CN114160090A - Magnetic magnesium hydroxide composite material and preparation method and application thereof - Google Patents

Magnetic magnesium hydroxide composite material and preparation method and application thereof Download PDF

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CN114160090A
CN114160090A CN202111442339.3A CN202111442339A CN114160090A CN 114160090 A CN114160090 A CN 114160090A CN 202111442339 A CN202111442339 A CN 202111442339A CN 114160090 A CN114160090 A CN 114160090A
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magnesium hydroxide
magnetic
composite material
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reaction
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CN114160090B (en
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殷炜
赵天磊
姚奇志
周根陶
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University of Science and Technology of China USTC
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract

The invention belongs to the technical field of inorganic materials, and particularly relates to a magnetic magnesium hydroxide composite material and a preparation method and application thereof. The invention provides a magnetic magnesium hydroxide composite material, which comprises: the nano-particle comprises a magnesium hydroxide nano-sheet and a ferroferric oxide nano-particle loaded on the magnesium hydroxide nano-sheet. The preparation method provided by the invention comprises the following steps: a) heating and mixing magnesium oxide and water for reaction to obtain a suspension; b) heating and mixing the suspension and ferric salt for reaction to obtain a precipitate; the iron salt contains Fe2+And Fe3+(ii) a c) To the precipitationDrying the mixture to obtain a magnetic magnesium hydroxide composite material; the magnetic magnesium hydroxide composite material comprises a magnesium hydroxide nanosheet and ferroferric oxide nanoparticles loaded on the magnesium hydroxide nanosheet. The technical scheme provided by the invention is environment-friendly, low in cost, easy to implement, good in silver removal nano-particle effect and good in economic benefit and environmental benefit.

Description

Magnetic magnesium hydroxide composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a magnetic magnesium hydroxide composite material and a preparation method and application thereof.
Background
In recent years, with the ever-increasing production and use of engineered silver-containing nanomaterials, more and more silver nanoparticles are being released into the environment through gaseous, solid and liquid waste streams. The action of wind and surface runoff can transport the released silver nanoparticles to the aquatic environment. The aquatic environment becomes a major sink and exposure source for silver nanoparticles.
Studies have shown that silver nanoparticles can interact with non-biological and biological components in the environment, leading to environmental and health risks. For example, the high specific surface area of silver nanoparticles enables them to act as carriers for inorganic and organic contaminants, thereby enhancing the migration of these contaminants and inducing the combined toxicity of the carried contaminants and silver nanoparticles. In addition, the fine size and high surface activity of silver nanoparticles enable their active and passive transport across cell membranes, which in turn interact with the internal structures of cells (such as the nucleus and ribosomes), thus disrupting some key biological processes (such as gene expression and protein transcription). In particular, silver nanoparticles can also migrate along the food chain, posing a serious health threat to advanced consumers, including humans.
Silver nanoparticles are currently a new class of contaminants that are of high interest. Therefore, the removal of silver nanoparticles from water is critical to eliminate its environmental and health risks.
Disclosure of Invention
In view of this, the invention aims to provide a magnetic magnesium hydroxide composite material, a preparation method and an application thereof, and the composite material provided by the invention can realize efficient adsorption removal of silver nanoparticle pollutants in a water body.
The invention provides a magnetic magnesium hydroxide composite material, which comprises the following components: the nano-particle comprises a magnesium hydroxide nano-sheet and a ferroferric oxide nano-particle loaded on the magnesium hydroxide nano-sheet.
Preferably, the BET specific surface area of the magnetic magnesium hydroxide composite material is 80-120 m2/g。
The invention provides a preparation method of a magnetic magnesium hydroxide composite material, which comprises the following steps:
a) heating and mixing magnesium oxide and water for reaction to obtain a suspension;
b) heating and mixing the suspension and ferric salt for reaction to obtain a precipitate; the iron salt contains Fe2+And Fe3+；
c) Drying the precipitate to obtain a magnetic magnesium hydroxide composite material; the magnetic magnesium hydroxide composite material comprises a magnesium hydroxide nanosheet and ferroferric oxide nanoparticles loaded on the magnesium hydroxide nanosheet.
Preferably, in the step a), the dosage ratio of the magnesium oxide to the water is (0.1-1) g:60 mL.
Preferably, in the step a), the reaction temperature is 40-90 ℃; the rotating speed of the reaction is 200-1000 rpm; the reaction time is 2-24 h.
