CN112755963A - Green synthetic magnetic composite nano material, preparation method and application thereof - Google Patents
Green synthetic magnetic composite nano material, preparation method and application thereof Download PDFInfo
- Publication number
- CN112755963A CN112755963A CN202011472566.6A CN202011472566A CN112755963A CN 112755963 A CN112755963 A CN 112755963A CN 202011472566 A CN202011472566 A CN 202011472566A CN 112755963 A CN112755963 A CN 112755963A
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- green
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- iron
- magnetic composite
- synthetic magnetic
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Abstract
The invention discloses a green synthetic magnetic composite nano material which is characterized by comprising the following components in parts by massEllipsoidal solid particles prepared by self-assembly: ferrous sulfate heptahydrate: green tea extract: tea residue: 1-calcium alginate: (4-6): (0.6-0.8): (1.8-2.5). The invention also discloses a preparation method and application thereof. The invention takes ferrous salt as raw material, calcium alginate as coating agent, green tea extract as reducing agent and dispersing agent, and green synthesizes calcium alginate coated nano-iron composite material by controlling reaction condition and material adding amount, and applies the composite material to Cr in water6+Quick removal of methylene blue. The invention has the advantages of wide raw material source, simple and convenient synthesis method, stable material performance, wide application range, good pollutant adsorption effect, no secondary pollution and the like, can be suitable for emergency treatment of pollutants in large-volume environmental water bodies, and can also be used for deep purification of general domestic sewage, environmental water bodies and drinking water bodies.
Description
Technical Field
The invention belongs to the technical field of nano materials and environmental protection, and particularly relates to a green synthetic magnetic composite nano material, a preparation method and application thereof.
Background
The nano iron has strong reducibility, large specific surface area and high reaction activity, and can effectively remove various organic pollutants and heavy metals. However, the nano iron particles have high surface energy and magnetism, so that the nano iron particles are easy to agglomerate when used alone to reduce the reaction activity, and the traditional nano iron synthesis and modification methods such as chemical reagents and modifiers are not properly selected, which may cause secondary pollution to the environment, and increase the application cost. Therefore, the research on the synthesis technology of the nano zero-valent iron particles focuses on the utilization of green biological materials, and the method not only realizes the purpose of changing waste into valuable, but also conforms to the development trend of green chemistry. At present, most of nano iron materials are prepared by a physical method and a chemical method, and have serious limitations. Generally, the preparation process has the disadvantages of high energy consumption, complex process, high cost and strong toxicity of a strong reducing agent (such as sodium borohydride) used in the preparation process. The nano iron has high activity, and is easy to agglomerate and oxidize.
The patent application No. 201410841223.0 discloses a calcium alginate coated nano-iron bead and an application and a preparation method thereof, and relates to a calcium alginate coated nano-iron bead, which is prepared by coating nano-scale iron powder on a bead formed by sodium alginate and calcium chloride, and can be used for adsorbing chromium-containing wastewater containing hexavalent chromium or trivalent chromium.
The document with the patent application number of 201610043182.X discloses an embedded nano-iron pellet and preparation and application thereof. Firstly, reducing ferrous ions into nano zero-valent iron by using phenols and other reducing agents in the leaf extracting solution to form a nano iron suspension, and preparing the nano iron suspension into calcium alginate-coated nano iron pellets by using a calcium alginate embedding technology. The nano iron pellets and hydrogen peroxide form a Fenton-like reagent, hydroxyl radicals are released, and the Fenton-like reagent has strong oxidizing property, so that oil substances in the wastewater are mineralized, and the purpose of advanced treatment of the wastewater is achieved.
However, the calcium alginate coated nano iron pellets have some defects: (1) the method can not be suitable for emergency sudden water body pollution accident disposal, and the nano-iron composite material is mainly applied in a powdery form, so that the problems of low strength, easy dispersion, difficulty in separation from the water body, recycling and the like exist. (2) After the reaction is finished, solid-liquid separation is carried out in the modes of centrifugation, external magnetic field and the like, so that the material has low recycling rate and poor recycling effect; (3) most of nano iron materials have the defect of iron leaching in the process of removing pollutants, particularly after pollutants are removed under the condition of high pH, iron mud is easily generated to cause iron pollution, and the reaction is too rapid and difficult to control.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a green synthetic magnetic composite nano material, which is prepared by coating magnetic nano iron on dry matters of calcium alginate, tea leaves and green tea extracting solution and on the dry matters or on the dry matters of the green synthetic magnetic composite nano material, wherein the components are randomly distributed, mutually bonded and self-assembled on a three-dimensional space based on the matching of respective particle size and physical and chemical properties to form solid particles with an ellipsoidal porous and three-dimensional slow-release structure, so that the green synthetic magnetic composite nano material has excellent performance and is convenient to use, recycle and reuse;
the invention also aims to provide a preparation method of the green synthetic magnetic composite nano material, which has the advantages of wide raw material source, low cost, simple preparation process, high stability of the prepared material, strong adsorption capacity to heavy metals and organic matters and short onset time.
