CN107096515A - Fe3O4 PSS@Co MOF preparation method and applications - Google Patents

Fe3O4 PSS@Co MOF preparation method and applications Download PDF

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CN107096515A
CN107096515A CN201710255199.6A CN201710255199A CN107096515A CN 107096515 A CN107096515 A CN 107096515A CN 201710255199 A CN201710255199 A CN 201710255199A CN 107096515 A CN107096515 A CN 107096515A
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pss
mof
preparation
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methanol solution
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杨清香
陈志军
方少明
任爽爽
路冉
赵倩倩
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Zhengzhou University of Light Industry
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    • 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
    • B01J20/02—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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic 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
    • C02F2101/30—Organic compounds
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur

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Abstract

The invention belongs to water-treatment technology field, it is related to a kind of Fe3O4PSS@Co MOF preparation method and applications.The invention discloses Fe3O4PSS Co MOF preparation method and its selective absorption to methyl orange and methylene blue mixed dye, magnetic hybrid Co MOF of the invention synthesis is under conditions of hydro-thermal, first by Fe3O4Surface PSS functionalization, is then added into sonic oscillation in the methanol solution for dissolve in cobalt nitrate, and it is completely dispersed wherein, first in the min of mechanical agitation 30 ~ 60；Another methanol solution for containing 2 methylimidazoles is added drop-wise in above-mentioned solution again, 8 ~ 12 h are stirred at room temperature, by certain post processing, the Fe of the present invention is obtained3O4PSS@Co MOF, Fe prepared by the present invention3O4PSS@Co MOF have magnetic responsiveness good, and stability is good, the advantages of MOF layers thicker.It is hereby achieved that relatively good sorbing material, has potential application in terms of organic molecule is adsorbed.

Description

Fe3O4-PSS@Co-MOF preparation method and applications
Technical field
The invention belongs to water-treatment technology field, it is related to a kind of Fe3O4- PSS@Co-MOF preparation method and applications.
Background technology
MOFs materials are a kind of metal-organic framework materials developed in recent decades, and it is metal ion or metal cluster The coordination polymerization with certain size and loose structure prepared with organic ligand using the method for molecule assembling and crystal engineering Thing.MOFs materials are a kind of less crystalline materials of density ratio, the characteristics of with high-specific surface area, high porosity, easy functionalization Higher heat endurance.They often have novel topological structure, in catalytic molecular identification, adion exchange, gas The field such as storage and bioactivity shows potential application prospect, is a study hotspot of current Material Field.
ZIFs, as a MOFs branch, is a kind of imidazoles metal-organic framework most potential in recent decades Material.Huan-Ping Jing in 2014 etc., which are reported, utilizes ZIF-8 degradation of methylene blue, 50mL l0mg/L methylene blue Addition 25mg ZIF-8 irradiates 120min degradation rates under 500W mercury lamps and reaches 85%.The report such as Kun-YiAndrewLin in 2015 Road utilizes ZIF-67 rhodamine B degradations.2015, Jian M, Liu B etc. utilized the ZIF-8 material Adsorption water synthesized Pentavalent arsenic and trivalent arsenic in body, adsorption capacity is respectively 49.4mg/g and 60.0mg/g.2015, Lin K Y A etc. were utilized The ZIF-67 materials of synthesis are used for Adsorption peacock green, and in reaction temperature, 20 DEG C are that its adsorption capacity is 2430mg/g.
The ZIF-67 materials that the present invention is selected, it is by Co2+Metal ion and 2-methylimidazole complexation reaction, so that shape Into imidazoles metal-organic framework materials (Co-MOF).The application is mainly the Fe by Co-MOF and PSS functionalization3O4Magnetic Particle is combined, and forms Fe3O4- PSS@Co-MOF composites, so as to study it to organic dye molecule methyl orange (MO) and methylene The selective absorption of base indigo plant (MB) mixed dye.
The content of the invention
The present invention is solved after magnetic particle is combined applied to the technical problem in terms of organic matter dye molecule absorption, is disclosed Fe3O4- PSS@Co-MOF preparation method and applications.
