CN115254045A - Modified starch/graphene oxide composite aerogel and preparation method and application thereof - Google Patents
Modified starch/graphene oxide composite aerogel and preparation method and application thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a modified starch/graphene oxide composite aerogel and a preparation method and application thereof. The prepared aerogel has the characteristics of obvious three-dimensional structure, abundant pore structure, thicker pore wall, high specific surface area, high porosity, light weight and stable structure, can effectively overcome the defects of poor mechanical strength, weak interaction of molecular chains in a gel network, insufficient toughness and the like of the existing starch-based aerogel, and has good conditions for adsorbing Pb (II). The modified starch/graphene oxide composite aerogel disclosed by the invention has a good adsorption effect on Pb (II).
Description
Technical Field
The invention belongs to the technical field of a novel composite material synthesis method of modified starch/graphene oxide composite aerogel, and particularly relates to modified starch/graphene oxide composite aerogel and a preparation method and application thereof.
Background
With the rapid development of various industries, water body pollution accidents happen occasionally, and waste water generated by different industries or living activities is generally polluted by a large amount of pollutants, wherein the pollutants comprise inorganic pollutants such as heavy metal ions and the like, organic matters such as dyes and medicines and the like, biological pollutants such as bacteria and the like, and radiation waste serving as radioactive nuclides. The removal of these harmful substances from water is a serious problem of great concern and high priority, since these harmful substances have direct and negative effects on both human beings and the environment, particularly heavy metal ion pollution, remain in the environment for a long time, finally enter the human body through the food chain and deposit in large quantities, causing various disease risks.
In recent years, various water purification treatment techniques have been developed, such as adsorption, ion exchange, precipitation, coagulation/flocculation, membrane treatment, oxidation, photodegradation, and the like. The adsorption method not only can effectively decolor, but also can adsorb heavy metal ions and remove substances which are difficult to be treated by chemical and biological methods in the wastewater, and becomes the most widely used and latest trend. Nowadays, due to the development of nanotechnology, some types of nano adsorbents, nano biological adsorbents or nano catalysts are receiving wide attention due to excellent and unique characteristics in removing multiple pollutants in the water treatment process, carbon nanomaterials become currently main functional adsorbents due to excellent thermal stability, mechanical toughness and adsorption performance, graphene is one of the hot emerging materials in recent years, and is a brand-new member in the carbon family, the graphene has good adsorbability due to the structural characteristics of high specific surface area, and a research on the application of graphene-based materials as adsorbents in sewage treatment has been reported in many documents.
The starch-based aerogel has the characteristics of high specific surface area, high porosity, excellent degradability and the like, is an excellent carrier material, is an ideal material for preparing the functional aerogel from the main raw material starch in a natural polymer, takes Cassava Starch (CS) as a matrix, N-isopropylacrylamide (NIPAM) as a monomer, ammonium persulfate as an initiator and N, N-methylenebisacrylamide as a cross-linking agent, and is used for preparing the cassava starch/sodium alginate temperature-sensitive Pb 2+ Imprinting material (CPIT) for the treatment of Pb 2+ The adsorption amount of (B) was 113.87mg/g. (preparation of sodium alginate/cassava starch-based temperature-sensitive molecularly imprinted material and study of metal ion adsorption property [ D]Hainan university, 2020). In order to improve the functional characteristics of starch, the application range of starch can be expanded by modifying the raw starch by physical, chemical, biological and other methods. However, the current pure starch-based aerogel has the defects of poor mechanical strength, insufficient toughness and the like due to non-uniform network, and the application range is greatly limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a modified starch/graphene oxide composite aerogel, and a preparation method and application thereof, so as to solve the problems of poor mechanical strength, weak interaction of molecular chains in a gel network and insufficient toughness of a pure starch-based aerogel.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a modified starch/graphene oxide composite aerogel, which has the following structural formula:
wherein m =1 to 10, n =1 to 20.
