CN107903408B - Cellulose-feather protein hydrogel nano metal compound and preparation method thereof - Google Patents
Cellulose-feather protein hydrogel nano metal compound and preparation method thereof Download PDFInfo
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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- C08K2003/085—Copper
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- C08K2003/0856—Iron
Abstract
The invention relates to a cellulose-feather protein hydrogel nano metal compound and a preparation method thereof, wherein the compound comprises cellulose-feather protein hydrogel, nano metal particles are adsorbed in the cellulose-feather protein hydrogel, and the cellulose-feather protein hydrogel is prepared by mixing cellulose dissolved by ionic liquid and feather protein dissolved by ionic liquid. The process not only realizes the reutilization of the solid waste, but also realizes the recovery and the utilization of the heavy metal, and realizes the treatment of wastes with processes of wastes against one another. The prepared hydrogel is a pure natural molecular material, has good degradability, and the ionic liquid used in the engineering of preparing the hydrogel spheres can be recycled. The cost is low in the whole process, the production process is simple and convenient, and the green environmental protection has wide application prospect.
Description
Technical Field
The invention relates to a cellulose-feather protein hydrogel nano metal compound and a preparation method thereof, belonging to the technical field of chemistry and environment.
Background
The hydrogel contains hydrophilic functional groups (-OH, -NH)2OOH) crosslinked polymers with a three-dimensional network structure, which can absorb a large amount of water in water without deforming. The functional group in the hydrogel can be complexed or chelated with metal ions, so that the hydrogel has a remarkable adsorption effect on heavy metals and is an ideal soft template of metal nanoparticles. The hydrogel structure can uniformly disperse the metal nanoparticles and prevent the metal nanoparticles from agglomerating, thereby ensuring the stability of the metal nanoparticles.
Crop wheat straw is a renewable biomass resource, the annual output of China is about 7 hundred million, most of the crop wheat straw is not effectively utilized, and huge waste of natural resources and a series of environmental pollution problems are caused. The main components of the straw are cellulose, hemicellulose and lignin. Cellulose contains a large number of free hydroxyl groups, so that the cellulose has strong adsorption capacity to water, and the cellulose can be used for synthesizing hydrogel, and the synthesized hydrogel belongs to degradable green chemical products. Thus not only utilizing waste resources, but also preparing new environment-friendly materials with development prospect.
In daily life, the chicken feather is used as a waste byproduct of the poultry industry, the annual output of the world exceeds 400 million tons, and most of the large chicken feather is directly buried and not well utilized. The method not only wastes resources, but also increases the burden of land and causes harm to the environment. The waste chicken feathers are important keratin resources, the keratin content in the chicken feathers is up to more than 80 percent, and the chicken feathers are very cheap protein resources. Keratin is a hard protein which is not dissolved under ordinary conditions because keratin molecules form a highly cross-linked stable three-dimensional molecular structure by disulfide bonds, hydrogen bonds, ionic bonds, and the like, whereas ionic liquids can dissolve keratin. Due to the unique properties of low melting point, good thermal stability, difficult volatilization, strong dissolving capacity and the like, the ionic liquid attracts attention in recent years, is considered to be a green solvent and a reaction medium which can replace the traditional volatile solvent, and has potential application value in the fields of extraction, synthesis, new energy and the like. In recent years, some feather protein is prepared by reduction method and ionic liquid dissolution method, even though the research on the preparation and utilization of keratin is still very little. No report is found on the blended hydrogel prepared by taking straw cellulose and chicken feather protein as raw materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a cellulose-feather protein hydrogel nano metal compound and a preparation method thereof.
Summary of the invention:
the invention takes straws and feathers as raw materials, utilizes ionic liquid (a novel green solvent) to dissolve straw cellulose and feather protein to prepare cellulose-feather protein hydrogel, and further prepares magnetic cellulose-feather protein hydrogel through chemical reaction. Groups (-NH) in hydrogels2-OH) can adsorb heavy metal ions by in situThe metal nano-particles are prepared in the hydrogel by a reduction method, and the obtained hydrogel nano-metal composite can be used for various catalytic reactions, such as reduction of nitro compounds, chlorohydrocarbons, degradation of colored dyes, catalytic hydrolysis of various hydrides and the like. The waste is recycled in the whole process, the waste is treated by the waste, and the prepared hydrogel belongs to a natural polymer material, is biodegradable and is an environment-friendly material with development prospect.
