CN114160090B - 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

Info

Publication number
CN114160090B
CN114160090B CN202111442339.3A CN202111442339A CN114160090B CN 114160090 B CN114160090 B CN 114160090B CN 202111442339 A CN202111442339 A CN 202111442339A CN 114160090 B CN114160090 B CN 114160090B
Authority
CN
China
Prior art keywords
magnesium hydroxide
nano
magnetic
composite material
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111442339.3A
Other languages
Chinese (zh)
Other versions
CN114160090A (en
Inventor
殷炜
赵天磊
姚奇志
周根陶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN202111442339.3A priority Critical patent/CN114160090B/en
Publication of CN114160090A publication Critical patent/CN114160090A/en
Application granted granted Critical
Publication of CN114160090B publication Critical patent/CN114160090B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compounds Of Iron (AREA)

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 magnetic magnesium hydroxide composite material provided by the invention comprises the following components: magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets. The preparation method provided by the invention comprises the following steps: a) Heating and mixing magnesium oxide and water for reaction to obtain suspension; b) Heating and mixing the suspension with ferric salt for reaction to obtain a precipitate; the ferric salt contains Fe 2+ And Fe (Fe) 3+ The method comprises the steps of carrying out a first treatment on the surface of the c) Drying the precipitate to obtain a magnetic magnesium hydroxide composite material; the magnetic magnesium hydroxide composite material comprises magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets. The technical scheme provided by the invention is environment-friendly, low in cost, easy to implement, good in silver removal nanoparticle effect and good in economic and environmental benefits.

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 growing fabrication 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 effects of wind and surface runoff can transport the released silver nanoparticles to the aquatic environment. The aquatic environment becomes a major sink and source of exposure for silver nanoparticles.
Studies have shown that silver nanoparticles can interact with non-biological and biological components of the environment, leading to environmental and health risks. For example, the high specific surface area of silver nanoparticles enables them to become carriers for inorganic and organic contaminants, thereby enhancing migration of these contaminants and inducing combined toxicity of the carrying contaminants and silver nanoparticles. In addition, the small size and high surface activity of silver nanoparticles enable them to pass through cell membranes by active and passive transport, thereby acting with internal structures of cells (such as nuclei 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.
Currently, silver nanoparticles are a new type of contaminant of great interest. Therefore, removal of silver nanoparticles from a body of water is critical to eliminate its environmental and health risks.
Disclosure of Invention
In view of the above, the invention aims to provide 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 following components: magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets.
Preferably, the BET specific surface area of the magnetic magnesium hydroxide composite material is 80-120 m 2 /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 suspension;
b) Heating and mixing the suspension with ferric salt for reaction to obtain a precipitate; the ferric salt contains Fe 2+ And Fe (Fe) 3+ ；
c) Drying the precipitate to obtain a magnetic magnesium hydroxide composite material; the magnetic magnesium hydroxide composite material comprises magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets.
Preferably, in step a), the ratio of magnesium oxide to water is (0.1 to 1) g:60mL.
Preferably, in step a), the temperature of the reaction is 40-90 ℃; the rotational speed of the reaction is 200-1000 rpm; the reaction time is 2-24 h.
Preferably, in step b), the Fe 2+ With Fe 3+ The molar ratio of (1-1.8): 1.
preferably, in step b), fe is used 2+ The ratio of the iron salt to the suspension by mass of magnesium oxide in terms of moles is (0.1 to 3) mmol: (0.1-1) g.
Preferably, in step b), the temperature of the reaction is 40-90 ℃; the rotational speed of the reaction is 200-1000 rpm; the reaction time is 20-120 min.
