CN106957438A - A kind of preparation of modified MIL 53 (Fe) metal organic framework and its method for organic wastewater treatment through persulfate activation - Google Patents
A kind of preparation of modified MIL 53 (Fe) metal organic framework and its method for organic wastewater treatment through persulfate activation Download PDFInfo
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Abstract
The invention discloses a kind of preparation of modified MIL 53 (Fe) metal organic framework and its method for organic wastewater treatment through persulfate activation.Compared to unmodified MIL 53 (Fe), modification MIL 53 (Fe) metal organic framework that the present invention is synthesized contains more ferrous active metal centres, it is used as active site, effective contact of metal-organic framework materials and persulfate can be strengthened and the potentiometric titrations with strong oxidizing property are produced, so as to effectively remove the Recalcitrant chemicals in waste water.The stability of material of the present invention is higher, after the reaction of catalytic activation persulfate, and higher catalytic activity is maintained to after can keeping the stability of crystalline structure, and repetitive cycling utilization.Organic wastewater is handled using the method for the present invention, easy to operate with environment-friendly, with low cost, catalyst activity is high and the advantages of good recycling.In addition this method applies also for the processing of all kinds of organic wastewaters.
Description
Technical field
The invention belongs to technical field of water pollution control, and in particular to a kind of modified MIL-53 (Fe) metal organic framework
Preparation and its method for organic wastewater treatment through persulfate activation.
Background technology
In recent years, potentiometric titrations (SO is produced using activating persulfate (PS, persulfate)4 -) senior oxygen
Change technology (Advanced Oxidation Technologies, AOTs) processing organic wastewater with difficult degradation thereby is wastewater processing technology
The study hotspot in field.Compared to traditional Fenton (Fenton) method, PS oxidation technologies need not can be produced under 3-5 acid condition
Raw SO4 -And realize effective degraded to pollutant.And SO4 -Standard oxidationreduction potential (E0=+2.5~+3.1v) ratio
Hydroxyl radical free radical (OH) (E that Fenton methods are produced0=+1.9~+2.7v) it is high, stability and half-life period (about 4s) are longer, with
Naturally occurring background organic matter reactivity is lower in waste water, therefore in oxidative degradation pollutant with higher efficiency.Together
When, and unlike OH, SO4 -Hydrogen, C=C additions can be not only taken out by C-H to aoxidize pollutant, and more incline
To in winning the electronics on pollutant phenyl ring by electron transfer, make its open loop chain rupture, be converted into small molecule hydrocarbon, go forward side by side one
Step is oxidized to CO2And H2O, therefore based on SO4 -PS advanced oxidation processes processing contaminant molecule in the difficult degradation containing phenyl ring
Organic wastewater has more advantage.
Iron catalytic activation is the most frequently used activation methods of PS, and conventional iron catalyst is broadly divided into ferrous or complexing Asia at present
Iron, Zero-valent Iron, ferriferous oxide, load typed iron catalyst etc..But above-mentioned traditional iron catalyst all has certain defect：(1)
During using ferrous iron activation PS, a large amount of deliquescent Fe in system2+Moment excessive active site can be provided, make SO4 -Release
Put excessive velocities, it is difficult to which contaminated thing makes full use of, and excessive Fe2+SO can be quenched with target contaminant competition4 -, reduction
The ability of PS system oxidative degradation pollutants；(2) complexing agent (such as EDTA, EDDS, oxalic acid, citric acid) is used though being complexed ferrous
The Fe dissociated in solution can be so controlled to a certain extent2+Concentration, but complexing agent is generally organic compound, and its introducing can make
Into secondary pollution, increase the COD of waste water, and SO can be competed with pollutant4 -·；(2) using Zero-valent Iron (ZVI) although activation PS energy
Enough slow down Fe2+Release raising system oxidation efficiency, but ZVI in itself have strong reducing property, connect with the PS with strong oxidizing property
The rapid active site that excess is provided is remained able to when tactile.And during activation PS, ZVI surfaces can be formed such as
Fe3O4、α-FeOOH、α-Fe2O3With the corrosion layer of the oxide such as FeO composition, covering part active site and make ZVI surfaces
Passivation, greatly suppresses the continuation that ZVI activates PS；(3) Fe is used3O4、Fe2O3Although or the catalysis such as loading type iron PS can
Reduce the generation of iron hydroxide sludge, but to show catalytic cycle again during activation PS long for such catalyst, recycles
Property difference the problems such as.
