placing the chitin nano-fiber microspheres in the third step into a tube furnace, introducing inert gas, heating to 800 ℃ at a heating rate of 5 ℃/min, keeping the constant temperature for 2 hours, keeping the air-permeable state after carbonization, naturally cooling to room temperature, and taking out to obtain chitin nano-fiber carbon spheres;
step five, preparing the Pd/NCM catalyst: and (2) dropwise adding a palladium acetate solution with the concentration of 3wt% of [ Pd ] into a chitin nanofiber carbon sphere acetone solution, magnetically stirring for 3 hours, washing off the unsupported Pd particles in the obtained solution by using the acetone solution, then putting the solution into a sodium borohydride aqueous solution, activating for 30 reduction min, washing redundant sodium borohydride by using water, and freeze-drying to obtain the chitin-based Pd/NCM catalyst.
2. The preparation method of the nano-metal catalyst loaded on the nano-fiber woven carbonized chitin microspheres according to claim 1, wherein the nano-metal catalyst is prepared by the following steps: in the step one, the chitin is pretreated, and the acid-base treatment condition is 5% NaOH and 7% HCl solution.
3. The preparation method of the nano-metal catalyst loaded on the nano-fiber woven carbonized chitin microspheres according to claim 1, wherein the nano-metal catalyst is prepared by the following steps: in the step two, the chitin solution is prepared, and the alkali and urea mixed aqueous solution is an aqueous solution of sodium hydroxide and urea, wherein the ratio of sodium hydroxide: urea: the mass ratio of water is 11 wt%: 4 wt%: 85wt% and the mass concentration of the chitin solution is 6 wt%.
4. The preparation method of the nano-metal catalyst loaded on the nano-fiber woven carbonized chitin microspheres according to claim 1, wherein the nano-metal catalyst is prepared by the following steps: in the third step, the chitin nano-fiber microspheres are prepared, and the PH is adjusted by using H with the ratio of 5:12And O is realized by HCl.
5. The preparation method of the nano-metal catalyst loaded on the nano-fiber woven carbonized chitin microspheres according to claim 1, wherein the nano-metal catalyst is prepared by the following steps: and in the fourth step, the inert gas is argon.
6. The application of the nano metal catalyst loaded on the carbonized chitin microspheres woven based on the nano fibers of any one of claims 1 to 5 in dye degradation is characterized in that: 1mgPd/NCM catalyst dispersed in 3ml water, and 1ml organic dye mixture, adding 0.4ml sodium borohydride to achieve degradation reaction.
7. The application of the nano-metal catalyst loaded on the carbonized chitin microspheres woven by nano-fibers in the dye degradation according to claim 6, is characterized in that: the organic dye comprises methylene blue, rhodamine B, phenol red, methyl orange, methyl red and Congo red.
8. The application of the nano-metal catalyst loaded on the nano-fiber woven carbonized chitin microspheres of claim 7 in dye degradation is characterized in that: the concentration of methylene blue is 640ppm, the concentration of rhodamine B is 920ppm, the concentration of phenol red is 700ppm, the concentration of methyl orange is 640ppm, the concentration of methyl red is 520ppm, and the concentration of Congo red is 1380 ppm.
9. The application of the nano-metal catalyst loaded on the carbonized chitin microspheres woven by nano-fibers in the dye degradation according to claim 6, is characterized in that: the degradation condition is reaction under the conditions of normal temperature and stirring at the rotating speed of 600 rpm.
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