The invention provides a method for removing silver nano particles in a water body, which comprises the following steps:
adsorbing and removing silver nano particles contained in the water body by using an adsorbent to obtain a treated water body;
the adsorbent is the magnetic magnesium hydroxide composite material prepared by the technical scheme or the preparation method of 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 magnetic magnesium hydroxide composite material provided by the invention comprises the following components: magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets. The preparation method provided by the invention comprises the following steps: a) Heating and mixing magnesium oxide and water for reaction to obtain suspension; b) Heating and mixing the suspension with ferric salt for reaction to obtain a precipitate; the ferric salt contains Fe 2+ And Fe (Fe) 3+ The method comprises the steps of carrying out a first treatment on the surface of the c) Drying the precipitate to obtain a magnetic magnesium hydroxide composite material; the magnetic magnesium hydroxide composite material comprises magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets. The invention takes magnesium oxide and ferric salt as reactants and water as solvent, and prepares the magnetic nanocomposite of magnesium hydroxide nano-sheet loaded ferroferric oxide nano-particles by a one-pot method, and the magnetic nanocomposite is used for silver nano-particlesThe particles have good adsorption capacity, and can realize the efficient adsorption removal of silver nanoparticle pollutants in water. In the technical scheme provided by the invention, the raw materials of magnesium oxide and ferric salt of the magnetic nanocomposite are nontoxic and harmless, are easy to obtain and have low price; the preparation process is simple and quick; the stronger magnetism can also lead the composite material to carry out magnetic separation conveniently and rapidly after silver nano particles in water are treated. The experimental results show that: the magnetic composite material provided by the invention has higher removal capacity for silver nano particles in a wider pH range; the removal kinetics is faster at different silver concentrations; the removal rate of more than 80% can be maintained after five times of cyclic use; the removal performance in actual water matrixes (such as tap water, lake water and sea water) is hardly disturbed; the maximum removal capacities for citric acid-stable and polyvinylpyrrolidone-stable silver nanoparticles reached 476.0mg/g and 442.4mg/g, respectively, which is far higher than the removal capacities for silver nanoparticles for most of the adsorbents already reported. The technical scheme provided by the invention is environment-friendly, low in cost, easy to implement, good in silver removal nanoparticle effect and good in economic and environmental benefits.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of a magnetic nanocomposite of ferroferric oxide-magnesium hydroxide provided in example 1 of the present invention;
FIG. 2 is a field emission scanning electron microscope image of the magnetic nanocomposite of ferroferric oxide-magnesium hydroxide provided in example 1 of the present invention;
FIG. 3 is a graph showing the hysteresis loop and the response to a magnet of the magnetic nanocomposite of ferroferric oxide-magnesium hydroxide according to example 1 of the present invention;
FIG. 4 is a diagram of the present inventionN of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 2 Adsorption-desorption curves and pore size distribution plots thereof;
FIG. 5 is a graph showing the comparative effect of the magnetic nanocomposite of ferroferric oxide-magnesium hydroxide provided in example 2 of the present invention on removal of silver nanoparticles under different initial pH conditions;
FIG. 6 is a graph of contact time versus removal capacity for the removal of citric acid stabilized silver nanoparticles at various concentrations for the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 3 of the present invention;
FIG. 7 is a graph of contact time versus removal capacity for the removal of varying concentrations of polyvinylpyrrolidone stabilized silver nanoparticles from the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 3 of the present invention;
FIG. 8 is a graph showing the evaluation of the cycle performance of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 4 of the present invention for removing silver nanoparticles;
fig. 9 is a graph comparing the effect of different water bases provided in example 5 of the present invention on removal of silver nanoparticles for a ferroferric oxide-magnesium hydroxide magnetic nanocomposite.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a magnetic magnesium hydroxide composite material, which comprises the following components: magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets. Wherein the BET specific surface area of the magnetic magnesium hydroxide composite material is preferably 80-120 m 2 Per g, in particular 80m 2 /g、82m 2 /g、85m 2 /g、87m 2 /g、90m 2 /g、93.1m 2 /g、95m 2 /g、97m 2 /g、100m 2 /g、102m 2 /g、105m 2 /g、107m 2 /g、110m 2 /g、112m 2 /g、115m 2 /g、117m 2 /g or 120m 2 /g; the pore size distribution of the magnetic magnesium hydroxide composite material is preferably concentrated in the range of 1 to 6 and 6 to 150nm, more preferably concentrated in the range of 2 to 6 and 6 to 131nm.
