CN110496608A - A kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101 and its preparation method and application - Google Patents
A kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101 and its preparation method and application Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- 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]
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- 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
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Abstract
The invention belongs to dissipated metal adsorbent synthesis technical fields, and in particular to a kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101, is with imidazole ion liquid [C2Vmir] [Cl] be monomer, 2,2- azodiisobutyronitrile AIBN be crosslinking agent, divinylbenzene DVB be used as basic framework, MIL-101 be adsorption matrix material by reaction synthesizes, wherein x=0.075,0.15,0.3,0.4,0.5,0.6.The present invention is for the absorption to Re in water (VII).The preparation method of the adsorbent is simple, safety, at low cost, separation and concentration is high-efficient, absorption Re (VII) that can be selective from the coexisting ions solution such as Cu (II), Fe (II), Zn (II), Mn (II).
Description
Technical field
The invention belongs to dissipated metal technical field of absorbent, and in particular to a kind of xPILs@MIL- of selective absorption rhenium
101 composite material adsorbents and its preparation method and application.
Background technique
Dissipated metal (RSE) can be described as eare scattered metals again, and wherein rhenium is VIIB element, be a kind of high-intensitive, Gao Rong
Dilute scattered infusibility precious metal of point.The content of rhenium in nature is very low, and its content is only 1 × 10 in the earth's crust-7%.Rhenium
Not only there is good plasticity, mechanical property and creep-resistant property, but also have many advantages, such as wear-resistant, anticorrosive.Due to rhenium and
Its alloy has special performance, it is made to be widely used in the modern high-tech such as national defence, Aeronautics and Astronautics, nuclear energy and electronics industry
Skill field is a kind of one of extremely important new material.
The method for extracting rhenium at present specifically includes that extraction separation method, ion-exchange, liquid-film method, oxidation-reduction method, precipitating
Method and electroosmose process etc..Cumbersome, operating cost when the most prominent disadvantage of these methods is to handle low-concentration metallic wastewater
Higher, energy consumption is big, and easily causes secondary pollution.The advantages of absorption method separates will not generate pollution to environment, and adsorption capacity is strong.
Ionic liquid is as a kind of " green solvent ", with steam forces down, fusing point is low, can design, can be recycled, stability height
Etc. characteristics, but ionic liquid is complicated as catalyst recovery process in the reaction system, viscosity is high, as solvent or catalyst
When service efficiency it is relatively low, seriously hinder their industrial application.We select for ionic liquid to be fixed on high table
In area and the porous material in given activity site, solve the above problems.Therefore, we have selected metal organic framework
(MOFs), this is a kind of porous crystalline material, and compared with other porous materials, MOFs most prominent feature is biggish in lattice
Unit cell has height interconnection, fine and close, open and orderly for a long time hole.With structure diversity abundant and adaptation
The advantages that property, selective adsorption capacity, high surface area, become good adsorption matrix material.Therefore, we have selected tool
There is highly porous MIL-101 nano particle as matrix, supported ion liquid is used for Adsorption of Rhenium as new composite adsorbent
Re(VII)。
Summary of the invention
It is an object of the present invention to provide a kind of xPILs@MIIL-101 composite materials, use poly ion liquid as adsorption function base
Group.The sorbent preparation method is simple, and power of regeneration is strong, has very high adsorption capacity to Re (VII), can be from rhenium-containing solution
In selective absorption rhenium well.Safety of the present invention, has practical application at energy conservation and environmental protection.
Object of the present invention is to what is be achieved through the following technical solutions: a kind of poly ion liquid@metal organic framework composite wood
Expect xPILs@MIL-101, the poly ion liquid@metal organic framework composite material xPILs@MIL-101, is with imidazoles
Ionic liquid [C2Vmir] [Cl] be monomer, 2,2- azodiisobutyronitrile AIBN are crosslinking agent, and divinylbenzene DVB is as basic
Skeleton, MIL-101 are that adsorption matrix material passes through reaction synthesis, wherein x=0.075,0.15,0.3,0.4,0.5,0.6.