In order to solve the above technical problems, using following technical scheme：
Fe3O4- PSS@Co-MOF preparation method, step is as follows：
（1）Fe3O4The preparation of nanoparticle：By FeCl3·6H2O is dissolved in ethylene glycol solution, is added anhydrous sodium acetate and is carried out Reaction, reaction terminates, after separating, washing, drying, obtains product as Fe3O4Nanoparticle；
（2）Fe3O4The preparation of-PSS nano-particles：By Fe3O4Nanoparticle is added in kayexalate solution and carried out instead Should, reaction terminates, and after scrubbed, separation, obtains product as Fe3O4- PSS nano-particles；
（3）The preparation of intermediate product：First by Fe3O4- PSS nano-particles are added in cobalt nitrate methanol solution, after being sufficiently mixed, then 2-methylimidazole methanol solution is added, reaction is complete, and separating, washing obtains intermediate product；
（4）Fe3O4- PSS@Co-MOF preparation：Use intermediate product replacement step（3）In Fe3O4- PSS nano-particles, are repeated Step（3）Operation, circulation 2 ~ 3 times after, complete Fe3O4- PSS@Co-MOF preparation.
The step（1）Concrete operations be：By 5 ~ 6g FeCl3·6H2O is dissolved in 40mL ethylene glycol, adds 3 ~ 4g Anhydrous sodium acetate, after ultrasonic mixing, is moved into ptfe autoclave liner, and temperature is 180 ~ 220 DEG C, reacts 8 ~ 10h, After reaction terminates, room temperature is cooled to, Magneto separate is carried out in the presence of externally-applied magnetic field, sediment is collected, is distinguished with water and ethanol Washing 2 ~ 5 times, after washes clean, 60 DEG C of vacuum drying 12h obtain product as Fe3O4Nanoparticle.
The step（2）Concrete operations be：0.01g Fe3O4Nanoparticle is added to dissolved with 0.05 ~ 0.12g polyphenyl second In the 30mL deionized waters of alkene sodium sulfonate, ultrasonically treated 10 ~ 30min, with water washing is distilled 3 times, is then collected with magnet, obtained Fe3O4- PSS nano-particles.
The step（3）Concrete operations be：First by Fe3O4- PSS nano-particles, add the nitre that concentration is 10 ~ 16g/L In sour cobalt methanol solution, 30 ~ 60min is stirred for after sonic oscillation, then dropwise by 26 ~ 36g/L 2-methylimidazole methanol solutions Add, 8 ~ 12h then is stirred at room temperature in obtained mixed solution, intermediate product is obtained after Magneto separate, ethanol washing.
The addition volume ratio of the cobalt nitrate methanol solution and 2-methylimidazole methanol solution is 1:1, Fe3O4- PSS nanometers Concentration of the particle in mixed solution is 1 ~ 3 g/L.
Described Fe3O4- PSS@Co-MOF preparation method, the Fe prepared3O4- PSS@Co-MOF are used as methyl orange With the application of the selective absorption of methylene blue mixed dye.
The beneficial effects of the present invention are：
（1）Fe produced by the present invention3O4- PSS@Co-MOF have core shell structure, and kernel is Fe3O4External magnetic field response is played to reach To the purpose of Magneto separate, the porous Co-MOF layers of outer layer, with high heat endurance and excellent water resistant, anti acid alkali performance energy, Fe3O4- PSS@Co-MOF have excellent absorption property to Organic Pollutants In Water, and centre is kayexalate (PSS) bridging Fe, is served3O4With Co-MOF effect.
（2）Fe produced by the present invention3O4- PSS@Co-MOF are compared to Fe3O4@MOF advantage is mainly：The present invention is logical Cross physics ultrasonic method and polymer P SS is attached to Fe3O4Surface, then by electrostatic interaction, Fe3O4- PSS surfaces The first and positively charged Co of sulfonate radical anion2+With reference to then Co2+Further with part 2-methylimidazole coordination growth Co- MOF layers, so that stable Chemical assembly structure is formed, and then the thickness of Co-MOF layers of controllable.