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 suspension;
b) Heating and mixing the suspension with 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, may specifically be 0.1g:60mL, 0.15g:60mL, 0.2g:60mL, 0.25g:60mL, 0.3g:60mL, 0.35g:60mL, 0.4g:60mL, 0.45g:60mL, 0.5g:60mL, 0.55g:60mL, 0.6g:60mL, 0.65g:60mL, 0.7g:60mL, 0.75g:60mL, 0.8g:60mL, 0.85g:60mL, 0.9g:60mL, 0.95g:60mL, 1g:60mL, most preferably 0.4g:60mL.
In the preparation method provided by the invention, in the step a), the temperature of the reaction is preferably 40-90 ℃, specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, and is most preferably 60 ℃; the rotational speed of the reaction is preferably 200 to 1000rpm, specifically 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm, 900rpm, 950rpm or 1000rpm, most preferably 600 rpm. The reaction time is preferably 2 to 24 hours, and may be specifically 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, and most preferably 6 hours.
In the preparation method provided by the invention, in the step b), the ferric salt comprises but is not limited to Fe 2+ And Fe (Fe) 3+ One or more of ferric chloride, ferric sulfate and ferric nitrate; the Fe is 2+ With Fe 3+ The molar ratio of (1) to (1.8): 1, may specifically be 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 used as 2+ The ratio of the amount of said iron salt to said suspension by mass of magnesium oxide in moles is preferably (0.1 to 3) mmol: (0.1 to 1) g, more preferably (0.1 to 3) mmol:0.4g, in particular 0.1mmol:0.4g, 0.3mmol:0.4g, 0.5mmol:0.4g, 0.7mmol:0.4g, 0.9mmol:0.4g, 1mmol:0.4g, 1.2mmol:0.4g, 1.5mmol:0.4g, 1.7mmol:0.4g, 2mmol:0.4g, 2.3mmol:0.4g, 2.5mmol:0.4g, 2.7mmol:0.4g or 3mmol:0.4g, most preferably 0.9mmol:0.4g.
In the preparation method provided by the invention, in the step b), the ferric salt is preferably mixed in the form of an aqueous ferric salt solution; fe in the ferric salt aqueous solution 2+ The concentration is preferably 5 to 150mmol/L, specifically 5mmol/L, 10mmol/L, 15mmol/L, 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 45mmol/L; the ratio of the amount of the aqueous iron salt solution to the suspension by mass of magnesium oxide is preferably 20mL: (0.1-1) g, specifically 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 temperature of the reaction is preferably 40-90 ℃, specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, and is most preferably 60 ℃; the rotational speed of the reaction is preferably 200 to 1000rpm, specifically 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm, 900rpm, 950rpm or 1000rpm, 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 60min.
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 it is dried.
The invention also provides a method for removing silver nano particles in a water body, which comprises the following steps:
adsorbing and removing silver nano particles contained in the water body by using an adsorbent to obtain a treated water body;
the adsorbent is the magnetic magnesium hydroxide composite material prepared by the technical scheme or the preparation method of 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 can be specifically 5, 6, 7, 8, 9, 10 or 11; the silver nanoparticles are preferably citric acid stable silver nanoparticles and/or polyvinylpyrrolidone stable silver nanoparticles; the content of the silver nano particles in the water body is preferably 1-100 mg/L, more preferably 2-60 mg/L, and particularly can be 2.7mg/L, 10.8mg/L, 21.6mg/L or 54mg/L; the addition amount of the adsorbent is preferably 0.02-0.5 mg/mL, specifically may be 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 0.1mg/mL; the adsorption removal is preferably performed under stirring conditions, and the stirring speed is preferably 200 to 1000rpm, and specifically may be 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm, 900rpm, 950rpm or 1000rpm; 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 to 48 hours, and specifically can be 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours, 36 hours, 40 hours, 44 hours or 48 hours.