Preferably, in step b), said Fe2+With Fe3+The molar ratio of (1-1.8): 1.
preferably, in step b), Fe2+The dosage ratio of the iron salt in terms of mole number to the suspension in terms of magnesium oxide mass is (0.1-3) mmol: (0.1-1) g.
Preferably, in the step b), the reaction temperature is 40-90 ℃; the rotating speed of the reaction is 200-1000 rpm; the reaction time is 20-120 min.
The invention provides a method for removing silver nanoparticles in a water body, which comprises the following steps:
adsorbing and removing silver nanoparticles contained in the water body by using an adsorbent to obtain a treated water body;
the adsorbent is the magnetic magnesium hydroxide composite material or the magnetic magnesium hydroxide composite material prepared by the preparation method in the technical scheme.
Preferably, the initial pH value of the water body is 5-11.
Compared with the prior art, the invention provides a magnetic magnesium hydroxide composite material and a preparation method and application thereof. The invention provides a magnetic magnesium hydroxide composite material, which comprises: the nano-particle comprises a magnesium hydroxide nano-sheet and a ferroferric oxide nano-particle loaded on the magnesium hydroxide nano-sheet. The preparation method provided by the invention comprises the following steps: a) heating and mixing magnesium oxide and water for reaction to obtain a suspension; b) heating and mixing the suspension and ferric salt for reaction to obtain a precipitate; the iron salt contains Fe2+And Fe3+(ii) a c) Drying the precipitate to obtain a magnetic magnesium hydroxide composite material; the magnetic magnesium hydroxide composite material comprises a magnesium hydroxide nanosheet and ferroferric oxide nanoparticles loaded on the magnesium hydroxide nanosheet. According to the invention, magnesium oxide and ferric salt are used as reactants, water is used as a solvent, and the magnetic nano composite material of magnesium hydroxide nanosheet loaded ferroferric oxide nano particles is prepared by a one-pot method. In the technical scheme provided by the invention, the raw materials of the magnetic nano composite material, namely magnesium oxide and ferric salt, are nontoxic and harmless, are easy to obtain and have low price; the preparation process is simple and quick; the stronger magnetism can also make the composite material conveniently and quickly carry out magnetic separation after the silver nanoparticles in the water are treated. The experimental results show that: the magnetic composite material provided by the invention shows higher removal capacity to silver nanoparticles in a wider pH range; the method has the advantages that the removal kinetics are rapid under different silver concentrations; the removal rate of more than 80 percent can be still maintained after five times of recycling; the removal performance in practical water substrates (such as tap water, lake water and sea water) is hardly disturbed; the maximum removal capacity of the silver nanoparticles stabilized by citric acid and polyvinylpyrrolidone reaches 476.0mg/g and 442.4mg/g respectively, which is far higher than the removal capacity of most reported adsorbents for the silver nanoparticles. The technical scheme provided by the invention is environment-friendly, low in cost and easy to implementThe silver removing nano particles have good effect and good economic benefit and environmental benefit.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an X-ray diffraction spectrum of a ferroferric oxide-magnesium hydroxide magnetic nano composite provided in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a field emission of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 of the present invention;
FIG. 3 is a hysteresis loop of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 of the present invention and a response graph of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite to a magnet;
FIG. 4 shows N of ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 of the present invention2Adsorption-desorption curves and their pore size distribution profiles;
fig. 5 is a comparison graph of the removal effect of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite on silver nanoparticles under different initial pH conditions according to embodiment 2 of the present invention;
fig. 6 is a graph of contact time-removal capacity for removing silver nanoparticles with stable citric acid at different concentrations from the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 3 of the present invention;
fig. 7 is a graph of contact time-removal capacity of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 3 of the present invention for removing different concentrations of polyvinylpyrrolidone-stabilized silver nanoparticles;
fig. 8 is a graph of evaluating the cycle performance of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite for removing silver nanoparticles, provided by embodiment 4 of the present invention;
FIG. 9 is a graph comparing the effect of different water bases on the removal of silver nanoparticles from a ferroferric oxide-magnesium hydroxide magnetic nanocomposite material according to example 5 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
The invention provides a magnetic magnesium hydroxide composite material, which comprises the following components: the nano-particle comprises a magnesium hydroxide nano-sheet and a ferroferric oxide nano-particle loaded on the magnesium hydroxide nano-sheet. Wherein the BET specific surface area of the magnetic magnesium hydroxide composite material is preferably 80-120 m2A specific value of 80 m/g2/g、82m2/g、85m2/g、87m2/g、90m2/g、93.1m2/g、95m2/g、97m2/g、100m2/g、102m2/g、105m2/g、107m2/g、110m2/g、112m2/g、115m2/g、117m2G or 120m2(ii)/g; the pore size distribution of the magnetic magnesium hydroxide composite material is preferably concentrated in 1-6 and 6-150 nm, and more preferably concentrated in 2-6 and 6-131 nm.