The preparation method of above-mentioned poly ion liquid@metal organic framework composite material xPILs@MIL-101 a kind of, including
Following steps:
1) imidazole ion liquid [C2Vmir] [Cl] synthesis: by N- vinyl imidazol and 1, the mixing of 2- dichloroethanes, then plus
Enter acetonitrile be uniformly mixed, react 9-24h at 60-80 DEG C, obtain white solid, wash, purifying, vacuum drying obtain imidazoles from
Sub- liquid [C2Vmir][Cl];
2) synthesis of MIL-101: by Cr (NO3)3·9H2O, terephthalic acid (TPA), glacial acetic acid are mixed with deionized water, room temperature
Lower stirring 30min, is transferred in reaction kettle, reacts 5-15h at 180-240 DEG C, obtains blue-green solid, washs, purifying, vacuum
It is dried to obtain MIL-101;
3) MIL-101, [C the synthesis of xPILs@MIL-101: are weighed2- Vmir] [Cl], DVB, AIBN and ethyl alcohol is in mortar
In, the powder after grinding is transferred in round-bottomed flask, N270 DEG C are heated under protection, reaction is for 24 hours.Products therefrom is collected, is washed
It washs, vacuum drying obtains target product.
The preparation method of above-mentioned poly ion liquid@metal organic framework composite material xPILs@MIL-101 a kind of, step
1) in, in molar ratio, N- vinyl imidazol: 1,2- dichloroethanes is 1:1-5.
The preparation method of above-mentioned poly ion liquid@metal organic framework composite material xPILs@MIL-101 a kind of, step
2) in, by solid-to-liquid ratio, Cr (NO3)3·9H2O: terephthalic acid (TPA): glacial acetic acid: deionized water 2-3g:1g:1-2mL:50-
55mL。
The preparation method of above-mentioned poly ion liquid@metal organic framework composite material xPILs@MIL-101 a kind of, step
3) in, in mass ratio, [C2Vmir] [Cl]: DVB 1-5:1.
The preparation method of above-mentioned poly ion liquid@metal organic framework composite material xPILs@MIL-101 a kind of, step
3) in, in mass ratio, MIL-101:[C2- Vmir] [Cl] be 1:0.5-4.
The preparation method of above-mentioned poly ion liquid@metal organic framework composite material xPILs@MIL-101 a kind of, step
3) in, in mass ratio, [C2- Vmir] [Cl]: AIBN 1:0.0125-0.0375.
Above-mentioned poly ion liquid@metal organic framework composite material xPILs@MIL-101 is in absorption dissipated metal rhenium
Application.
Above-mentioned application, in the solution of Yu Hanyou rhenium, the pH for adjusting solution is 1-7, and above-mentioned composite material is added
After xPILs@MIL-101, oscillation absorption 8-12h, eluted with eluant, eluent.
Above-mentioned application, the eluant, eluent are that concentration is 0.3-1.2molL-1Hydrochloric acid.
The beneficial effects of the present invention are:
(1) the xPILs@MIL-101 composite material prepared of the present invention is high as adsorbent separative efficiency, can from mix from
Highly selective Adsorption of Rhenium in sub- solution has large amount of adsorption and recycled for multiple times performance, applied widely, has and actually answers
The property used.
(2) adsorption rate of the present invention is fast, and desorption performance is good, and selectivity is high, reachable to the maximal absorptive capacity of Re (VII)
536.41 mg·g-1。
(3) present invention is using poly ion liquid as functional group, using DVB as basic framework, using MIL-101 as binding matrix material
Material is by polymerization reaction synthesizing new adsorbent, for the absorption to Re in water (VII).The preparation method of the adsorbent is simple,
Safety, at low cost, separation and concentration is high-efficient, can select from the coexisting ions solution such as Cu (II), Fe (II), Zn (II), Mn (II)
The absorption Re (VII) of selecting property.
Detailed description of the invention
Fig. 1 a is PILs FT-IR figure prepared by embodiment 1.