In the silver nanoparticle removal method provided by the present invention, it is preferable that the method further comprises: and (3) desorbing and regenerating the adsorbent adsorbed with the silver nano particles. Wherein the reagent used for desorption and regeneration is preferably thiourea solution; the concentration of the thiourea solution is preferably 0.02 to 0.5mol/L, and specifically may 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 0.5mol/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 nanocomposite material of the magnesium hydroxide nano-sheet loaded ferroferric oxide nano-particles is prepared by a one-pot method, and has good adsorption capacity on silver nano-particles, so that the efficient adsorption removal of silver nano-particle pollutants in water can be realized. More specifically, the technical method provided by the invention has the following advantages and positive effects:
1) For the magnetic composite material provided by the invention, the material has stronger magnetism, so that the material can be subjected to magnetic separation conveniently and rapidly after silver nano particles in water are treated; the silver nano particles show higher removal capacity in a wider pH range; the removal kinetics is faster at different silver concentrations; the regeneration agent has good regeneration capacity, and can still maintain the removal rate of more than 80% after five times of cyclic use; the removal performance in actual water matrixes (such as tap water, lake water and sea water) is hardly disturbed; the maximum removal capacity of the silver nano-particles stabilized by citric acid and polyvinylpyrrolidone is far higher than that of most of the reported adsorbents, and the removal capacities of the silver nano-particles reach 476.0mg/g and 442.4mg/g respectively;
2) In terms of the preparation method provided by the invention, the preparation raw materials of magnesium oxide and ferric salt are nontoxic and harmless, are easy to obtain and have low 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 nanoparticle removal effect and good in economic and environmental benefits.
For clarity, the following examples are provided in detail.
In the following examples of the present invention, the silver nanoparticle wastewater used was a laboratory-prepared silver nanoparticle solution, and there were two specific preparation processes as follows: under the condition of magnetic stirring (800 rpm), adding 10mL of sodium borohydride (10 g/L) solution into 400mL of solution containing silver nitrate (0.625 mM) and trisodium citrate (0.5 g/L) or polyvinylpyrrolidone (1.25 g/L), reacting for 12 hours, and then fixing the volume to 500mL of obtained citric acid-stable or polyvinylpyrrolidone-stable silver nanoparticle solution, wherein the concentration of silver nanoparticles is 54mg/L, and diluting the solution to obtain silver nanoparticle simulated wastewater with different silver concentrations.
Example 1
Preparation of ferroferric oxide-magnesium hydroxide magnetic nanocomposite:
dispersing 0.4g MgO in 60mL deionized water, and reacting for 6 hours in a water bath at 60 ℃ under the stirring condition of 600rpm to form a white suspension; then 20mL of Fe is added 2+ And Fe (Fe) 3+ Is mixed with the solution ([ Fe) 2+ ]＝45mM，[Fe 3+ ]:[Fe 2+ ]=1:1.5), the reaction was continued in a 60 ℃ water bath with stirring at 600rpm for 60 minutes, forming a black precipitate; the precipitate is filtered, washed and dried in vacuum to obtain the ferroferric oxide-magnesium hydroxide magnetic nano-composite.
The X-ray diffraction identification was performed on the ferroferric oxide-magnesium hydroxide magnetic nanocomposite prepared in this example, and the result is shown in fig. 1, and 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 consists of ferroferric oxide and magnesium hydroxide.
The field emission scanning electron microscope observation is carried out on the ferroferric oxide-magnesium hydroxide magnetic nano-composite prepared in the embodiment, the result is shown in fig. 2, and fig. 2 is a field emission scanning electron microscope image of the ferroferric oxide-magnesium hydroxide magnetic nano-composite provided in the embodiment 1. As can be seen from fig. 2, the microstructure of the product prepared in this example is the structure of the nanosheet-loaded nanoparticle.