（3）Fe produced by the present invention3O4- PSS@Co-MOF composites, while containing magnetic Fe3O4With Co-MOF layers, Co- MOF is a kind of porous adsorbing material of highly crystalline, Fe3O4Magnetic particle has superparamagnetism, therefore the porous Fe prepared3O4- PSS@Co-MOF composites can carry out selective absorption to methyl orange and methylene blue mixed dye, then again with magnet point From, and separating effect is preferably, it is easy to operate, easy.
（4）A kind of simple, quick magnetic MOF porous materials preparation method of preparation method of the present invention, cost of material It is cheap, possess industrialization advantage, simple and easy to do, the Fe prepared3O4- PSS@Co-MOF have magnetic responsiveness good, stability It is good, the advantages of Co-MOF thickness degree is adjustable, so that Fe3O4- PSS@Co-MOF have in organic molecule absorption, separation field Potential application.
Brief description of the drawings
Fig. 1 is the Fe of embodiment 13O4- PSS@Co-MOF and Fe3O4The XRD compares figures of standard card and Co-MOF.
Fig. 2 is the Fe of embodiment 13O4- PSS@Co-MOF transmission electron microscope (TEM) figure and ESEM (SEM) figure.
Fig. 3 is the Fe of embodiment 13O4- PSS@Co-MOF infrared spectrogram.
Fig. 4 is the Fe of embodiment 13O4- PSS@Co-MOF TG figures.
Fig. 5 is the Fe of embodiment 13O4- PSS@Co-MOF N2Adsorption-desorption isothermal.
Fig. 6 is the pH of the dyestuff of embodiment 1 to Fe3O4- PSS@Co-MOF adsorb the influence figure of Adsorption of Methyl Orange amount.
Fig. 7 is the Fe of change adsorption time in embodiment 13O4The Study on adsorption properties figures of-PSS@Co-MOF to methyl orange.
Fig. 8 is the Fe of change dye strength in embodiment 13O4The Study on adsorption properties figures of-PSS@Co-MOF to methyl orange.
Fig. 9 is the Fe of the amount of change adsorbent in embodiment 13O4Study on adsorption properties of-PSS@the Co-MOF to methyl orange Figure.
Figure 10 is the pH of the dyestuff of embodiment 1 to Fe3O4- PSS@Co-MOF adsorb the influence figure of methylene blue adsorption number amount.
Figure 11 is the Fe of change adsorption time in embodiment 13O4Study on adsorption properties of-PSS@the Co-MOF to methylene blue Figure.
Figure 12 is the Fe of change dye strength in embodiment 13O4Adsorptivities of-PSS@the Co-MOF to methylene blue.
Figure 13 is Fe in embodiment 13O4- PSS@Co-MOF are to the ultraviolet suction before and after MO/MB mixed dye selective absorptions Receive spectrogram.
Embodiment
Fe3O4- PSS@Co-MOF preparation method, step is as follows：
（1）Fe3O4The preparation of nanoparticle：By FeCl3·6H2O is dissolved in ethylene glycol solution, is added anhydrous sodium acetate and is carried out Reaction, reaction terminates, after separating, washing, drying, obtains product as Fe3O4Nanoparticle；
（2）Fe3O4The preparation of-PSS nano-particles：By Fe3O4Nanoparticle is added in kayexalate solution and carried out instead Should, reaction terminates, and after scrubbed, separation, obtains product as Fe3O4- PSS nano-particles；
（3）The preparation of intermediate product：First by Fe3O4- PSS nano-particles are added in cobalt nitrate methanol solution, after being sufficiently mixed, then 2-methylimidazole methanol solution is added, reaction is complete, and separating, washing obtains intermediate product；
（4）Fe3O4- PSS@Co-MOF preparation：Use intermediate product replacement step（3）In Fe3O4- PSS nano-particles, are repeated Step（3）Operation, circulation 2 ~ 3 times after, complete Fe3O4- PSS@Co-MOF preparation.
The step（1）Concrete operations be：By 5 ~ 6g FeCl3·6H2O is dissolved in 40mL ethylene glycol, adds 3 ~ 4g Anhydrous sodium acetate, after ultrasonic mixing, is moved into ptfe autoclave liner, and temperature is 180 ~ 220 DEG C, reacts 8 ~ 10h, After reaction terminates, room temperature is cooled to, Magneto separate is carried out in the presence of externally-applied magnetic field, sediment is collected, is distinguished with water and ethanol Washing 2 ~ 5 times, after washes clean, 60 DEG C of vacuum drying 12h obtain product as Fe3O4Nanoparticle.
The step（2）Concrete operations be：0.01g Fe3O4Nanoparticle is added to dissolved with 0.05 ~ 0.12g polyphenyl second In the 30mL deionized waters of alkene sodium sulfonate, ultrasonically treated 10 ~ 30min, with water washing is distilled 3 times, is then collected with magnet, obtained Fe3O4- PSS nano-particles.
The step（3）Concrete operations be：First by Fe3O4- PSS nano-particles, add the nitre that concentration is 10 ~ 16g/L In sour cobalt methanol solution, 30 ~ 60min is stirred for after sonic oscillation, then dropwise by 26 ~ 36g/L 2-methylimidazole methanol solutions Add, 8 ~ 12h then is stirred at room temperature in obtained mixed solution, intermediate product is obtained after Magneto separate, ethanol washing.
The addition volume ratio of the cobalt nitrate methanol solution and 2-methylimidazole methanol solution is 1:1, Fe3O4- PSS nanometers Concentration of the particle in mixed solution is 1 ~ 3 g/L.
Described Fe3O4- PSS@Co-MOF preparation method, the Fe prepared3O4- PSS@Co-MOF are used as methyl orange With the application of the selective absorption of methylene blue mixed dye.
Explanation is further explained to the present invention with reference to specific embodiment：
Embodiment 1
0.73 g cobalt nitrates are dissolved in 50 mL methanol, ultrasonic dissolution obtains cobalt nitrate methanol solution, then by 1.62 g 2- first Base imidazoles is dissolved in 50 mL methanol, and ultrasonic dissolution obtains 2-methylimidazole methanol solution.At room temperature, by 0.10 g Fe3O4- PSS nano-particles are added in the there-necked flask containing cobalt nitrate methanol solution, sonic oscillation, in the h of mechanical agitation 1；Again by 2- methyl Imidazolemethanol solution is slowly dropped in above-mentioned solution, and finally by obtained mixed solution, 10 h are stirred at room temperature, through magnetic point From, wash, be dried to obtain final product Fe3O4-PSS@Co-MOF。
Embodiment 2
0.67 g cobalt nitrates are dissolved in 50 mL methanol, ultrasonic dissolution obtains cobalt nitrate methanol solution, then by 1.45 g 2- first Base imidazoles is dissolved in 50 mL methanol, and ultrasonic dissolution obtains 2-methylimidazole methanol solution.At room temperature, by 0.10 g Fe3O4- PSS nano-particles are added in the there-necked flask containing cobalt nitrate methanol solution, sonic oscillation, in the h of mechanical agitation 1；Again by 2- methyl Imidazolemethanol solution is slowly dropped in above-mentioned solution, and finally by obtained mixed solution, 8 h are stirred at room temperature, through Magneto separate, Wash, be dried to obtain final product Fe3O4-PSS@Co-MOF。
Embodiment 3
0.70 g cobalt nitrates are dissolved in 50 mL methanol, ultrasonic dissolution obtains cobalt nitrate methanol solution, then by 1.60 g 2- first Base imidazoles is dissolved in 50 mL methanol, and ultrasonic dissolution obtains 2-methylimidazole methanol solution.At room temperature, by 0.11 g Fe3O4- PSS nano-particles are added in the there-necked flask containing cobalt nitrate methanol solution, sonic oscillation, in the min of mechanical agitation 50；Again by 2- Methylimidazole methanol solution is slowly dropped in above-mentioned solution, finally by obtained mixed solution, 9 h is stirred at room temperature, through magnetic Separate, wash, being dried to obtain final product Fe3O4-PSS@Co-MOF。