The invention also provides a preparation method of the magnetic magnesium hydroxide composite material, which comprises the following steps:
a) heating and mixing magnesium oxide and water for reaction to obtain a suspension;
b) heating and mixing the suspension and ferric salt for reaction to obtain a precipitate;
c) and drying the precipitate to obtain the magnetic magnesium hydroxide composite material.
In the preparation method provided by the invention, in the step a), the dosage ratio of the magnesium oxide to the water is preferably (0.1-1) g:60mL, specifically, may be 0.1 g/60 mL, 0.15 g/60 mL, 0.2 g/60 mL, 0.25 g/60 mL, 0.3 g/60 mL, 0.35 g/60 mL, 0.4 g/60 mL, 0.45 g/60 mL, 0.5 g/60 mL, 0.55 g/60 mL, 0.6 g/60 mL, 0.65 g/60 mL, 0.7 g/60 mL, 0.75 g/60 mL, 0.8 g/60 mL, 0.85 g/60 mL, 0.9 g/60 mL, 0.95 g/60 mL, 1 g/60 mL, most preferably 0.4 g/60 mL.
In the preparation method provided by the invention, in the step a), the reaction temperature is preferably 40-90 ℃, and specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, and most preferably 60 ℃; the rotation speed of the reaction is preferably 200-1000 rpm, specifically 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm, 900rpm, 950rpm or 1000rpm, and most preferably 600 rpm; the reaction time is preferably 2-24 h, specifically 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, and most preferably 6 h.
In the preparation method provided by the invention, in the step b), the iron salt includes but is not limited to Fe2+And Fe3+One or more of ferric chloride salt, ferric sulfate salt and ferric nitrate salt; said Fe2+With Fe3+The molar ratio of (1) to (1.8): 1, specifically 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1, 1.5:1, 1.55:1, 1.6:1, 1.65:1, 1.7:1, 1.75:1 or 1.8:1, most preferably 1.5: 1.
In the preparation method provided by the invention, in the step b), Fe is used2+The use ratio of the iron salt in terms of moles to the suspension in terms of the mass of magnesium oxide is preferably (0.1-3) mmol: (0.1-1) g, more preferably (0.1-3) mmol:0.4g, specifically, 0.4g, 0.3g, 0.4g, 0.5g, 0.4g, 0.7g, 0.4g, 0.9g, 0.4g, 1.4 g, 1.2 g, 0.4g, 1.5 g, 0.4g, 1.7 g, 0.4g, 2.4 g, 0.3g, 2.5 g, 0.4g, 2.7 g, 0.4g or 3mmol, and most preferably 0.9g to 0.4 g.
In the preparation method provided by the invention, in the step b), the iron salt preferably takes part in mixing in the form of an iron salt aqueous solution; fe in the aqueous iron salt solution2+The concentration is preferably 5-150 mmol/L, specifically 5mmol/L, 10mmol/L, 15 mmol/LL, 20mmol/L, 25mmol/L, 30mmol/L, 35mmol/L, 40mmol/L, 45mmol/L, 50mmol/L, 55mmol/L, 60mmol/L, 70mmol/L, 80mmol/L, 90mmol/L, 100mmol/L, 120mmol/L or 150mmol/L, most preferably 45 mmol/L; the ratio of the aqueous iron salt solution to the suspension by mass of magnesium oxide is preferably 20mL: (0.1 to 1) g, specifically, may be 20mL:0.1g, 20mL:0.15g, 20mL:0.2g, 20mL:0.25g, 20mL:0.3g, 20mL:0.35g, 20mL:0.4g, 20mL:0.45g, 20mL:0.5g, 20mL:0.55g, 20mL:0.6g, 20mL:0.65g, 20mL:0.7g, 20mL:0.75g, 20mL:0.8g, 20mL:0.85g, 20mL:0.9g, 20mL:0.95g or 20mL:1g, most preferably 20mL:0.4 g.
In the preparation method provided by the invention, in the step b), the reaction temperature is preferably 40-90 ℃, and specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, and most preferably 60 ℃; the rotation speed of the reaction is preferably 200-1000 rpm, specifically 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm, 900rpm, 950rpm or 1000rpm, and most preferably 600 rpm; the reaction time is preferably 20-120 min, specifically 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, 90min, 100min, 110min or 120min, and most preferably 60 min.
In the preparation method provided by the invention, in the step c), the drying mode is preferably vacuum drying; the precipitate is preferably washed before drying.
The invention also provides a method for removing silver nanoparticles in a water body, which comprises the following steps:
adsorbing and removing silver nanoparticles contained in the water body by using an adsorbent to obtain a treated water body;
the adsorbent is the magnetic magnesium hydroxide composite material or the magnetic magnesium hydroxide composite material prepared by the preparation method in the technical scheme.
In the silver nanoparticle removal method provided by the invention, the initial pH value of the water body is preferably 5-11, and specifically can be 5, 6, 7, 8, 9, 10 or 11; the silver nanoparticles are preferably citric acid-stabilized silver nanoparticles and/or polyvinylpyrrolidone-stabilized silver nanoparticles; the content of the silver nanoparticles in the water body is preferably 1-100 mg/L, more preferably 2-60 mg/L, and specifically can be 2.7mg/L, 10.8mg/L, 21.6mg/L or 54 mg/L; the dosage of the adsorbent is preferably 0.02-0.5 mg/mL, specifically 0.02mg/mL, 0.05mg/mL, 0.07mg/mL, 0.1mg/mL, 0.12mg/mL, 0.15mg/mL, 0.17mg/mL, 0.2mg/mL, 0.25mg/mL, 0.3mg/mL, 0.35mg/mL, 0.4mg/mL, 0.45mg/mL or 0.5mg/mL, and most preferably 0.1 mg/mL; the adsorption removal is preferably carried out under a stirring condition, and the stirring speed is preferably 200-1000 rpm, and specifically can be 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm, 900rpm, 950rpm or 1000 rpm; the temperature for adsorption removal is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the adsorption removal time is preferably 4-48 h, and specifically can be 4h, 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h or 48 h.
In the silver nanoparticle removal method provided by the present invention, it is preferable that the method further comprises: and (3) carrying out desorption regeneration on the adsorbent adsorbed with the silver nanoparticles. Wherein, the reagent used for desorption regeneration is preferably thiourea solution; the concentration of the thiourea solution is preferably 0.02-0.5 mol/L, and specifically can be 0.02mol/L, 0.05mol/L, 0.07mol/L, 0.1mol/L, 0.12mol/L, 0.15mol/L, 0.17mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L or 0.5 mol/L.
According to the technical scheme provided by the invention, magnesium oxide and ferric salt are used as reactants, water is used as a solvent, and the magnetic nano composite material of magnesium hydroxide nanosheet loaded ferroferric oxide nano particles is prepared by a one-pot method. More specifically, the technical method provided by the invention has the following advantages and positive effects:
1) as for the magnetic composite material provided by the invention, the material has stronger magnetism, so that the material can be conveniently and quickly subjected to magnetic separation after silver nanoparticles in water are treated; the silver nanoparticles show higher removal capacity in a wider pH range; the method has the advantages that the removal kinetics are rapid under different silver concentrations; the catalyst has good regeneration capacity, and can still maintain the removal rate of more than 80 percent after five times of circulation use; the removal performance in practical water substrates (such as tap water, lake water and sea water) is hardly disturbed; the maximum removal capacity of the silver nanoparticles stable to citric acid and polyvinylpyrrolidone is far higher than that of most reported adsorbents, and the removal capacity of the adsorbents to the silver nanoparticles respectively reaches 476.0mg/g and 442.4 mg/g;
2) according to the preparation method provided by the invention, the raw materials of magnesium oxide and ferric salt are nontoxic and harmless, are easy to obtain and are low in price; the preparation process is simple and quick, and is easy to popularize;
in conclusion, the technical scheme provided by the invention is environment-friendly, low in cost, easy to implement, good in silver removal nano-particle effect and good in economic benefit and environmental benefit.