The invention also discloses a preparation method of the modified starch/graphene oxide composite aerogel, which comprises the following steps:
step one, adding 10-15 parts of corn starch into 10-20 parts of ethyl acetate by mass part, and stirring to obtain a starch suspension; adding 1-5 parts of pyridine into the starch suspension, continuously stirring, dropwise adding 0.5-1.0 part of acryloyl chloride for reaction, then adding 5-10 parts of ethanol for terminating the reaction, standing, washing, centrifuging and drying to obtain modified starch;
step two, adding 20-25 parts of H into 1-5 parts of graphite powder by mass 2 SO 4 Stirring, adding 1-5 parts of KMnO 4 Reaction, ultrasonic dispersion, adding 40-50 portions of deionized water for continuous reaction, diluting, adding 10-15 portions of H 2 O 2 Washing and drying the solution until no bubbles are generated, thereby obtaining dark brown flaky graphene oxide;
adding 0.06-0.07 part of ammonium persulfate and 0.1-0.5 part of N, N-methylene bisacrylamide into the starch paste, stirring, dropwise adding 0.1-2.0 parts of acrylic acid, continuously stirring, adding 0.01-0.03 part of graphene oxide, stirring, standing to form hydrogel, and freeze-drying the hydrogel to obtain the modified starch/graphene oxide composite aerogel.
Preferably, in the step one, stirring for 10-20 min at 20-30 ℃ to obtain a starch suspension; adding pyridine and continuing stirring for 10-30 min;
dripping acryloyl chloride at the speed of 3-5 drops per second, and reacting for 20-30 min at the temperature of 20-30 ℃; standing for 20-30 min, and drying at 75-85 ℃ for 20-30 h;
the centrifugal speed is 5000-8000 r/min, and the centrifugal time is 5-10 min.
Preferably, in the first step, the molecular weight of the corn starch is 16000-500000, and the mass fraction of the acryloyl chloride is 5-10%.
Preferably, in step two, H is added 2 SO 4 Stirring at 15-20 deg.c while adding KMnO for 1-2 hr 4 Continuously reacting for 1-2 h;
the ultrasonic dispersion treatment time is 8-12 h, deionized water is added for continuous reaction for 10-20 min, and 100-150 parts of deionized water with the temperature of 75-90 ℃ is used for dilution.
Preferably, in the second step, 10 to 15 parts by weight of 30 percent H is added under the stirring condition 2 O 2 A solution; repeatedly washing with 5-10% by mass of dilute HCl solution and deionized water until the pH value is 5-7, and carrying out vacuum drying at 55-60 ℃ to obtain the graphene oxide.
Preferably, in the second step, the molecular weight of the graphite powder is 16-17,H 2 SO 4 The mass fraction of (A) is 80-85%.
Preferably, in the third step, the ratio of the modified starch to the deionized water is 1.
Preferably, in the third step, stirring for 20-30 min at 80-90 ℃ for gelatinization, dripping acrylic acid and continuously stirring for 10-20 min;
adding graphene oxide, stirring for 10-20 min, standing for 20-30 min to form hydrogel, and freeze-drying the hydrogel for 40-50 h.
The invention also discloses an application of the modified starch/graphene oxide composite aerogel in preparation of a heavy metal ion adsorbent.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a modified starch/graphene oxide composite aerogel, which has a porous network structure, contains a large number of oxygen-containing groups such as hydroxyl, carboxyl, carbonyl and the like on the surface and among lamella, and can be combined with polyvalent metal ions through electrostatic attraction and coordination bonds, so that the modified starch/graphene oxide composite aerogel can be used for adsorption of dyes and heavy metals, air purification, water pollution treatment and the like.
The invention discloses a preparation method of modified starch/graphene oxide composite aerogel, which comprises the steps of taking a graphene oxide nano material and modified starch as raw materials, taking acrylic acid as a cross-linking agent, adding the graphene oxide nano material into a modified starch acrylic acid copolymerization solution, and preparing the modified starch/graphene oxide composite aerogel by a sol-gel method. The nano-scale material graphene oxide is introduced into the modified starch matrix in a chemical bond crosslinking mode, and the aim of improving the mechanical strength and mechanical toughness of the aerogel is fulfilled by virtue of strong interaction such as hydrogen bonds between the nano-scale material graphene oxide and the modified starch matrix. Compared with pure starch-based aerogel, the tensile strength, the elongation at break and the compressive strength of the modified starch/graphene oxide composite aerogel are improved to some extent, and the defects of poor mechanical strength, weak interaction of molecular chains in a gel network and insufficient toughness of the starch-based aerogel can be effectively overcome.