The invention also aims to provide the application of the green synthetic magnetic composite nano material, and Cr6+ and organic pollutant methylene blue MB in the water body are quickly removed by utilizing the three-dimensional slow-release structure and the synergistic action of reduction, adsorption and degradation and the synergistic action of reduction and adsorption, so that the green synthetic magnetic composite nano material is suitable for emergency sudden water body pollution accident disposal.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the green synthetic magnetic composite nano material is characterized by being an ellipsoidal solid particle prepared by self-assembling the following components in parts by mass: ferrous sulfate heptahydrate: green tea extract: tea residue: 1-calcium alginate: (4-6): (0.6-0.8): (1.8-2.5).
The green synthetic magnetic composite nano material is characterized in that a finished product is an ellipsoidal solid particulate matter with the average diameter of 1.5 +/-0.5 mm, the particulate matter is formed by coating tea dregs and nano iron by using dry matters of calcium alginate and green tea extracting solution, and then forming a composite material GT-Fe NPs @ CA in which the dry matters of the calcium alginate, the tea dregs and the green tea extracting solution or the dry matters of the green tea extracting solution and the magnetic nano iron coated by the dry matters of the calcium alginate, the tea dregs and the green tea extracting solution or the magnetic nano iron coated by the dry matters of the tea dregs and the green tea extracting solution are randomly distributed, mutually bonded and self-assembled on a three-dimensional space based on the matching of respective particle size and physical and chemical properties to form the ellipsoidal porous solid particulate matter with the three-dimensional slow-release structure.
The green synthetic magnetic composite nano material is characterized in that the green tea extracting solution is prepared by adding 1L of distilled water into 60g of dry green tea, heating in a water bath at 80 ℃ for 1h, and then carrying out vacuum filtration to obtain filtrate, namely tea extracting solution; the tea residue is solid dry substance powder obtained by drying the green tea solid remaining after preparing green tea extract in an oven, and grinding and sieving with 100 mesh sieve.
The preparation method of the green synthetic magnetic composite nano material is characterized by comprising the following steps of:
(1) preparing green tea extract and tea residue;
(2) preparing sodium alginate sol by using green tea extract and sodium alginate;
(3) adding the tea leaves and ferrous sulfate heptahydrate into the sodium alginate sol according to a set proportion to prepare sodium alginate-coated nano-iron sol;
(4) adding the sodium alginate-coated nano-iron sol into a calcium chloride solution, uniformly mixing, performing crosslinking reaction and material self-assembly, and then drying to obtain spherical solid particles of calcium alginate, tea leaves and green tea extract dry matter coated with nano-iron, namely the green synthetic magnetic composite nano-material GT-Fe NPs @ CA.
The preparation of the calcium alginate sol in the step (2) is to mix the tea extract and sodium alginate according to a set proportion under the conditions of water bath at 30-50 ℃ and rapid magnetic stirring, and to obtain the calcium alginate sol; the set proportion is that the addition amount of sodium alginate is 1.1-1.3g per 50ml of green tea extract.
And (3) slowly dripping the tea leaves and the ferrous sulfate heptahydrate solution into the calcium alginate sol, continuously stirring, and continuously stirring for 5-30 min after the dripping of the solution is finished to obtain the sodium alginate coated nano iron sol.
The step (4) is to drop the sol into CaCl by an injector at a distance of 15cm from the liquid level2Continuously stirring the solution, and reacting for 3-6 h to form a nano-iron composite material precursor; and then washing the composite material precursor with distilled water for 2-6 times, placing the composite material precursor in a vacuum drier for freeze-drying for 24-72 hours, and self-assembling and forming the components to obtain green and synthetic spherical solid particles of the nano-iron composite material GT-Fe NPs @ CA, wherein the nano-iron composite material GT-Fe NPs @ CA is coated by dry substances of calcium alginate, tea residues and green tea extract.