The magnetic test was performed on the ferroferric oxide-magnesium hydroxide magnetic nanocomposite prepared in this example, and the result is shown in fig. 3, and fig. 3 is a hysteresis loop of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 and a response graph thereof to a magnet, wherein the interpolation graph is a response to the magnet. As can be seen from FIG. 3, the saturated magnetization of the nanocomposite was 47.8emu/g, and the product exhibited a strong magnetic response capability.
N-method for the ferroferric oxide-magnesium hydroxide magnetic nanocomposite prepared in this example 2 The adsorption-desorption analysis results are shown in FIG. 4, and FIG. 4 shows N of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 1 of the present invention 2 Adsorption-desorption curves and pore size distribution diagrams thereof, wherein the inner inset is pore size distribution. As can be seen from FIG. 4, the BET specific surface area prepared in this example is 93.10m 2 And/g, the corresponding pore size distribution is concentrated at 2-6 and 6-131 nm.
Comparative example 1
Fe in example 1 2+ And Fe (Fe) 3+ When the concentrations of (a) were reduced to 0, a white product was obtained.
The product could not be collected by a magnet, identified by X-ray diffraction as a pure phase of magnesium hydroxide, and observed under a field emission scanning electron microscope as a smooth surfaced nanoplatelet, without the nanoparticles of example 1. It can be further confirmed that the nano-sheet is magnesium hydroxide and the nano-particle is ferroferric oxide in fig. 2.
Example 2
Removal of silver nanoparticles at different initial pH conditions:
measuring a series of 50mL of simulated wastewater with silver nanoparticle concentration of 10.8mg/L in a 100mL beaker, adjusting pH 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 nanocomposite prepared in example 1 under the condition of electric stirring (400 rpm); after 24 hours of adsorption at room temperature, the adsorbent was separated by a magnet, the concentration of the remaining silver nanoparticles was measured, and the removal capacity of the magnetic nanocomposite for silver nanoparticles was calculated.
The results are shown in fig. 5, and fig. 5 is a graph showing 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 represent citric acid-stable silver nanoparticles and polyvinylpyrrolidone-stable silver nanoparticles, respectively. As can be seen from fig. 5, the initial pH has less effect on removal of silver nanoparticles by the ferroferric oxide-magnesium hydroxide magnetic nanocomposite, and the removal capacity of the magnetic nanocomposite for both silver nanoparticles is 450±30mg/g at a pH ranging from 5.0 to 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 respectively in a 50mL beaker, adjusting the pH to 7.0, and adding 5mg of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite prepared in example 1 under stirring; after adsorption for a certain time at room temperature, the adsorbent is separated by a magnet, and then the concentration of the residual silver nano particles is measured, and the removal capacity of the magnetic nano composite for the silver nano particles is calculated.
As a result, as shown in fig. 6 and 7, fig. 6 is a graph of contact time-removal capacity for removing citric acid-stabilized silver nanoparticles at different concentrations from the magnetic iron oxide-magnesium hydroxide nanocomposite provided in example 3 of the present invention, and fig. 7 is a graph of contact time-removal capacity for removing polyvinylpyrrolidone-stabilized silver nanoparticles at different concentrations from the magnetic iron oxide-magnesium hydroxide nanocomposite provided in example 3 of the present invention. As can be seen from fig. 6 to 7, the removal of silver nanoparticles by the ferroferric oxide-magnesium hydroxide magnetic nanocomposite can be substantially balanced within 24 hours, and the maximum removal capacities of silver nanoparticles stabilized against citric acid and polyvinylpyrrolidone reach 476.0mg/g and 442.4mg/g, respectively.
