CN109806844A - A kind of magnetic metal organic framework materials of dephosphorization and preparation method thereof - Google Patents
A kind of magnetic metal organic framework materials of dephosphorization and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to pollution control fields, and in particular to a kind of magnetic metal organic framework materials of dephosphorization and its preparation method and application.Preparation method of the invention is directly by Fe3O4It is mixed with the raw material for preparing MOF, then temperature reaction obtains；Method compared to general preparation magnetism MOF is more simple, completes without first preparing MOF, then makes MOF and Fe3O4Reaction preparation magnetism MOF again, just because of the particularity of the method for the present invention, the partial size of magnetic MOF of the invention is slighter, and specific surface area agent is up to 415 m2/ g, absorption property is more excellent, is up to 333.3mg/g to the adsorption capacity of phosphorus.Therefore, magnetic MOF of the invention has huge application value in water treatment field.
Description
Technical field
The invention belongs to pollution control fields, and in particular to a kind of magnetic metal organic framework materials of dephosphorization and its preparation
Methods and applications.
Background technique
Nitrogen phosphorus is the main reason for causing water eutrophication, and phosphorus be often considered as the main control of water eutrophication because
The excessive consumption of one of element, phosphorus product is inevitably generated a large amount of phosphorus-containing wastewaters, causes serious water eutrophication, causes
Water biological species death, algae reproduction and parasitic infection.Therefore, the removal of phosphorus has control water eutrophication in phosphorus-containing wastewater
It is significant.
Existing sewage treatment plant's dephosphorization technique mainly has a biological phosphate-eliminating, chemical precipitation dephosphorization, but at high cost and difficult reach row
Put standard.Zeolite, ferrihydrite, red mud, the metal oxide etc. that common adsorbent has steel slag, surface modified, these adsorbents
Although being conveniently easy to get economy, its adsorption and dephosphorization is inefficient, and reusable rate is low, therefore designs efficient, segregative magnetic
Property dephosphorization adsorbent is very necessary.Metal organic frame (MOF) has the characteristics that big specific surface area, controllable aperture, can lead to
It crosses and suitable metal center is selected to prepare efficient dephosphorization adsorbent.And the advantages of preparing dephosphorization adsorbent with iron-based MOF material, is
There are a large amount of iron oxygen cluster Fe-O in Fe base MOF material, since Fe and phosphate have good affinity, it can be achieved that efficient phosphorus
It removes.In order to further increase separative efficiency, researcher is usually also modified iron-based MOF material, it is made to have magnetism.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of the magnetic organic metal framework material of dephosphorization, party's legal systems
Standby magnetic organic metal framework material has excellent phosphor-removing effect, is up to 333.3mg/g to phosphatic absorption.
A kind of preparation method of the magnetic organic metal framework material of dephosphorization, with Fe3O4, soluble trivalent iron salt and equal three
Benzoic acid uses solvent structure；The Fe3O4, soluble trivalent iron salt and Trimesic acid the mass ratio of the material be 2-4:
2-4∶1-2。
Preferably, the solvent in the solvent-thermal method includes one of water, ethyl alcohol or DMF (n,N-Dimethylformamide)
Or it is a variety of, more preferably, the solvent is water, ethyl alcohol or DMF, it is preferred that the solubility trivalent iron salt FeCl3、Fe2
(SO4)3、Fe(NO3)3And its one of crystalline hydrate or a variety of.
Preferably, the specific steps of the above method are as follows:
(1) Fe is taken3O4, soluble trivalent iron salt, Trimesic acid and solvent be placed in closed container, reaction system heating
To 140-180 DEG C of reaction 12-18h；
(2) after the reaction was completed, reaction system is cooled to room temperature, and washing is dried to obtain magnetic organic metal framework of the invention
Material.
Preferably, the Fe3O4、Fe(NO3)3The mass ratio of the material with Trimesic acid is 3: 3: 1.
Preferably, the reaction temperature is 160 DEG C.
Preferably, the amount concentration of the parent material of Trimesic acid is 20-40mmol/L in reaction system, is more highly preferred to
, in reaction system, the amount concentration of the parent material of Trimesic acid is 33.3mmol/L.