The application of the green synthetic magnetic composite nano material is characterized in that the green synthetic magnetic composite nano material is used as a purifying agent, has a three-dimensional slow release structure and synergistic effects of reduction, adsorption and degradation, and uses the synergistic effects of reduction and adsorption to remove Cr in a water body6+Removing rapidly; and rapidly remove Cr in water body6+Then, the green synthetic magnetic composite nano material is recycled and reused; the dosage of GT-Fe NPs @ CA is 0.3-0.5 g/100ml, and the purification of reduction-adsorption is realizedThe reaction time is 4-48 h.
The application of the green synthetic magnetic composite nano material is characterized in that the green synthetic magnetic composite nano material is used as a purifying agent, and the purifying agent has a three-dimensional slow release structure and synergistic effects of reduction, adsorption and degradation, so that organic pollutant Methylene Blue (MB) in a water body is rapidly removed; and after organic pollutant methylene blue MB in the water body is rapidly removed, the green synthetic magnetic composite nano material is recycled and reused.
The invention has the beneficial effects that:
(1) the invention relates to a green synthetic magnetic composite nano material, which is prepared by mixing Fe2+Uniformly dispersing the calcium-containing nano-iron composite material into CA sol, crosslinking and gelating by using calcium water, using waste tea residues as rigid filler to improve the mechanical property of the material, and finally, green-synthesizing the calcium alginate-coated nano-iron composite material GT-Fe NPs @ CA by using green tea extract to obtain a green, economic and inorganic-biomass-polymer ternary novel composite material with good strength.
(2) The green tea extract used for green synthesis of the magnetic composite nano material comprises organic components, such as polyphenol, flavone, polysaccharide, caffeine and the like, which can react with iron salt to generate nano iron particles, and the organic components can also be used as a dispersing agent and a stabilizing agent, so that the problems that the synthesized nano iron particles are easy to agglomerate and oxidize and the like are effectively solved. The sodium alginate adopted by the invention as natural polysaccharide is non-toxic and biodegradable. The molecular chain of the sodium alginate is rich in negative charge groups such as-COOH and the like, and has strong adsorption force on positive charge dyes; and the molecular chain can be mixed with polyvalent metal ion such as nontoxic Ca2+Forming Calcium Alginate gel microspheres (Calcum Alginate, CA) with a 3D network structure with set rigidity and strength through complexation; and the iron ions can be coordinated with-COOH in the molecular chain to be fixed, so that the catalytic reaction activity of the iron ions is not influenced, the leaching rate of the iron ions can be reduced, and the nano iron is protected.
(3) The green synthetic magnetic composite nano material provided by the invention adopts the calcium alginate to coat the nano iron material, so that the problem of effectively solving the problem of low cost is effectively solvedThe nano iron has the defects of high activity, easy agglomeration and easy passivation, can avoid iron leaching and has small harm degree to the environment; the water-soluble metabolites (such as polyphenol, sugar, alkaloid, phenolic acid and protein) and coenzyme in green tea extractive solution can reduce Fe2+Or Fe3+Ions, and simultaneously, nano iron interacts with free phenolic hydroxyl, carboxyl, amino or protein to form a covering layer to serve as a wrapping agent to reduce the aggregation of nano particles; the multi-component composite material has high strength, easy reaction control and easy recovery. By controlling sodium alginate and CaCl2、Fe2+The calcium alginate coated nano-iron composite material (GT-Fe NPs @ CA) can be synthesized in a green way under the conditions of adding proportion and the like. The composite nano-particles prepared by the method have high pollutant removal efficiency, are widely applied to pollutant degradation, and can be applied in a large scale.
(4) The green synthetic magnetic composite nano material provided by the invention can be widely applied to emergency sudden water body pollution accident disposal. The nano-iron composite material is mainly applied in a powdery form, and has the problems of low strength, easy dispersion, difficult separation from water, recycling and the like. The composite material is in a particle ball shape, and after the reaction is finished, solid-liquid separation in the modes of centrifugation, external magnetic field and the like is not needed, so that the recycling efficiency is greatly improved. And the multi-component composite material has high strength and good recycling effect.