Example 4
Recycling of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite:
measuring 50mL of simulated wastewater with the silver nanoparticle concentration of 10.8mg/L in a 50mL beaker, adjusting the pH value to 7.0, and adding 5mg of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite prepared in the example 1 under the stirring condition; separating the adsorbent through a magnet after adsorbing for 24 hours at room temperature, measuring the concentration of the residual silver nano particles, and calculating the removal percentage of the magnetic nano compound on the silver nano particles; meanwhile, the separated adsorbent is added into 0.1M thiourea solution to desorb silver nano particles, and the adsorbent is further washed with water for five times and then is continuously used for adsorption removal experiments of the next batch of silver nano particles, and a total of 5 batches of experiments are carried out.
As a result, as shown in fig. 8, fig. 8 is a graph showing evaluation of the cycle performance of removal of silver nanoparticles by the magnetic iron oxide-magnesium hydroxide nanocomposite provided in example 4 of the present invention, in which Cit-AgNPs and PVP-AgNPs represent citric acid-stable silver nanoparticles and polyvinylpyrrolidone-stable silver nanoparticles, respectively. As can be seen from fig. 8, the removal percentage of the silver nanoparticles by the ferroferric oxide-magnesium hydroxide magnetic nanocomposite after 5 cycles of use can be maintained to be more than 80%.
Example 5
Removal of silver nanoparticles from different aqueous matrices:
diluting the simulated wastewater with the silver nanoparticle concentration of 54mg/L to 10.8mg/L by using deionized water, tap water (from a laboratory), lake water (from a nest lake) and seawater (from yellow sea, qingda), and adding 5mg of the ferroferric oxide-magnesium hydroxide magnetic nanocomposite prepared in the example 1 under the stirring condition; 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, and the percentage of removal of silver nanoparticles by the magnetic nanocomposite was calculated.
Results as shown in fig. 9, fig. 9 is a comparative graph of the effect of different water bases on removal of silver nanoparticles by the ferroferric oxide-magnesium hydroxide magnetic nanocomposite provided in example 5 of the present invention, in which Cit-AgNPs and PVP-AgNPs represent citric acid-stable silver nanoparticles and polyvinylpyrrolidone-stable silver nanoparticles, respectively. As can be seen from fig. 9, the ferroferric oxide-magnesium hydroxide magnetic nanocomposite still has a nearly consistently high percentage of removal of silver nanoparticles in tap water, lake water and seawater environments, all reaching 95% or more.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. A method for removing silver nanoparticles from a body of water comprising the steps of:
adsorbing and removing silver nano particles contained in the water body by using an adsorbent to obtain a treated water body;
the adsorbent is a magnetic magnesium hydroxide composite material, and comprises: magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets.
2. The method according to claim 1, wherein the magnetic magnesium hydroxide composite material has a BET specific surface area of 80 to 120m 2 /g。
3. The method of claim 1, wherein the magnetic magnesium hydroxide composite is prepared by:
a) Heating and mixing magnesium oxide and water for reaction to obtain suspension;
b) Heating and mixing the suspension with ferric salt for reaction to obtain a precipitate; the ferric salt contains Fe 2+ And Fe (Fe) 3+ ；
c) Drying the precipitate to obtain a magnetic magnesium hydroxide composite material; the magnetic magnesium hydroxide composite material comprises magnesium hydroxide nano-sheets and ferroferric oxide nano-particles loaded on the magnesium hydroxide nano-sheets.
4. The method according to claim 3, wherein in the step a), the ratio of the magnesium oxide to the water is (0.1 to 1) g:60mL.
5. A method according to claim 3, wherein in 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 hours.
6. A method according to claim 3, wherein in step b), the Fe 2+ With Fe 3+ The molar ratio of (1-1.8): 1.
7. a process according to claim 3, wherein in step b) Fe 2+ The ratio of the iron salt to the suspension by mass of magnesium oxide is (0.1 to 3) mmol: (0.1-1 g).
8. A method according to claim 3, wherein in step b), the temperature of the reaction is 40-90 ℃; the rotating speed of the reaction is 200-1000 rpm; the reaction time is 20-120 min.
