CN105107467B - One kind utilizes preparation of rear modification MIL 101 (Cr) adsorbent and application thereof - Google Patents
One kind utilizes preparation of rear modification MIL 101 (Cr) adsorbent and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation using rear modification MIL 101 (Cr) material and its new application.The purposes be it as adsorbent selective removal Heavy Metals in Waters ion application.MIL 101 (Cr) compound adsorbent after modification being capable of the effective simultaneously heavy metal ion such as lead, mercury in selective removal water body.Its method and step is：（1）Hydro-thermal method prepares synthesis metallic framework（MOFs）Material MIL 101 (Cr) or the NH of MIL 1012(Cr);（2）Utilize the method for rear modification, by the success grafting of nitrogenous organic molecule on MIL 101 (Cr), MIL 101 (Cr) of the synthesis with amino or pyrimidine modification;（3）It is applied to the heavy metal ion such as lead, mercury in selective removal water body using (Cr) composites of MIL 101 that rear modification synthesizes as adsorbent.One kind of the present invention using rear modification MIL 101 (Cr) compound adsorbent can the heavy metal ion such as lead, mercury efficiently and in selective removal water body, widened the new opplication of MIL 101 (Cr) class material.
Description
Technical field
The invention belongs to the preparation field of Heavy Metals in Waters pollutant absorbent, and in particular to one kind is modified after utilizing to be changed
The property preparation of MIL-101 (Cr) adsorbent and its application of the heavy metal ion in selective removal water body.
Background technology
In today's society, the pollution that water body contains caused by heavy metal is quite serious, and pole is produced to environment and human health
Big harm.Heavy metal pollution has caused the great attention of countries in the world scientist, and the heavy metal effectively handled in water body is carved
Do not allow to delay.China's water body is also faced with the various problems such as heavy metal pollution.According to statistics, the lead of China's underground water, mercury pollution compare
Seriously, and many basins content of beary metal it is exceeded.These metals have great harm to human and livestock health, such as destroy protein
Structure, the metabolism for hindering nucleic acid etc..They may not only cause mutation or the missing of biological function, can also disturb dimension
Hold the synthesis of the necessary material of organism balance.Micro heavy metal is enriched with the presence of biological chain in human body, in mankind's body
Various illnesss will be produced when having gathered excessive heavy metal.Therefore the processing of heavy metal ion is also Environmental Protection in China industry in water
A big weight difficult point.
Metal-organic framework materials (metal-organic frameworks, MOFs), it is to utilize organic ligand and metal
A kind of class boiling for having much future of interionic metal-ligand complexing and the supermolecule microporous network structure that is self-assembly of
Stone (organic zeolite analog) material.This stephanoporate framework crystalline material, different metal ions and various rigid bridges can be passed through
Even organic ligand is complexed, and the metal-organic framework of different pore size is designed and synthesize, so that MOFs structure change
It is infinite, and such as-Br ,-NH can be taken on organic ligand2、-OC3H7Deng some functional modification groups so that MOFs
Microporous polymer can according to performance requirements such as catalytic reaction or absorption functionalization.Because it has structure diversity, larger
The features such as specific surface area and porosity, Modulatory character, the research and development of MOFs materials are concentrated mainly on point by very big concern
Sub- identification, gas storage, fluoroscopic examination, adsorbing separation, catalysis and biological medicine etc..
However, so far, it is also seldom to the report of Heavy Metals in Waters ionic adsorption on metal-organic framework materials
See.Ke et al. has metal unsaturation site using metal-organic framework materials HKUST-1, has synthesized sulfenyl functionalization
HKUST-1, and adsorbent is utilized it as, mercury ion [Ke, F, Qiu, L G, Yuan, Y P, et in adsorption treatment water
al. J. Hazard. Mater. 2011, 196, 36−43.].Experiment shows that HKUST-1 is basic to the mercury ion in water
There is no adsorption capacity, after HKUST-1 sulfenyl functionalization, the adsorption capacity of mercury ion is dramatically increased.Because after functionalization
HKUST-1 in substantial amounts of-SH groups be present, it is easily coordinated with mercury ion, so as to significantly increase metal organic framework
Absorption of the material to mercury ion, but the selectivity that metal ion is removed to it is not yet studied.In general, MOFs can be adsorbed point
It is the sieving actoion based on MOFs pore structures itself from organic molecule, adsorbate is made in diffusion rate of material surfaces externally and internally etc.
With.And the radius of heavy metal ion, particularly transition metal ions is very close, therefore via size heavy metal ion can not be led to
Carry out effective adsorbing separation.Therefore the research of MOFs material selectivities absorption heavy metal ion is also few.Therefore, how
Improve the adsorption capacity of MOFs heavy metal ions, and assign MOFs being capable of the heavy metal such as lead, mercury in selective removal water body
Ion turns into study hotspot and difficult point.
MIL-101 has the characteristics of not available for other MOFs materials, and it had both had meso-hole structure or had had micropore canals,
With huge pore volume and specific surface area, and can be stable in the presence of in air and water body, high temperature resistant.In addition, MIL-
There is a large amount of unsaturated active metal sites on 101 (Cr) central metal chromium, it can be chelated with electron rich functional group
Reaction, obtains functionalization MIL-101.The characteristics of due in these properties and structure, MIL-101 is by extensive researcher
Concern, the modification of applications and material of the particularly MIL-101 in terms of environmental treatment.And the present invention is exactly to have synthesized one kind
MIL-101 (Cr) compound adsorbent after modification, and assign the ability of the heavy metal ion in its selective removal water body.
The content of the invention
It is an object of the invention to provide a kind of preparation using rear modification MIL-101 (Cr) adsorbent and its can
The heavy metal ion such as lead, mercury, has widened the new opplication of MIL-101 (Cr) class material in efficient and selective removal water body.
The present invention uses following scheme：A kind of preparation side of MIL-101 (Cr) compound adsorbent with amido modified modification
Method, it is characterised in that method and step is as follows:
（1）Nine water chromic nitrates and terephthalic acid (TPA) are dissolved in deionized water solution, are added a certain amount of hydrofluoric acid and are entered
Row ultrasonic agitation is treated uniformly；
（2）The mixed liquor being stirred by ultrasonic is poured into hydrothermal reaction kettle, good seal puts it into constant temperature air blast later
In drying box, thermostatic crystallization 7h ~ 10h at being 200 ~ 230 DEG C in temperature；
（3）7min ~ 10min is centrifuged under the conditions of rotating speed is 6000rpm ~ 9000rpm, obtains light green solid product, first
Light green solid product is washed using ultra-pure water, washed 3 ~ 4 times；Using N,N-dimethylformamide to light green solid
Product is washed, and is washed 3 ~ 4 times；Ethanol is added, 18 ~ 22h is reacted in 80 ~ 110 DEG C of constant temperature blast drying oven to product
Purified；
（4）Product after being washed, vacuum drying 10h ~ 15h is carried out at being 130 ~ 160 DEG C in temperature, obtains light green
MOFs materials MIL-101；
（5）Take the MIL-101 samples of above-mentioned synthesis to be dispersed in anhydrous organic solvent, add different amounts of amine
Compound（0.5~5mmol）, 12 ~ 24h of condensing reflux；
（6）Filter after being cooled to room temperature, solid product is washed 3 ~ 4 times with ethanol；
（7）Product after being washed is put into drying box in 90 ~ 120 DEG C of freeze-day with constant temperature, is ground, is obtained after being cooled to room temperature
To with amido modified MOFs materials.
The preparation method of a kind of MIL-101 (Cr) compound adsorbent with pyrimidine modification, it is characterised in that method walks
It is rapid as follows：
（1）Nine water chromic nitrates and 2- amino-terephthalic acid (TPA) are dissolved in deionized water solution, add a certain amount of hydrogen
Sodium oxide molybdena carries out ultrasonic agitation and treated uniformly；
（2）The mixed liquor being stirred by ultrasonic is poured into hydrothermal reaction kettle, good seal puts it into constant temperature air blast later
In drying box, thermostatic crystallization 12h ~ 14h at being 140 ~ 160 DEG C in temperature；
（3）Reaction terminates, and is cooled to room temperature, then rotating speed be 6000rpm ~ 9000rpm under the conditions of centrifuge 7min ~
10min, obtain greenish solid product；Powder is fully transferred in conical flask, adds the DMF of certain volume in batches, continuously
Shake a hour；Mixed solution is filtered, obtained green powder is transferred in reactor, and adds ethanol solution, 80 ~
18 ~ 22h is reacted in 110 DEG C of constant temperature blast drying oven；
（4）Product after being washed, vacuum drying 10h ~ 15h is carried out at being 60 ~ 90 DEG C in temperature, obtains green MOFs
Material MIL-101-NH2；
（5）Pyrimidines are dissolved in anhydrous organic solvent, adds after DIEA to be stirred vigorously and treats uniformly；
（6）Then 0 DEG C is cooled to ice-water bath, is slowly added to the organic solution dissolved with TBTU under a nitrogen atmosphere, holds
Temperature is raised after 40 ~ 50min of continuous stirring to room temperature, stirs 1h；Then the MIL-101-NH of above-mentioned synthesis is added2Sample, reaction
46~48h；
（7）Filter after being cooled to room temperature, solid product is washed 3 ~ 4 times with substantial amounts of water；
（8）Product after being washed, vacuum drying 10h ~ 15h is carried out at being 60 ~ 90 DEG C in temperature, is obtained with pyrimidine
The MOFs materials of modification.
A kind of MIL-101 (Cr) compound adsorbent using after modification removes Heavy Metals in Waters ion, its feature
Method and step is as follows：MIL-101 (Cr) compound adsorbent after modification is added to containing pending heavy metal ion first
Water body in, low whipping speed be 300rpm ~ 500rpm under stir 5h ~ 8h, be then 6000rpm ~ 9000rpm conditions in rotating speed
Lower centrifugation 3min ~ 5min, takes clarified solution, produces water body after processing.
A kind of preparation method of MIL-101 (Cr) compound adsorbent with amido modified modification, described aminated compounds
For ethylenediamine, 1,3- propane diamine, hexamethylene diamine or diethylenetriamine etc..
A kind of preparation method of MIL-101 (Cr) compound adsorbent with amido modified modification, described MIL-101 matter
The ratio between amount and the mole of aminated compounds are 1:0.5~5.
A kind of preparation method of MIL-101 (Cr) compound adsorbent with amido modified modification, described organic solvent are
Methanol, ethanol, isopropanol, benzene or toluene etc..
A kind of preparation method of MIL-101 (Cr) compound adsorbent with pyrimidine modification, described miazines chemical combination
Thing is thymidine -1- acetic acid, 2,4- dihydroxy-pyrimidine -5- carboxylic acids, 5- carboxymethyl urea pyrimidine -1- acetic acid or 5- methyl -2- sulphur
Urea pyrimidine -1- acetic acid etc..
A kind of preparation method of MIL-101 (Cr) compound adsorbent with pyrimidine modification, described MIL-101-NH2
Mass ratio with pyrimidines is 1:0.2~2.
A kind of preparation method of MIL-101 (Cr) compound adsorbent with pyrimidine modification, described organic solvent are
N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or tetrahydrofuran etc..
After is 8 ~ 10min is stirred by ultrasonic every time after addition detergent in described washing methods, 6000rpm ~ 9000rpm conditions
Lower centrifugation 7min ~ 10min.
A kind of MIL-101 (Cr) compound adsorbent using after modification removes Heavy Metals in Waters ion, described
The ratio between the quality of MIL-101 (Cr) compound adsorbent after modification and the water body volume containing pending heavy metal ion are 1:
1。
It is an advantage of the invention that：Successfully synthesize MIL-101 (Cr) adsorbent after a kind of modification, and their energy
The heavy metal ion such as lead, mercury, has widened the new opplication of MIL-101 (Cr) class material in enough effective and selective removal water bodys.
Brief description of the drawings
Fig. 1 is the synthesis and its adsorption mechanism of MIL-101 (Cr) compound adsorbent of the ethylene diamine-modified modification of the present invention
Figure.
(a) metal unsaturation site generates；(b) ED-MIL-101 synthesis and adsorption mechanism figure.
Fig. 2 be the present invention thymidine -1- acetic acid modifications MIL-101 (Cr) compound adsorbent synthesis and its
Adsorption mechanism figure.