(5) The preparation method of the green synthetic magnetic composite nano material overcomes the defects of large energy consumption, complex process, higher cost and strong toxicity of strong reducing agent (such as sodium borohydride) used in the preparation process of most of the existing nano iron materials prepared by physical methods and chemical methods; and the defects of high activity, easy agglomeration and easy oxidation of the nano-iron per se. The green tea extract adopted by the invention can be used as a dispersant and a masking agent in the process of synthesizing the nano-iron, so that the stability of the nano-iron composite material is greatly improved. The green synthetic nano-iron adopted by the invention has the characteristics of good reduction effect, simple and convenient preparation process, low cost, economy, green and the like, and China is a large tea country, can generate a large amount of tea residue residues in the production and consumption links, and has strong resource reutilization property.
(6) The green synthetic magnetic composite nano material, the preparation method and the application thereof provided by the invention overcome the defect that most nano iron materials are leached out by iron in the process of removing pollutants, particularly after pollutants are removed under the condition of high pH, iron mud is easily generated to cause iron pollution, and the reaction is too rapid and difficult to control. The composite nano material provided by the invention adopts environment-friendly material sodium alginate, which contains a large amount of oxygen-containing groups, iron ions can be coordinated with carboxyl to be fixed, the reaction activity is not influenced, the leaching rate of iron can be reduced, the generation amount of iron oxide is low, the reaction is allowed to be carried out in a wider pH range, the removal effect is fast, and the removal effect is good.
(7) The invention provides a Green synthetic magnetic composite nano material, a preparation method and application thereof. By applying the chromium-free chromium-6+And Methylene Blue (MB) is rapidly removed, and the invention has the advantages of wide raw material source, simple and convenient synthesis method, stable material performance, wide application range, good pollutant adsorption effect, no secondary pollution and the like. The invention can be suitable for emergency treatment of pollutants in large-volume environmental water bodies, and can also be used for deep purification of general domestic sewage, environmental water bodies and drinking water bodies.
Drawings
FIG. 1 is a schematic diagram (50 times) of the three-dimensional structure of the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention;
FIG. 2 is a scanning electron microscope (2000 times) of the surface of the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention;
FIG. 3 is a scanning electron microscope (1 ten thousand times) of the surface of the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention;
FIG. 4 is a scanning electron microscope (5 ten thousand times) of the surface of the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention;
FIG. 5 is a scanning electron microscope (10 ten thousand times) of the surface of the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention;
FIG. 6 is an elemental energy spectrum of a green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention;
FIG. 7 is a graph showing the pore size distribution of the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention;
FIG. 8 shows the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) Fe of the present invention2pXPS analysis of the rail;
FIG. 9 shows the green synthetic magnetic composite nano-material (GT-Fe NPs @ CA) of the present invention vs. Cr6+The adsorption amount characteristic of (1);
FIG. 10 shows Cr in the green synthesized magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention after reaction2pXPS analysis of the rail;
FIG. 11 is a graph showing the effect of pH on MB removal of the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention.
FIG. 12 is a methylene blue standard curve measured using a UV-1800 UV-VIS spectrophotometer;
FIG. 13 is a graph showing the degradation performance of the green synthetic magnetic composite nanomaterial (GT-Fe NPs @ CA) of the present invention on MB in water.
FIG. 14 is FT-IR comparative analysis chart of the green synthetic magnetic composite nano material (GT-Fe NPs @ CA) of the present invention before and after reacting with MB and Calcium Alginate (CA).
The present invention will be described in further detail with reference to the following drawings and examples.
Detailed Description
Referring to the attached drawings 1-10, the green synthetic magnetic composite nano-material provided by the embodiment of the invention is an ellipsoidal solid particle prepared by self-assembly of the following components in parts by mass: ferrous sulfate heptahydrate: green tea extract: tea residue: 1-calcium alginate: (4-6): (0.6-0.8): (1.8-2.5).
The dried finished product of the green synthetic magnetic composite nano material is ellipsoidal solid particles with the average diameter of 1.5 +/-0.5 mm, the particles are formed by coating the dry matters of the calcium alginate and the green tea extracting solution with the tea residue and the nano iron, and the formed composite material GT-Fe NPs @ CA is formed by coating the dry matters of the calcium alginate, the tea residue and the green tea extracting solution with the magnetic nano iron respectively or together.