Embodiment 4
0.72 g cobalt nitrates are dissolved in 50 mL methanol, ultrasonic dissolution obtains cobalt nitrate methanol solution, then by 1.70 g 2- first Base imidazoles is dissolved in 50 mL methanol, and ultrasonic dissolution obtains 2-methylimidazole methanol solution.At room temperature, by 0.12 g Fe3O4- PSS nano-particles are added in the there-necked flask containing cobalt nitrate methanol solution, sonic oscillation, in the min of mechanical agitation 45；Again by 2- Methylimidazole methanol solution is slowly dropped in above-mentioned solution, finally by obtained mixed solution, 10 h is stirred at room temperature, through magnetic Separate, wash, being dried to obtain final product Fe3O4-PSS@Co-MOF。
Embodiment 5
0.80 g cobalt nitrates are dissolved in 50 mL methanol, ultrasonic dissolution obtains cobalt nitrate methanol solution, then by 1.75 g 2- first Base imidazoles is dissolved in 50mL methanol, and ultrasonic dissolution obtains 2-methylimidazole methanol solution.At room temperature, by 0.15 g Fe3O4- PSS nano-particles are added in the there-necked flask containing cobalt nitrate methanol solution, sonic oscillation, in the min of mechanical agitation 50；Again by 2- Methylimidazole methanol solution is slowly dropped in above-mentioned solution, finally by obtained mixed solution, 9 h is stirred at room temperature, through magnetic Separation, washing obtain, are dried to obtain final product Fe3O4-PSS@Co-MOF。
Embodiment 6
0.75 g cobalt nitrates are dissolved in 50 mL methanol, ultrasonic dissolution obtains cobalt nitrate methanol solution, then by 1.70 g 2- first Base imidazoles is dissolved in 50 mL methanol, and ultrasonic dissolution obtains 2-methylimidazole methanol solution.At room temperature, by 0.10 g Fe3O4- PSS nano-particles are added in the there-necked flask containing cobalt nitrate methanol solution, sonic oscillation, in the min of mechanical agitation 50；Again by 2- Methylimidazole methanol solution is slowly dropped in above-mentioned solution, finally by obtained mixed solution, 11 h is stirred at room temperature, through magnetic Separate, wash, being dried to obtain final product Fe3O4-PSS@Co-MOF。
Embodiment 7
0.80 g cobalt nitrates are dissolved in 50 mL methanol, ultrasonic dissolution obtains cobalt nitrate methanol solution, then by 1.80 g 2- first Base imidazoles is dissolved in 50 mL methanol, and ultrasonic dissolution obtains 2-methylimidazole methanol solution.At room temperature, by 0.12 g Fe3O4- PSS nano-particles are added in the there-necked flask containing cobalt nitrate methanol solution, sonic oscillation, in the min of mechanical agitation 45；Again by 2- Methylimidazole methanol solution is slowly dropped in above-mentioned solution, finally by obtained mixed solution, 9 h is stirred at room temperature, through magnetic Separate, wash, being dried to obtain final product Fe3O4-PSS@Co-MOF。
Fe prepared by embodiment 13O4- PSS@Co-MOF structural characterization and Study on adsorption properties：
（1）Fe3O4- PSS@Co-MOF structural characterization
Using D8 Advance x-ray diffractometers (XRD), to the Fe of preparation3O4- PSS@Co-MOF hybrid particles carry out table Levy.Thing phase and Crystalline form analysis are carried out to sample.The kV of operating voltage 40, pipe stream 30 mA, Cu target K ray are incident, and 2 θ scopes are from 5 ° To 70 °, 0.04 ° of step-length.And and Fe3O4Standard card and Co-MOF typical peak are compareed, such as Fig. 1.