Metal organic framework (Metal Organic Frameworks, MOFs) be a class by metal center ion with it is organic
Bridging ligand passes through the novel hybride materials that are self-assembly of.By selecting suitable raw material and synthesis condition, you can generation tool
The orderly crystal in activated centre needed for having catalytic reaction, therefore MOFs has the advantages that structural controllability.MOFs also has big
Specific surface area, ensure that the fully dispersed property of active site in catalytic reaction process.In addition, MOFs is how high in high temperature
Synthesized under conditions of pressure so that MOFs has a higher chemical stability, therefore relatively conventional catalyst, MOFs highly acid,
The stability of holding self structure is easier in the reaction system of strong oxidizing property.Thus MOFs has as PS new catalyst
Wide research and application prospect.At present, researchs of the MOFs in AOTs fields has achieved preliminary progress.For example, MIL-88A
It is successfully applied to activate PS oxidative degradation dye, rhodamine B and gold orange-G (RSC Advances.2015,5:32520-32530；
RSC Advances.2016,6:112502-112511)；MIL-100(Fe)、[Cu2(btec)(btx)1.5]nIt is proved to be effective
Class Fenton's reaction catalyst, H can be activated2O2Decompose and produce OH (Journal of Molecular Catalysis
A:Chemical.2015,400:81-89；CrystEngComm.2012,14:4210-4216)；And research discovery ZIF-67,
Co3(BTC)2·12H2O is catalyst (the Journal of of the efficient single peroxosulphuric hydrogen salt (PMS) of heterogeneous catalysis activation
the Taiwan Institute of Chemical Engineers.2015,53:40-45；Journal of Hazardous
Materials.2016,318:154-163).Start within 2014, the author team has carried out a series of research that MOFs activate PS,
It was found that MIL-53 (Fe) is effective heterogeneous PS catalyst, MIL-53 (Fe) activates PS oxidative degradation OG in optimal conditions,
React after 120min, OG mineralization rates can reach 95%, and repeat back to after 5 cycles, and system still has very high oxidation
Degradation capability (Catalysis Science＆Technology.2017,7:1129-1140).But the system consumption PS amounts compared with
It is many, illustrate that MIL-53 (Fe) catalysis PS efficiency is still not high enough.Due to MOFs synthesis condition have to its catalytic activity it is larger
Influence, therefore change MIL-53 (Fe) synthesis condition, improve its be catalyzed PS activity be necessary.There are some researches show,
When synthesizing MIL-53 (Fe), using FeCl2Instead of FeCl3It is used as precursor salt solution, the MIL-53 (Fe) of synthesis iron activity
Contain substantial amounts of+divalent iron in center, it is thus possible to effectively improve it and be catalyzed H2O2Activity and promote it from conventional structure to Fe (BDC)
Transformation (the Dalton Transactions.2016,45 of (DMF, F) type structure:7952-7959).
In view of discussed above, the invention discloses the synthesis of a kind of modified MIL-53 (Fe) metal organic framework and should
Material is used for the method for heterogeneous organic wastewater treatment through persulfate activation.Organic wastewater is handled using this method, with operation
Simplicity, with low cost, catalytic activity is high, the advantages of catalyst recycling is good.
The content of the invention
It is not enough, dispersed it is an object of the invention to solve activated centre site during conventional iron catalyst activation PS
There is provided a kind of modified MIL-53 (Fe) so as to technical problems such as circulating and recovering differences for difference, length reaction time, catalyst easy in inactivation
The preparation of metal organic framework and its method for organic wastewater treatment through persulfate activation.
The present invention is achieved through the following technical solutions.
A kind of preparation method of modified MIL-53 (Fe) metal organic framework, comprises the following steps：
(1) by terephthalic acid (TPA) (1,4-BDC), Iron dichloride tetrahydrate (FeCl2·4H2) and N,N-dimethylformamide O
(DMF) it is well mixed, obtains mixed liquor；
(2) mixed liquor is placed in heating response in hydrothermal synthesis reaction kettle；
(3) after the completion of reacting, room temperature is naturally cooled to, is washed, dries, obtains being modified the organic bone of MIL-53 (Fe) metal
Frame.
It is preferred that, the mol ratio of terephthalic acid (TPA) and Iron dichloride tetrahydrate described in step (1) is 1:1；It is described to benzene
The mol ratio of dioctyl phthalate and N,N-dimethylformamide is 1:52~1:65.
It is preferred that, incorporation time described in step (1) is 20min.
It is preferred that, the temperature of heating response described in step (2) is 150~170 DEG C, and the time is 5~72h.
It is preferred that, washing described in step (3) is that solid successively is cleaned multiple times using a certain amount of methanol and deionized water
Particle.
It is preferred that, it is dry a few hours at 65 DEG C to be dried described in step (3).
A kind of modified MIL-53 (Fe) metal organic framework as made from above-described preparation method.
A kind of application of above-described modified MIL-53 (Fe) metal organic frameworks in processing organic wastewater.
It is preferred that, the application comprises the following steps：
(1) COD of pending organic wastewater is determinedCrValue and pH value；
(2) persulfate (PS) and modified MIL-53 (Fe) metal organic framework, fully shaking are added into organic wastewater
Or stirring carries out wastewater treatment reaction, persulfate is set to decompose the potentiometric titrations (SO for producing strong oxidizing property4 -), to organic
Waste water carries out oxidative degradation processing.
It is further preferred that the COD of step (1) described organic wastewaterCrIt is worth for 120~300mg/L；PH value is 2~9.
It is further preferred that persulfate described in step (2) is sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate.
It is further preferred that PS (mg/L) and waste water COD described in step (2)Cr(mg/L) mass concentration ratio for (30~
50)/1。
It is further preferred that the dosage (mg/L) of modified MIL-53 (Fe) metal organic framework described in step (2) with
Waste water CODCr(mg/L) mass concentration ratio is (2.5~12.5)/1.
It is further preferred that consumption of step (2) modified MIL-53 (Fe) metal organic framework in organic wastewater
For 0.3~1.5g/L, consumption of the persulfate in organic wastewater is 4.0~7.6g/L, it is further preferred that step (2) institute
The time for stating reaction is 1.0~2.5h.The dosage of modified MIL-53 (Fe) metal organic frameworks and PS is useless according to processing
The COD of waterCrDepending on.Organic wastewater CODCrFor 120~300mg/L best results, the organic bone of MIL-53 (Fe) metal is now modified
The dosage of frame is preferably 0.3~1.5g/L, and PS dosages are preferably 4.0~7.6g/L, and the reaction time is preferably 1.0~
2.5h, CODCrClearance can reach 85~90%.
The pH of modified MIL-53 (Fe) the metal organic framework organic wastewater treatment through persulfate activation method adapts to model
Enclosing is：PH=2~9.Preferably, during pH≤3, the removal effect of waste water COD is optimal.
Relative to prior art, the invention has the advantages that：
(1) tradition MIL-53 (Fe), modification MIL-53 (Fe) metal organic framework of the invention are compared.Iron activated centre+2
Is increased before the relative amount of valency iron is more unmodified, adds more catalysis PS avtive spots, on certain level its
Catalysis PS activity is improved, therefore the degradation efficiency of pollutant is improved, so that the treatment effect of organic wastewater is optimized.
(2) present invention is using modified MIL-53 (Fe) metal organic framework organic wastewater treatment through persulfate activation, operation
Simplicity, it is with low cost.And modified MIL-53 (Fe) metal organic frameworks can keep crystal formation knot before and after catalytic activation PS reactions
The stability of structure, compared to conventional iron catalytic activation methods such as ferrous iron activation, Zero-valent Iron activation, catalyst recycling is strong.
Brief description of the drawings
Fig. 1 is the fine spectrograms of x-ray photoelectron power spectrum (XPS) Fe2p of modified MIL-53 (Fe) metal organic framework.
Fig. 2 is X-ray diffraction (XRD) spectrogram of modified MIL-53 (Fe) metal organic framework.
Fig. 3 is Fourier transform infrared (FTIR) spectrogram of modified MIL-53 (Fe) metal organic framework.
Embodiment
In order to be better understood from content of the present invention, the present invention is made furtherly with reference to embodiment and accompanying drawing
It is bright, but embodiments of the present invention are not limited to this, the scope of protection of present invention is also not limited to what embodiment was represented
Scope.
Embodiment 1
The preparation and its processing gold orange-G simulation of catalytic activation persulfate of modified MIL-53 (Fe) metal organic framework are useless
Water, concrete operation step is as follows：
(1) preparation method 1 of modified MIL-53 (Fe) metal organic framework：0.995g (5mmol) FeCl is weighed respectively2·
4H2O and 0.831g (5mmol) Isosorbide-5-Nitraes-BDC are poured into 25mL DMF, and stirring 20min is with well mixed.Mixed liquor is poured into
In the reactor of 100mL polytetrafluoroethyllining linings, it is placed in and is previously heated in 150 DEG C of electric heating constant-temperature blowing drying box.After 5h
Take out reactor and naturally cool to room temperature.Filtering or centrifugation make separation of solid and liquid, and successively solid using methanol and deionized water cleaning
Body.Above-mentioned solid is finally placed in drying to obtain in 65 DEG C of baking oven and is modified MIL-53 (Fe) metal organic framework.
(2) preparation method 2 of modified MIL-53 (Fe) metal organic framework：It is polytetrafluoroethyl-ne with the difference of method 1
The reactor of alkene liner, is placed in and is previously heated in 150 DEG C of electric heating constant-temperature blowing drying box.Reactor is taken out after 72h natural
It is cooled to room temperature.Other steps are consistent with preparation method 1.
(3) preparation method 3 of modified MIL-53 (Fe) metal organic framework：It is with the difference of method 1, in method 3
FeCl2·4H2O and Isosorbide-5-Nitrae-BDC consumption are respectively 0.796g (4mmol) and 0.670g (4mmol), other steps and preparation side
Method 1 is consistent.
(4) preparation method 4 of modified MIL-53 (Fe) metal organic framework：It is with the difference of method 1, in method 4
FeCl2·4H2O and Isosorbide-5-Nitrae-BDC consumption are respectively 0.796g (4mmol) and 0.670g (4mmol), and catalyst generated time
For 72h, other steps are consistent with preparation method 1.
(5) preparation method 5 of modified MIL-53 (Fe) metal organic framework：It is with the difference of method 1, in method 5
Reactor is placed in being previously heated in 160 DEG C of electric heating constant-temperature blowing drying box.
(6) preparation method 6 of modified MIL-53 (Fe) metal organic framework：It is with the difference of method 1, in method 6
Reactor is placed in being previously heated in 170 DEG C of electric heating constant-temperature blowing drying box.
(7) MIL-53 (Fe) preparation method：It is that presoma molysite is by 0.995g (5mmol) with the difference of method 1
FeCl2·4H2O is changed to 1.350g (5mmol) FeCl3·6H2O, other steps are consistent with preparation method 1.
(8) degraded of organic wastewater：Using 250mL conical flasks as reaction bulb, COD is preparedCrFor 120mg/L gold orange-G
(OG) waste water from dyestuff, does not adjust wastewater pH, sets six treatment groups：Add after 7.6g/L sodium peroxydisulfates, respectively to four groups of reactions
1.0g/L is added in bottle catalyst is made using modification MIL-53 (Fe) metal organic framework of the preparation of the above method 1,2,3,4,5,6
(be respectively treatment group 1,2,3,4,5,6), is sufficiently stirred for being reacted at 25 DEG C, reaction 20min, 40min, 60min,
It is separately sampled and determine waste water COD during 90min and 120minCr, the results are shown in Table 1.
Table 1
The result of table 1 shows that modification MIL-53 (Fe) metal organic framework prepared using 6 kinds of different preparation conditions is activated
Persulfate can the efficient oxidation degraded gold orange-G waste water, reaction 1h after, CODCrClearance can reach 54%~
After 72%, reaction 2h, CODCrClearance can reach 86%~90%.The modification that this explanation is synthesized using the inventive method
MIL-53 (Fe) metal organic framework all has higher catalytic activity, but the catalyst activity that distinct methods are prepared
Difference.
Embodiment 2
The preparation method 1 of modified MIL-53 (Fe) metal organic framework is the material for preparing of condition to urge using in embodiment 1
Agent, sodium peroxydisulfate is oxidant, the initial COD of simulation gold orange-G waste waterCrFor 120mg/L, four treatment groups are set, are respectively：
(1) add 1.0g/L and be modified MIL-53 (Fe) metal organic framework -7.6g/L sodium peroxydisulfates-gold orange-G waste water；(2) add
1.0g/L is modified MIL-53 (Fe) metal organic framework-gold orange-G waste water；(3) 7.6g/L sodium peroxydisulfates-gold orange-G waste water is added；
(4) the unmodified MIL-53 of 1.0g/L (Fe) -7.6g/L sodium peroxydisulfates-gold orange-G waste water is added.Take four 250mL conical flasks
As reaction bulb, the solution set by above three treatment group is added into reaction bulb respectively, is sufficiently stirred for carrying out at 25 DEG C
Reaction, it is separately sampled and determine waste water COD during reaction 20min, 40min, 60min, 90min and 120minCr, the results are shown in Table 2.
Table 2
The result of table 2 shows, modified MIL-53 (Fe) metal organic frameworks are used alone and sodium peroxydisulfate system is used alone
All fail to carry out gold orange-G waste water effective oxidative degradation, and be modified MIL-53 (Fe) metal organic framework activation sodium peroxydisulfate
COD of the system to waste waterCrRemoval effect significantly, is reacted after 120min, CODCrClearance reaches 90.1%.The modified MIL- of contrast
53 (Fe) metal organic frameworks and unmodified MIL-53 (Fe), the former activates useless during sodium peroxydisulfate oxidative degradation gold orange-G waste water
Water CODCrRemoval efficiency is significantly improved, and illustrates that the present invention can fast and effectively handle organic wastewater.
Embodiment 3
Using 250mL conical flasks as reaction bulb, COD is preparedCrFor 120mg/L gold orange-G (OG) waste water from dyestuff, to implement
The preparation method 1 of modified MIL-53 (Fe) metal organic framework is that material prepared by condition is catalyst in example 1, and sodium peroxydisulfate is
Oxidant, does not adjust wastewater pH, sets five treatment groups：Add after 7.6g/L sodium peroxydisulfates, add respectively into five groups of reaction bulbs
Enter catalyst 0.1g/L (treatment group 1), 0.3g/L (treatment group 2), 0.5g/L (treatment group 3), 1.0g/L (treatment group 4), 1.5g/
L (treatment group 5), is sufficiently stirred for being reacted at 25 DEG C, distinguishes during reaction 20min, 40min, 60min, 90min and 150min
Sample and determine waste water CODCr, the results are shown in Table 3.
Table 3
The result of table 3 shows that modified MIL-53 (Fe) metal organic framework dosages are to activation sodium peroxydisulfate oxidative degradation gold
Orange G waste water has a certain impact, waste water CODCrRemoval rate increases with the increase of catalyst amountses：Catalyst amountses
During for 0.5g/L, after reaction 2.5h, CODCrClearance reaches 90.5%；When dosage is 1.0g/L, after reaction 90min, CODCr
Clearance reaches 88.2%；When continuing to increase dosage to 1.5g/L, only 1.5h, COD need to be reactedCrClearance is that can reach
90.1%.Illustrate in the range of 0.1g/L~1.5g/L, the dosage of modified MIL-53 (Fe) metal organic framework of control
Control the speed and waste water COD of oxidative degradationCrClearance.Therefore, can be initial according to waste water during practical application
CODCrSize and CODCrThe requirement of clearance carrys out the dosage of selecting catalyst, and processing cost is at utmost reduced to realize
Purpose.
Embodiment 4
Using 250mL conical flasks as reaction bulb, COD is preparedCrFor 120mg/L gold orange-G (OG) waste water from dyestuff, to implement
The preparation method 1 of modified MIL-53 (Fe) metal organic framework is that material prepared by condition is catalyst in example 1, and sodium peroxydisulfate is
Oxidant, does not adjust wastewater pH, sets six treatment groups：Respectively into six groups of reaction bulbs add 1.9g/L (treatment group 1),
3.8g/L (treatment group 2), 5.7g/L (treatment group 3), 7.6g/L (treatment group 4), 9.5g/L (treatment group 5), 11.4g/L (processing
6) sodium peroxydisulfate is organized, 1.0g/L is then separately added into all treatment groups and is modified MIL-53 (Fe) metal organic framework, 25
It is sufficiently stirred for being reacted at DEG C, it is separately sampled and determine waste water during reaction 20min, 40min, 60min, 90min and 150min
CODCr, the results are shown in Table 4.
Table 4
The result of table 4 shows that the dosage of sodium peroxydisulfate has a certain impact to the system oxidative degradation gold orange-G waste water.PS
Dosage is in 1.9~7.6g/L, waste water CODCrRemoval rate increases with the increase of PS dosages, but continues to increase PS's
Dosage, waste water CODCrRemoval rate reduces on the contrary.Illustrate that PS is excessive, excessive PS when PS consumptions are more than 7.6g/L
The free radical produced in system is caused mutually to be quenched, so as to reduce free-radical oxidation CODCrEfficiency.Therefore, PS dosages are excellent
Elect 4.0~7.6g/L as.
Embodiment 5
Using 250mL conical flasks as reaction bulb, COD is preparedCrFor 120mg/L gold orange-G (OG) waste water from dyestuff, to implement
The preparation method 1 of modified MIL-53 (Fe) metal organic framework is that material prepared by condition is catalyst in example 1, and sodium peroxydisulfate is
Oxidant, sets five treatment groups：Wherein, reaction starts to add 7.6g/L sodium peroxydisulfates in forward reaction bottle, then respectively will
The pH of waste water is adjusted to 2.43 (treatment groups 1), 3.07 (treatment groups 2), 4.94 (treatment groups 3), 6.99 (treatment groups 4), 9.47 (places
Reason group 5), it is sufficiently stirred for being reacted at 25 DEG C, 1.0g/L is then added into all treatment groups and is modified MIL-53 (Fe) gold
Belong to organic backbone, it is separately sampled and determine during reaction 20min, 40min, 60min, 90min, 150min, 210min and 330min
Waste water CODCr, the results are shown in Table 5.
Table 5
As shown in Table 5, during pH >=3, COD of the system to waste waterCrWhen removal efficiency starts reduction, pH=5 or so, reaction
After 330min, CODCrClearance is 45.2%；During pH=7 or so, after reaction 330min, CODCrClearance is 30.9%；PH=
When 9, after reaction 330min, CODCrClearance only reaches 18.6%.Show that the system still has to waste water in pH≤9 certain
Oxidative degradation ability, but system oxidative degradation ability in pH≤3 best results.
Embodiment 6
Using 250mL conical flasks as reaction bulb, COD is preparedCrFor 120mg/L gold orange-G (OG) waste water from dyestuff, to reaction
Modification MIL-53 (Fe) metal organic framework that 0.5g/L is prepared with preparation method 1 in embodiment 1 for condition is added in bottle, then
Add 5.7g/L sodium peroxydisulfates, be sufficiently stirred for being reacted at 25 DEG C, reaction 20min, 40min, 60min, 90min,
It is separately sampled and determine waste water COD during 150minCr；After reaction terminates, catalyst is reclaimed, is dried, and put into identical reactant
Reused in system, so circulation four times, the results are shown in Table 6.
Table 6
As shown in Table 6：Modified MIL-53 (Fe) metal organic framework shows relatively stable repetitive cycling and uses spy
Property, when recycling the 4th cycle, using activation of catalyst PS degraded gold orange-G waste water, react after 150min, waste water
CODCrClearance is still up to 80%, and the reusable edible of modified MIL-53 (Fe) metal organic framework of this explanation is preferable.
Experiment test explanation：
Catalyst elements are constituted and each element valence state is characterized：
XPS signs are carried out to modified MIL-53 (Fe) metal organic framework, swarming is carried out to Fe2p spectrograms, as a result such as Fig. 1
It is shown.The ferro element component presentation+divalent of modified MIL-53 (Fe) metal organic framework and the mixed valence of+trivalent, according to fitting
As a result, the percentage composition of each valence state is：Fe2+/Fe3+=68.5/31.5=2.17.In catalytic activation PS courses of reaction, Fe2 +And Fe3+Come-at-able effective active site is can serve as, compared to unmodified MIL-53 (Fe) (Fe2+/Fe3+=
1.76)(Catalysis Science&Technology.2017,7:1129-1140), the Fe that modified material contains2+Group
Divide content higher, due to Fe2+It is maximally effective active specy during activation PS, therefore modified catalyst activity is stronger.
Catalyst structure is characterized：
To being that modification MIL-53 (Fe) metal organic framework prepared by condition is carried out respectively with preparation method 1 in embodiment 1
XRD and FTIR is characterized, as a result as shown in Figure 2 and Figure 3.As shown in Figure 2, according to a process for preparing modification MIL-53 (Fe) gold
The XRD spectra of category organic backbone is a 9.1 °, 10.6 °, 12.5 °, 17.5 °, 18.2 °, 19.1 °, 25.3 ° and 27.2 ° left sides in 2 θ values
It is right to contain characteristic peak respectively, wherein compared to unmodified preceding MIL-53 (Fe), 10.6 ° or so of peak is a new characteristic peak,
Documents, the appearance explanation at this new feature peak is using modification MIL-53 (Fe) the crystalline form knot of ferrous salt as precursor synthesis
Structure is intended to change to Fe (BDC) (DMF, F) structure.Traditional MIL-53 can be different from by the position of characteristic peak
(Fe) metal-organic framework materials.Activate before and after PS reactions, obvious change does not occur for the quantity of characteristic peak and position, and explanation changes
Property MIL-53 (Fe) crystalline structure before and after catalysis PS reactions do not occur obvious change.
And analysis chart 3 is understood, modified MIL-53 (Fe) metal organic framework is in 1382cm-1、1534cm-1The peak of left and right is returned
Belong to benzene ring side chain-(- O-C-O-)-vibration peak, 1633cm-1The peak at place belongs to-C=O, 751cm-1And 1109cm-1Place is returned
Belong to the vibration peak and 1017cm of c h bond-1And 1152cm-1The spike at place belongs to the vibration peak of C-O keys, and unmodified
MIL-53 (Fe) FTIR compares, and modified MIL-53 (Fe) FTIR characteristic peak positions do not occur significantly to change
Become, and significant change does not all occur in the activation reacted characteristic peak quantity good positions of PS for it, shows the material organic ligand portion
Divide and do not destroyed significantly after catalysis PS reactions, above-mentioned conclusion explanation is steady as precursor synthesis structure using ferrous salt
Fixed metal-organic framework materials are feasible.
Above-described embodiment is not limited for the present invention preferably embodiment, but embodiments of the present invention by above-described embodiment
System, other it is any without departing from Spirit Essences and the change made under principle of the present invention, modification, replacement, combine, simplification, all should
For equivalent substitute mode, it is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified MIL-53 (Fe) metal organic framework, it is characterised in that comprise the following steps：
（1）Terephthalic acid (TPA), Iron dichloride tetrahydrate and DMF are well mixed, mixed liquor is obtained；
（2）Mixed liquor is placed in heating response in hydrothermal synthesis reaction kettle；
（3）After the completion of reaction, natural cooling is washed, and is dried, is obtained being modified MIL-53 (Fe) metal organic framework.
2. a kind of preparation method of modified MIL-53 (Fe) metal organic framework according to claim 1, it is characterised in that
Step（1）Described in terephthalic acid (TPA) and Iron dichloride tetrahydrate mol ratio be 1:1；Terephthalic acid (TPA) and N, the N- diformazan
The mol ratio of base formamide is 1:52~1:65.
3. a kind of preparation method of modified MIL-53 (Fe) metal organic framework according to claim 1, it is characterised in that
Step（2）Described in heating response temperature be 150 ~ 170 DEG C.
4. a kind of preparation method of modified MIL-53 (Fe) metal organic framework according to claim 1, it is characterised in that
Step（2）Described in heating response time be 5 ~ 72h.
5. a kind of modified MIL-53 (Fe) metal organic framework as made from the preparation method described in claim any one of 1-4.
6. a kind of modified MIL-53 (Fe) metal organic framework organic wastewater treatment through persulfate activation described in claim 5
Method, it is characterised in that comprise the following steps：
（1）Determine the COD of pending organic wastewaterCrValue and pH value；
（2）Add persulfate and modified MIL-53 (Fe) metal organic framework into organic wastewater, fully shaking or stir into
Row wastewater treatment is reacted, and persulfate is decomposed the potentiometric titrations for producing strong oxidizing property, oxidation drop is carried out to organic wastewater
Solution processing.
7. application according to claim 6, it is characterised in that step（1）The initial pH value of the organic wastewater is 2 ~ 9.
8. application according to claim 6, it is characterised in that step（2）The persulfate is sodium peroxydisulfate, persulfuric acid
Potassium or ammonium persulfate.
9. application according to claim 6, it is characterised in that step（2）The organic bone of modified MIL-53 (Fe) metal
Dosage of the frame in organic wastewater and organic wastewater CODCrThe ratio of value is（2.5~12.5）/1.
10. application according to claim 6, it is characterised in that step（2）Throwing of the persulfate in organic wastewater
Dosage and organic wastewater CODCrThe ratio of value is（30~50）/1.
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