The green synthetic magnetic composite nano material is characterized in that the green tea extracting solution is prepared by adding 1L of distilled water into 60g of dry green tea, heating in a water bath at 80 ℃ for 1 hour, and carrying out vacuum filtration to obtain a filtrate, namely the tea extracting solution; the tea residue is solid dry substance powder obtained by drying the green tea solid remaining after preparing green tea extract in an oven, and grinding and sieving with 100 mesh sieve.
A preparation method of a green synthetic magnetic composite nano material comprises the following steps:
(1) preparing green tea extract and tea residue; wherein the green tea extract is prepared by adding 1L distilled water into 60g of dried green tea, heating in 80 deg.C water bath for 1 hr, and vacuum filtering to obtain filtrate; wherein the tea residue is solid dry substance powder obtained by drying the residual green tea solid after preparing green tea extract in an oven, grinding and sieving with 100 mesh sieve;
(2) preparing sodium alginate sol by using green tea extract and sodium alginate; wherein the preparation of the calcium alginate sol is obtained by mixing the tea extract and sodium alginate according to a set proportion under the conditions of water bath at 30-50 ℃ and rapid magnetic stirring, and stirring uniformly; the set proportion is that the addition amount of sodium alginate is 1.1-1.3g per 50ml of green tea extract;
(3) adding the tea leaves and ferrous sulfate heptahydrate into the sodium alginate sol according to a set proportion to prepare sodium alginate-coated nano-iron sol; slowly dripping the tea leaves and a ferrous sulfate heptahydrate solution into the calcium alginate sol, continuously stirring, and continuously stirring for 5-30 min after the solution is dripped to obtain sodium alginate-coated nano iron sol;
(4) adding the sodium alginate-coated nano-iron sol into a calcium chloride solution, uniformly mixing, performing crosslinking reaction and material self-assembly, and then drying to obtain spherical solid particles of calcium alginate, tea leaves and green tea extract dry matter coated with nano-iron, namely preparing a green synthetic magnetic composite nano-material (GT-Fe NPs @ CA); specifically, the sol is dropped into CaCl by an injector at a distance of 15cm from the liquid level2Continuously stirring the solution, and reacting for 3-6 h to form a nano-iron composite material precursor; and then washing the composite material precursor with distilled water for 2-6 times, placing the composite material precursor in a vacuum drier for freeze-drying for 24-72 hours, and self-assembling and forming the components to obtain green and synthetic spherical solid particles of the nano-iron composite material GT-Fe NPs @ CA, wherein the nano-iron composite material GT-Fe NPs @ CA is coated by dry substances of calcium alginate, tea residues and green tea extract.
The component proportion table of each specific example (in parts by mass):
in other embodiments, other proportions can be selected within the above range according to actual needs, and the technical effects of the invention can be achieved.
Referring to the attached drawings 1-8, the invention provides a green synthetic magnetic composite nano material and a preparation method thereof, and solves the defect of narrow pH reaction range of the traditional nano iron material in a Fenton method by uniformly coating nano iron in calcium alginate.
The green synthetic magnetic composite nano material provided by the invention has a large number of pore channels distributed in the sphere, and the diameter of the pore channels is dozens of micrometers; the pore structure is self-assembled in the vacuum freeze drying of the microsphere, water molecules in the microsphere are condensed into solid in the process of rapidly reducing the temperature from 25 ℃ to-60 ℃, ice is sublimated in the freeze drying process, and finally the pore structure is formed in the microsphere, so that pollutants can be favorably diffused in the pore.
The GT-Fe NPs @ CA provided by the invention contains a large number of polar groups (mainly from calcium alginate), so that not only can nano iron be fixed to reduce leaching, but also cations MB can be adsorbed, and the pH reaction range (pH influence experiment evidence) is widened; the active substances of the green tea extract are coated on the surface layer of the nano iron, so that the defect that the nano iron is easy to agglomerate and oxidize is overcome.
Referring to fig. 1-8, the GT-Fe NPs @ CA provided by the present invention is formed by coating magnetic nano-iron on dry substances of calcium alginate, tea leaves, green tea extract and on each or both of the dry substances, and randomly distributing, mutually bonding and self-assembling the components in a three-dimensional space based on the matching of respective particle size and physical and chemical properties, so as to form solid particles with an ellipsoidal porous and three-dimensional slow-release structure, which has excellent performance and is convenient to use and recycle. As can be seen from figure 1, the dry matters of the calcium alginate, the tea dregs and the green tea extract are mutually bonded by the coated magnetic nano iron to form spherical particles with uneven outer surfaces; in fig. 2, the tea dregs are in a sheet-shaped dark color at the lower right part and the position right above the tea dregs, and calcium alginate aggregates are in a mastoid shape at a flatter middle part; in FIG. 3, the components are randomly distributed, mutually bonded and self-assembled in a three-dimensional space to form a porous structure; in fig. 4 and 5, the magnetic nano-iron coated in the areas of the spherical papilla is shown.