Preferably, the Fe3O4The preparation method comprises the following steps: to divalent iron salt and trivalent iron salt mixed solution and dripping ammonium hydroxide
Reaction stands after the reaction was completed, washs, dry Fe3O4, the divalent iron salt and trivalent iron salt are soluble-salt.
More preferably, the divalent iron salt is selected from FeCl2、FeSO4And its one of crystalline hydrate or a variety of；
Preferably, the Fe3O4Preparation method specific steps are as follows: under stirring condition, added into divalent iron salt solution
Trivalent iron salt is uniformly mixed to obtain mixed solution, under ultrasound condition, reacts, has reacted to mixed solution and dripping ammonium hydroxide
At it is rear stand, washing, dry Fe3O4。
More preferably, the mass ratio of the material of the divalent iron salt and trivalent iron salt is 2: 1, the amount of the substance of the ammonium hydroxide
Concentration is 3.5mol/L.
The magnetic organic metal framework material of above method preparation also belongs to protection scope of the present invention.
The present invention also provides a kind of dephosphorization adsorbents, including above-mentioned magnetic organic metal framework material.
A method of removal Phosphorus From Wastewater includes the following steps, by above-mentioned magnetic organic metal framework material investment to
In the waste water of processing, the dosage of adsorption and dephosphorization, the magnetism organic metal framework material is 0.02g-1g/L.
The beneficial effects of the present invention are:
1. magnetic metal organic framework materials prepared by preparation method of the invention are compared to existing magnetic ferrous metals MOF
With excellent phosphor-removing effect, adsorption capacity is up to 333.3mg/g, and the material has magnetism convenient for separation, and reproducibility is good,
It can be widely applied for water treatment field；
2. preparation method of the invention is directly by Fe3O4It is mixed with the raw material for preparing MOF, then temperature reaction obtains；It compares
It is more simple in the method for general preparation magnetism MOF, it is completed without first preparing MOF, then makes MOF and Fe again3O4It is anti-again
Magnetic MOF should be prepared；Just because of the particularity of the method for the present invention, the partial size of magnetic MOF of the invention is slighter, specific surface area
Up to 415m2/ g, absorption property are excellent.
3. magnetic metal organic framework materials prepared by the present invention adsorb phosphatic excellent effect, solvent green used
Environmental protection, the material settling out prepared have preferable adsorption effect at wide pH.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram (XRD) of the magnetic organic metal framework material of embodiment 1-3；
Fig. 2 is the saturated magnetization curve of the magnetic organic metal framework material of embodiment 1-3；
Fig. 3 is the N of the magnetic organic metal framework material of embodiment 1-32Adsorption-desorption figure；
Fig. 4 is the graph of pore diameter distribution of the magnetic organic metal framework material of embodiment 1-3；
Fig. 5 is the electron microscope of FMC prepared by embodiment 1, wherein (a) is scanning electron microscope diagram (SEM), is (b) height
Times transmission electron microscope (HRTEM) figure；
Fig. 6 is that the magnetic organic metal framework material of embodiment 1-3 adsorbs phosphatic dynamics；
Fig. 7 is that the magnetic organic metal framework material of embodiment 1-3 adsorbs phosphatic thermoisopleth；
Fig. 8 is absorption infrared spectrogram (FT-IR) of the FMC of the preparation of embodiment 1 before and after adsorbing phosphate；
Fig. 9 is x-ray photoelectron spectroscopy (XPS) figure of the FMC of the preparation of embodiment 1 before and after adsorbing phosphate, wherein
(a) it is the total peak XPS, (b) is O 1s swarming；
Figure 10 is influence of the salt to the FMC absorption property of embodiment 1 of various concentration；
Figure 11 is influence of the humic acid to the FMC absorption property of embodiment 1 of various concentration；
Figure 12 is different influence of the pH to the phosphorus adsorbance of the magnetic organic metal framework material of embodiment 1-3；
Figure 13 is influence of the FMC dosage to the phosphorus adsorbance of FMC；
Figure 14 is tp removal rate of the FMC of embodiment 1 after the recycling of different numbers.
Specific embodiment
Invention is further detailed with attached drawing with reference to embodiments.
If reagent of the present invention and material without specified otherwise, can be bought by commercially available channel and be obtained.
The preparation of 1 magnetic metal organic framework materials of embodiment
(1) ferroso-ferric oxide is prepared
At normal temperatures and pressures, in iron chloride: the ratio that ferrous sulfate molar ratio is 1:2 is uniformly mixed in ultrapure water,
Manner of formulation is under agitation, iron chloride to be added into ferrous sulfate solution, be uniformly mixed；Under ultrasound condition
3.5mol/L ammonium hydroxide is added dropwise dropwise, is added dropwise after ammonium hydroxide, is taken second place after room temperature reaction 30min, standing with milli-Q water 3
Afterwards, 60 DEG C drying material 12 hours in baking oven.
(2) solvent structure magnetism MOF adsorbent
At room temperature, in ferroso-ferric oxide: ferric nitrate: the ratio that trimesic acid molar ratio is 3:3:1 is uniformly mixed, molten
In alcohol solvent；Prepared solution is put into reaction kettle and is reacted, is reacted 15 hours at 160 DEG C, is cooled to room temperature,
With after ethanol washing 3 times in baking oven 60 DEG C drying 24 hours, obtain magnetic organic metal framework material of the present invention
FMC.MC is that ferroso-ferric oxide is not added, and is directly synthesized according to the method described above.
The preparation of 2 magnetic metal organic framework materials of embodiment
(1) ferroso-ferric oxide is prepared
At normal temperatures and pressures, in iron chloride: the ratio that ferrous sulfate molar ratio is 1:2 is uniformly mixed in ultrapure water,
Manner of formulation is under agitation, iron chloride to be added into ferrous sulfate solution, be uniformly mixed；Under ultrasound condition
3.5mol/L ammonium hydroxide is added dropwise dropwise, is added dropwise after ammonium hydroxide, is taken second place after room temperature reaction 30min, standing with milli-Q water 3
Afterwards, 60 DEG C of drying material 12h in baking oven.
(2) solvent structure magnetism MOF adsorbent
At room temperature, in ferroso-ferric oxide: ferric nitrate: the ratio that trimesic acid molar ratio is 3:3:1 is uniformly mixed, molten
In ultrapure water；Prepared solution is put into reaction kettle and is reacted, in 160 DEG C of reaction 15h, is cooled to room temperature, with super
60 DEG C of dryings for 24 hours, obtain magnetic organic metal framework material FMH of the present invention in baking oven after pure water 3 times.
The preparation of 3 magnetic metal organic framework materials of embodiment
(1) ferroso-ferric oxide is prepared
At normal temperatures and pressures, in iron chloride: the ratio that ferrous sulfate molar ratio is 1:2 is uniformly mixed in ultrapure water,
Manner of formulation is under agitation, iron chloride to be added into ferrous sulfate solution, be uniformly mixed；Under ultrasound condition
3.5mol/L ammonium hydroxide is added dropwise dropwise, is added dropwise after ammonium hydroxide, is taken second place after room temperature reaction 30min, standing with milli-Q water 3
Afterwards, 60 DEG C of drying material 12h in baking oven.
(2) solvent structure magnetism MOF adsorbent
At room temperature, in ferroso-ferric oxide: ferric nitrate: the ratio that trimesic acid molar ratio is 3:3:1 is uniformly mixed, molten
In N,N-dimethylformamide (DMF) solvent；Prepared solution is put into reaction kettle and is reacted, is reacted at 160 DEG C
15h is cooled to room temperature, with 60 DEG C of dryings for 24 hours, it is organic to obtain magnetism of the present invention in baking oven after milli-Q water 3 times
Metal framework material FMD.
Further, it is as follows to carry out characterization result to the magnetic MOF of embodiment 1-3 by inventor:
The XRD of the magnetic MOF of embodiment 1-3 preparation is as shown in Figure 1, the results showed that, they contain four oxidations three that are magnetic
The characteristic peak of iron, respectively at 18.2 °, 30.1 °, 35.4 °, 37.1 ° and 43.1 °.
Shown in the saturated magnetization curve graph 2 of the magnetic MOF of embodiment 1-3 preparation, the saturation magnetization of three kinds of magnetism MOF
Respectively 11.5emu/g, 9.3emu/g, 5.9emu/g, it was demonstrated that their uniform good superparamagnetism are able to carry out magnetic point
From the regeneration and recycling of adsorbent is better achieved.
The N of the magnetic MOF of embodiment 1-3 preparation2Absorption-desorption figure and graph of pore diameter distribution are shown in Fig. 3 and Fig. 4, synthesis
The BET specific surface area of FMC, FMH, FMD are respectively 415m2/ g, 283m2/ g, 122m2/ g, average pore size are respectively 36.1nm,
50.9nm, 65.5nm, show it is a large amount of it is mesoporous be present in adsorbent surface, can carry out absorption phosphate well, and the ratio of MC
Surface area is 441m2/ g, average pore size 32.9nm reduce its specific surface area after ferroso-ferric oxide is added.
Inventor also carries out electron-microscope scanning, scanning electron microscope (SEM) and high power to magnetic MOF prepared by embodiment 1
For transmission electron microscope (HRTEM) result referring to Fig. 5, morphosis is the spherical material reunited together, as TEM schemes institute
Show, it can be seen that it is the nano particle of core-shell structure, and outer casing thickness is about 10nm.
The phosphorus removal property of 4 magnetic metal organic framework materials of embodiment is studied
1. adsorption isotherm
The dephosphorization absorption property of the magnetic MOF of embodiment 1-3 is studied, prepare initial concentration be 5,10,20,30,
40,50,80,100,150, the phosphate of 200mg/L is (with PO4 3-Indicate) liquid is used, use the sodium hydroxide and salt of 0.1mol/L
Acid solution adjusts pH=7, and the phosphoric acid for successively pipetting each concentration uses liquid 50ml into conical flask, adds tri- kinds of realities of 2mg respectively
Then conical flask is put into 25 DEG C of constant temperature oscillators and turns 12 with 180rpm per minute by the adsorbent of example in wherein
H, sufficiently after reaction, Magnetic Isolation adsorbent and solution, its remaining phosphate with Ammonium Molybdate Spectrophotometric Method for Determination
Concentration.Finally three kinds of example adsorbent adsorbances are calculated according to the following formula:
In formula: C0For initial phosphate concentration (mg/L), CeFor remaining phosphate concn (mg/L), V is liquor capacity
(mL), m is adsorbent mass (mg), qeFor Phosphate Adsorption amount (mg/g).
The adsorption curve drawn according to above-mentioned adsorbance is as shown in fig. 7, the adsorbance of adsorbent is first with phosphate concn
Increase and increase, then keeps relative stability.Under conditions of different solvents, the absorption of the magnetic metal organic framework materials of preparation
Performance is different, for equilibrium adsorption capacity, FMC > FMH > FMD.It further is fitted experimental data with Lang Gemiaoer isotherm model,
It the results are shown in Table 1.
1 thermoisopleth Adsorption Model fitting data of table and related parameter values
According to table 1, the adsorbance to phosphorus of magnetic metal organic framework materials of the invention is up to 333.3mg/g,
Phosphorus in water can be efficiently removed, can be widely applied to the Adsorption phosphorus of environmental water sample.
2. adsorption dynamics adsorption kinetics
In the adsorption kinetic data, a series of 50mg/L phosphate solutions (50mL) are adjusted to pH 7.0, by itself plus
Enter into the erlenmeyer for having 2mg magnetism MOF adsorbent, these shaking flasks are then put into 25 DEG C of reaction time in constant temperature oscillator
To reach balance from 30 minutes to 24 hour.In order to analyze the kinetic mechanism of adsorption process, by subject to fitting experimental data one
Grade dynamics, pseudo-second order kinetic model obtain absorption property.Calculation formula is as follows:
Pseudo-first-order kinetics equation: ln (qe-qt)=lnqe-k1t
Pseudo-second order kinetic equation:
As shown in fig. 6, the adsorbance of FMC, FMH, FMD increase sharply in initial 3 hours, reach saturated extent of adsorption
90% or more.As time increases, since adsorbent surface can use the limitation of adsorption site, adsorbance starts to slow down.Finally,
The adsorption capacity of these adsorbents reached adsorption equilibrium in 10 hours.In order to make it that equilibrium adsorption capacity, Wo Menxuan be fully achieved
Select the 12 hours reaction time as further experiment work.From fig. 5, it can be seen that saturated adsorption capacity (the 269.7mg/ of FMC
G) it is greater than FMH (209.9mg/g) and FMD (168.8mg/g).The possible reason is these adsorbents have different absorption affine
Power.In order to study the adsorption mechanism and potential rate control method that phosphate removes, pseudo-first-order and pseudo-second order kinetic are used
Model describes magnetic iron-based MOF to Phosphate Adsorption process.As shown in table 2, kinetic parameter and related coefficient (R2) provide
The kinetic parameter that fitting experimental data obtains.Table 2 lists quasi- first order modeling ginseng related to quasi- second-order dynamic model
Several numerical value.When being 50mg/L for initial phosphate concn, it is (related that experimental data is preferably fitted with quasi- second order rate model
The related coefficient for the pseudo-first-order kinetic model that coefficient is higher than).In addition, and FMC, FMH, FMD (table 2) Phosphate Adsorption standard
First order dynamic model is compared, the adsorption capacity q that pseudo-second order kinetic model calculateseWith experiment value qexpMore match.The above results
Show that the phosphate of magnetic MOF absorption meets pseudo-second order kinetic model.Pseudo-second order kinetic model shows phosphate and FMC,
Chemisorption has occurred between FMH, FMD nano particle, it is related to FMC, FMH, the electronics between FMD nanoparticle and phosphate
Chemical bond power between shared or exchange.
The dynamics relevant parameter of 2 Phosphate Adsorption of table
3.FT-IR spectrum and xps energy spectrum
Fig. 8 is the infrared spectrogram of the FMC of embodiment 1, and display MC and FMC peak shape is essentially identical, it may be possible to because
Fe3O4Peak position it is Chong Die with MC.FT-IR before absorption statistics indicate that, about 2500-3333cm-1Band correspond to OH base
The stretching vibration of group.In addition, 1720cm-1The peak at place is attributed to the bonding of the C=O in carboxylate, 1382cm-1The peak at place comes from C-C
Vibration mode.And in 769cm-1The peak at place is the C-H vibration in phenyl ring.About 800-1159cm-1Band correspond to Fe-
The stretching vibration of OH group.The 441-666cm observed in the sample-1Band be due to caused by iron oxygen stretching vibration.
FTIR data after absorption, which are shown, has identical dominant spectral band with before absorption.In FT-IR data especially after absorption,
It was found that corresponding to P-O vibrates (555cm-1) peak and correspond to P-O-Fe vibrate (1050cm-1) peak, it was demonstrated that phosphate by from
Son successfully adsorbs, and forms interior ball compound by-OH base exchange on P and FMC and forms.
Fig. 9 is the XPS photoelectron spectroscopy figure of the FMC of embodiment 1, be can be seen that in Fig. 9 (a), the XPS energy of the FMC before absorption
Spectrum shows there are Fe, O, N and C element, and then more P elements after adsorbing, it was demonstrated that adsorbent successfully adsorbs phosphorus.Fig. 9 (b)
In, O 1s spectrum can be divided into positioned at 531.7,532.2,532.7eV 3 peaks before absorption, represent Fe-O-Fe, Fe-
OH, O-C=O, and after Phosphate Adsorption, spectrum is made of five peaks, respectively O-C=O (532.7eV), P-OH
(532.0eV), Fe-O-Fe (530.7eV), Fe-OP (531.3eV) and-OH (530.3eV).In these data confirm thats FMC
High-affinity of the Fe-OH group to phosphoric acid molecules.
4. the influence of salinity and humic acid
When studying influence of the salinity to absorption, we have prepared NaCl, the NaNO often contained in water body3And Na2SO4Deng 3
The phosphate solution of the 50ml 50ppm of kind of salt, salinity are respectively 0,10ppm, 20ppm, 50ppm, 100ppm, then plus
Enter 2mg FMC adsorbent, shaking flask is put into constant temperature oscillator with reaction condition 180rpm, 25 DEG C of oscillation 12h, is carried out after filtering
Measurement, calculates adsorbance.It is similar to above-mentioned experiment condition when probing into the influence experiment of the humic acid often contained in water body, only
It is to change humic acid concentration from 0 to 40mg/L, 2mg adsorbent is added to later the phosphate of the 50ml 50ppm containing humic acid
Solution reacts 12h in constant temperature oscillator, and filtering measures its absorbance after the completion of absorption, and adsorbance is calculated.As Figure 10 can
To find out, Cl-, SO4 2-And NO3 -There is inappreciable influence to adsorption capacity.These show that adsorbent has phosphate removal
It is highly selective, there is very strong anti-interference ability.As shown in figure 11, humic acid adsorbs phosphatic process substantially without shadow to FMC
Ring, show we prepare material can be stable in water body adsorb.
The influence of 5.pH and absorbent concentration
In order to probe into pH to the influence in absorption phosphate system, we use 0.1mol/L NaOH or 0.1mol/L HCl
The pH of 50ppm 50ml phosphate solution is adjusted from 3 to 10, is added in the 100mL erlenmeyer of 2mg adsorbent FMC, so
These shaking flasks are put into constant temperature oscillator with revolving speed 180rpm afterwards, 25 DEG C of reactions of temperature carry out 12h, pass through syringe mistake later
After filter, analysis is carried out to the solution of different pH and measures its absorbance, calculates its adsorbance at different pH.As shown in figure 12,
FMC increases to pH=7 from pH=3 to Phosphate Adsorption amount, then as pH value increase and reduce.Meanwhile FMH and FMD exist
There is optimal adsorption ability when pH=8.When pH is neutrality about 6-8, adsorbance is relatively high.Within the scope of entire pH we
Adsorbance 100mg/g it is described above we adsorbent wide pH applicability.
It probes into influence experiment of the absorbent concentration to Phosphate Sorption, it is 7 that we, which keep pH constant, and control adsorbent FMC is dense
Degree is from 0.02g/L to 1.0g/L, and with revolving speed 180rpm in constant temperature oscillator, 25 DEG C of reactions of temperature carry out 12h, after filtering
Ultra-violet analysis measurement is carried out to the phosphorus solution after the absorption of different absorbent concentrations, obtains adsorbance result.As shown in figure 13, when
When MOF dosage increases to 1.0g from 0.02g/L, adsorbance is reduced to 38.14mg/L from 296.19mg/L, causes such case
The reason is that adsorbent surface active site is fully utilized in low dosage FMC.When phosphatic amount is enough, the absorption of adsorbent
Site all exposures, then more rapidly can more effectively adsorb, therefore adsorption capacity is high.On the other hand, work as quantity of sorbent
When enough compared with phosphate, and many adsorption sites are not fully utilized, and adsorption capacity is caused to reduce.
6. recycling
Inventor also carries out recycling research to magnetic metal organic framework materials of the present invention, prepared by embodiment 1
It is as follows that magnetic MOF carries out regeneration method after use:
The adsorbent deionized water used after Phosphate Adsorption, ethyl alcohol and sodium hydroxide washing.Then by regenerated MOF
Adsorbent is for regenerating up to five circulations to test its recycling rate of waterused.In this work, alkaline scrubbing media is for inhaling
The FMC for adsorbing upper phosphorus is distributed in the 0.5mol/L NaOH solution of 100mL and is ultrasonically treated 30 minutes, then by attached dose of regeneration
It is vibrated 6 hours in constant temperature vibration device.Then, reach its pH with deionized water and ethanol washing adsorbent to be neutralized
Neutrality, and it is 6 hours dry in 60 DEG C of baking oven.In our work, this absorption and desorption process have been carried out five times, with
Assess the reusability of FMC.
It is the molten of 50ppm 50mL by adding by 0.04mg/L concentration into phosphate concentration for multiple regenerated magnetism MOF
It is adsorbed in liquid, the removal rate of phosphate radical is as shown in figure 14, it can be seen that, magnetic MOF of the invention makes by 5 repetitions
With rear, 80% is still higher than to the removal of phosphate radical.
Claims (10)
1. the preparation method of the magnetic organic metal framework material of a kind of dephosphorization, with Fe3O4, soluble trivalent iron salt and mesitylene
Formic acid uses solvent structure；The Fe3O4, soluble trivalent iron salt and Trimesic acid the mass ratio of the material be 2-4: 2-4
∶1-2。
2. preparation method according to claim 1, which is characterized in that the solvent in the solvent-thermal method includes water, ethyl alcohol
Or one of DMF (n,N-Dimethylformamide) or a variety of, more preferably, the solvent is water, ethyl alcohol or DMF.
3. preparation method according to claim 1, which is characterized in that the solubility trivalent iron salt FeCl3、Fe2(SO4)3、
Fe(NO3)3And its one of crystalline hydrate or a variety of.
4. preparation method according to claim 1-3, which is characterized in that the specific steps of the preparation method
Are as follows:
(1) Fe is taken3O4, soluble trivalent iron salt, Trimesic acid and solvent be placed in closed container, reaction system is warming up to
140-180 DEG C of reaction 12-18h；
(2) after the reaction was completed, reaction system is cooled to room temperature, and washing is dried to obtain magnetic organic metal framework material of the invention
Material.
5. the preparation method according to claim 4, which is characterized in that the Fe3O4、Fe(NO3)3With the object of Trimesic acid
The amount ratio of matter is 3: 3: 1；Preferably, in the step (1), reaction temperature is 160 DEG C.
6. the preparation method according to claim 4, which is characterized in that the parent material of Trimesic acid in reaction system
Measuring concentration is 20-40mmol/L, and more preferably, in reaction system, the amount concentration of the parent material of Trimesic acid is
33.3mmol/L。
7. preparation method according to claim 1-6, which is characterized in that the Fe3O4The preparation method comprises the following steps: to
The mixed solution and dripping ammonium hydroxide reaction of soluble divalent iron salt and soluble trivalent iron salt, stands after the reaction was completed, washs, is dry
It is dry to obtain Fe3O4；Preferably, the divalent iron salt is selected from FeCl2、FeSO4And its one of crystalline hydrate or a variety of.
8. preparation method according to claim 7, which is characterized in that the Fe3O4Preparation method specific steps are as follows:
Under stirring condition, trivalent iron salt is added into divalent iron salt solution, is uniformly mixed to obtain mixed solution, under ultrasound condition,
It is reacted to mixed solution and dripping ammonium hydroxide, stands, washs after the reaction was completed, dry Fe3O4；Preferably, the divalent iron salt and
The mass ratio of the material of trivalent iron salt is 2: 1, and the substance withdrawl syndrome of the ammonium hydroxide is 3.5mol/L.
9. a kind of magnetism organic metal framework material, which is characterized in that the magnetism organic metal framework material is by claim
The described in any item preparation method preparations of 1-8.
10. a kind of dephosphorization adsorbent, which is characterized in that the dephosphorization adsorbent includes the organic gold of magnetism as claimed in claim 9
Belong to frame material.
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| CN110523395A (en) * | 2019-09-06 | 2019-12-03 | 南京师范大学 | A kind of load MOF resin compounded adsorbent and its preparation method and application |
| WO2021007988A1 (en) * | 2019-07-12 | 2021-01-21 | 华南理工大学 | Iron-oxide-doped iron metal organic framework, green macro preparation method therefor and application thereof |
| CN112316906A (en) * | 2020-09-21 | 2021-02-05 | 中国建筑第二工程局有限公司 | Preparation method of ferromagnetic amino-modified lanthanide metal organic framework material and application of material in adsorption and dephosphorization |
| CN114405475A (en) * | 2021-12-30 | 2022-04-29 | 广东省科学院化工研究所 | Adsorbing material and preparation method and application thereof |
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| CN112316906B (en) * | 2020-09-21 | 2023-08-11 | 中国建筑第二工程局有限公司 | Preparation method of ferromagnetic amino-modified lanthanide metal organic framework material and application of ferromagnetic amino-modified lanthanide metal organic framework material in adsorption dephosphorization |
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