For the sake of clarity, the following examples are given in detail.
In the following examples of the present invention, the silver nanoparticle wastewater used is a laboratory-prepared silver nanoparticle solution, and there are two specific preparation processes: under the condition of magnetic stirring (800rpm), 10mL of sodium borohydride (10g/L) solution is added into 400mL of solution containing silver nitrate (0.625mM) and trisodium citrate (0.5g/L) or polyvinylpyrrolidone (1.25g/L), after 12 hours of reaction, the volume is increased to 500mL of obtained citric acid-stable or polyvinylpyrrolidone-stable silver nanoparticle solution, the silver nanoparticle concentration is 54mg/L, and silver nanoparticle simulation wastewater with different silver concentrations can be obtained by diluting the silver nanoparticle simulation wastewater.
Example 1
Preparing a ferroferric oxide-magnesium hydroxide magnetic nano composite:
0.4g MgO is dispersed in 60mL deionized water and reacted for 6h under the stirring condition of 600rpm in a water bath at 60 ℃ to form a white suspension(ii) a Then 20mL of Fe was added2+And Fe3+Mixed solution of ([ Fe ]2+]＝45mM，[Fe3+]:[Fe2+]1:1.5) and continuously reacting for 60 minutes in a water bath at 60 ℃ under the stirring condition of 600rpm to form black precipitates; filtering, washing and vacuum drying the precipitate to obtain the ferroferric oxide-magnesium hydroxide magnetic nano composite.
The results of X-ray diffraction identification of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite prepared in this example are shown in fig. 1, where fig. 1 is an X-ray diffraction spectrum of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 of the present invention. As can be seen from FIG. 1, the product prepared in this example consisted of ferroferric oxide and magnesium hydroxide.
The results of field emission scanning electron microscope observation of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite prepared in this example are shown in fig. 2, and fig. 2 is a field emission scanning electron microscope image of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 of the present invention. As can be seen from fig. 2, the product micro-morphology prepared in this embodiment is the structure of nano-sheet supported nano-particles.
The results of the magnetic tests on the magnetic iron oxide-magnesium hydroxide magnetic nanocomposite prepared in this example are shown in fig. 3, where fig. 3 is a hysteresis loop of the magnetic iron oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 of the present invention and a response graph of the magnetic iron oxide-magnesium hydroxide magnetic nanocomposite, where an interpolated graph is a response to a magnet. As can be seen from FIG. 3, the saturation magnetization of the nanocomposite is 47.8emu/g, and the product shows a strong magnetic response capability.
The ferroferric oxide-magnesium hydroxide magnetic nano composite prepared in the embodiment is subjected to N treatment2The results of the adsorption-desorption analysis are shown in fig. 4, and fig. 4 shows the N of the ferriferrous oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 of the present invention2Adsorption-desorption curve and its aperture distribution diagram, wherein the interpolation diagram is aperture distribution. As can be seen from FIG. 4, the BET specific surface area prepared in this example was 93.10m2(ii)/g, corresponding pore size distribution is concentrated in the range of 2 to 6 and 6 to 131 nm.
Comparative example 1
Fe in example 12+And Fe3+When the concentration of (b) was reduced to 0, a white product was obtained.
The product can not be collected by a magnet, is identified as a pure phase of magnesium hydroxide by X-ray diffraction, is observed as a nanosheet with a smooth surface under a field emission scanning electron microscope, and does not have the nanoparticles in example 1. Therefore, the nano-sheet in fig. 2 is further proved to be magnesium hydroxide, and the nano-particles are ferroferric oxide.
Example 2
Removal of silver nanoparticles at different initial pH conditions:
measuring a series of 50mL simulated wastewater with silver nanoparticle concentration of 10.8mg/L into a 100mL beaker, adjusting the pH values to 5.0, 6.0, 7.0, 8.0, 9.0, 10.0 and 11.0 respectively by using dilute nitric acid and sodium hydroxide solution, and adding 5mg of the ferroferric oxide-magnesium hydroxide magnetic nano composite prepared in the example 1 under the condition of electric stirring (400 rpm); and (3) separating the adsorbent by a magnet after adsorbing for 24 hours at room temperature, then measuring the concentration of the residual silver nanoparticles, and calculating the removal capacity of the magnetic nano-composite on the silver nanoparticles.
Results are shown in fig. 5, and fig. 5 is a graph comparing the removal effect of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 2 of the present invention on silver nanoparticles under different initial pH conditions, wherein Cit-AgNPs and PVP-AgNPs respectively represent citric acid-stable silver nanoparticles and polyvinylpyrrolidone-stable silver nanoparticles. As can be seen from FIG. 5, the initial pH has a small influence on the removal of silver nanoparticles by the ferroferric oxide-magnesium hydroxide magnetic nanocomposite, and the removal capacity of the magnetic nanocomposite on two kinds of silver nanoparticles is 450 +/-30 mg/g within the pH range of 5.0-11.0.
Example 3
Effect of contact time on silver nanoparticle removal:
measuring a series of 50mL of simulated wastewater with silver nanoparticle concentrations of 2.70, 10.8, 21.6 and 54.0mg/L in a 50mL beaker, adjusting the pH to 7.0, and adding 5mg of the ferroferric oxide-magnesium hydroxide magnetic nano composite prepared in the example 1 under the stirring condition; and (3) separating the adsorbent by a magnet after adsorbing for a certain time at room temperature, then measuring the concentration of the residual silver nanoparticles, and calculating the removal capacity of the magnetic nano-composite on the silver nanoparticles.
As shown in fig. 6 and 7, fig. 6 is a graph of contact time-removal capacity of the ferriferrous oxide-magnesium hydroxide magnetic nanocomposite provided in example 3 of the present invention for removing citric acid-stable silver nanoparticles with different concentrations, and fig. 7 is a graph of contact time-removal capacity of the ferriferrous oxide-magnesium hydroxide magnetic nanocomposite provided in example 3 of the present invention for removing polyvinylpyrrolidone-stable silver nanoparticles with different concentrations. As can be seen from the graphs in FIGS. 6 to 7, the removal of the silver nanoparticles by the ferroferric oxide-magnesium hydroxide magnetic nano composite can be basically balanced within 24 hours, and the maximum removal capacity of the silver nanoparticles with stable citric acid and stable polyvinylpyrrolidone reaches 476.0mg/g and 442.4mg/g respectively.
Example 4
Recycling the ferroferric oxide-magnesium hydroxide magnetic nano compound:
measuring 50mL of simulated wastewater with silver nanoparticle concentration of 10.8mg/L in a 50mL beaker, adjusting the pH to 7.0, and adding 5mg of the ferroferric oxide-magnesium hydroxide magnetic nano composite prepared in the example 1 under the stirring condition; adsorbing for 24 hours at room temperature, separating the adsorbent by a magnet, measuring the concentration of the residual silver nanoparticles, and calculating the removal percentage of the magnetic nano-composite to the silver nanoparticles; and simultaneously adding the separated adsorbent into a 0.1M thiourea solution for desorption of the silver nanoparticles, washing with water for five times, and continuing to perform an adsorption removal experiment on the next batch of silver nanoparticles, wherein the experiment is performed for 5 batches in total.
As shown in fig. 8, fig. 8 is a graph of evaluation of the cycle performance of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite for removing silver nanoparticles according to example 4 of the present invention, wherein Cit-AgNPs and PVP-AgNPs respectively represent citric acid-stable silver nanoparticles and polyvinylpyrrolidone-stable silver nanoparticles. As can be seen from fig. 8, after 5 cycles of usage, the percentage of silver nanoparticles removed by the ferriferrous oxide-magnesium hydroxide magnetic nanocomposite can still be maintained above 80%.
Example 5
Removal of silver nanoparticles in different water matrices:
diluting the simulated wastewater with the silver nanoparticle concentration of 54mg/L to 10.8mg/L by using deionized water, tap water (taken from a laboratory), lake water (taken from a brook lake) and seawater (taken from yellow sea and Qingdao), respectively, and adding 5mg of the ferroferric oxide-magnesium hydroxide magnetic nano composite prepared in the example 1 under stirring; after 24 hours of adsorption at room temperature, the adsorbent was separated by a magnet, and the concentration of the remaining silver nanoparticles was measured to calculate the percentage of silver nanoparticles removed by the magnetic nanocomposite.