Furthermore, pyridine is added to serve as a catalyst, and acryloyl chloride is added to serve as a starch modifier to modify the starch.
Further, dripping acrylic acid as a cross-linking agent to react with the modified starch for cross-linking.
The invention also discloses application of the modified starch/graphene oxide composite aerogel in preparation of a heavy metal ion adsorbent, wherein the composite aerogel has selectivity on adsorption of lead ions and has the best adsorption performance on the lead ions; meanwhile, the composite aerogel is in a good state in waste liquid, the form of the composite aerogel is kept stable and insoluble, the adsorbed aerogel is rich in elasticity after being taken out, and molecular chains in a gel network have strong interaction.
Drawings
FIG. 1 is a chart of the infrared spectra of starch and modified starch of the present invention;
FIG. 2 is a schematic diagram of the synthesis of a modified starch according to the present invention;
fig. 3 is a schematic diagram illustrating the synthesis of the modified starch/graphene oxide composite aerogel according to the present invention;
fig. 4 is an inductance coupling diagram of the modified starch/graphene oxide composite aerogel for adsorbing lead ions, wherein the adsorption time is 24 hours.
Detailed Description
In order to make the technical solutions of the present invention better understood, 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. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a modified starch/graphene oxide composite aerogel and a preparation method thereof.
The method specifically comprises the following steps:
step one, weighing 10-15 parts of corn starch, adding 10-20 parts of ethyl acetate into a beaker, and stirring the solution at 20-30 ℃ for 10-20 min to obtain a starch suspension; adding 1-5 parts of pyridine into the solution, and continuously stirring for 10-30 min; after stirring, dropwise adding 0.5-1.0 part of acryloyl chloride into the beaker at the dropping speed of 3-5 drops per second, continuously reacting for 20-30 min at the temperature of 20-30 ℃ under the stirring condition after dropwise adding, then adding 5-10 parts of ethanol to stop the reaction, washing and centrifuging for 2-5 times by using ethanol after standing for 20-30 min, placing the centrifuged product in a 75-85 ℃ blast oven for drying for 20-30 h, and preparing and obtaining modified starch, which is finely ground for later use;
step two, weighing 1-5 parts of graphite powder and adding 20-25 parts of H 2 SO 4 Stirring at 15-20 deg.c for 1-2 hr, and adding KMnO in 1-5 weight portions 4 And continuously reacting for 1-2 h. Stopping stirring, performing ultrasonic dispersion treatment for 8-12H, adding 40-50 parts of deionized water, reacting for 10-20 min, diluting with 100-150 parts of 75-90 ℃ deionized water, and adding 10-15 parts of 30 mass percent H under stirring 2 O 2 And (3) repeatedly washing the solution until no bubbles are generated, then repeatedly washing the solution by using 5-10% of dilute HCl solution and deionized water until the pH value is 5-7, and finally drying the solution in vacuum at 55-60 ℃ to obtain the dark brown flaky graphene oxide for later use.
Step three, according to the modified starch: stirring the modified starch at the temperature of 80-90 ℃ for 20-30 min for gelatinization according to the proportion of deionized water being 1; sequentially adding 0.06-0.07 part of ammonium persulfate and 0.1-0.5 part of N, N-methylene bisacrylamide which are weighed into the starch paste, stirring for 20-30 min, then dropwise adding 0.1-2.0 parts of acrylic acid, and continuously stirring for 10-20 min; and (3) adding 0.01-0.03 part of graphene oxide prepared in the step two into the solution, continuously stirring for 10-20 min, pouring into a culture dish, standing for 20-30 min, pre-freezing the formed hydrogel for 5-10 h at-18 ℃, and finally freeze-drying in a freeze-drying machine for 40-50 h to obtain the light porous solid material, namely the modified starch/graphene oxide composite aerogel.
The molecular weight of the corn starch is 16000-500000, and the mass fraction of the acryloyl chloride is 5-10%.
The molecular weight of the graphite powder is 16-17,H 2 SO 4 The mass fraction of the graphene oxide is 80-85%, the mass fraction of the dilute HCl is 5-10%, and the molecular weight of the graphene oxide is 12-13.
The centrifugal separation speed of the centrifugal machine is 5000-8000 r/min, and the centrifugal time is 5-10 min.
The modified starch/graphene oxide composite aerogel prepared by the preparation method has the synthesis principle that: the double bonds in the modified starch and the cross-linking agent acrylic acid are subjected to polymerization reaction, and then further interact with the oxygen-containing groups of the graphene oxide to form a cross-linked three-dimensional network system.
When 0.1-2.0 parts of acrylic acid, 0.01-0.03 part of GO and the pH value is about 4-5, the modified starch/acrylic acid/graphene oxide composite aerogel has the best adsorption performance on Pb (II), basically achieves adsorption balance after 6-24 hours of adsorption, and has the adsorption capacity of 250.50-466.55 mg/g.
Example one
Step one, weighing 10 parts of corn starch, adding 10 parts of ethyl acetate into a beaker, and stirring the solution at 20 ℃ for 10min to obtain a starch suspension; adding 1 part of pyridine into the solution, and continuously stirring for 10min; after stirring, dropwise adding 0.5 part of acryloyl chloride into the beaker at the speed of 3 drops per second, reacting for 20min at 20 ℃ under the stirring condition after dropwise adding, then adding 5 parts of ethanol to stop the reaction, standing for 20min, washing with ethanol, centrifuging for 3 times, placing the centrifuged product in a 75 ℃ blast oven for drying for 20h, preparing modified starch, and grinding for later use; referring to FIG. 1, the IR spectrum of the modified starch compared to native corn starch revealed that the modified starch was at 1730cm -1 Has obvious characteristic absorption new peak, which is the stretching vibration absorption peak of carbonyl (C = O) in acryloyl group introduced after acryloyl chloride modified starch, and simultaneously the modified starch is 1640cm -1 And the absorption peak is also a characteristic stretching vibration peak of double bonds (C = C) in the acryloyl groups in the modified starch, so that carbonyl and double bond absorption peaks existing in an infrared spectrum of the modified starch indicate that the acryloyl oxidation reaction is successfully carried out, which indicates that the acryloyl groups are successfully introduced into the starch, and the starch is converted into the acryloyl oxidized starch.
Step two, weighing 1 part of graphite powder and adding 20 parts of H 2 SO 4 Stirring at 15 deg.C, adding 1 part of KMnO in 1 hr 4 The reaction was continued for 1h. Stopping stirring, performing ultrasonic dispersion treatment for 8h, adding 40 parts of deionized water, reacting for 10min, and then performing deionization at 100 parts of 75 DEG CDiluting with water, and adding 10 parts of 30% H under stirring 2 O 2 And (3) repeatedly washing the solution until no bubbles are generated, then repeatedly washing the solution by using a 5% diluted HCl solution and deionized water until the pH value is 5, and finally performing vacuum drying at 55 ℃ to obtain dark brown flaky graphene oxide for later use.
Step three, according to the modified starch: stirring the modified starch at the temperature of 80 ℃ for 20min for gelatinization according to the proportion of deionized water being 1; sequentially adding 0.06 part of weighed ammonium persulfate and 0.1 part of N, N-methylene bisacrylamide into the starch paste, stirring for 20min, then dropwise adding 0.1 part of acrylic acid, and continuously stirring for 10min; and (3) adding 0.01 part of graphene oxide prepared in the step two into the solution, continuously stirring for 10min, pouring into a culture dish, standing for 20min, pre-freezing the formed hydrogel for 5h at-18 ℃, and finally freeze-drying in a freeze dryer for 40h to obtain the light porous solid material, namely the modified starch/graphene oxide composite aerogel.
The modified starch/graphene oxide composite aerogel prepared by the preparation method has obvious application performance and characteristics of Pb (II) adsorption capacity. Respectively putting 20mg of the composite aerogel material into a test tube, and weighing 5 parts of 5000mg/L Pb 2+ Adding the solution into the test tubes respectively, adjusting pH to 4, standing for 6h for adsorption, vacuum-filtering to obtain clear liquid, measuring the ion concentration of the adsorbed clear liquid by inductively coupled plasma emission spectrum, and calculating the adsorption amount. The adsorption capacity for Pb (II) was 290.75mg/g.
Example two
Step one, weighing 15 parts of corn starch, adding 20 parts of ethyl acetate into a beaker, and stirring the solution at 30 ℃ for 20min to obtain a starch suspension; adding 5 parts of pyridine into the solution, and continuously stirring for 30min; dropwise adding 1.0 part of acryloyl chloride into the beaker after stirring, wherein the dropwise adding speed is 5 drops per second, reacting for 30min at 30 ℃ under the stirring condition after the dropwise adding is finished, then adding 10 parts of ethanol to stop the reaction, standing for 30min, washing and centrifuging for 5 times by using ethanol, placing the centrifuged product into a blast oven at 85 ℃ for drying for 30h, preparing modified starch, and grinding for later use;
step two, weighing 5 parts of graphite powder and adding 25 parts of H 2 SO 4 Stirring at 20 deg.C, adding 5 parts of KMnO in 2 hr 4 The reaction was continued for 2h. Stopping stirring, performing ultrasonic dispersion treatment for 12H, adding 50 parts of deionized water, reacting for 20min, diluting with 150 parts of 90 ℃ deionized water, and adding 15 parts of H with the mass fraction of 30% under the stirring condition 2 O 2 And (3) repeatedly washing the solution until no bubbles are generated, then repeatedly washing the solution by using 10% diluted HCl solution and deionized water until the pH value is 7, and finally performing vacuum drying at 60 ℃ to obtain dark brown flaky graphene oxide for later use.
Step three, according to the modified starch: stirring the modified starch at the temperature of 90 ℃ for 30min for gelatinization according to the proportion of deionized water being 1; sequentially adding 0.07 part of ammonium persulfate and 0.5 part of N, N-methylene bisacrylamide which are weighed into the starch paste, stirring for 30min, then dropwise adding 2.0 parts of acrylic acid, and continuously stirring for 20min; and (3) adding 0.03 part of graphene oxide prepared in the step two into the solution, continuously stirring for 20min, pouring into a culture dish, standing for 30min, pre-freezing the formed hydrogel for 10h at-18 ℃, and finally freeze-drying in a freeze dryer for 50h to obtain the light porous solid material, namely the modified starch/graphene oxide composite aerogel.
The modified starch/graphene oxide composite aerogel prepared by the preparation method has obvious application performance and characteristics of Pb (II) adsorption capacity. Respectively putting 20mg of the composite aerogel material into a test tube, and weighing 5 parts of 5000mg/L Pb 2+ Adding the solution into the test tubes respectively, adjusting pH to 5, standing for adsorption for 24h, vacuum-filtering to obtain clear liquid, measuring the ion concentration of the adsorbed clear liquid by inductively coupled plasma emission spectrum, and calculating the adsorption amount. The adsorption capacity for Pb (II) was 349.65mg/g.
EXAMPLE III
Step one, weighing 12 parts of corn starch, adding 15 parts of ethyl acetate into a beaker, and stirring the solution at 25 ℃ for 15min to obtain a starch suspension; adding 3 parts of pyridine into the solution, and continuously stirring for 20min; after stirring, dropwise adding 0.75 part of acryloyl chloride into the beaker at a speed of 4 drops per second, reacting at 25 ℃ for 25min under a stirring condition after dropwise adding, then adding 8 parts of ethanol to stop the reaction, standing for 25min, washing with ethanol, centrifuging for 3 times, placing the centrifuged product in a blast oven at 80 ℃ for drying for 24h, preparing modified starch, and grinding for later use;
step two, weighing 3 parts of graphite powder and adding 22 parts of H 2 SO 4 Stirring at 16 deg.C, maintaining the stirring state, and adding 3 parts of KMnO within 1.5h 4 The reaction was continued for 1.5h. Stopping stirring, performing ultrasonic dispersion treatment for 10H, adding 45 parts of deionized water, reacting for 15min, diluting with 120 parts of 80 ℃ deionized water, and adding 12 parts of 30 mass percent H under stirring 2 O 2 And repeatedly washing the solution until no bubbles are generated, then repeatedly washing the solution by using 6% diluted HCl solution and deionized water until the pH value is 6, and finally performing vacuum drying at 56 ℃ to obtain dark brown flaky graphene oxide for later use.
Step three, according to the modified starch: stirring modified starch at the temperature of 85 ℃ for 25min for gelatinization according to the proportion of deionized water being 1; sequentially adding 0.06 part of weighed ammonium persulfate and 0.3 part of N, N-methylene bisacrylamide into the starch paste, stirring for 25min, then dropwise adding 1 part of acrylic acid, and continuously stirring for 15min; and (3) adding 0.02 part of the graphene oxide prepared in the step two into the solution, continuously stirring for 15min, pouring into a culture dish, standing for 25min, pre-freezing the formed hydrogel at-18 ℃ for 8h, and finally freeze-drying in a freeze-drying machine for 45h to obtain the light porous solid material, namely the modified starch/graphene oxide composite aerogel.
Referring to FIG. 1, it is an infrared spectrum of the corn starch and the modified starch of this example, which can be seen from the figure
The modified starch/graphene oxide composite aerogel prepared by the preparation method has obvious application performance and characteristics of Pb (II) adsorption capacity. Respectively putting 20mg of the composite aerogel material into a test tube, and weighing 5 parts of 5000mg/L Pb 2+ Adding the solution into the test tubes respectively, adjusting pH to 4.6, standing for 12h for adsorption, and vacuum filtering to obtain clear liquid, measuring the ion concentration after adsorption by inductively coupled plasma emission spectrum, and calculating the adsorption amount. The adsorption capacity for Pb (II) was 466.55mg/g, and the results are shown in FIG. 4.
Example four
Step one, weighing 11 parts of corn starch, adding 16 parts of ethyl acetate into a beaker, and stirring the solution at 22 ℃ for 12min to obtain a starch suspension; adding 2 parts of pyridine into the solution, and continuously stirring for 13min; after stirring, dropwise adding 0.8 part of acryloyl chloride into the beaker at the speed of 3 drops per second, reacting for 30min at 25 ℃ under the stirring condition after dropwise adding, then adding 7 parts of ethanol to stop the reaction, standing for 22min, washing and centrifuging for 3 times by using ethanol, placing the centrifuged product in a blast oven at 80 ℃ for drying for 24h to prepare modified starch, and grinding for later use;
step two, weighing 4 parts of graphite powder and adding 23 parts of H 2 SO 4 Stirring at 16 deg.C, maintaining the stirring state, and adding 4 parts of KMnO within 2 hr 4 And continuing the reaction for 2h. Stopping stirring, performing ultrasonic dispersion treatment for 9H, adding 46 parts of deionized water, reacting for 12min, diluting with 130 parts of 85 ℃ deionized water, and adding 13 parts of H with the mass fraction of 30% under the stirring condition 2 O 2 And repeatedly washing the solution until no bubbles are generated, then repeatedly washing the solution by using 8% diluted HCl solution and deionized water until the pH value is 7, and finally performing vacuum drying at 56 ℃ to obtain dark brown flaky graphene oxide for later use.
Step three, according to the modified starch: stirring modified starch at the temperature of 85 ℃ for 30min for gelatinization according to the proportion of deionized water being 1; sequentially adding 0.06 part of weighed ammonium persulfate and 0.4 part of N, N-methylene bisacrylamide into the starch paste, stirring for 23min, then dropwise adding 1.2 parts of acrylic acid, and continuously stirring for 12min; and (3) adding 0.02 part of graphene oxide prepared in the step two into the solution, continuously stirring for 12min, pouring into a culture dish, standing for 22min, pre-freezing the formed hydrogel for 6h at-18 ℃, and finally freeze-drying in a freeze dryer for 48h to obtain the light porous solid material, namely the modified starch/graphene oxide composite aerogel.
The modified starch/graphene oxide composite aerogel prepared by the preparation method has obvious application performance and characteristics of Pb (II) adsorption capacity. 20mg of the composite aerogel materials are respectively put into a test tube, and 5 parts of 5000mg/L Pb are weighed 2+ Adding the solution into the test tubes respectively, adjusting the pH value to 4.6,standing for adsorption for 16h, and performing suction filtration to obtain clear liquid, wherein the clear liquid is subjected to inductive coupling plasma emission spectroscopy to measure the ion concentration after adsorption and calculate the adsorption quantity. The adsorption capacity for Pb (II) was 310.50mg/g.
EXAMPLE five
Step one, weighing 13 parts of corn starch, adding 18 parts of ethyl acetate into a beaker, and stirring the solution at 25 ℃ for 10min to obtain a starch suspension; adding 4 parts of pyridine into the solution, and continuously stirring for 15min; after stirring, dropwise adding 0.5 part of acryloyl chloride into the beaker at a speed of 4 drops per second, reacting for 30min at 25 ℃ under a stirring condition after dropwise adding, then adding 10 parts of ethanol to stop the reaction, standing for 30min, washing with ethanol, centrifuging for 3 times, placing the centrifuged product in a blast oven at 80 ℃ for drying for 24h, preparing modified starch, and grinding for later use;
step two, weighing 2 parts of graphite powder and adding 22 parts of H 2 SO 4 Stirring at 16 deg.C, adding 2 parts of KMnO in 2 hr 4 The reaction was continued for 2h. Stopping stirring, performing ultrasonic dispersion treatment for 12H, adding 48 parts of deionized water, reacting for 15min, diluting with 120 parts of 80 ℃ deionized water, and adding 11 parts of 30 mass percent H under stirring 2 O 2 And repeatedly washing the solution until no bubbles are generated, then repeatedly washing the solution by using 9% diluted HCl solution and deionized water until the pH value is 7, and finally performing vacuum drying at 60 ℃ to obtain the dark brown flaky graphene oxide for later use.
Step three, according to the modified starch: stirring modified starch at the temperature of 85 ℃ for 26min for gelatinization according to the proportion of deionized water being 1; sequentially adding 0.06 part of weighed ammonium persulfate and 0.2 part of N, N-methylene bisacrylamide into the starch paste, stirring for 20min, then dropwise adding 1.5 parts of acrylic acid, and continuously stirring for 10min; and (3) adding 0.03 part of graphene oxide prepared in the step two into the solution, continuously stirring for 20min, pouring into a culture dish, standing for 30min, pre-freezing the formed hydrogel at-18 ℃ for 9h, and finally freeze-drying in a freeze-drying machine for 46h to obtain the light porous solid material, namely the modified starch/graphene oxide composite aerogel.
A modified starch prepared by the above methodThe graphene oxide composite aerogel has remarkable application performance and characteristics of Pb (II) adsorption capacity. Respectively putting 20mg of the composite aerogel material into a test tube, and weighing 5 parts of 5000mg/L Pb 2+ And adding the solutions into the test tubes respectively, adjusting the pH value to be 4.6, standing for 20 hours for adsorption, performing suction filtration to obtain clear liquid, measuring the ion concentration of the adsorbed clear liquid by using an inductively coupled plasma emission spectrum, and calculating the adsorption quantity. The adsorption capacity for Pb (II) was 250.50mg/g.
Comparative example
Step one, weighing 10 parts of corn starch, adding 14 parts of ethyl acetate into a beaker, and stirring the solution for 10min to obtain a starch suspension; adding 1 part of pyridine into the solution, and continuously stirring for 15min; after stirring, dropwise adding 0.5 part of acryloyl chloride into the beaker at a speed of 5 drops per second, reacting for 30min at 25 ℃ under a stirring condition after dropwise adding, then adding 10 parts of ethanol to stop the reaction, standing for 30min, washing with ethanol, centrifuging for 3 times, drying the centrifuged product in a blast oven at 80 ℃ for 24h, preparing modified starch, and grinding for later use;
step two, according to the corn starch: stirring modified starch at the temperature of 85 ℃ for 30min for gelatinization according to the proportion of deionized water being 1; and pouring the mixture into a culture dish, standing for 30min, pre-freezing the formed hydrogel for 8h at the temperature of-18 ℃, and finally freeze-drying the hydrogel for 48h in a freeze dryer to obtain the light porous solid material, namely the starch aerogel.
The adsorption capacity of the starch aerogel prepared by the preparation method on Pb (II) is tested. 20mg of each aerogel material is put into a test tube, and 5 parts of 5000mg/L Pb are weighed 2+ And adding the solutions into the test tubes respectively, adjusting the pH value to 4.6, standing, adsorbing for 24h, and performing suction filtration to obtain clear liquid, measuring the ion concentration of the clear liquid after adsorption by using an inductively coupled plasma emission spectrum, and calculating the adsorption quantity to obtain the Pb (II) adsorption capacity of 143.35mg/g.
The results of the adsorption application of the aerogels for Pb (II) are compared in Table 1.