Application example 1: the method is applied to Cr in water6+Is removed quickly
The application of the green synthetic magnetic composite nano material as a purifying agent is applied to emergency treatment of water body pollution accidents: by utilizing the three-dimensional slow-release structure and the synergistic effect of reduction, adsorption and degradation, and utilizing the synergistic effect of reduction and adsorption and the complexing effect of polar groups and pollutants in the water body, the Cr in the water body is subjected to the treatment6+Quickly remove Cr in water body6+Then, the green synthetic magnetic composite nano material can be recycled and reused; the dosage of the GT-Fe NPs @ CA is 0.3-0.5 g/100ml, and the purification reaction time of reduction-adsorption is 4-48 h.
Specifically, the method comprises the following steps: the removal reaction was carried out in a 250ml conical flask with a stopper, and 20 mg. multidot.L was taken-1Cr6+100ml of standard solution, adjusting the solution with 0.1M sodium hydroxide and hydrochloric acidAfter the pH, 0.5g of the composite material was added and the mixture was heated at 150 r.min-1The constant temperature oscillator is oscillated, a liquid transfer gun is used for absorbing supernatant liquid at a set time point to pass through a 0.45 mu m filter membrane, and the Cr is measured on a UV-1800 type ultraviolet-visible spectrophotometer by adopting a dibenzoyl dihydrazide spectrophotometry at the wavelength of 540nm after standing and diluting6+The concentration of (c).
According to the change of the target concentration before and after the reaction, the Cr pair of the composite material is calculated by the following formula6+Adsorption amount Q oftAnd a removal rate η.
In the formula, QtFor material to Cr in t time6+Unit removal amount of (g, mg)-1)，C0Is Cr6+Initial concentration (mg. L)-1)，CtIs Cr in solution at time t6+Concentration of (mg. L)-1) V is the volume of the solution (L) and M is the mass of the material (g).
Referring to FIG. 9, green synthesized calcium alginate coated nano-iron composite (GT-Fe NPs @ CA) versus Cr6+The adsorption amount of (3). When the dosage of GT-Fe NPs @ CA is 0.1, 0.3 and 0.5g respectively, the removal rate of Cr (VI) in the water body after 4 hours of adsorption respectively reaches 24 percent, 61 percent and 83 percent. After 48 hours of adsorption, the removal rate of the three adding amounts to Cr (VI) can reach 26%, 78% and 95%; therefore, the removal effect is quick and good. .
Referring to FIG. 10, XPS was used to analyze Cr6+Bonding characteristics of GT-Fe NPs @ CA after reaction indicate that Cr appears at the binding energies 586 and 576.9eV respectively3+2p of1/2And Cr3+2p of3/2Peak of (2), Cr appears at a binding energy of 589, 579eV6+2p of1/2And Cr6+2p of3/2Peak of (2). Description of the composite Cr6+The removal is the synergistic action of reduction and adsorptionThe application is as follows. Comparative Cr6+And Cr3+Area of peak, it can be seen that Cr6+Content of (C) is higher than that of Cr3+Is small, which indicates that the composite material removes Cr6+Adsorption is less than chemical.
Application example 2: the method is applied to the rapid degradation of the organic pollutant methylene blue MB in water
The application of the green synthetic magnetic composite nano material as a purifying agent is applied to emergency treatment of water body pollution accidents: the organic pollutant methylene blue MB in the water body is rapidly removed by utilizing the three-dimensional slow release structure and the synergistic effect of reduction, adsorption and degradation; and after organic pollutant methylene blue MB in the water body is rapidly removed, the green synthetic magnetic composite nano material is recycled and reused.
Specifically, the removal reaction was carried out in a 250ml conical flask with a stopper to obtain 100 mg. multidot.L-1Methylene blue solution 100ml, adding 0.5g composite material, adjusting solution pH with 0.1M sodium hydroxide and hydrochloric acid, adding a set amount of 30% H2O2Starting a catalytic reaction, oscillating in a constant-temperature oscillator of 180r/min, setting a time point, sucking supernatant liquor by a pipette through a 0.45-micrometer filter membrane, standing and diluting, testing absorbance at 664nm on a UV-1800 ultraviolet-visible spectrophotometer, taking deionized water as reference, and calculating the adsorption quantity Qt and the removal rate eta of the composite microspheres to MB by adopting a standard curve method according to the following formula.
In the formula, QtThe unit removal of MB (mg. g) in the time t is the material-1)，C0As the initial concentration of MB (mg. L)-1)，CtThe concentration of MB in the solution at time t (mg. L)-1) V is the volume of the solution (L) and M is the mass of the material (g).
Referring to FIG. 11, both GT-Fe NPs @ CA are effective in degrading MB under acid-base conditions. Under the condition of high pH, the traditional iron-based material can generate an iron oxide passivation layer on the surface, thereby inhibiting the degradation performance and limiting the pH reaction range. In comparison, the calcium alginate of GT-Fe NPs @ CA provided by the invention contains a large number of polar groups, and cationic MB molecules are easier to access catalytic active sites. Under the condition of higher pH, the stronger fixation effect of carboxyl on iron ions reduces the generation of iron hydroxide. Therefore, the composite material provided by the invention can effectively degrade the MB in water within the pH range of 3.0-11.0.
Referring to FIG. 12, a MB standard curve is prepared using UV-1800 UV-visible spectrophotometer, and r is measured at 644nm2Is 0.9993, and can meet the water quality monitoring requirement.
Referring to fig. 13, under the condition of normal temperature (25 ℃), the dosages of GT-Fe NPs @ CA are 0, 0.1, 0.2 and 0.5g, after 200min, the removal rates of MB are 14%, 88%, 94% and 99%, respectively, and the removal effect is quick and good.
Referring to FIG. 14, FT-IR was used to characterize the surface functional groups of GT-Fe NPs @ CA pellets before and after Calcium Alginate (CA) and Methylene Blue (MB) degradation, and the results are shown. CA (line a) at 3371 cm-1The strong absorption peak is the O-H stretching vibration absorption peak with the length of 1429 cm-1Is a symmetric stretching vibration peak of-C-O-O, and in contrast, GT-Fe NPs @ CA (line b) is respectively shifted to 3421 cm-1And 1432 cm-1Indicating that the iron ions and the negative electricity groups in the alginate have cross-linking effect. The shift in peak for GT-Fe NPs @ CA (line c) after MB degradation reaction may be due to functional group complexation of the negatively charged group with the cationic dye MB. Combined with relevant literature, line b is 823cm-1Is aromatic C-H at 1029 cm-1Is the stretching vibration peak of saccharide C-O-C, 1629 cm-1And 1344 cm-1The peak indicates that C ═ C and aromatic amine functional group C-N which can play a stabilizing role exist on the surface of the material, and the peak is 2925 cm-1Is an aliphatic functional group-CH2The stretching vibration peak of (1). It was further confirmed that the Fe NPs were coated with calcium alginate and that the bioactive substances were attached to the surface layer of the Fe NPs. In phase with line (b)The characteristic peak of the specific spectral line (c) is not obviously changed, which indicates that the bioactive component still exists after the reaction. In lines (b) (c), 562cm-1And 585cm-1The peak is the vibration absorption peak of Fe-O bond, which shows that the composite material is relatively stable, and the iron oxide in the material has no obvious change in the reaction.
The invention provides a Green synthetic magnetic composite nano material, a preparation method and application thereof6+And Methylene Blue (MB) removal experiments show that the invention has the advantages of wide raw material source, simple and convenient synthesis method, stable material performance, wide application range, good pollutant adsorption effect, no secondary pollution and the like. The device can be suitable for emergency treatment of pollutants in large-volume environmental water bodies, and can also be used for deep purification of general domestic sewage, environmental water bodies and drinking water bodies.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications within the scope of the present invention are within the protection scope of the present invention.
Claims (10)
1. The green synthetic magnetic composite nano material is characterized by being an ellipsoidal solid particle prepared by self-assembling the following components in parts by mass: ferrous sulfate heptahydrate: green tea extract: tea residue: 1-calcium alginate: (4-6): (0.6-0.8): (1.8-2.5).