With JEM-2100 types transmission electron microscope (TEM) and JSM-6490LV types ESEM (SEM) to magnetic nano-particle Pattern and particle diameter characterized, such as Fig. 2.
Infrared spectrum analysis uses the type infrared spectrometers of Nicolet 5700, and the structure and skeletal vibration of sample use KBr Support chip, in 400 ~ 4000 cm-1In the range of, record the skeletal vibration infrared absorption peak of sample, such as Fig. 3.
Determined with Diamond TG/DTA synthesis thermal analyzers, with α-Al2O3For standard specimen.Its measure temperature range be Room temperature is to 800 DEG C, and test condition is atmosphere, and heating rate is 10 °C of min−1.Such as Fig. 4.
The specific surface area of material, method of testing are measured with BELSORP mini type specific surface area and porosities tester:First 10 at 150 DEG C- 5 Instrument is transferred under Pa after the h of degassing process 10 to be tested, such as Fig. 5.
（2）Fe3O4Performance studies of-PSS@the Co-MOF to the selective absorption of methyl orange and methylene blue.
Ultraviolet-visible spectrophotometer test is carried out to methyl orange homogencous dyes, its uv-absorption maximum wavelength is 463 Nm, by changing dyestuff pH respectively, adsorption time, dyestuff initial concentration, the variable such as the amount of adsorbent is ground to absorption property Study carefully, see Fig. 6, Fig. 7, Fig. 8 and Fig. 9.By studying dyestuff pH, adsorption time, dyestuff initial concentration, quantity of sorbent respectively to absorption The influence of performance, as a result shows：As dyestuff pH=8, with the increase of adsorption time, unit adsorbance also increases, and 10 h reach Adsorption equilibrium.When the concentration of methyl orange in solution reaches 400 mg/L, and the amount of magnetic porous material reaches 5 mg, unit absorption Amount is up to 738 mg/g.
Ultraviolet-visible spectrophotometer test is carried out to methylene blue homogencous dyes, its uv-absorption maximum wavelength is 664 Nm, by changing dyestuff pH respectively, adsorption time, the variable such as dyestuff initial concentration is studied absorption property, sees Figure 10, figure 11 and Figure 12.By studying the influence of dyestuff pH, adsorption time, dyestuff initial concentration, quantity of sorbent to absorption property respectively, knot Fruit shows：As dyestuff pH=11, with the increase of adsorption time, unit adsorbance also increases, and 24 h reach adsorption equilibrium.When The concentration of methyl orange reaches 60 mg/L in solution, when the amount of magnetic porous material reaches 5 mg, and unit adsorbance is up to 43.8 mg/g。
Research to the selective absorption of methyl orange and methylene blue mixed dye, with Fe3O4- PSS@ZIF-67 are absorption During agent, the color of MO/MB mixed solution is substantially changed, and blueness is changed into from the green of original mixed solution, this and it is single The blueness of one component MB solution is consistent, and single MO color is Chinese red, and this illustrates the magnetic MOF composites selected by us It is capable of the absorption MO of selectivity, and then effective as selective separates both MO/MB mixed dye molecules.Figure 13 is mixed for MO/MB Close the uv absorption spectra before and after dye selection absorption.As seen from the figure, the absorption light of MO/MB mixed dye solutions before adsorbing Correspond to MO and MB characteristic absorption peak in spectral curve respectively at 464 nm and 664 nm.As the adsorbent Fe for adding 5mg3O4- After PSS@ZIF-67, the absorbance at 464 nm drops to almost nil, and the absorbance at 664 nm is slightly decreased, explanation MO molecules are almost adsorbed by adsorbent, and MB molecules only have less amount of absorption.
