CN109126721A - Magnetic metal organic framework nano material, the preparation method and applications of three-layer nuclear shell structure - Google Patents

Magnetic metal organic framework nano material, the preparation method and applications of three-layer nuclear shell structure Download PDF

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CN109126721A
CN109126721A CN201810924858.5A CN201810924858A CN109126721A CN 109126721 A CN109126721 A CN 109126721A CN 201810924858 A CN201810924858 A CN 201810924858A CN 109126721 A CN109126721 A CN 109126721A
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nano material
organic framework
metal organic
nanometer
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姜炜
沃荣
胡玉冰
郝嘎子
李秋琳
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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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
    • B01J20/22—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]
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/28014—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 form
    • B01J20/28016—Particle form
    • 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
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The invention discloses magnetic metal organic framework nano material, the preparation method and applications of a kind of three-layer nuclear shell structure.The method is first by Fe3O4@SiO2Particle carries out hydroxylating modification, obtains nanometer Fe3O4@SiO2- OH particle, then surface amination are modified to obtain nanometer Fe3O4@SiO2‑NH2Then particle is connect with Zn-MOF, finally obtain the magnetic metal organic framework nano material Fe of three-layer nuclear shell structure3O4@SiO2@Zn-MOF.The magnetic metal organic framework nano material of three-layer nuclear shell structure prepared by the present invention can be used for the absorption of organic dyestuff in water, it is good to Congo red and methylene blue adsorption effect, Congo red removal rate reaches 100% under the conditions of pH=5, methylene blue removal rate reaches 75% or more under the conditions of pH=7, the adsorbent material can be recycled easily by externally-applied magnetic field, effectively realize the reuse of material.

Description

The magnetic metal organic framework nano material of three-layer nuclear shell structure, preparation method and its Using
Technical field
The present invention relates to a kind of magnetic metal organic framework nano material of three-layer nuclear shell structure, preparation method and its rigid Application in arnotto and methylene blue adsorption number processing, belongs to adsorbent material technical field.
Background technique
Fe3O4It is extremely unstable in acidic environment as a kind of common magnetic material, it is easy to lose original magnetism, Therefore it needs in Fe3O4Surface carries out coating modification.Wherein silica coats Fe as a kind of common cladding substance3O4It can To form hud typed Fe3O4@SiO2Compound particle, to Fe3O4Form protection.Generally use solvent-thermal method preparation Fe3O4, in room temperature Lower addition tetraethyl orthosilicate stirring preparation Fe3O4@SiO2.The Fe of preparation3O4@SiO2Compound particle surface is meso-hole structure, can To remove water pollutant as adsorbent.According to reported document, Fe at present3O4@SiO2And its derivative is as adsorbent It is already used to absorbing heavy metal ions in water Cu, methylene blue and malachite green etc., but their adsorption effect is all paid no attention to Think.
Congo red and methylenum careuleum is two kinds of common dyestuffs.Congo red (CR) is a kind of common secondary diazo colours, it Waste water mainly from textile, printing and dyeing, paper, rubber, plastics industry etc..Congo red derivative naphthalenedicarboxylic acid and metabolite Benzidine may result in disease, and Congo red stable structure, it is difficult to which biodegrade not directly enters biochemical treatment system Processing.Adsorbent currently used for removing Congo red has clay mineral (Evaluation of D113 cation exchange resin for the removal of Eu(III)from aqueous solution,J.Rare Earth 28(2010) 862-867), oxide (Enhanced immobilization of ReO4-by nanoscale zerovalent iron supported on layered double hydroxide via an advanced XAFS approach: implications for TcO4_ sequestration, Appl.Catal.B-Environ.192 (2016) 268-276) and Carbon nanomaterial (Naphthalene adsorption and desorption from aqueous C60fullerene, J.Chem.Eng.Date 49(2004)675–683).Methylene blue (MB) is used as a kind of phenthazine salt, can be used for cotton, timber With the dyeing of silk, but it is harmful to the human body.It is existing for remove the adsorbent material of methylene blue to include natural polymer, such as Cellulose (Modified pineapple peel cellulose hydrogels embedded with sepia ink For effective removal of methylene blue, Carbohydr.Polym.148 (2016) 1-10) and shell it is poly- Sugar (CS) (Highly enhanced adsorption of congo red onto graphene oxide/chitosan fibers by wet-chemical etching off silica nanoparticles,Chem.Eng.J.245(2014) 99-106), carbonaceous material (Coal based magnetic activated carbon as a high performance Adsorbent for methylene blue, J.Porous Mater.23 (2016) 877-884), zeolite (Promoted dye adsorption performance over desilicated natural zeolite,Microporous Mesoporous Mater.145 (2011) 157-164.) etc..But there are some disadvantages for the above method, if any the generation of by-product Cause secondary pollution；Dyestuff degradation rate is not high；It cannot be recycled, effective, quick, green, efficient requirement is not achieved.
Summary of the invention
The purpose of the present invention is to provide a kind of magnetic metal organic framework nano materials of three-layer nuclear shell structure, preparation side Method and its adsorbing the application in Congo red and methylene blue.
To achieve the above object, technical scheme is as follows:
The preparation method of the magnetic metal organic framework nano material of three-layer nuclear shell structure, includes the following steps:
Step 1, nanometer Fe3O4@SiO2Surface functional group modification:
Fe3O4@SiO2Particle carries out hydroxylating modification: by nanometer Fe3O4@SiO2Particle and dodecyl sodium sulfate are added to In water, ultrasonic disperse is uniform, is stirred to react, and after reaction, second alcohol and water alternately washs, and is drying to obtain nanometer Fe3O4@SiO2- OH particle；
Nanometer Fe3O4@SiO2Surface amination modification: by nanometer Fe3O4@SiO2- OH particle and 3- aminopropyl trimethoxy silicon Alkane (APTMS) is added in ethyl alcohol, is stirred to react, and after reaction, ethanol washing is drying to obtain nanometer Fe3O4@SiO2-NH2 Particle；
Step 2, nanometer Fe3O4@SiO2-NH2The metal organic framework nano material (Zn-MOF) of particle and Zn connection: will Nanometer Fe3O4@SiO2-NH2Particle, the metal organic framework nano material (Zn-MOF) of Zn, 1- (3- dimethylamino-propyl) -3- Ethyl-carbodiimide hydrochloride (EDC) and n-hydroxysuccinimide (NHS) are added to the water, and are stirred to react, after reaction, It is alternately washed with second alcohol and water, is drying to obtain the magnetic metal organic framework nano material Fe of three-layer nuclear shell structure3O4@SiO2@ Zn-MOF。
Preferably, in step 1, the nanometer Fe3O4@SiO2Mass particle, dodecyl sodium sulfate quality, water body Product is than being 0.1~0.3:0.3-~0.4:70~80, g:g:mL.
Preferably, in step 1, the ultrasonic time is 10~20min.
Preferably, in step 1, the mixing time is 3.5~4.5h, 1 hour 10~20min of ultrasound of every stirring.
Preferably, in step 2, the nanometer Fe3O4@SiO2-NH2The metal organic framework nanometer material of mass particle, Zn Expect (Zn-MOF) quality, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride quality (EDC), N- hydroxysuccinimidyl acyl Imines quality (NHS) quality, the volume ratio of water are 0.2~0.4:0.5~0.7:70~80:50~55:65~85, g:g:mg: mg:mL。
Preferably, in step 2, mixing time is 40~80min.
The present invention also provides the magnetic metal organic framework nanometers for the three-layer nuclear shell structure that above-mentioned preparation method is prepared Material.
Further, the magnetic metal organic framework nano material that the present invention provides above-mentioned three-layer nuclear shell structure is containing Application in Congo red and/or methylene blue waste water adsorption treatment, includes the following steps:
The magnetic metal organic framework nano material of three-layer nuclear shell structure is added to containing Congo red and/or methylene blue Waste water in, adjust pH value be 5~7.
Preferably, the adsorption time is 20~60min.
Compared with prior art, the invention has the following advantages that
The magnetic metal organic framework nano material of three-layer nuclear shell structure of the invention, wherein metal-organic framework materials (Zn-MOF) it is evenly coated at magnetic material Fe3O4@SiO2On, core@shell@shell three-decker is formed, to Congo red and methylene blue Adsorption effect it is good, Congo red removal rate reaches methylene blue removal rate under the conditions of 100%, pH=7 under the conditions of pH=5 Reach 75% or more.
Detailed description of the invention
Fig. 1 is the magnetic metal organic framework nano material Fe of three-layer nuclear shell structure3O4@SiO2@Zn-MOF synthesis flow shows It is intended to.
Fig. 2 is Fe3O4、Fe3O4@SiO2And Fe3O4@SiO2-NH2Infrared spectrum, a.Fe3O4；b.Fe3O4@SiO2； c.Fe3O4@SiO2-NH2。
Fig. 3 is Fe3O4@SiO2The scanning electron microscope and transmission electron microscope picture of@Zn-MOF.
Fig. 4 is adsorbent mass and Congo red and methylene blue removal rate relationship line chart.
Fig. 5 is adsorption time and Congo red and methylene blue removal rate relationship line chart.
Fig. 6 is pH value and Congo red and methylene blue removal rate relationship line chart.
Fig. 7 is ionic strength and Congo red and methylene blue removal rate relationship line chart.
Specific embodiment
Invention is further described below with reference to embodiment and attached drawing.
The metal organic framework nano material (Zn-MOF) based on Zn in following embodiment prepares bibliography [Adual functional MOF as a luminescent sensor for quantitatively detecting The concentration of nitrobenzene and temperature, Chemical Communication 49 (2013) 8964-8966], specific steps are as follows:
Metal organic framework nano material (Zn-MOF) using solvent structure based on Zn, by 0.038g organic ligand 2,4,6- tri- (3,5- dicarboxyphenyi amino) -1,3,5- triazine (H6TDPAT),0.079gZn(NO3)2·6H2O is added to In the mixed solution of 4mlDMF, 2ml ethylene glycol and 0.5ml water, 30min is stirred, 0.5mL nitric acid is then added, and (DMF of 3.5M is molten Liquid), after stirring 30min dissolution, it is transferred in reaction kettle and is reacted 3 days at 80 DEG C.Cooled to room temperature is collected by filtration, and uses DMF is washed and is dried in air, obtains colourless bulk crystals Zn-MOF.
Nanometer Fe in following embodiment3O4@SiO2Particle prepares bibliography [Silica coated Fe3O4magnetic nanospheres for high removal of organic pollutants from Wastewater, Chemical Engineering Journal 306 (2016) 280-288], specific steps are as follows:
(1) by 5.2g Iron(III) chloride hexahydrate, 11.5g anhydrous sodium acetate is dissolved in 100ml ethylene glycol, is stirred 0.5h is transferred in reaction kettle after completely dissolution, is reacted 8 hours at 200 DEG C.Solution is fallen from reaction kettle after the reaction was completed Out, Magneto separate is carried out to solution with magnet, is then alternately washed with water and ethyl alcohol, finally dry nano ferriferrous oxide grain Son.
(2) 0.2g nano ferriferrous oxide particle is added to 100ml ethyl alcohol, the three necks burning of 30ml water and 1.5ml ammonium hydroxide In bottle, stirring 0.5h dissolves it sufficiently, then measures 2ml tetraethyl orthosilicate and is added dropwise, stirs 6 hours under room temperature.Instead Should after solution carry out Magneto separate, then alternately washed with water and ethyl alcohol, finally dry nanometer Fe3O4@SiO2Particle.
The magnetic metal organic framework nano material Fe of three-layer nuclear shell structure of the invention3O4@SiO2The synthesis of@Zn-MOF Flow chart is as shown in Figure 1.Step 1: preparing core@shell structure Fe3O4@SiO2, and surface functional group modification is carried out to it；Second Step: preparation Zn-MOF material；Step 3: by the Fe after the resulting modified with functional group of the first step3O4@SiO2Product and second step system Standby Zn-MOF material is combined, and forms the Fe of final product core@shell@shell three-decker3O4@SiO2@Zn-MOF。
Embodiment 1: the preparation of the magnetic metal organic framework nano material of three-layer nuclear shell structure
(1) nanometer Fe3O4@SiO2Surface functional group modification
Fe3O4@SiO2Surface hydroxylation modification: by 0.2gFe3O4@SiO2, 0.35g dodecyl sodium sulfate is dissolved in 50ml water In, ultrasonic 15min dissolves it sufficiently, then stirs 4 hours at normal temperature.Each hour takes off ultrasonic 15min. reaction Solution carries out Magneto separate afterwards, is then alternately washed with water and ethyl alcohol, finally dry product.
Fe3O4@SiO2Surface amination modification: by 0.15gFe3O4@SiO2- OH and 0.66mlAPTMS is dissolved in 75ml ethyl alcohol In, it is stirred 20 hours under room temperature.Solution carries out Magneto separate after reaction, three times with ethanol washing, then dry product.
Wherein Fe3O4、Fe3O4@SiO2And Fe3O4@SiO2-NH2Infrared spectrum as shown in Fig. 2, Fe3O4、Fe3O4@SiO2With Fe3O4@SiO2-NH2All in 553cm-1Appearance, this is Fe-O oscillating bond, illustrates that three kinds of particles all have ferroso-ferric oxide particle； Fe3O4@SiO2And Fe3O4@SiO2-NH2In 1065,946,795cm-1There is absorption peak at place, this is stretching vibration and the change of Si-O key Shape vibration illustrates coated with silica success；Fe3O4@SiO2-NH21563,1482cm-1There is absorption peak at place, this is amino Stretching vibration and bending vibration.In 2800-3025cm-1The absorption peak at place then with Fe3O4@SiO2-NH2The flexible vibration of methylene It moves related.2940,2879cm-1Locate appearance, explanation-NH2In the presence of all proving that amino is successfully connected with the appearance of upward peak.
(2) nanometer Fe3O4@SiO2-NH2The connection of the metal organic framework nano material (Zn-MOF) of particle and Zn
By the amidized Fe of 0.3g3O4@SiO2Particle, 0.6gZn-MOF, 75mgEDC, 52.5mgNHS are dissolved in 75ml water Stirring one hour.Solution carries out Magneto separate after reaction, is alternately washed with second alcohol and water, then dry product Fe3O4@SiO2@ Zn-MOF.Wherein the metal organic framework nano material (Zn-MOF) of Zn is uniformly coated on amidized Fe3O4@SiO2On, it sweeps Electronic Speculum and transmission electron microscope are retouched as shown in figure 3, material has apparent three-decker, formation is using ferroso-ferric oxide as core, silica For second layer shell, the metal organic framework nano material (Zn-MOF) of Zn is the core@shell@shell structure of third layer shell, is more advantageous to Sample adsorbs in pollutant and Magneto separate.
2. adsorbent mass of embodiment is to the magnetic metal organic framework nano material adsorption effect of three-layer nuclear shell structure It influences
It is separately added into 20mg, 40mg, 60mg into the Congo red and methylene blue solution that 25ml concentration is 50mg/L, The magnetic metal organic framework nano material absorbent of the three-layer nuclear shell structure of 80mg, 100mg is adsorbed.As a result such as Fig. 4 institute Show, with the increase of adsorbent mass, Congo red and methylene blue removal rate all increases.The Congo red removal rate in 60mg is big Amplitude improves, but as the increase of the increase removal rate of quality is unobvious.Methylene blue with adsorbent mass increase removal rate Although being promoted, promoted little.The result shows that Congo red and methylene blue be all selected adsorbent quality be 60mg when the most Properly.
Shadow of 3. adsorption time of embodiment to the magnetic metal organic framework nano material adsorption effect of three-layer nuclear shell structure It rings
The magnetism of 60mg three-layer nuclear shell structure is added in the Congo red and methylene blue solution that 25ml concentration is 50mg/L Metal organic framework nano material.Solution supernatant liquor is taken out when reacting 20,30,40,50,60min respectively to be tested.It is real Test result as shown in figure 5, with adsorption time increase, Congo red and methylene blue removal rate all increases.60min is arrived When, Congo red and methylene blue removal rate all reaches 80% or more, therefore selects 60min the most suitable for adsorption time.
Influence of the embodiment 4.pH value to the magnetic metal organic framework nano material adsorption effect of three-layer nuclear shell structure
The pH value difference for the Congo red and methylene blue solution that 25ml concentration is 50mg/L is adjusted with hydrochloric acid and sodium hydroxide It is 3,5,7,9,11.Experimental result substantially achieves 100% as shown in fig. 6, the Congo red removal rate maximum when pH is 5；And it is sub- Methyl blue is 7 maximum in pH, reaches 75% or more.Therefore the Congo red adsorption effect when pH is 5 is best；Methylene blue is in pH Adsorption effect is best when 7.
Shadow of 5. ionic strength of embodiment to the magnetic metal organic framework nano material adsorption effect of three-layer nuclear shell structure It rings
The NaCl of different quality ratio is added into the Congo red and methylene blue solution that 25ml concentration is 50mg/L, adjusts molten The ionic strength of liquid is 0.01,0.1,1.0mol/L.Experimental result as shown in fig. 7, with NaCl concentration increase, it is Congo red and The removal rate of methylene blue all declines.Illustrate that prepared adsorbent is larger by effects of ion intensity effect, ionic strength increases Add and be unfavorable for adsorbent absorption dyestuff, therefore prepared adsorbent is not suitable for the high salinity waste water from dyestuff of processing.Therefore Congo red It is all best for 0.01mol/L adsorption effect in NaCl concentration with methylene blue.
6. three-layer nuclear shell structure magnetic metal organic framework nano material removal effect of embodiment and Congo red and methylene The linear relationship of blue concentration
1. ultraviolet specrophotometer condition:
It is measured using standard quartz cuvette, the measurement factor is 1.0, low speed 50nm/cm, scanning speed 240nm/min, light Source UV+VIS lamp, measurement method are absorbance, response time 1s, optical path 10mm.Congo red absorbing wavelength is 496nm；It is sub- The absorbing wavelength of methyl blue is 665nm.
The Congo red analysis parameter with methylene blue of table 1.
The results are shown in Table 1, and Congo red and methylene blue the range of linearity is all 10-50mg/L, related coefficient (R2) be situated between In 0.93-0.99, good linear relationship is shown.

Claims (10)

1. the preparation method of the magnetic metal organic framework nano material of three-layer nuclear shell structure, which is characterized in that including walking as follows It is rapid:
Step 1, nanometer Fe3O4@SiO2Surface functional group modification:
Fe3O4@SiO2Particle carries out hydroxylating modification: by nanometer Fe3O4@SiO2Particle and dodecyl sodium sulfate are added to water In, ultrasonic disperse is uniform, is stirred to react, and after reaction, second alcohol and water alternately washs, and is drying to obtain nanometer Fe3O4@SiO2-OH Particle；
Nanometer Fe3O4@SiO2Surface amination modification: by nanometer Fe3O4@SiO2- OH particle and 3- aminopropyl front three oxosilane add Enter into ethyl alcohol, be stirred to react, after reaction, ethanol washing is drying to obtain nanometer Fe3O4@SiO2-NH2Particle；
Step 2, nanometer Fe3O4@SiO2-NH2The metal organic framework nano material of particle and Zn connection: by nanometer Fe3O4@SiO2- NH2Particle, the metal organic framework nano material of Zn, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- HOSu NHS is added to the water, and is stirred to react, and after reaction, is alternately washed with second alcohol and water, is drying to obtain three layers The magnetic metal organic framework nano material Fe of core-shell structure3O4@SiO2@Zn-MOF。
2. preparation method according to claim 1, which is characterized in that in step 1, the nanometer Fe3O4@SiO2Particle Quality, dodecyl sodium sulfate quality, the volume ratio of water are 0.1~0.3:0.3-~0.4:70~80, g:g:mL.
3. preparation method according to claim 1, which is characterized in that in step 1, the ultrasonic time be 10~ 20min。
4. preparation method according to claim 1, which is characterized in that in step 1, the mixing time be 3.5~ 4.5h, 1 hour 10~20min of ultrasound of every stirring.
5. preparation method according to claim 1, which is characterized in that in step 2, the nanometer Fe3O4@SiO2-NH2Grain Protonatomic mass, the metal organic framework nano material quality of Zn, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride matter Amount, n-hydroxysuccinimide quality quality, the volume ratio of water be 0.2~0.4:0.5~0.7:70~80:50~55:65~ 85, g:g:mg:mg:mL.
6. preparation method according to claim 1, which is characterized in that in step 2, mixing time is 40~80min.
7. the magnetic metal for the three-layer nuclear shell structure that preparation method according to any one of claims 1 to 6 is prepared is organic Skeleton nano material.
8. the magnetic metal organic framework nano material of three-layer nuclear shell structure according to claim 7 is containing Congo red And/or the application in the waste water adsorption treatment of methylene blue.
9. application according to claim 8, which comprises the steps of:
The magnetic metal organic framework nano material of three-layer nuclear shell structure is added to containing Congo red and/or methylene blue useless In water, adjusting pH value is 5~7.
10. application according to claim 9, which is characterized in that the adsorption time is 20~60min.
CN201810924858.5A 2018-08-14 2018-08-14 Magnetic metal organic framework nano material, the preparation method and applications of three-layer nuclear shell structure Pending CN109126721A (en)

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CN110028144A (en) * 2019-02-26 2019-07-19 华中师范大学 A kind of multilayered structure defluorinating agent and its preparation method and application
CN110508252A (en) * 2019-09-29 2019-11-29 合肥海关技术中心 A kind of preparation method of the magnetic metal organic framework material for Adsorption of Mercury
CN116282338A (en) * 2023-04-27 2023-06-23 东华工程科技股份有限公司 Chemical wastewater treatment agent and preparation method thereof

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Application publication date: 20190104