The technical scheme of the invention is as follows:
a cellulose-feather protein hydrogel nano metal compound comprises cellulose-feather protein hydrogel, nano metal particles are adsorbed in the cellulose-feather protein hydrogel, the loading capacity of the nano metal particles is 21.7-35.25, unit: mg/g, the cellulose-feather protein hydrogel is prepared by mixing cellulose dissolved by ionic liquid and feather protein dissolved by ionic liquid.
According to the invention, the preparation method of the cellulose-feather protein hydrogel nano metal compound comprises the following steps:
dissolving the treated straw raw material by using ionic liquid to prepare dissolved straw cellulose;
dissolving the treated feather with ionic liquid to prepare dissolved feather protein;
mixing the dissolved straw cellulose and the dissolved feather protein to prepare nonmagnetic/magnetic cellulose-feather protein hydrogel;
and (3) adsorbing heavy metal ions by the nonmagnetic/magnetic cellulose-feather protein hydrogel and converting the heavy metal ions adsorbed on the hydrogel spheres into nano metal to obtain the nonmagnetic/magnetic cellulose-feather protein hydrogel nano metal compound.
According to the invention, the preferable step of dissolving the treated straw raw material by using the ionic liquid to prepare the dissolved straw cellulose is as follows: cleaning, drying, crushing and sieving the straws, and then mixing the straws with HNO3Mixing the solutions, heating and stirring for reaction, cleaning, drying and sieving the solid obtained after the reaction to obtain straw cellulose, mixing the straw cellulose with the ionic liquid, and heating and stirring to obtain the dissolved straw cellulose.
Preferably, the straws are wheat straws or corn straws, the drying temperature of the straws is 65-80 ℃, the sieving mesh number is 90-110 meshes, and HNO is adopted3The mass percentage of the solution is 5 percent to 15 percent, and the straw and the HNO3The mass ratio of the solution is 1: (40-60), the heating and stirring temperature is 100-120 ℃, and the stirring time is 6-10 h.
Further preferably, the ionic liquid is 1-butyl-3-methylimidazolium chloride (B [ MIMCl ]) or 1-allyl-3-methylimidazolium chloride (A [ MIMCl ]), and the mass ratio of the straw cellulose to the ionic liquid is 3-10: 100, heating the dissolved straw cellulose to 90-110 ℃, and stirring for 6-10 h.
Preferably, the step of dissolving the treated feather by using the ionic liquid to prepare the dissolved feather protein comprises the following steps: washing and drying the feather, crushing to obtain crushed feather, mixing the crushed feather with ionic liquid and ionic liquid, and heating and stirring to obtain dissolved feather protein.
Preferably, the feather is chicken feather or duck feather, the drying temperature of the feather is 55-70 ℃, the ionic liquid used for dissolving the feather is the same as the ionic liquid used for dissolving the straw cellulose, and the mass ratio of the feather to the ionic liquid is 1-7: 100, the heating temperature for dissolving feather is 120-.
According to the invention, the step of preparing the nonmagnetic/magnetic cellulose-feather protein hydrogel by mixing the dissolved straw cellulose and the dissolved feather protein comprises the following steps: uniformly mixing dissolved straw cellulose and dissolved feather protein, and dropwise adding the obtained mixed solution into deionized water for soaking to obtain nonmagnetic cellulose-feather protein hydrogel; adding Fe into non-magnetic cellulose-feather protein hydrogel2+And Fe3+Placing the mixed solution in NaOH solution after vibration adsorption, and cleaning to obtain the magnetic cellulose-feather protein hydrogel.
Preferably, the soaking is carried out by soaking in water and replacing the water once at intervals, the ionic liquid is replaced into the water, the soaking interval is 6-10 hours, the soaking time is 3 days, the deionized water is collected after soaking, the ionic liquid is evaporated and recycled for recycling, and the evaporation and recycling temperature is 60-80 ℃.
Further preferably, the mass ratio of the dissolved straw cellulose to the dissolved feather protein is as follows: (5-10):(1-3).
Further preferably, Fe2+And Fe3+Fe in the mixed solution of2+With Fe3+In a molar ratio of 1:1.5-3, Fe2+With Fe3+The concentration of the adsorbent is 0.4-0.7mol/L, the oscillation adsorption time is 10-30h, and the preferred oscillation adsorption time is 8-12 h.
Further preferably, the solution is placed in NaOH solution with the concentration of 0.4-0.7mol/L after shaking and adsorption.
According to the invention, the preferable method for adsorbing the heavy metal ions by the nonmagnetic/magnetic cellulose-feather protein hydrogel is as follows: respectively placing the nonmagnetic/magnetic cellulose-feather protein hydrogel in a heavy metal ion solution, performing shock adsorption for 10-30h at room temperature, and cleaning with deionized water to remove unadsorbed heavy metal ions after adsorption is completed.
Further preferably, the heavy metal ions are copper ions and nickel ions;
further preferably, the concentration of the heavy metal ion solution is 50-2000mg/L, more preferably 1500-2000 mg/L; the adsorption time is 12-24 h.
According to the invention, preferably, the conversion of the heavy metal ions adsorbed on the hydrogel spheres into nano-metals is specifically as follows: and placing the nonmagnetic/magnetic hydrogel spheres adsorbing the heavy metal ions into a sodium borohydride solution, and continuously stirring for 0.5-2h at room temperature to convert the heavy metal ions adsorbed on the hydrogel spheres into nano metal, thereby obtaining the nonmagnetic/magnetic cellulose-feather protein hydrogel nano metal compound.
Further preferably, the concentration of the sodium borohydride solution is 0.1-2g/L, and preferably, the concentration of the sodium borohydride solution is 0.2-1.2 g/L; the ratio of the mass of the nonmagnetic/magnetic hydrogel nano-metal complex to the volume of the sodium borohydride solution is 1: 100.
According to the invention, the application of the cellulose-feather protein hydrogel nano metal compound is used for degrading nitrobenzoic acid, p-nitrophenol, chloramphenicol or methylene blue pollutants.
Further preferably, the degradation method is as follows: placing the hydrogel nano-metal compound in a solution containing a pollutant, and adding NaBH into the solution4Catalytically degrading pollutants under the condition of stirring, wherein the degradation temperature is 20-40 ℃; the concentration of the pollutants is 25-125 mg/L.
Further preferably, the addition amount of the hydrogel nano metal composite is as follows: adding 0.5g-1.0g of hydrogel nano metal composite into every 500mL of solution containing the pollutants; NaBH4The addition amount of (A) is as follows: 0.2g-0.5 g.
The invention has the beneficial effects that:
1. the preparation method is simple, the used straw and feather raw materials are cheap and easy to obtain, the ionic liquid can be recycled, the cost is low, and the straw and feather are used as the raw materials to realize waste utilization.
2. The non-magnetic/magnetic cellulose-feather protein hydrogel prepared by the invention can effectively adsorb copper ions and prepare a hydrogel nano metal compound. The non-magnetic/magnetic hydrogel nano metal compound can be used for catalyzing and degrading nitro compounds, dyes and chlorohydrocarbons. The invention not only treats heavy metal pollutants, but also realizes the recycling of heavy metals
3. The non-magnetic/magnetic hydrogel nano metal complex prepared by the invention can be recycled.
4. The cellulose-feather protein hydrogel prepared by the method is easy to degrade and environment-friendly.
Drawings
FIG. 1 is a scanning electron microscope of the nonmagnetic cellulose-feather protein hydrogel nano metal complex obtained in example 4 of the present invention.
FIG. 2 is a scanning electron microscope of the magnetic cellulose-feather protein hydrogel nano metal complex obtained in example 5 of the present invention.
FIG. 3 is a graph showing the effect of the amount of the non-magnetic hydrogel nanometal complex on the degradation of nitrobenzoic acid in Experimental example 1 of the present invention.
FIG. 4 NaBH in Experimental example 2 of the present invention4In an amount ofInfluence on the degradation of nitrobenzoic acid.
FIG. 5 Effect of initial concentration of nitrobenzoic acid solution on nitrobenzoic acid degradation in Experimental example 3 of the present invention.
FIG. 6 influence of reaction temperature on degradation of nitrobenzoic acid in Experimental example 4 of the present invention.
FIG. 7 effect of amount of magnetic hydrogel nanometal complex on nitrobenzoic acid degradation in Experimental example 5 of the present invention.
FIG. 8 NaBH in Experimental example 6 of the present invention4The amount is the effect on the degradation of nitrobenzoic acid.
FIG. 9 Effect of initial concentration of nitrobenzoic acid solution on nitrobenzoic acid degradation in Experimental example 7 of the present invention.