Results as shown in fig. 9, fig. 9 is a graph comparing the effect of different water bases on the removal of silver nanoparticles by ferroferric oxide-magnesium hydroxide magnetic nanocomposites provided in example 5 of the present invention, wherein Cit-AgNPs and PVP-AgNPs represent citric acid-stabilized silver nanoparticles and polyvinylpyrrolidone-stabilized silver nanoparticles, respectively. As can be seen from fig. 9, in tap water, lake water and sea water environments, the ferriferrous oxide-magnesium hydroxide magnetic nano composite still has a high removal percentage of silver nanoparticles almost consistent with that of silver nanoparticles in deionized water, and all the removal percentages reach more than 95%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A magnetic magnesium hydroxide composite comprising: the nano-particle comprises a magnesium hydroxide nano-sheet and a ferroferric oxide nano-particle loaded on the magnesium hydroxide nano-sheet.
2. The magnetic magnesium hydroxide composite material according to claim 1, wherein the magnetic magnesium hydroxide composite material has a BET specific surface area of 80 to 120m2/g。
3. A preparation method of a magnetic magnesium hydroxide composite material comprises the following steps:
a) heating and mixing magnesium oxide and water for reaction to obtain a suspension;
b) heating and mixing the suspension and ferric salt for reaction to obtain a precipitate; the iron salt contains Fe2+And Fe3+；
c) Drying the precipitate to obtain a magnetic magnesium hydroxide composite material; the magnetic magnesium hydroxide composite material comprises a magnesium hydroxide nanosheet and ferroferric oxide nanoparticles loaded on the magnesium hydroxide nanosheet.
4. The method according to claim 3, wherein in the step a), the ratio of the magnesium oxide to the water is (0.1-1) g:60 mL.
5. The preparation method according to claim 3, wherein in the step a), the temperature of the reaction is 40-90 ℃; the rotating speed of the reaction is 200-1000 rpm; the reaction time is 2-24 h.
6. The method according to claim 3, wherein in step b), the Fe is2+With Fe3+The molar ratio of (1-1.8): 1.
7. the method according to claim 3, wherein in step b), Fe is used2+The dosage ratio of the iron salt in terms of mole number to the suspension in terms of magnesium oxide mass is (0.1-3) mmol: (0.1-1) g.
8. The preparation method according to claim 3, wherein in the step b), the reaction temperature is 40-90 ℃; the rotating speed of the reaction is 200-1000 rpm; the reaction time is 20-120 min.
9. A method for removing silver nanoparticles in a water body comprises the following steps:
adsorbing and removing silver nanoparticles contained in the water body by using an adsorbent to obtain a treated water body;
the adsorbent is the magnetic magnesium hydroxide composite material as set forth in any one of claims 1 to 2 or the magnetic magnesium hydroxide composite material prepared by the preparation method as set forth in any one of claims 3 to 8.
10. The method of claim 9, wherein the initial pH of the body of water is between 5 and 11.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100151030A1 (en) * 2008-12-17 2010-06-17 Moore Robert C Use of MgO Doped with a Divalent or Trivalent Metal Cation for Removing Arsenic from Water
CN102050472A (en) * 2009-10-28 2011-05-11 中国科学院过程工程研究所 Method for preparing submicron flaky magnesium hydroxide from magnesium oxide
CN106512943A (en) * 2016-12-02 2017-03-22 秦皇岛中科瀚祺科技有限公司 Nano composite material as well as preparation method and application thereof to water treatment
CN107081123A (en) * 2017-05-26 2017-08-22 湖南农业大学 Magnetic magnesium hydroxide adsorbent and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100151030A1 (en) * 2008-12-17 2010-06-17 Moore Robert C Use of MgO Doped with a Divalent or Trivalent Metal Cation for Removing Arsenic from Water
CN102050472A (en) * 2009-10-28 2011-05-11 中国科学院过程工程研究所 Method for preparing submicron flaky magnesium hydroxide from magnesium oxide
CN106512943A (en) * 2016-12-02 2017-03-22 秦皇岛中科瀚祺科技有限公司 Nano composite material as well as preparation method and application thereof to water treatment
CN107081123A (en) * 2017-05-26 2017-08-22 湖南农业大学 Magnetic magnesium hydroxide adsorbent and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MENG LIU ET AL.: ""High-efficient removal of organic dyes from model wastewater using Mg (OH)2-MnO2 nanocomposite: Synergistic effects of adsorption, precipitation, and photodegradation"", 《SEPARATION AND PURIFICATION TECHNOLOGY》 *
韩文生等: ""Fe3O4/Mg(OH)2复合材料的制备及形貌控制"", 《盐湖研究》 *

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