CN109054401B - Uio-66/polyaromatic amine composite material with core-shell structure and preparation method and application thereof - Google Patents

Uio-66/polyaromatic amine composite material with core-shell structure and preparation method and application thereof Download PDF

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CN109054401B
CN109054401B CN201810762705.5A CN201810762705A CN109054401B CN 109054401 B CN109054401 B CN 109054401B CN 201810762705 A CN201810762705 A CN 201810762705A CN 109054401 B CN109054401 B CN 109054401B
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王海鹰
侯兰晶
柴立元
杨卫春
史美清
王升
颜旭
王庆伟
李青竹
杨志辉
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Abstract

The invention discloses an Uio-66/polyaromatic amine composite material with a core-shell structure and a preparation method and application thereof. Firstly, dispersing Uio-66 in aqueous solution, then adding aromatic amine monomer and surfactant, stirring for 0.5-24h, and fully contacting; then dropping persulfate aqueous solution to initiate polymerization reaction, and continuously stirring for 3-24 h. The Uio-66/polyaromatic amine composite material can be obtained after centrifugal separation and washing. The specific surface area of the composite material reaches 319.77m2The specific surface area of the polyaromatic amine is effectively increased, and the Uio-66 surface is successfully subjected to amination modification. The method can be used for efficiently preparing Uio-66/polyaromatic amine composite materials, is economical and effective, is simple to operate, and has wide application prospect in the technical field of water treatment.

Description

Uio-66/polyaromatic amine composite material with core-shell structure and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal organic framework and polyaromatic amine composite materials, and particularly discloses an Uio-66/polyaromatic amine composite material with a core-shell structure, and a preparation method and application thereof.
Background
Uio-66 is a zirconium-based metal-organic framework (MOFs), has high heat resistance, acid and alkali corrosion resistance, can stably exist in a water phase, and is one of series of materials with optimal stability in MOFs. It has high specific surface area, and the specific surface area of Uio-66 synthesized by various methods at present is mostly more than 1000m2And/g, has good application prospect in many fields. However, Uio-66 has a low surface functional group content, which limits its application in the field of adsorption. Uio-66 is compounded with a polymer rich in functional groups to be an effective means for modifying the surface.
The polyaromatic amine is a conjugated polymer, has good environmental stability and redox property, contains a large amount of amino on the surface, and has been widely noticed in the fields of water treatment and the like. However, the specific surface area of the synthesized polyaromatic amine is very low, and is only dozens to dozens of m2The use of/g is greatly limited.
Therefore, it would be of great interest to develop a composite material and a method of making the same that combines the advantages of both Uio-66 and polyaramids.
The invention provides a method for preparing Uio-66/polyaromatic amine composite material with a nanoscale core-shell structure by using a surface activity induction method. It combines high stability, high specific surface area, excellent redox properties and chelating properties. Has good application prospect in the field of treatment of wastewater containing heavy metals.
Disclosure of Invention
The invention aims to provide an Uio-66/polyaromatic amine composite material with a core-shell structure, and a preparation method and application thereof. The preparation method is simple, the repeatability is good, the prepared composite material shows a core-shell structure, the specific surface area of the polyaromatic amine is effectively improved, the Uio-66 surface is successfully subjected to amination modification, and the advantages of the two components are combined.
The object of the present invention is achieved as follows.
An Uio-66/polyaromatic amine composite material with a core-shell structure, wherein Uio-66 is a core, and polyaromatic amine is a shell. The aromatic amine monomer comprises one or more of m-phenylenediamine, aniline and pyrrole.
The particle size range of the composite material is between 200 and 800nm, and the shell thickness is about 20-80 nm.
Within the range of the particle size and the shell thickness, the specific surface area of the composite material is reduced along with the increase of the shell thickness, and although the overall adsorption performance of the composite material is improved, the utilization rate of the PmPD is reduced.
The preparation method of the Uio-66/polyaromatic amine composite material with the core-shell structure comprises the following steps of adding Uio-66 and aromatic amine monomer into a solution, and uniformly stirring; then persulfate aqueous solution is dripped to initiate oxidative polymerization reaction, and the mixture is continuously stirred for reaction, solid-liquid separation and washing are carried out to obtain Uio-66/polyaromatic amine composite material.
According to the preparation method of the Uio-66/polyaromatic amine composite material with the core-shell structure, the mass ratio of Uio-66 to aromatic amine monomer is 1: 5-1: 0.25; preferably 1: 1-0.25; further preferably 1: 0.5.
According to the preparation method of the Uio-66/polyaromatic amine composite material with the core-shell structure, in a reaction system, the mass concentration of Uio-66 is 1-10 g/L, preferably 4g/L, and the mass concentration of aromatic amine monomers is 1-10 g/L, preferably 2 g/L.
According to the preparation method of the Uio-66/polyaromatic amine composite material with the core-shell structure, a surfactant is added into a reaction system, and the surfactant comprises one or two of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate. Sodium dodecylbenzenesulfonate is preferred.
According to the preparation method of the Uio-66/polyaromatic amine composite material with the core-shell structure, the mass ratio of Uio-66 to the surfactant is 1: 2-1: 0.3, and preferably 1: 0.5.
The use amount of the surfactant is too much, a reaction system can generate a lot of foams, the sample cleaning process is complicated and is not easy to clean, the use amount is too little, the surface induction effect is weakened, and the dispersibility of the product is poor.
According to the preparation method of the Uio-66/polyaromatic amine composite material with the core-shell structure, the persulfate comprises one or more of sodium persulfate, ammonium persulfate and potassium persulfate.
According to the preparation method of the Uio-66/polyaromatic amine composite material with the core-shell structure, the molar ratio of the persulfate to the aromatic amine monomer is 1: 1-3: 1, preferably 1:1, and the concentration of the persulfate solution is 0.01-0.5 mol/L, preferably 0.025 mol/L.
The preparation method of Uio-66/polyaromatic amine composite material with core-shell structure comprises the steps of firstly dispersing Uio-66 in aqueous solution containing surfactant, then adding aromatic amine monomer, stirring for at least 0.5h, and fully contacting; then adding persulfate aqueous solution at a constant speed of 0.5-10 ml/min to initiate oxidative polymerization reaction, and continuously stirring for at least 3 h; and carrying out solid-liquid separation and washing to obtain the Uio-66/polyaromatic amine composite material.
In the preparation method, Uio-66 is dispersed in an aqueous solution containing a surfactant, and a stirring process is needed after the aromatic amine monomer is added so as to be fully contacted. The stirring time is at least 0.5h, preferably 0.5-24h, more preferably 0.5-2 h. Because the aromatic amine monomer is self-assembled on the surface of Uio-66 by the action of the surfactant after the monomer is added, the aromatic amine monomer can be oxidized and polymerized on the surface of Uio-66 after the oxidant is added to form a subsequent core-shell structure, and therefore, the aromatic amine monomer and the oxidant need a period of time to be fully contacted to complete the self-assembly.
In the above preparation method, the persulfate solution cannot be rapidly added, but is slowly added at a constant rate, preferably at a rate of about 2.5 ml/min.
In the above-mentioned production method, the oxidative polymerization is initiated and the stirring is continued for at least 3 hours, preferably 3 to 24 hours, and more preferably 6 hours. The stirring is performed in order to allow the polymerization reaction to proceed sufficiently, and the polymerization is incomplete when the time is too short.
In the method, after the oxidative polymerization reaction is finished, the reaction is preferably carried out at 0-60 ℃. Solid-liquid separation by centrifugation is preferred.
The invention also provides application of the Uio-66/polyaromatic amine composite material with the core-shell structure in treating heavy metal chromium.
Further, the Uio-66/polyaromatic amine composite material is used for treating acid wastewater containing hexavalent Cr.
Furthermore, the initial concentration of hexavalent Cr in the acidic wastewater is 10-300 mg/L, and the pH value is 1-5.
Further, the pH value of the hexavalent Cr acidic wastewater is 2.
Further, the Uio-66/polyaromatic amine composite material is added into waste water containing hexavalent Cr according to the solid-to-liquid ratio of 0.02 g/L-2 g/L for mixing, then the oscillation reaction is carried out, and the filtration and the separation are carried out.
Further, the Uio-66/polyaromatic amine composite material is added into waste water containing hexavalent Cr to be mixed, and then the mixture is vibrated to react for 5-720 min, filtered and separated.
The invention has the beneficial effects that:
1) the invention provides an Uio-66/polyaromatic amine composite material with a novel structure, which takes Uio-66 as a core and polyaromatic amine as a shell. The specific surface area of the composite material reaches 319.77m2The specific surface area of the polyaromatic amine is effectively increased, and Uio-66 surface is successfully subjected to amination modification, so that the advantages of the two components are combined.
2) The invention also provides a preparation method of the Uio-66/polyaromatic amine composite material based on interface hydrophobic induction, and the preparation process is simple and efficient. Because the adopted raw materials Uio-66 have undersized nano-particles, the nano-particles are easy to agglomerate in the solution, the contact property with polyaromatic amine molecules is reduced, and effective poly surface modification is difficult to realize. According to the invention, the surfactant is introduced to promote the interface of Uio-66 particles to be hydrophobic, so that the particle dispersibility is improved, the oxidative polymerization efficiency of the polyaromatic amine is greatly improved, and the Uio-66/polyaromatic amine composite material with a core-shell structure is prepared.
3) The invention provides a method for performing amination modification on the surface of an Uio-66 nano structure by using aromatic amine, and provides a new idea for the appearance and surface modification of Uio-66 MOFs structural materials.
4) The Uio-66 is synthesized by a microwave method, the reaction is fast, and the yield is high; aromatic amine monomers such as m-phenylenediamine and the like are conventional raw materials in the industrial fields of dyes, coatings and the like, and the Uio-66 and aromatic amine compound reaction is carried out at normal temperature, so that no harsh reaction conditions are required, no special post-treatment means is required, and the cost is low.
5) The composite material obtained by the invention combines the advantages of Uio-66 and polyarylamine, has good stability in aqueous solution, is beneficial to the application in the fields of water treatment and the like, and particularly has obvious application effect on treating heavy metal chromium.
Description of the drawings:
FIG. 1 is an SEM image of the products obtained in examples 1 to 5 and comparative example 1;
(a)Uio‐66/PmPD‐1:3(b)Uio‐66/PmPD‐1:1(c)Uio‐66/PmPD‐1:0.5；
(d)Uio‐66/PANI‐1:0.5(e)Uio‐66/PPY‐1:0.5(f)Uio‐66/PmPD‐1:0.5‐NSDS；
as can be seen from comparison of (a), (b) and (c), the morphology of the compound obtained by different compound proportions is different, the compound is agglomerated along with the increase of the addition amount of mPD, and the specific surface area has a certain influence, when the addition amount is reduced to 1: at 0.5, the composite was uniform and dispersed in morphology, as listed in table 1; as can be seen from the comparison of (c), (d) and (e), the morphology of the compound obtained by compounding different polyaromatic amines with Uio-66 is not greatly different; as can be seen from the comparison of (c) and (f), the Uio-66/polyaromatic amine compound synthesized by adding the surfactant and adopting the interfacial hydrophobic oxidative polymerization method has better dispersibility and more uniform compounding.
FIG. 2 is a TEM image and a line scan of the product obtained in example 1 and comparative examples Uio-66;
(a) uio-66, (b) Uio-66/PmpD, which shows that compared with Uio-66, the composite material of the invention has a rougher surface, is wrapped by a layer of film and shows a core-shell structure;
(c) EDS line scan characterization (d) was performed across the diameter of composites Uio-66 @ PmPD (1:0.5), and it can be seen that the Zr and O elements are distributed predominantly in the core portion and the C and N are relatively uniformly distributed throughout, further demonstrating the composition of the core-shell structure in the composite, i.e., Uio-66 surfaces uniformly coated with a layer of PmPD.
FIG. 3 is an XRD pattern and an infrared pattern of comparative PmPD of the product obtained in example 1 and comparative Uio-66; (a) the XRD patterns for the product of example 1 and comparative examples Uio-66; (b) an infrared plot of the product obtained in example 1 and comparative Uio-66, PmPD;
according to an XRD (X-ray diffraction) pattern, the phase composition of Uio-66 is not changed after compounding, and the structure is not collapsed;
known by an infrared spectrum at 3400-3000 cm‐1Two absorption peaks are amino stretching vibration at 1620cm‐1The nearby absorption corresponds to the quinoid structure, 746cm‐1The absorption peak corresponds to Zr-O bond, the characteristic absorption peaks of the two components exist in the compound at the same time, and a large number of amino groups are contained.
In conclusion, a series of representations of morphology, structure and phase can prove that the composite material with Uio-66 as the core and polyaromatic amine as the shell is successfully prepared.
FIG. 4 shows N of the product obtained in example 12Adsorption and desorption isotherms;
as can be seen, the adsorption-desorption isotherms belong to the class I adsorption isotherms, indicating that the composite contains a large number of micropores, which are presumed to be contributed from Uio to 66. And the existence of a large number of micropores is an important reason for the high specific surface area of the composite.
FIG. 5 is a thermogravimetric plot of the products obtained in examples 1-3 and comparative Uio-66, PmPD;
the loading of PmPD in the composite was calculated by analyzing the thermogram and using the mass ratio of the residue according to equation 1. The calculations show that Uio-66 @ PmPD (1:0.5), Uio-66 @ PmPD (1:1), Uio-66 @ PmPD (1:3) correspond to composite loadings of 11.50%, 25.83% and 56.30%, respectively (data are shown in Table 1). Obviously, the input ratio of the reaction raw material mPD is increased, and the proportion of the PmPD in the composite material can be obviously increased.
If the adsorbed amount of Uio-66 is subtracted from the adsorbed amount of the composite, the mass of PmPD in the composite is used to calculate the mass of PmPD according to equation 2The adsorption capacities of PmPD in Uio-66 @ PmPD (1:0.5), Uio-66 @ PmPD (1:1) and Uio-66 @ PmPD (1:3) were 745, 680 and 600mg g, respectively, as calculated for adsorption capacity‐1Higher than pure PmPD particles (415mg g) in this experiment‐1) And literature reports of pure PmPD particles (373 mg g)‐1). This indicates that the configuration of the core-shell structure exposes the active ingredient on the outer surface, strengthening the adsorption sites, compared to the PmPD particles of comparable size.
Equation 1 for calculating the amount of PmpD load
Figure BDA0001728246540000051
wPmPDRepresents mass percent,%, of PmPD;
Figure BDA0001728246540000052
represents H2Percent mass loss of O: (<150℃)，％；wrIs the mass percent of residue,%; eta is the mass percent of Uio-66 residues in Uio-66;
Figure BDA0001728246540000061
wr(Uio-66) represents the final mass percent residue,%, of the Uio-66 thermogravimetric curve;
Figure BDA0001728246540000066
Figure BDA0001728246540000067
represents Uio-66 percent by mass of water lost on heat loss<150℃)，％
Equation 2 for calculating the amount of PmPD Cr (VI) adsorbed in the composite
Figure BDA0001728246540000063
QPmPDIn the complexAdsorption amount of PmPD, mg g‐1；QUio-66@PmPD(1:x)Denotes the amount of adsorption of the complex, mg g‐1；QUio-66Denotes the amount of Uio-66 adsorbed in mg g‐1；wUio-66Represents Uio-66 mass percent of the composite;
Figure BDA0001728246540000064
table 1 shows the BET specific surface area, pore volume and average pore diameter of the products obtained in examples 1 to 3
TABLE 1 comparison of specific surface area, pore volume, mean pore diameter for 1 Uio-66/PmPD (1: x) series composites
Figure BDA0001728246540000065
It can be seen that as the amount of mPD added increases, the specific surface area of the composite decreases significantly, and the pore volume decreases gradually, which is probably caused by the outer layer of PmPD blocking the micropores of Uio-66.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples without restricting it.
Example 1
600mg of Uio-66 was accurately weighed and charged into a 250ml round-bottomed flask, 150ml of distilled water was added thereto, stirred and ultrasonically dispersed, and 300mg of m-phenylenediamine monomer and 300mg of sodium dodecylsulfate were accurately weighed and charged into the flask, and stirred for 16 hours to be brought into full contact. 900mg of sodium persulfate was accurately weighed and dissolved in 50ml of distilled water to be sufficiently dissolved, and 37ml of sodium persulfate was used. Sodium persulfate solution was gradually added dropwise to the round bottom flask over about 15min to initiate oxidative polymerization. The reaction was continued at room temperature (about 20 ℃ C.) for 5 hours, and the reaction system gradually changed from white to black brown. After the reaction, the reaction mixture was centrifuged (8000 rpm), and the residual sodium persulfate and sodium dodecylsulfate were washed with distilled water. The product was dried in an oven for 12 hours and the resulting black solid powder was a nanoscale Uio-66/PmPD composite, designated Uio-66/PmPD-1: 0.5(PmPD means poly (m-phenylenediamine), 1:0.5 means a Uio-66 to aromatic amine monomer dosing mass ratio of 1:0.5, and so forth, hereinafter the nomenclature).
Example 2
200mg of Uio-66 was accurately weighed and charged into a 250ml round-bottomed flask, 150ml of distilled water was added thereto, stirred and ultrasonically dispersed, 600mg of m-phenylenediamine monomer and 200mg of sodium dodecylsulfate were accurately weighed and charged into the flask, and stirred for 16 hours to be brought into full contact. 1.8g of sodium persulfate was accurately weighed and dissolved in 50ml of distilled water to be sufficiently dissolved, and 37ml of sodium persulfate was used. Sodium persulfate solution was gradually added dropwise to the round bottom flask over about 15min to initiate oxidative polymerization. The reaction was continued at room temperature (about 20 ℃ C.) for 5 hours, and the reaction system gradually changed from white to black brown. After the reaction, the reaction mixture was centrifuged (8000 rpm), and the residual sodium persulfate and sodium dodecylsulfate were washed with distilled water. The product was dried in an oven for 12 hours and the resulting black solid powder was a nano-scale Uio-66/PmPD composite, designated Uio-66/PmPD-1: 3.
Example 3
200mg of Uio-66 was accurately weighed and charged into a 250ml round-bottomed flask, 150ml of distilled water was added thereto, stirred and ultrasonically dispersed, and 200mg of m-phenylenediamine monomer and 200mg of sodium dodecylsulfate were accurately weighed and charged into the flask, and stirred for 16 hours to be brought into full contact. 600mg of sodium persulfate was accurately weighed and dissolved in 50ml of distilled water to be sufficiently dissolved, and 37ml of sodium persulfate was used. Sodium persulfate solution was gradually added dropwise to the round bottom flask over about 15min to initiate oxidative polymerization. The reaction was continued at room temperature (about 20 ℃ C.) for 5 hours, and the reaction system gradually changed from white to black brown. After the reaction, the reaction mixture was centrifuged (8000 rpm), and the residual sodium persulfate and sodium dodecylsulfate were washed with distilled water. The product was dried in an oven for 12 hours and the resulting black solid powder was a nano-scale Uio-66/PmPD composite, designated Uio-66/PmPD-1: 1.
Example 4
300mg of Uio-66 was accurately weighed and added to a 250ml round bottom flask, 150ml of distilled water was added, stirred and ultrasonically dispersed, 147.06 μ l of aniline monomer was accurately weighed, 300mg of sodium dodecyl sulfate was weighed and added to the flask, and stirred for 16 hours to be fully contacted. 524mg of sodium persulfate was accurately weighed and dissolved in 50ml of distilled water to be sufficiently dissolved, and 37ml of the solution was used. Sodium persulfate solution was gradually added dropwise to the round bottom flask over about 15min to initiate oxidative polymerization. The reaction was continued at room temperature (about 20 ℃) for 5 h. After the reaction, the reaction mixture was centrifuged (8000 rpm), and the residual sodium persulfate and sodium dodecylsulfate were washed with distilled water. The product was dried in an oven for 12 hours to give a yellow solid powder as a nanoscale Uio-66/PANI composite, designated Uio-66/PANI-1: 0.5(PANI means polyaniline).
Example 5
300mg of Uio-66 was accurately weighed and added to a 250ml round bottom flask, 150ml of distilled water was added, stirred and ultrasonically dispersed, 155. mu.l of pyrrole monomer was accurately weighed, 300mg of sodium dodecyl sulfate was weighed and added to the flask, and stirred for 16 hours to be fully contacted. 719mg of sodium persulfate was accurately weighed and dissolved in 50ml of distilled water to dissolve it sufficiently, and 37ml of it was used. Sodium persulfate solution was gradually added dropwise to the round bottom flask over about 15min to initiate oxidative polymerization. The reaction was continued at room temperature (about 20 ℃) for 5 h. After the reaction, the reaction mixture was centrifuged (8000 rpm), and the residual sodium persulfate and sodium dodecylsulfate were washed with distilled water. The product was dried in an oven for 12 hours to give a dark brown solid powder in the form of a nanoscale Uio-66/PPY composite, designated Uio-66/PPY-1: 0.5(PPY stands for polypyrrole).
Comparative example 1
No surfactant was added. 600mg of Uio-66 was accurately weighed and charged into a 250ml round bottom flask, 150ml of distilled water was added thereto, stirred and ultrasonically dispersed, and 300mg of m-phenylenediamine monomer was accurately weighed and charged into the flask, stirred for 16 hours, and sufficiently contacted. 900mg of sodium persulfate was accurately weighed and dissolved in 50ml of distilled water to be sufficiently dissolved, and 37ml of sodium persulfate was used. Sodium persulfate solution was gradually added dropwise to the round bottom flask over about 15min to initiate oxidative polymerization. The reaction was continued at room temperature (about 20 ℃ C.) for 5 hours, and the reaction system gradually changed from white to black brown. After the reaction, the reaction mixture was centrifuged (8000 rpm), and the residual sodium persulfate was washed with distilled water. The product was dried in an oven for 12 hours and the resulting black solid powder was a nano-sized Uio-66/PmPD composite, designated Uio-66/PmPD-1: 0.5-NSDS (-NSDS means no surfactant added, compare Uio-66/PmPD-1: 0.5 for example 1).
Example 6
Preparation Uio-66/Poly (m-phenylenediamine) composite adsorbent (I)
600mg of Uio-66 was accurately weighed and charged into a 250ml round-bottomed flask, 150ml of distilled water was added thereto, stirred and ultrasonically dispersed, and 300mg of m-phenylenediamine monomer and 300mg of sodium dodecylsulfate were accurately weighed and charged into the flask, and stirred for 16 hours to be brought into full contact. 900mg of sodium persulfate was accurately weighed and dissolved in 50ml of distilled water to be sufficiently dissolved, and 37ml of sodium persulfate was used. Sodium persulfate solution was gradually added dropwise to the round bottom flask over about 15min to initiate oxidative polymerization. The reaction was continued at room temperature (about 20 ℃ C.) for 5 hours, and the reaction system gradually changed from white to black brown. After the reaction was completed, the product was obtained by centrifugation (8000 rpm), and the residual sodium persulfate and sodium dodecylsulfate were washed off with distilled water. The product was dried in an oven for 12 hours to give a black solid powder of Uio-66/poly (m-phenylenediamine) nano-scale composite, designated Uio-66/PmPD-1: 0.5.
The manner of detecting the adsorption of Cr (VI) by the Uio-66/poly (m-phenylenediamine) composite material prepared in the above is as follows:
transferring 50ml of Cr (VI) solution with a certain concentration into a 125ml polytetrafluoroethylene bottle, adjusting the pH value to a certain value by using hydrochloric acid and a sodium hydroxide solution, then weighing 50mg of Uio-66/poly (m-phenylenediamine) composite material, putting the composite material into the Cr (VI) solution, putting the composite material into a water bath at 30 ℃, oscillating and adsorbing for a certain time, filtering, measuring the residual Cr (VI) in the filtrate by adopting a dibenzoyl dihydrazide spectrophotometry, then calculating the adsorption quantity of the adsorbent according to the formula (1), and calculating the removal rate of the Cr (VI) according to the formula (2).
Figure BDA0001728246540000091
Figure BDA0001728246540000092
Q: the amount of Cr (VI) adsorbed (mg/g); q is the removal rate of Cr (VI); c0: initial Cr (VI) concentration (mg/L); c: residual Cr (VI) concentration after adsorption (mg/L); v: volume (L) of solution containing Cr (VI); w: mass of adsorbent (g) added.
The Uio-66/poly (m-phenylenediamine) composite material prepared by the method is used as an adsorbent, and the initial concentration of Cr (VI) is changed to obtain the relationship between the initial concentration and the adsorption quantity and removal rate.
According to the change of the adsorption amount and the removal rate of Uio-66/poly (m-phenylenediamine) composite material with certain concentration of Cr (VI) solution along with the initial pH value, the optimal initial pH value of the Cr (VI) solution can be obtained by the adsorption reaction.
According to the change of the adsorption amount and the removal rate of the Uio-66/poly (m-phenylenediamine) composite material with time when adsorbing a Cr (VI) solution with a certain concentration, the relation between the adsorption time and the adsorption amount and the removal rate of the Cr (VI) solution with a certain concentration can be obtained.
Example 7
Preparation Uio-66/Poly (m-phenylenediamine) composite adsorbent (II)
200mg of Uio-66 was accurately weighed and charged into a 250ml round-bottomed flask, 150ml of distilled water was added thereto, stirred and ultrasonically dispersed, 600mg of m-phenylenediamine monomer and 200mg of sodium dodecylsulfate were accurately weighed and charged into the flask, and stirred for 16 hours to be brought into full contact. 1.8g of sodium persulfate was accurately weighed and dissolved in 50ml of distilled water to be sufficiently dissolved, and 37ml of sodium persulfate was used. Sodium persulfate solution was gradually added dropwise to the round bottom flask over about 15min to initiate oxidative polymerization. The reaction was continued at room temperature (about 20 ℃ C.) for 5 hours, and the reaction system gradually changed from white to black brown. After the reaction was completed, the product was obtained by centrifugation (8000 rpm), and the residual sodium persulfate and sodium dodecylsulfate were washed off with distilled water. The product was dried in an oven for 12 hours and the resulting black solid powder was a nano-scale Uio-66/PmPD composite, designated Uio-66/PmPD-1: 3.
Example 8
The initial pH value of 50ml of Cr (VI) solution with the concentration of 50, 100, 200 and 300mg/L is adjusted to 2, 50mg of Uio-66/poly (m-phenylenediamine) composite material (I) is weighed as an adsorbent and is respectively added into the Cr (VI) solution, the mixture is shaken in a water bath at the temperature of 30 ℃ for reaction for 12 hours, and the residual Cr (VI) in filtrate after filtration is measured by a dibenzoyl dihydrazide spectrophotometry method, so that the adsorption amounts of Uio-66/poly (m-phenylenediamine) composite material (I) to Cr (VI) are 47.93, 90.86, 149.59 and 169.53mg/g respectively, and the removal rates are 98.56%, 98.20%, 78.60% and 61.12% respectively when the initial concentration of the Cr (VI) solution is 50, 100, 200 and 300 mg/L.
Example 9
The initial pH value of 50ml of Cr (VI) solution with the concentration of 50, 100, 200 and 300mg/L is adjusted to 2, 50mg of Uio-66/poly (m-phenylenediamine) composite material (II) is weighed as an adsorbent and is respectively added into the Cr (VI) solution, the mixture is shaken in a water bath at the temperature of 30 ℃ for 12 hours, the residual Cr (VI) in the filtrate after filtration is measured by a dibenzoyl dihydrazide spectrophotometry method, and the results show that when the initial concentration of the Cr (VI) solution is 50, 100, 200 and 300mg/L, the adsorption amount of the Uio-66/poly (m-phenylenediamine) composite material (II) to the Cr (VI) is gradually increased to 48.19, 91.65, 186.99 and 263.69mg/g, and the removal rate is respectively 99.10%, 99.05%, 98.25% and 95.06%.
Comparative examples 2 and 3
The initial pH value of 50ml of Cr (VI) solution with the concentration of 50, 100, 200 and 300mg/L is adjusted to 2, 50mg of Uio-66 which is not compounded with poly-m-phenylenediamine is weighed as an adsorbent and is respectively added into the Cr (VI) solution, the mixture is shaken in a water bath at the temperature of 30 ℃ for reaction for 12 hours, and the residual Cr (VI) in the filtrate after filtration is measured by a dibenzoyl dihydrazide spectrophotometry method, so that the adsorption amounts of Uio-66 to Cr (VI) are 31.27, 49.65, 73.74 and 78.02mg/g and the removal rates are 64.30%, 53.66%, 38.75% and 28.12% respectively when the initial concentration of the Cr (VI) solution is 50, 100, 200 and 300 mg/L.
Therefore, compared with Uio-66 which is not compounded with poly-m-phenylenediamine, the adsorption performance of the compounded material to Cr (VI) in a water body is greatly improved.
Example 10
The pH values of 50ml of 300mg/L Cr (VI) solution are respectively adjusted as follows: 2. 3, 5, adding 50mg of Uio-66/poly (m-phenylenediamine) composite material (I) into a Cr (VI) solution, oscillating for 8 hours at 30 ℃, and measuring the residual Cr (VI) in the filtrate after filtering by using a dibenzoyl dihydrazide spectrophotometry, wherein the results show that the adsorption amounts of Uio-66/poly (m-phenylenediamine) composite material (I) are 143.25, 53.32 and 38.70mg/g when the initial pH values are 2, 3 and 5.
Example 11
The pH values of 50ml of 300mg/L Cr (VI) solution are respectively adjusted as follows: 2. 3, 5, adding 50mg of Uio-66/poly (m-phenylenediamine) composite material (II) into a Cr (VI) solution, oscillating for 8 hours at 30 ℃, and measuring the residual Cr (VI) in the filtrate after filtering by using a dibenzoyl dihydrazide spectrophotometry, wherein the results show that the adsorption amounts of Uio-66/poly (m-phenylenediamine) composite material (I) are 261.85, 79.43 and 49.27mg/g when the initial pH values are 2, 3 and 5.
Example 12
Weighing 50mg of Uio-66/poly-m-phenylenediamine composite material (I) and putting into 50ml of Cr (VI) solution with initial concentration of 300mg/L and initial pH of 2, oscillating and reacting for a certain time at 30 ℃, and measuring the residual Cr (VI) in the filtrate after filtering by a dibenzoyl dihydrazide spectrophotometry. The results showed that the removal rates obtained by varying the adsorption time to 5 minutes, 10 minutes, 20 minutes, 30 minutes, 1 hour, 2 hours, 5 hours, 8 hours, and 12 hours were 22.50%, 24.32%, 27.73%, 32.27%, 36.82%, 40.00%, 41.95%, 47.86%, and 61.12%, respectively, and the adsorption amounts were 63.54, 68.67, 78.30, 91.13, 103.97, 112.95, 121.29, 143.25, and 169.53mg/g, respectively.
Example 13
Weighing 50mg of Uio-66/poly (m-phenylenediamine) composite material (II), putting the composite material into 50ml of Cr (VI) solution with the initial concentration of 300mg/L and the initial pH value of 2, oscillating the solution at 30 ℃ for reaction for a certain time, and measuring the residual Cr (VI) in the filtrate after filtering by a dibenzoyl dihydrazide spectrophotometry. The results showed that by varying the adsorption time to 5 minutes, 10 minutes, 20 minutes, 30 minutes, 1 hour, 2 hours, 5 hours, 8 hours, 12 hours, the removal rates were 49.55%, 53.64%, 62.50%, 64.55%, 66.59%, 71.36%, 79.32%, 89.48%, 95.06%, respectively, and the adsorption amounts were 139.91, 151.46, 176.49, 182.26, 188.04, 201.51, 223.98, 261.85, 263.69mg/g, respectively.
As can be seen from the above examples, the Uio-66/poly (m-phenylenediamine) composite material prepared by the in-situ chemical oxidative polymerization of m-phenylenediamine monomers on the surface of Uio-66 is simple and easy to implement, low in cost, high in yield and stable in property. Uio-66/poly m-phenylenediamine composite material has maximum adsorption amount of 263.69mg/g for Cr (VI) and has a Cr (VI) solution removal rate of 100mg/L and below of more than 99 percent, thus being an economically usable adsorbent for treating industrial Cr (VI) containing acidic wastewater.

Claims (8)

1. An Uio-66/polyaromatic amine composite material with a core-shell structure for treating heavy metal chromium, which is characterized in that Uio-66 is a core and polyaromatic amine is a shell; the particle size range of the composite material is between 200 and 800nm, and the shell thickness is between 20 and 80 nm;
the preparation method of the Uio-66/polyaromatic amine composite material with the core-shell structure comprises the following steps of firstly dispersing Uio-66 in an aqueous solution containing a surfactant, then adding an aromatic amine monomer, and stirring for at least 0.5h to ensure that the aromatic amine monomer is fully contacted; then adding persulfate aqueous solution at a constant speed of 0.5-10 ml/min to initiate oxidative polymerization; continuously stirring for reacting for at least 3h, and carrying out solid-liquid separation and washing to obtain Uio-66/polyaromatic amine composite material; the surfactant comprises one or two of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
2. Uio-66/polyaromatic amine composite material with core-shell structure according to claim 1, characterized in that the aromatic amine monomer comprises one or more of m-phenylenediamine, aniline, pyrrole.
3. The Uio-66/polyaromatic amine composite material with the core-shell structure of claim 1, wherein the mass ratio of Uio-66 to aromatic amine monomer is 1: 5-1: 0.25.
4. The Uio-66/polyaromatic amine composite material with the core-shell structure of claim 1, wherein in the reaction system, the mass concentration of Uio-66 is 1-10 g/L, and the mass concentration of the aromatic amine monomer is 1-10 g/L.
5. The Uio-66/polyaromatic amine composite material with the core-shell structure as claimed in claim 1, wherein the mass ratio of Uio-66 to the surfactant is 1: 2-1: 0.3.
6. The Uio-66/polyaromatic amine composite material with core-shell structure of claim 1, wherein the persulfate includes one or more of sodium persulfate, ammonium persulfate, and potassium persulfate.
7. The Uio-66/polyaromatic amine composite material with the core-shell structure according to claim 1, wherein the molar ratio of the persulfate to the aromatic amine monomer is 1: 1-3: 1, and the concentration of the persulfate solution is 0.01-0.5 mol/L.
8. Use of Uio-66/polyaromatic amine composite material with a core-shell structure according to claim 1 or 2 in the treatment of chromium as heavy metal.
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