In selection separation process, MO concentration is 16.58 mg/L, and MB concentration is 12.61 mg/L, MO：MB concentration ratio For 1.32, adsorbent amount is 5 mg, surveys the change of its absorbance with the change of time, adsorption process continues 5 min and reached Good separating effect, concentration ratio MO after now adsorbing:MB is 0.04.It can be calculated and be mixed according to uv absorption spectra The separative efficiency of solution reaches 96%, and separating effect is fine.Calculate the formula (1) of separative efficiency：
S(%) = c(MO)f / [c(MB)f+ c(MO)f］ × 100% (1)
S (%)=removal efficiency, c (MO)fMO concentration after=absorption, c (MB)fMB concentration after=absorption.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry Art personnel are it should be appreciated that the present invention is not limited to the above embodiments, and described in above-described embodiment and specification is explanation The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and Its equivalent thereof.

Claims (6)

1.Fe3O4- PSS@Co-MOF preparation method, it is characterised in that step is as follows：
（1）Fe3O4The preparation of nanoparticle：By FeCl3·6H2O is dissolved in ethylene glycol solution, is added anhydrous sodium acetate and is carried out instead Should, reaction terminates, after separating, washing, drying, obtains product as Fe3O4Nanoparticle；
（2）Fe3O4The preparation of-PSS nano-particles：By Fe3O4Nanoparticle is added to be reacted in kayexalate solution, Reaction terminates, and after scrubbed, separation, obtains product as Fe3O4- PSS nano-particles；
（3）The preparation of intermediate product：First by Fe3O4- PSS nano-particles are added in cobalt nitrate methanol solution, after being sufficiently mixed, then 2-methylimidazole methanol solution is added, reaction is complete, and separating, washing obtains intermediate product；
（4）Fe3O4- PSS@Co-MOF preparation：Use intermediate product replacement step（3）In Fe3O4- PSS nano-particles, repeat to walk Suddenly（3）Operation, circulation 2 ~ 3 times after, complete Fe3O4- PSS@Co-MOF preparation.
2. Fe according to claim 13O4- PSS@Co-MOF preparation method, it is characterised in that the step（1）Tool Gymnastics conduct：By 5 ~ 6g FeCl3·6H2O is dissolved in 40mL ethylene glycol, 3 ~ 4g anhydrous sodium acetates is added, through ultrasonic mixing Afterwards, move into ptfe autoclave liner, temperature is 180 ~ 220 DEG C, react 8 ~ 10h, after reaction terminates, be cooled to room Temperature, carries out Magneto separate in the presence of externally-applied magnetic field, collects sediment, 2 ~ 5 times, washes clean are washed respectively with water and ethanol Afterwards, 60 DEG C of vacuum drying 12h, obtain product as Fe3O4Nanoparticle.
3. Fe according to claim 13O4- PSS@Co-MOF preparation method, it is characterised in that the step（2）Tool Gymnastics conduct：0.01g Fe3O4Nanoparticle is added to the 30mL deionized waters dissolved with 0.05 ~ 0.12g kayexalates In, ultrasonically treated 10 ~ 30min, with water washing is distilled 3 times, is then collected with magnet, obtains Fe3O4- PSS nano-particles.
4. Fe according to claim 13O4- PSS@Co-MOF preparation method, it is characterised in that the step（3）Tool Gymnastics conduct：First by Fe3O4- PSS nano-particles, add concentration in 10 ~ 16g/L cobalt nitrate methanol solution, to shake through ultrasound It is stirred for 30 ~ 60min after swinging, then dropwise adds 26 ~ 36g/L 2-methylimidazoles methanol solution, it is then that obtained mixing is molten 8 ~ 12h is stirred at room temperature in liquid, and intermediate product is obtained after Magneto separate, ethanol washing.
5. Fe according to claim 43O4- PSS@Co-MOF preparation method, it is characterised in that：The cobalt nitrate methanol The addition volume ratio of solution and 2-methylimidazole methanol solution is 1:1, Fe3O4Concentration of-PSS the nano-particles in mixed solution For 1 ~ 3 g/L.
6. the Fe according to claim 1-53O4- PSS@Co-MOF preparation method, the Fe prepared3O4-PSS@Co- MOF as the selective absorption of methyl orange and methylene blue mixed dye application.
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