FIG. 10 influence of reaction temperature on degradation of nitrobenzoic acid in Experimental example 8 of the present invention.
Detailed Description
The present invention will be further described with reference to the following detailed description of embodiments thereof, but not limited thereto, in conjunction with the accompanying drawings.
The starting materials used in the examples are all conventional commercial products.
Examples 1,
Preparation of cellulose-feather protein hydrogel:
(1) drying wheat straws at 70 +/-5 ℃, then crushing and sieving with a 100-mesh sieve, collecting sieved enteromorpha powder for later use, cleaning chicken feathers, drying and crushing at 60 +/-5 ℃ for later use;
(2) taking 4g of wheat straw powder in a round-bottom flask, and adding 200mL of 10% HNO3Adding the solution into a round-bottom flask, stirring and reacting at 110 ℃ for 8h, taking out the mixed solution after 8h, washing with deionized water until the supernatant is colorless and transparent to obtain wheat straw cellulose, drying the wheat straw cellulose at 70 +/-5 ℃, then crushing and sieving with a 100-mesh sieve, and collecting the sieved straw cellulose powder for later use;
(3) putting 0.5g of the straw cellulose prepared in the step (2) into a round-bottom flask, adding 9.5g of ionic liquid, and continuously stirring at 100 +/-5 ℃ for reacting for 8 hours, wherein the straw cellulose is completely dissolved;
(4) putting 0.3g of the chicken feather prepared in the step (1) into a round-bottom flask, adding 9.7g of ionic liquid, and continuously stirring at 130 +/-5 ℃ for reacting for 6 hours until feather protein is completely dissolved;
(5) and (4) completely and uniformly mixing the liquid which is well dissolved in the step (3) and the step (4), dropwise adding the mixed liquid into a beaker filled with deionized water by using an injector, soaking, changing water every 8 hours, and soaking for 3 days to obtain the cellulose-feather protein hydrogel. Collecting the soaked water solution, evaporating at 60 + -5 deg.C to recover ionic liquid, and recycling.
And (3) detection: placing 0.5g of the 5% + 3% cellulose-feather protein hydrogel prepared in the step (5) in a copper ion solution, and performing vibration adsorption for 24 hours at room temperature; the adsorption capacity of the 5% + 3% cellulose-feather protein mixed hydrogel spheres to copper is measured by a flame atomic absorption method. The adsorbed amount was 24.7 mg/g.
Examples 2,
The preparation of cellulose-feather protein hydrogel as described in example 1, except that the amounts of cellulose and feather protein were varied:
0.7g (0.3g, 0.5g, 1g) of cellulose and 0.3g (0.1g, 0.2g) of chicken feathers are respectively taken and dissolved in the ionic liquid in the step (3), and the rest operation and the use amount are completely the same as those in the example 1. Preparing cellulose-feather protein mixed hydrogel spheres with different proportions of 5% + 3%, 7% + 1%, 7% + 2%, 7% + 3%, 10% + 3%, 10% + 2%, 10% + 1%. The rest of the operation and the amount are completely the same as those in the example 1.
The cellulose-feather protein mixed hydrogel spheres obtained in the example with the concentration of 7% + 3% have the best adsorption effect on copper ions, and the adsorption amount is 35.25 mg/g.
Examples 3,
Preparation of cellulose-feather protein hydrogel with magnetism
The magnetic cellulose-feather protein hydrogel is prepared by using the cellulose-feather protein hydrogel with the optimal proportion obtained in the example 2, and the method comprises the following steps:
(1) 0.5g of 7% + 3% cellulose-feather protein mixed hydrogel spheres are put into a 0.5mol/L iron ion mixed solution (Fe)2+：Fe3+1:2 (molar ratio)) is shaken and adsorbed for 24h at room temperature;
(2) and taking out the adsorbed hydrogel spheres, putting the hydrogel spheres into 0.5mol/L NaOH solution for reaction for 2 hours, and then washing redundant impurities on the hydrogel spheres with deionized water to obtain the magnetic cellulose-feather protein hydrogel.
Examples 4,
Preparing a non-magnetic cellulose-feather protein hydrogel nano metal compound:
(1) 0.5g of the optimal nonmagnetic cellulose-feather protein hydrogel in the example 2 is placed in a 100mL conical flask, 50mL of copper nitrate solution with the copper ion content of 2000mg/L is added, and the mixture is placed in a water bath oscillator at the temperature of 20 ℃ for oscillation and adsorption for 24 hours.