The FT-IR figure that Fig. 1 b is xPILs@MIL-101 prepared by embodiment 1.
Fig. 1 c is the postdigestive FT-IR figure of xPILs@MIL-101 prepared by embodiment 1.
Fig. 2 is PILs, the SEM of MIL-101, xPILs@MIL-101 scheme;
Wherein, a:PILs;b:MIL-101;c:0.075PILs@MIL-101,d:0.15PILs@MIL-101, e:
0.3PILs@MIL-101、f:0.4PILs@MIL-101、g:0.5PILs@MIL-101、h:0.6PILs@MIL-101。
Fig. 3 is the XRD diagram of MIL-101, xPILs@MIL-101.
Fig. 4 is the N of MIL-101,0.5PILs@MIL-1012Absorption figure.
Fig. 5 is the influence of MIL-101, xPILs@MIL-101 under different acidity to absorption Re (VII).
Fig. 6 a is the adsorption isotherm of 0.075PILs@MIL-101 absorption Re (VII).
Fig. 6 b is the adsorption isotherm of 0.15PILs@MIL-101 absorption Re (VII).
Fig. 6 c is the adsorption isotherm of 0.3PILs@MIL-101 absorption Re (VII).
Fig. 6 d is the adsorption isotherm of 0.4PILs@MIL-101 absorption Re (VII).
Fig. 6 e is the adsorption isotherm of 0.5PILs@MIL-101 absorption Re (VII).
Fig. 6 f is the adsorption isotherm of 0.6PILs@MIL-101 absorption Re (VII).
Fig. 7 a be 0.5PILs@MIL-101 under different acidity to the stability of Re (VII).
Fig. 7 b is 0.5PILs@MIL-101 XRD diagram under different acidity.
Fig. 8 be 0.5PILs@MIL-101 under different acidity to the selectivity of Re (VII).
Fig. 9 is 0.5PILs@MIL-101 in 0.5molL-1Recycling elution in HCl.
Specific embodiment
The preparation of 1 0.075PILs@MIL-101 composite material of embodiment
1) synthesis of imidazole ion liquid: 4.71g N- vinyl imidazol is taken to be added to 4.95g 1,2- dichloroethanes
In 100mL single-necked flask, adds 40mL acetonitrile and be uniformly mixed, reacted at 70 DEG C for 24 hours, obtain white solid, wash, purifying,
Vacuum drying obtains intermediate product glyoxaline ion liquid [C2Vmir][Cl]。
2) synthesis of MIL-101: 3.2g Cr (NO3)3·9H2O, 1.32g terephthalic acid (TPA), 2.20mL glacial acetic acid and 40
ML deionized water, stirs 30min at room temperature, is transferred in reaction kettle.9h is reacted at 200 DEG C, obtains blue-green solid, is washed,
Purifying, vacuum drying obtain intermediate product MIL-101.
3) synthesis of 0.075PILs@MIL-101 composite material: 150mg MIL-101,75mg [C2- Vmir] [Cl] and 25
Mg DVB, 2mg AIBN, 3mL ethyl alcohol grinds 30min in mortar.Powder after grinding is transferred to 50mL round-bottomed flask
It is interior, N270 DEG C are heated under protection, reaction is for 24 hours.Products therefrom, washing are collected, vacuum drying obtains 0.075PILs@MIL-
101。
The preparation of 2 0.15PILs@MIL-101 composite material of embodiment
Step 1), step 2) are the same as embodiment 1.
3) synthesis of 0.15PILs@MIL-101 composite material: 150mg MIL-101,150mg [C2- Vmir] [Cl] and 50
Mg DVB, 4mg AIBN, 3mL ethyl alcohol grinds 30min in mortar.Powder after grinding is transferred in 50mL round-bottomed flask,
N270 DEG C are heated under protection, reaction is for 24 hours.Products therefrom, washing are collected, vacuum drying obtains 0.15PILs@MIL-101.
The preparation of 3 0.3PILs@MIL-101 composite material of embodiment
Step 1), step 2) are the same as embodiment 1.
3) synthesis of 0.3PILs@MIL-101 composite material: 150mg MIL-101,300mg [C2- Vmir] [Cl] and 98
Mg DVB, 8mg AIBN, 3mL ethyl alcohol grinds 30min in mortar.Powder after grinding is transferred in 50mL round-bottomed flask,
N270 DEG C are heated under protection, reaction is for 24 hours.Products therefrom, washing are collected, vacuum drying obtains 0.3PILs@MIL-101.
The preparation of 4 0.4PILs@MIL-101 composite material of embodiment
Step 1), step 2) are the same as embodiment 1.
3) synthesis of 0.4PILs@MIL-101 composite material: 150mg MIL-101,400mg [C2- Vmir] [Cl] and 130
Mg DVB, 11mg AIBN, 3mL ethyl alcohol grinds 30min in mortar.Powder after grinding is transferred to 50mL round-bottomed flask
It is interior, N270 DEG C are heated under protection, reaction is for 24 hours.Products therefrom, washing are collected, vacuum drying obtains 0.4PILs@MIL-101.
The preparation of 5 0.5PILs@MIL-101 composite material of embodiment
Step 1), step 2) are the same as embodiment 1.
3) synthesis of 0.5PILs@MIL-101 composite material: 150mg MIL-101,500mg [C2- Vmir] [Cl] and 168
Mg DVB, 13mg AIBN, 3mL ethyl alcohol grinds 30min in mortar.Powder after grinding is transferred to 50mL round-bottomed flask
It is interior, N270 DEG C are heated under protection, reaction is for 24 hours.Products therefrom, washing are collected, vacuum drying obtains 0.5PILs@MIL-101.
The preparation of 6 0.6PILs@MIL-101 composite material of embodiment
Step 1), step 2) are the same as embodiment 1.
3) synthesis of 0.6PILs@MIL-101 composite material: 150mg MIL-101,600mg [C2- Vmir] [Cl] and
196mg DVB, 16mg AIBN, 3mL ethyl alcohol grinds 30min in mortar.Powder after grinding is transferred to 50 mL round bottoms to burn
In bottle, N270 DEG C are heated under protection, reaction is for 24 hours.Products therefrom, washing are collected, vacuum drying obtains 0.6PILs@MIL-
101。
The preparation of 1 poly ion liquid PILs of comparative example
The synthesis of poly ion liquid: 0.965g [C is taken2Vmir] [Cl], 0.325g DVB, 0.026g AIBN be added to
In 100mL three-necked flask, adds 40mL acetonitrile and be uniformly mixed, N270 DEG C are heated under protection, reaction for 24 hours, it is solid to obtain white
Body washs, and purifying, vacuum drying obtains product PILs.
The characterization of 7 xPILs@MIL-101 composite material of embodiment
1) IR is analyzed: to [C2- Vmir] [Cl], DVB, MIL-101, PILs and embodiment 1-6 preparation xPILs@
MIL-101 carries out IR analysis: result is as shown in Fig. 1 a, Fig. 1 b and Fig. 1 c, it can be seen that [C from Fig. 1 a2Vmir] [Cl] In
1653cm-1It is the stretching vibration peak of the C=C and the C=C in imidazole ring of vinyl on N- vinyl imidazole, in 3067cm-1
There is the stretching vibration peak of the stretching vibration peak of C-H and the C-H on imidazole ring in C=C in place, in 1000~650cm-1Range
Inside there is the in-plane bending vibration peak of alkene C-H, this can prove [C2Vmir] [Cl] successful synthesis.1653cm in PILs-1
Locate stretching vibration peak compared to [C2Vmir] [Cl] obviously die down, show [C2- Vmir] double bond on C=C and DVB in [Cl]
Polymerization reaction has occurred.Meanwhile 3067cm-1The peak width at place becomes larger, 1554cm-1With 1443 cm-1There is the characteristic peak of phenyl ring in place,
This also demonstrates DVB and [C2- Vmir] [Cl] participation polymerization, illustrate that PILs is successfully synthesized.