TABLE 1 comparison of aerogel adsorption application results
| Example numbering | Adsorption capacity mg/g |
| Example one | 290.75 |
| Example two | 349.65 |
| EXAMPLE III | 466.55 |
| Example four | 310.50 |
| EXAMPLE five | 250.50 |
| Comparative example | 143.35 |
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The modified starch/graphene oxide composite aerogel is characterized in that the structural formula of the modified starch/graphene oxide composite aerogel is as follows:
wherein m =1 to 10, n =1 to 20.
2. The preparation method of the modified starch/graphene oxide composite aerogel described in claim 1, comprising the following steps:
step one, adding 10-15 parts of corn starch into 10-20 parts of ethyl acetate by mass, and stirring to obtain a starch suspension; adding 1-5 parts of pyridine into the starch suspension, continuously stirring, dropwise adding 0.5-1.0 part of acryloyl chloride for reaction, then adding 5-10 parts of ethanol for terminating the reaction, standing, washing, centrifuging and drying to obtain modified starch;
step two, adding 20-25 parts of H into 1-5 parts of graphite powder by mass 2 SO 4 Stirring, adding 1-5 parts of KMnO 4 Reaction, ultrasonic dispersion, adding 40-50 portions of deionized water for continuous reaction, diluting, adding 10-15 portions of H 2 O 2 Washing and drying the solution until no bubbles are generated, thereby obtaining dark brown flaky graphene oxide;
adding 0.06-0.07 part of ammonium persulfate and 0.1-0.5 part of N, N-methylene bisacrylamide into the starch paste, stirring, dropwise adding 0.1-2.0 parts of acrylic acid, continuously stirring, adding 0.01-0.03 part of graphene oxide, stirring, standing to form hydrogel, and freeze-drying the hydrogel to obtain the modified starch/graphene oxide composite aerogel.
3. The preparation method of the modified starch/graphene oxide composite aerogel according to claim 2, wherein in the first step, the mixture is stirred at 20-30 ℃ for 10-20 min to obtain a starch suspension; adding pyridine and continuing stirring for 10-30 min;
dropping acryloyl chloride at the speed of 3-5 drops per second, and reacting for 20-30 min at the temperature of 20-30 ℃; standing for 20-30 min, and drying at 75-85 ℃ for 20-30 h;
the centrifugal speed is 5000-8000 r/min, and the centrifugal time is 5-10 min.
4. The preparation method of the modified starch/graphene oxide composite aerogel according to claim 2, wherein in the first step, the molecular weight of the corn starch is 16000-500000, and the mass fraction of the acryloyl chloride is 5-10%.
5. The preparation method of the modified starch/graphene oxide composite aerogel according to claim 2, wherein in the second step, H is added 2 SO 4 Stirring at 15-20 deg.c while adding KMnO for 1-2 hr 4 Continuously reacting for 1-2 h;
the ultrasonic dispersion treatment time is 8-12 h, deionized water is added for continuous reaction for 10-20 min, and 100-150 parts of deionized water with the temperature of 75-90 ℃ is used for dilution.
6. The preparation method of the modified starch/graphene oxide composite aerogel according to claim 2, wherein 10-15 parts by mass of 30% H is added under stirring in the second step 2 O 2 A solution; and repeatedly washing with 5-10% by mass of dilute HCl solution and deionized water until the pH value is 5-7, and carrying out vacuum drying at 55-60 ℃ to obtain the graphene oxide.
7. The preparation method of the modified starch/graphene oxide composite aerogel according to claim 2, wherein in the second step, the molecular weight of graphite powder is 16-17,H 2 SO 4 The mass fraction of (A) is 80-85%.
8. The preparation method of the modified starch/graphene oxide composite aerogel according to claim 2, wherein in the third step, the ratio of the modified starch to the deionized water is 1.
9. The preparation method of the modified starch/graphene oxide composite aerogel according to claim 2, characterized in that in the third step, the mixture is stirred at 80-90 ℃ for 20-30 min to be gelatinized, and then acrylic acid is added dropwise to continue stirring for 10-20 min;
adding graphene oxide, stirring for 10-20 min, standing for 20-30 min to form hydrogel, and freeze-drying the hydrogel for 40-50 h.
10. The use of the modified starch/graphene oxide composite aerogel according to claim 1 in the preparation of heavy metal ion adsorbents.
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