(2) Taking out the hydrogel adsorbed with the copper ions in the step (1), soaking the hydrogel in sufficient deionized water, and washing away the copper ions not adsorbed on the hydrogel for 1 h;
(3) taking out the hydrogel ball cleaned in the step (2), adding 50mL of sodium borohydride solution with the sodium borohydride content of 1.0g/L into a beaker, continuously stirring for 1h at room temperature, and converting heavy metal ions adsorbed on the hydrogel into nano metal to obtain a non-magnetic cellulose-feather protein hydrogel nano metal compound;
the application comprises the following steps: taking 500mL of nitrobenzoic acid solution with the concentration of 50mg/L into a beaker, placing 0.5g of hydrogel nano metal composite into the beaker, adding 0.5g of NaBH4The nitrobenzoic acid is degraded under magnetic stirring at 20 ℃.
The application effect is as follows: the degradation rate of nitrobenzoic acid was determined by diluting 1mL of sample at intervals and measuring absorbance at 267nm using an ultraviolet reflectance photometer.
Examples 5,
Preparing a magnetic cellulose-feather protein hydrogel nano metal compound:
(1) 0.5g of the magnetic cellulose-feather protein hydrogel obtained in example 3 was placed in a 100mL conical flask, 50mL of a copper nitrate solution with a copper ion content of 2000mg/L was added, and the mixture was placed in a 20 ℃ water bath shaker for shaking adsorption for 24 hours.
(2) Taking out the hydrogel adsorbed with the copper ions in the step (1), soaking the hydrogel in sufficient deionized water, and washing away the copper ions not adsorbed on the hydrogel for 1 h;
(3) taking out the magnetic hydrogel cleaned in the step (2), adding 50mL of sodium borohydride solution with the sodium borohydride content of 1.0g/L into a beaker, continuously stirring for 1h at room temperature, and converting heavy metal ions adsorbed on hydrogel spheres into nano metal to obtain a magnetic cellulose-feather protein hydrogel nano metal compound;
the application comprises the following steps: taking 500mL of nitrobenzoic acid solution with the concentration of 50mg/L into a beaker, placing 0.5g of magnetic hydrogel nano metal compound into the beaker, and adding 0.25g of NaBH4The nitrobenzoic acid is degraded under magnetic stirring at 20 ℃.
The application effect is as follows: the degradation rate of nitrobenzoic acid was determined by diluting 1mL of sample at intervals and measuring absorbance at 267nm using an ultraviolet reflectance photometer.
Examples 6,
The procedure and the amount were exactly the same as in example 4 except that the amount of the cellulose-feather protein hydrogel in step (1) was 0.75g, as described in example 4.
Example 7,
The procedure and the amount were exactly the same as in example 4 except that 1g of the cellulose-feather protein hydrogel was used in step (1) as described in example 4.
Example 8,
As described in example 4, except that in step (4), NaBH4The amount of (2) was 0.3g, and the other operations and amounts were exactly the same as in example 4.
Examples 9,
As described in example 4, except that in step (4), NaBH4The amount of (2) was 0.4g, and the remaining operations and amounts were exactly the same as in example 4.
Examples 10,
The procedure and the amount used were the same as in example 4 except that in step (4), the concentration of nitrobenzoic acid was 75 mg/L.
Examples 11,
The procedure and the amount were exactly the same as in example 4 except that the concentration of nitrobenzoic acid in step (4) was 100mg/L, as described in example 4.
Examples 12,
The procedure and the amounts used were exactly the same as in example 4, except that in step (4), the reaction temperature was 30 ℃.
Examples 13,
The procedure and the amounts used were exactly the same as in example 4, except that in step (4), the reaction temperature was 40 ℃.
Examples 14,
The procedure and the amount were exactly the same as in example 5 except that the amount of the magnetic cellulose-feather protein hydrogel in step (1) was 0.75g, as described in example 5.
Examples 15,
The procedure and the amount were exactly the same as in example 5 except that 1g of the magnetic cellulose-feather protein hydrogel was used in step (1) as described in example 5.
Examples 16,
As described in example 5, except that in step (4), NaBH4The amount of (2) was 0.2g, and the other operations and amounts were exactly the same as in example 5.
Examples 17,
As described in example 5, except that in step (4), NaBH4The amount of (2) was 0.3g, and the other operations and amounts were exactly the same as in example 5.
Examples 18,
The procedure and the amount were exactly the same as in example 5 except that the concentration of nitrobenzoic acid in step (4) was 75mg/L as described in example 5.
Examples 19,
The procedure and the amount were identical to those in example 5 except that in step (4), the nitrobenzoic acid concentration was 100mg/L, as described in example 5.
Examples 20,
The procedure and the amounts used were exactly the same as in example 5, except that in step (4), the reaction temperature was 30 ℃.
Examples 21,
The procedure and the amounts used were exactly the same as in example 5, except that in step (4), the reaction temperature was 40 ℃.
The following is an experiment conducted on the effect of different conditions on the degradation effect of nitrobenzoic acid.
Experimental example 1:
the results of the experiments for degrading nitrobenzoic acid in examples 4, 6 and 7 are shown in FIG. 3.
Experimental example 2:
the results of the experiments for degrading nitrobenzoic acid in examples 4, 8 and 9 are shown in FIG. 4.
Experimental example 3
The results of the experiments for degrading nitrobenzoic acid in examples 4, 10 and 11 are shown in FIG. 5.
Experimental example 4
The experiments for degrading nitrobenzoic acid in examples 4, 12 and 13 were carried out under the same conditions, and the results are shown in FIG. 6.
Experimental example 5
The results of the experiments for degrading nitrobenzoic acid in examples 5, 14 and 15 are shown in FIG. 7.
Experimental example 6
The results of the experiments for degrading nitrobenzoic acid in examples 5, 16 and 17 are shown in FIG. 8.
Experimental example 7
The results of the experiments for degrading nitrobenzoic acid in examples 5, 18 and 19 are shown in FIG. 9.
Experimental example 8
The experiments for degrading nitrobenzoic acid in examples 5, 20 and 21 were carried out under the same conditions, and the results are shown in FIG. 10.
The results show that: the degradation rate of nitrobenzoic acid is increased along with the increase of the amount of the nonmagnetic/magnetic cellulose-feather protein hydrogel nano metal compound, the amount of sodium borohydride, the initial concentration of nitrobenzoic acid and the temperature; the degradation of the magnetic hydrogel nano metal compound p-nitrophenol is better than that of the non-magnetic hydrogel nano metal compound.
Claims (7)
1. An application of cellulose-feather protein hydrogel nano metal compound is used for degrading nitrobenzoic acid, p-nitrophenol, chloramphenicol or methylene blue pollutants; the cellulose-feather protein hydrogel nano metal compound comprises cellulose-feather protein hydrogel, nano metal particles are adsorbed in the cellulose-feather protein hydrogel, the loading capacity of the nano metal particles is 21.7-35.25, unit: mg/g, the cellulose-feather protein hydrogel is prepared by mixing cellulose dissolved by ionic liquid and feather protein dissolved by ionic liquid;
the preparation method of the cellulose-feather protein hydrogel nano metal compound comprises the following steps:
dissolving the treated straw raw material by using ionic liquid to prepare dissolved straw cellulose;
dissolving the treated feather with ionic liquid to prepare dissolved feather protein;
mixing the dissolved straw cellulose and the dissolved feather protein to prepare nonmagnetic/magnetic cellulose-feather protein hydrogel; uniformly mixing dissolved straw cellulose and dissolved feather protein, and dropwise adding the obtained mixed solution into deionized water for soaking to obtain nonmagnetic cellulose-feather protein hydrogel; adding Fe into non-magnetic cellulose-feather protein hydrogel2+And Fe3+Placing the mixed solution in NaOH solution after vibration adsorption, and cleaning to obtain magnetic cellulose-feather protein hydrogel; the mass ratio of the dissolved straw cellulose to the dissolved feather protein is as follows: (5-10) and (1-3); fe2+And Fe3+Fe in the mixed solution of2 +With Fe3+In a molar ratio of 1:1.5-3, Fe2+With Fe3+The concentration of (A) is 0.4-0.7mol/L, and the vibration adsorption timeIs vibrated and adsorbed for 10 to 30 hours, and then is placed in NaOH solution with the concentration of 0.4 to 0.7 mol/L;
the non-magnetic/magnetic cellulose-feather protein hydrogel absorbs heavy metal ions, and the heavy metal ions absorbed on the hydrogel spheres are converted into nano metal to obtain a non-magnetic/magnetic cellulose-feather protein hydrogel nano metal compound;
the degradation method specifically comprises the following steps: placing the hydrogel nano-metal compound in a solution containing a pollutant, and adding NaBH into the solution4Catalytically degrading pollutants under the condition of stirring, wherein the degradation temperature is 20-40 ℃; the concentration of the pollutants is 25-125 mg/L; the addition amount of the hydrogel nano metal compound is as follows: adding 0.5g-1.0g of hydrogel nano metal composite into every 500mL of solution containing the pollutants; NaBH4The addition amount of (A) is as follows: 0.2g-0.5 g.
2. The application of the cellulose-feather protein hydrogel nano-metal compound as claimed in claim 1, wherein the step of dissolving the treated straw raw material with ionic liquid to prepare the dissolved straw cellulose is as follows: cleaning, drying, crushing and sieving the straws, and then mixing the straws with HNO3Mixing the solutions, heating and stirring for reaction, cleaning, drying and sieving the solid obtained after the reaction to obtain straw cellulose, mixing the straw cellulose with the ionic liquid, and heating and stirring to obtain the dissolved straw cellulose.
3. The application of the cellulose-feather protein hydrogel nano metal compound as claimed in claim 2, wherein the straw is wheat straw or corn straw, the drying temperature of the straw is 65-80 ℃, the sieving mesh number is 90-110 meshes, and the HNO is HNO3The mass percentage of the solution is 5 percent to 15 percent, and the straw and the HNO3The mass ratio of the solution is 1: (40-60), the heating and stirring temperature is 100-120 ℃, and the stirring time is 6-10 h; the ionic liquid is 1-butyl-3-methylimidazolium chloride (B [ MIMCl ]]) Or 1-allyl-3-methylimidazolium chloride salt (A [ MIMCl ]]) The mass ratio of the straw cellulose to the ionic liquid is 3-10: 100, the heating temperature for dissolving the straw cellulose is 90-110 ℃, and the stirring time is 6-10 h。
4. The use of the cellulose-feather protein hydrogel nanometal complex of claim 1 wherein the step of dissolving the treated feather with ionic liquid to prepare dissolved feather protein is: washing and drying the feather, crushing to obtain crushed feather, mixing the crushed feather with ionic liquid and ionic liquid, and heating and stirring to obtain dissolved feather protein; the feather is chicken feather or duck feather, the drying temperature of the feather is 55-70 ℃, the ionic liquid used for dissolving the feather is the same as the ionic liquid used for dissolving the straw cellulose, and the mass ratio of the feather to the ionic liquid is 1-7: 100, the heating temperature for dissolving feather is 120-.
5. The use of the cellulose-feather protein hydrogel nanometal complex as claimed in claim 1 wherein the soaking is soaking in water with an interval of time to exchange water, ionic liquid is exchanged into water with an interval of 6-10h and a soaking time of 3 days, the deionized water is collected after soaking, and the ionic liquid is recovered by evaporation at an evaporation recovery temperature of 60-80 ℃ for recycling.
6. The use of the cellulose-feather protein hydrogel nanometal complex of claim 1, wherein the non-magnetic/magnetic cellulose-feather protein hydrogel adsorbs heavy metal ions specifically as follows: respectively placing the nonmagnetic/magnetic cellulose-feather protein hydrogel in a heavy metal ion solution, performing shock adsorption for 10-30h at room temperature, and cleaning with deionized water to remove unadsorbed heavy metal ions after adsorption is completed.
7. The use of the cellulose-feather protein hydrogel nanometal complex of claim 1 wherein the heavy metal ions are copper ions, nickel ions; the concentration of the heavy metal ion solution is 50-2000 mg/L; the adsorption time is 12-24 h; the conversion of the heavy metal ions adsorbed on the hydrogel spheres into nano metal is specifically as follows: placing the non-magnetic/magnetic hydrogel spheres adsorbing the heavy metal ions into a sodium borohydride solution, continuously stirring for 0.5-2h at room temperature, converting the heavy metal ions adsorbed on the hydrogel spheres into nano metal, and obtaining a non-magnetic/magnetic cellulose-feather protein hydrogel nano metal compound; the concentration of the sodium borohydride solution is 0.1-2 g/L; the ratio of the mass of the nonmagnetic/magnetic hydrogel nano-metal complex to the volume of the sodium borohydride solution is 1: 100.
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