It can be seen that the infrared figure of the substance obtained after PILs and composite material digestion, therefrom it can be seen that, disappears in Fig. 1 b
Substance after solution is as PILs, in 1653cm-1It is the C=C and the C=in imidazole ring of vinyl on N- vinyl imidazole
The stretching vibration peak of C, in 1600cm-1Nearby there is the stretching vibration peak of imidazoles ring skeleton, illustrates PILs in the composite
It successfully synthesizes.
It can see in our experiment from Fig. 1 c, weighed [the C of different quality2- Vmir] [Cl] (x=
0.075,0.15,0.3,0.4,0.5,0.6) compound with MIL-101, the infared spectrum of the different materials of preparation, in MIL-101
Stretching vibration peak all occurred in the material of all preparations, and with the increase of ionic liquid additional amount, imidazole ring bone
The characteristic peak of frame is more and more obvious.These can illustrate that the success of MIL-101 and PILs are compound.
2) sem analysis: SEM result as shown in Fig. 2, it can clearly be seen that (a) be PILs microscopic appearance figure, can observe
It arrives, PILs shows the sponge structure of foam-like;(b) microscopic appearance figure for being MIL-101, it is observed that MIL-101 is in
Reveal octahedral structure.(c)-(h) is the composite material for having loaded different quality ionic liquid in Fig. 2, it can be seen from the figure that
Poly ion liquid wraps up MIL-101, also, with the increase of ionic liquid additional amount, package it is further tight, can
The structure of the MIL-101 observed is increasingly fuzzyyer.
3) XRD analysis: XRD result is as shown in figure 3, the MIL-101 for being compounded with PILs still remains MIL-101 crystal form knot
Structure, this phenomenon can illustrate that the addition of PILs does not change or destroy the structure of MIL-101 well.
4) elemental analysis: the results are shown in Table 1.Can be seen that N% from the data in table is to gradually increase, it was demonstrated that compound
The amount of poly ion liquid increasing, this is consistent with the phenomenon that seeing in scanning figure.The N% of 0.5PILs@MIL-101 is up to
11.874%, it was demonstrated that the ionic liquid of 0.5PILs@MIL-101 load is most, and N% drops instead in 0.6PILs@MIL-101
It is low, it is that excessive ionic liquid is added since the MIL-101 of fixed mass has had reached the ability of maximum compound ion liquid
Body is polymerize, and can also be lost in washing process.
The elemental analysis result of 1 xPILs@MIL-101 adsorbent of table
N2Adsorption experiment: result is as shown in figure 4, the specific surface of MIL-101 is 2584.155m2·g-1, and it is compound after material
The specific surface area for expecting 0.5PILs@MIL-101 is only 407.037m2·g-1, and the meso-hole structure of MIL-101 script also disappears
.This is because PILs occupies the duct of MIL-101, specific surface area is caused to decline, to also turn out ionic liquid and not only
It is only to be polymerize on the surface MIL-101, also some is entered in the hole of MIL-101.
Recycling of the 8 xPILs@MIL-101 composite material of embodiment as adsorbent to rhenium
(1) Adsorption Effect of the adsorbent of ionic liquid additional amount difference synthesis to Re (VII)
Take respectively 5mg MIL-101,0.075PILs@MIL-101,0.15PILs@MIL-101,0.3PILs@MIL-101,
0.4PILs@MIL-101,0.5PILs@MIL-101,0.6PILs@MIL-101, be separately added into different pH (pH=1,2,3,4,
5,6,7) 5mL, 20mgL-1It is vibrated 12h in oscillation case, as a result as shown in Figure 5 by the solution of Re (VII).
Experimental result shows that xPILs@MIL-101 is all larger than MIL- for the adsorbance of rhenium in entire Acidity Range
101, in pH > 2, adsorption rate is all close to 100%, and under conditions of 3 pH, adsorption rate highest.Therefore, we select pH
3 be optimal adsorption acidity.
(2) influence of the concentration of difference Re (VII) to absorption
Method: take respectively 5mg 0.075PILs@MIL-101,0.15PILs@MIL-101,0.3PILs@MIL-101,
0.4PILs@MIL-101,0.5PILs@MIL-101,0.6PILs@MIL-101, are separately added into 5mL pH=3, and Re (VII) is dense
Degree is respectively 20mgL-1、50mg·L-1、80mg·L-1、100mg·L-1、150mg·L-1、200mg·L-1、300mg·L-1、
400mg·L-1、500mg·L-1、600mg·L-1、800mg·L-1Rhenium-containing solution in, by its oscillation case in vibrate 12 h,
As a result as shown in Fig. 6 a- Fig. 6 f.
By Fig. 6 a- Fig. 6 f as it can be seen that when low concentration, adsorbance increases with the increase of the concentration of Re (VII).Adsorbent
0.5PILs@MIL-101 is maximum to the saturated extent of adsorption of rhenium, is 536.41mgg-1.It is fitted from different type adsorption isotherm
Related coefficient is it can be concluded that absorption meets Langmuir adsorption isotherm model.
(3) 0.5PILs@MIL-101 adsorbent stabilizing effect under different acidity
By 0.5PILs@MIL-101 adsorbent respectively in pH 1-7 and 0.5molL-1It is impregnated in the solution of HCl for 24 hours, meter
Calculation obtains residual weight and carries out XRD analysis.As shown in Figure 7a.As a result, it has been found that in 0.5molL-1In HCl, 0.5PILs@
The residual weight of MIL-101 still can keep 80% or more stability.As shown in Figure 7b, discovery adsorbent material still retains
Original characteristic peak, structure not destroyed, this result shows that, in the Acidity Range studied, 0.5PILs@
MIL-101 is with good stability.
(4) separating effect of the 0.5PILs@MIL-101 adsorbent to Re (VII) in mixed metal solution under different acidity
It is taken respectively containing Re (VII), Cu (II), Zn (II), Mn (II), Fe (III) 20mgL-1Each 10mL of solution, point
Not Tiao Jie pH value of solution=1,2,3,4 and 5, then be added 10mg 0.5PILs@MIL-101 adsorbent, shake 12h, measure solution
In each ion concentration, as a result as shown in Figure 8.
As seen from Figure 8, in pH 3,0.5PILs@MIL-101 to the absorption of Re (VII) can achieve 90% with
On, and pair other metal ions hardly adsorb, illustrate 0.5PILs@MIL-101 to Re (VII) selectivity with higher,
And the interference very little of other coexistent metallic ions.
(5) different eluant, eluents elute effect to Re (VII)
Method: it is 100mgL that 80mg adsorbent (0.5PILs@MIL-101), which is placed in 80mL pH=3 concentration,-1Re
(VII) it in solution, shakes after 12h reaches adsorption saturation and filters at room temperature, it is dry.Adsorbent 10mg after drying is weighed, is put it into
In bottle containing different eluant, eluents, 12h filtering is shaken at room temperature, measures the concentration of rhenium in filtrate, as a result such as table 2.
Eluting rate of the 0.5PILs@MIL-101 adsorbent of 2 embodiment 1 of table preparation under different eluant, eluents
Show hydrochloric acid as eluant, eluent, significant effect, concentration 0.5molL in table 2-1Parsing of the hydrochloric acid to Re (VII)
Effect is best, and eluting rate is up to 95.74%.
(6) sorbent circulation service performance
Method: it weighs 70mg adsorbent (0.5PILs@MIL-101) and is placed in 70mL, pH=3, concentration 100mgL-1's
In Re (VII) solution, is filtered after shaking 12h adsorption saturation at room temperature, then use 0.5molL-1Hydrochloric acid solution eluted,
By 4 absorption-elution cycles, as a result such as Fig. 9.
As seen from Figure 9, after 4 absorption-elution cycles, absorption of the adsorbent 0.5PILs@MIL-101 to Re (VII)
Amount remains to reach 95% or more, it was demonstrated that adsorbent 0.5PILs@MIL-101 is with good stability and reproducibility.
Claims (10)
1. a kind of poly ion liquid@metal organic framework composite material xPILs@MIL-101, which is characterized in that it is described gather from
Sub- liquid@metal organic framework composite material xPILs@MIL-101, is with imidazole ion liquid [C2Vmir] [Cl] be monomer,
2,2- azodiisobutyronitrile AIBN are crosslinking agent, and for divinylbenzene DVB as basic framework, MIL-101 is adsorption matrix material
It is synthesized by reaction, wherein x=0.075,0.15,0.3,0.4,0.5,0.6.
2. the preparation side of poly ion liquid@metal organic framework composite material xPILs@MIL-101 described in claim 1 a kind of
Method, which comprises the steps of:
1) imidazole ion liquid [C2Vmir] [Cl] synthesis: by N- vinyl imidazol and 1, the mixing of 2- dichloroethanes adds acetonitrile
It is uniformly mixed, reacts 9-24h at 60-80 DEG C, obtain white solid, wash, purifying, vacuum drying obtains glyoxaline ion liquid
[C2Vmir][Cl];
2) synthesis of MIL-101: by Cr (NO3)3·9H2O, terephthalic acid (TPA), glacial acetic acid are mixed with deionized water, are stirred at room temperature
30min is mixed, is transferred in reaction kettle, reacts 5-15h at 180-240 DEG C, obtains blue-green solid, is washed, is purified, vacuum drying
Obtain MIL-101;
3) MIL-101, [C the synthesis of xPILs@MIL-101: are weighed2- Vmir] [Cl], DVB, AIBN and ethyl alcohol in mortar, will
Powder after grinding is transferred in round-bottomed flask, N260-80 DEG C is heated under protection, reaction is for 24 hours.Products therefrom is collected, is washed,
Vacuum drying obtains target product.
3. the system of poly ion liquid@metal organic framework composite material xPILs@MIL-101 according to claim 1 a kind of
Preparation Method, which is characterized in that in step 1), in molar ratio, N- vinyl imidazol: 1,2- dichloroethanes is 1:1-5.
4. the system of poly ion liquid@metal organic framework composite material xPILs@MIL-101 according to claim 1 a kind of
Preparation Method, which is characterized in that in step 2), by solid-to-liquid ratio, Cr (NO3)3·9H2O: terephthalic acid (TPA): glacial acetic acid: deionized water
For 2-3g:1g:1-2mL:30-55mL.
5. the system of poly ion liquid@metal organic framework composite material xPILs@MIL-101 according to claim 1 a kind of
Preparation Method, which is characterized in that in step 3), in mass ratio, [C2Vmir] [Cl]: DVB 1-5:1.
6. the system of poly ion liquid@metal organic framework composite material xPILs@MIL-101 according to claim 1 a kind of
Preparation Method, which is characterized in that in step 3), in mass ratio, MIL-101:[C2- Vmir] [Cl] be 1:0.5-4.
7. the system of poly ion liquid@metal organic framework composite material xPILs@MIL-101 according to claim 1 a kind of
Preparation Method, which is characterized in that in step 3), the quality of AIBN is [C2- Vmir] [Cl] and DVB gross mass 1-3%.
8. poly ion liquid@metal organic framework composite material xPILs@MIL-101 described in claim 1 is adsorbing dilute scattered gold
Belong to the application in rhenium.
9. application according to claim 8, which is characterized in that in the solution of Yu Hanyou rhenium, the pH for adjusting solution is 1-7,
Composite material xPILs@MIL-101 described in claim 1 is added to be eluted after 8-12h is adsorbed in oscillation with eluant, eluent.
10. application according to claim 9, which is characterized in that the eluant, eluent is that concentration is 0.3-1.2molL-1
Hydrochloric acid.
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