2. The green synthetic magnetic composite nanomaterial as claimed in claim 1, wherein the finished product is an ellipsoidal solid microparticle with an average diameter of 1.5 ± 0.5mm, the microparticle is formed by coating tea leaves and nano-iron with dry matters of calcium alginate and green tea extract, and then forming a composite material GT-Fe NPs @ CA in which the dry matters of calcium alginate, tea leaves and green tea extract or the magnetic nano-iron coated on each or both of the dry matters of tea leaves and green tea extract are randomly distributed, bonded and self-assembled in a three-dimensional space based on the matching of respective particle size and physicochemical characteristics, thereby forming the ellipsoidal porous solid microparticle with the three-dimensional slow-release structure.
3. The green synthetic magnetic composite nanomaterial as claimed in claim 1 or 2, wherein the green tea extract is prepared by drying green tea 60g, adding distilled water 1L, heating in water bath at 80 deg.C for 1h, vacuum filtering to obtain filtrate; the tea residue is solid dry substance powder obtained by drying the green tea solid remaining after preparing green tea extract in an oven, and grinding and sieving with 100 mesh sieve.
4. The method for preparing green synthetic magnetic composite nano-material according to any one of claims 1 to 3, characterized by comprising the following steps:
(1) preparing green tea extract and tea residue;
(2) preparing sodium alginate sol by using green tea extract and sodium alginate;
(3) adding the tea leaves and ferrous sulfate heptahydrate into the sodium alginate sol according to a set proportion to prepare sodium alginate-coated nano-iron sol;
(4) adding the sodium alginate-coated nano-iron sol into a calcium chloride solution, uniformly mixing, performing crosslinking reaction and material self-assembly, and then drying to obtain spherical solid particles of calcium alginate, tea leaves and green tea extract dry matter coated with nano-iron, namely the green synthetic magnetic composite nano-material GT-Fe NPs @ CA.
5. The green synthetic magnetic composite nanomaterial of claim 4, wherein the calcium alginate sol of step (2) is prepared by mixing a tea extract and sodium alginate according to a set proportion under the conditions of water bath at 30-50 ℃ and rapid magnetic stirring, and uniformly stirring; the set proportion is that the addition amount of sodium alginate is 1.1-1.3g per 50ml of green tea extract.
6. The green synthetic magnetic composite nanomaterial of claim 4, wherein the step (3) is to slowly drop the tea leaves and the ferrous sulfate heptahydrate solution into the calcium alginate sol while continuously stirring, and the solution is continuously stirred for 5-30 min after the dropping is finished, so as to obtain the sodium alginate-coated nano iron sol.
7. The green synthetic magnetic composite nanomaterial of claim 4, wherein step (4) is performed by dropping the sol into CaCl with a syringe at a distance of 15cm from the liquid surface2Continuously stirring the solution, and reacting for 3-6 h to form a nano-iron composite material precursor; and then washing the composite material precursor with distilled water for 2-6 times, placing the composite material precursor in a vacuum drier for freeze-drying for 24-72 hours, and self-assembling and forming the components to obtain green and synthetic spherical solid particles of the nano-iron composite material GT-Fe NPs @ CA, wherein the nano-iron composite material GT-Fe NPs @ CA is coated by dry substances of calcium alginate, tea residues and green tea extract.
8. The application of the green synthetic magnetic composite nano material as claimed in any one of claims 1 to 3, characterized in that the purifying agent is used as a purifying agent, the three-dimensional slow release structure and the synergistic effect of reduction, adsorption and degradation are utilized, and the reduction and adsorption synergistic effect is utilized to remove Cr in the water body6+Removing rapidly; and rapidly remove Cr in water body6+And then, the green synthesized magnetic composite nano material is recycled and reused.
9. The use of claim 8, wherein the GT-Fe NPs @ CA is added in an amount of 0.3-0.5 g/100ml, and the purification reaction time of reduction-adsorption is 4-48 h.
10. The application of the green synthetic magnetic composite nano material as claimed in any one of claims 1 to 3, characterized in that the purifying agent is used as a purifying agent, and the purifying agent has a three-dimensional slow release structure and synergistic effects of reduction, adsorption and degradation, so that the organic pollutant methylene blue MB in a water body is rapidly removed; and after organic pollutant methylene blue in the water body is rapidly removed, the green synthetic magnetic composite nano material is recycled and reused.
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Application publication date: 20210507 |