Fig. 3 is the adsorption isothermal curve and choosing of MIL-101 (Cr) compound adsorbent of the ethylene diamine-modified modification of the present invention
Selecting property absorption figure.
ED-MIL-101 (a) adsorption isothermal curve and (b) selective absorption figure.
Fig. 4 is the isothermal adsorption of MIL-101 (Cr) compound adsorbent of the thymidine -1- acetic acid modifications of the present invention
Curve and selective absorption figure.
MIL-101-Thymine (a) adsorption isothermal curve and (b) selective absorption figure.
Embodiment
The reagent and material of the present invention
Nine water chromic nitrates, terephthalic acid (TPA), 2- amino terephthalic acid (TPA), hydrofluoric acid, sodium hydroxide, ethylenediamine, thymus gland are phonetic
Pyridine -1- acetic acid, toluene, N,N-dimethylformamide, N, N- diisopropylethylamine, BTA base-N, N, N', N' tetra-, methyl
Urea tetrafluoro boric acid, mercury chloride, caddy, nitrate trihydrate copper, six water nickel nitrates, cobalt nitrate hexahydrate, absolute ethyl alcohol, nitric acid etc. are
Analyze more than pure.
Embodiment 1
（1）The water chromic nitrates of 2g nine and 0.82 g terephthalic acid (TPA)s are weighed, is then added into 35mL deionized water solutions
In, then liquid-transfering gun takes 0.1mL hydrofluoric acid to add, then carries out 30 min are stirred by ultrasonic and treat that its all dissolves；
（2）The mixed liquor being stirred by ultrasonic is poured into hydrothermal reaction kettle, good seal puts it into constant temperature air blast later
It is 220 DEG C that temperature is set in drying box, thermostatic crystallization 8h.After being cooled to room temperature, reactant is moved into plastic centrifuge tube, centrifuged,
Outwell supernatant；
（3）With each 3 times of ultra-pure water, DMF washing precipitates, each ultrasonic 10min, 8000r/min centrifugations 15min.Then
It is poured into after being filtered again to it in reactor, adds 50mL ethanol, a purge process is carried out to material, at 100 DEG C
20h is reacted in constant temperature blast drying oven；
（4）Filter（Ethanol）After be put into drying box in 150 DEG C of freeze-day with constant temperature, take out, carried out after being cooled to room temperature
Grinding, sieving；
（5）Take 1g MIL-101 samples to be put into after being dehydrated 12h at 150 DEG C in dried round-bottomed flask, add 75mL
Dry toluene, 5mmol ethylenediamines, the condensing reflux 12h at 112 DEG C；
（6）It is filtered after being cooled to room temperature（Ethanol）, it is put into drying box in 110 DEG C of freeze-day with constant temperature, is cooled to
Take out, be ground after room temperature.
MIL-101 (Cr) compound adsorbent being modified using ethylenediamine made from the present embodiment, ethylenediamine grafting amount are
5mmol.Experiment shows that compound adsorbent obtained above has good removal effect, maximum adsorption capacity to lead ion in water
For 87.64mg/g, the material has stronger selectivity to the lead ion in water body in addition.
Embodiment 2
（1）It is accurate to weigh the water chromic nitrates of 0.4g nine, 0.18g 2- amino terephthalic acid (TPA)s, 0.1g sodium hydroxides, add
7.5mL deionized waters, stir solution 5min；
（2）Then the solution is transferred in the reactor of 25mL polytetrafluoroethyllining linings, closed the lid, be in temperature
Reaction 12h, reaction terminate in 150 DEG C of baking oven, are cooled to room temperature, centrifuge, outwell supernatant；
（3）Solid product is fully transferred in conical flask, adds the DMF of certain volume, continuous concussion one in batches
Hour.Mixed solution is filtered, obtained green powder is transferred in reactor, and adds 50mL ethanol solution.Will reaction
Kettle is put into baking oven to react 20 hours at 100 DEG C；
（4）Room temperature is cooled to, filters, gained powder is washed with ethanol.By baking oven of the green powder at 80 DEG C
Interior vacuum drying, take out, be ground after being cooled to room temperature；
（5）Precise 1.1245g thymidine -1- acetic acid, is dissolved in the DMF solution that 40mL newly steams；
（6）Precise 1.5497g DIEA, add in above-mentioned solution, be stirred vigorously, 0 DEG C is cooled to ice-water bath,
Lead to nitrogen and the DMF solution that 10mL is dissolved with 1.9265g TBTU is slowly added under conditions of being stirred vigorously, lasting stirring
40min, temperature is then raised to room temperature；
（7）A hour is stirred, then adds 0.8g MIL-101-NH2Material reacts 48h；
（8）Reacted mixed liquor is filtered, filters the substantial amounts of water washing of obtained green powder.Taken out after washing
Filter, the then dried overnight rear grinding in baking oven by powder.
MIL-101 (Cr) compound adsorbents being modified using thymidine made from the present embodiment are had to mercury ion in water
Good removal effect, maximum adsorption capacity 51.27mg/g, in addition selectivity experiment show that the material can be selected effectively
Property remove water body in mercury ion.
Claims (4)
- A kind of 1. preparation method of MIL-101 (Cr) compound adsorbent with pyrimidine modification, it is characterised in that method and step It is as follows：（1）Nine water chromic nitrates and 2- amino-terephthalic acid (TPA) are dissolved in deionized water solution, add a certain amount of hydroxide Sodium carries out ultrasonic agitation and treated uniformly；（2）The mixed liquor being stirred by ultrasonic is poured into hydrothermal reaction kettle, good seal puts it into constant temperature forced air drying later In case, thermostatic crystallization 12h ~ 14h at being 140 ~ 160 DEG C in temperature；（3）Reaction terminates, and is cooled to room temperature, then centrifuges 7min ~ 10min under the conditions of rotating speed is 6000rpm ~ 9000rpm, obtains To greenish solid product；Powder is fully transferred in conical flask, adds the DMF of certain volume, continuous concussion one in batches Hour；Mixed solution is filtered, obtained green powder is transferred in reactor, and adds ethanol solution, at 80 ~ 110 DEG C 18 ~ 22h is reacted in constant temperature blast drying oven；（4）Product after being washed, vacuum drying 10h ~ 15h is carried out at being 60 ~ 90 DEG C in temperature, obtains green MOFs materials MIL-101-NH2；（5）Pyrimidines are dissolved in anhydrous organic solvent, adds after DIEA to be stirred vigorously and treats uniformly；Described MIL-101-NH2Mass ratio with pyrimidines is 1:0.2~2；The pyrimidines be thymidine -1- acetic acid, 2,4- dihydroxy-pyrimidine -5- carboxylic acids, 5- carboxymethyl urea pyrimidine -1- acetic acid or 5- methyl -2- deracil -1- acetic acid；（6）Then 0 DEG C is cooled to ice-water bath, is slowly added to the organic solution dissolved with TBTU under a nitrogen atmosphere, persistently stirs Temperature is raised to room temperature after mixing 40 ~ 50min, stirs 1h；Then the MIL-101-NH of above-mentioned synthesis is added2Sample, reaction 46 ~ 48h；（7）Filter after being cooled to room temperature, solid product is washed 3 ~ 4 times with substantial amounts of water；（8）Product after being washed, vacuum drying 10h ~ 15h is carried out at being 60 ~ 90 DEG C in temperature, is obtained with pyrimidine modification MOFs materials.
- 2. preparation method according to claim 1, it is characterised in that the organic solvent be DMF, DMAC N,N' dimethyl acetamide or tetrahydrofuran.
- 3. MIL-101 (Cr) composite adsorption with pyrimidine modification that preparation method is prepared according to claim 1 Application of the agent in Heavy Metals in Waters ion is removed, it is characterised in that step is as follows：First by with pyrimidine modification MIL-101 (Cr) compound adsorbent is added in the water body containing pending heavy metal ion, low whipping speed be 300rpm ~ 5h ~ 8h is stirred under 500rpm, then 3min ~ 5min is centrifuged under the conditions of rotating speed is 6000rpm ~ 9000rpm, takes clarified solution, i.e., Water body after being handled.
- 4. application according to claim 3, it is characterised in that the MIL-101 (Cr) with pyrimidine modification is multiple It is 1 to close the ratio between the quality of adsorbent and water body volume containing pending heavy metal ion:1.
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