9. The method of claim 1, wherein the initial pH of the body of water is 5-11.
CN202111442339.3A 2021-11-30 2021-11-30 Magnetic magnesium hydroxide composite material and preparation method and application thereof Active CN114160090B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111442339.3A CN114160090B (en) 2021-11-30 2021-11-30 Magnetic magnesium hydroxide composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111442339.3A CN114160090B (en) 2021-11-30 2021-11-30 Magnetic magnesium hydroxide composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114160090A CN114160090A (en) 2022-03-11
CN114160090B true CN114160090B (en) 2023-06-16

Family

ID=80481689

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111442339.3A Active CN114160090B (en) 2021-11-30 2021-11-30 Magnetic magnesium hydroxide composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114160090B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8507004B2 (en) * 2008-12-17 2013-08-13 Sandia Corporation Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water
CN102050472B (en) * 2009-10-28 2013-06-05 中国科学院过程工程研究所 Method for preparing submicron flaky magnesium hydroxide from magnesium oxide
CN106512943B (en) * 2016-12-02 2019-09-17 秦皇岛中科瀚祺科技有限公司 A kind of nanocomposite and preparation method thereof and the application in water process
CN107081123B (en) * 2017-05-26 2020-09-18 湖南农业大学 Magnetic magnesium hydroxide adsorbent and preparation method thereof

Also Published As

Publication number Publication date
CN114160090A (en) 2022-03-11

Similar Documents

Publication Publication Date Title
Shi et al. Synthesis and properties of Li1. 6Mn1. 6O4 and its adsorption application
CN107029671B (en) Modified Fe3O4Preparation method and application of @ MOF composite material
Ni et al. Honeycomb-like Ni@ C composite nanostructures: synthesis, properties and applications in the detection of glucose and the removal of heavy-metal ions
Wei et al. Efficient removal of uranium (vi) from simulated seawater using amidoximated polyacrylonitrile/FeOOH composites
CN103191699B (en) Ferrite/graphene composite adsorbent and preparation and using methods thereof
Qi et al. Enhanced oxidative and adsorptive capability towards antimony by copper-doping into magnetite magnetic particles
JP2019193926A (en) Manufacturing method of magnetic hydrothermal charcoal, and application thereof
Li et al. Thiol-functionalized metal–organic frameworks embedded with chelator-modified magnetite for high-efficiency and recyclable mercury removal in aqueous solutions
CN107281999B (en) Iron oxide/manganese dioxide nano composite material and preparation method and application thereof
CN107512738B (en) Porous MnFe2O4Nano material and preparation method thereof
CN103272553B (en) Preparation method of magnetic nanometer iron oxide adsorbent for removing arsenic from water
CN104014314B (en) Bio-adsorbent, preparation method and application
Wang et al. Electroactive magnetic microparticles for the selective elimination of cesium ions in the wastewater
JP5352853B1 (en) Method of treating radioactive Cs contaminated water
CN114225895B (en) La-Fe-Al composite metal oxide, preparation method and application
CN112342378A (en) Lithium ion adsorbent and preparation method thereof
Jia et al. Efficient degradation of ciprofloxacin in wastewater by CuFe2O4/CuS photocatalyst activated peroxynomosulfate
CN106669592A (en) Preparation method of iron-nickel loaded nano calcium peroxide used for micro-polluted water treatment
CN110479203A (en) A kind of glycine MODIFIED Fe Mg-LDH and its preparation and application
CN114160090B (en) Magnetic magnesium hydroxide composite material and preparation method and application thereof
CN113908799A (en) Preparation method and application of magnetic Prussian blue nano clay
CN111085159B (en) Magnetic nano adsorbent for removing arsenic and preparation method and application thereof
CN110668546B (en) Method for catalytic reduction of uranyl ions in uranium-containing wastewater
CN109731548B (en) Activated carbon/zirconium-manganese oxide composite material and preparation method and application thereof
CN115779847B (en) In-situ adsorption material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant