CN114345305A - NH2-UiO-66@ LS composite material, and preparation method and application thereof - Google Patents
NH2-UiO-66@ LS composite material, and preparation method and application thereof Download PDFInfo
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- CN114345305A CN114345305A CN202210043238.7A CN202210043238A CN114345305A CN 114345305 A CN114345305 A CN 114345305A CN 202210043238 A CN202210043238 A CN 202210043238A CN 114345305 A CN114345305 A CN 114345305A
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000013207 UiO-66 Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 244000280244 Luffa acutangula Species 0.000 claims abstract description 9
- 235000009814 Luffa aegyptiaca Nutrition 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- -1 fluoride ions Chemical class 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 241000219138 Luffa Species 0.000 claims 2
- 235000003956 Luffa Nutrition 0.000 claims 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 229910007926 ZrCl Inorganic materials 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 15
- 150000001450 anions Chemical class 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 description 16
- 239000011737 fluorine Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 206010016818 Fluorosis Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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Abstract
The invention discloses NH2The composite material takes natural Loofah Sponge (LS) after pretreatment as a carrier, and NH is added by an in-situ growth method2the-UiO-66 is loaded on the pretreated LS surface, the fluorine ion adsorption efficiency is greatly improved compared with that of the LS only pretreated, and F is treated‑The adsorption rate of (2) reaches 77.59%; the composite material pair F under the condition of other anions coexisting‑Has specific adsorption performance, simple preparation process, easily obtained raw materials, large-scale preparation and high-efficiency recycling.
Description
Technical Field
The invention relates to the technical field of removing harmful ions in sewage, in particular to NH2-UiO-66@ LS composite material, preparation method and application.
Background
Water is a source of everything, but water pollution problems have severely affected human life and development. The fluorine ions exist in the water solution, are easy to migrate and can enter the human body through biological accumulation, and F in the human body-Excessive intake of such amounts can cause a number of health problems. For example: in the human body F-Too much can lead to perforation and chipping of the teeth; if F-Poisoning can lead to extreme pain and even stiffness in the joints, ultimately leading to paralysis. On earth, fluorosis affects millions, even tens of millions, of people, F-Contamination is a global problem, WHO stipulates F in drinking water for human life-The limiting value of the concentration is 1.5 mg.L-1. Definition F in national drinking water standard' sanitary Standard for Drinking Water-The maximum allowable concentration of (b) is 1.0 mg.L-1. Therefore, it is necessary to research an efficient and inexpensive water treatment material for removing fluorine ions from sewage.
Metal organic framework Materials (MOFs) are three-dimensional porous structures composed of metal atoms or clusters of atoms coordinated by organic ligands. MOFs have good applications in adsorptive separation, sensing, catalysis, drug delivery, etc., but also have problems of poor stability, difficult recovery, etc. The MOFs and the substrate material are compounded, so that the agglomeration of the MOFs can be effectively prevented, and the recycling of the material is facilitated.
Disclosure of Invention
The invention aims to provide NH2-UiO-66@ LS composite material, preparation method and application thereof, and NH2the-UiO-66 @ LS composite material can specifically and efficiently adsorb fluorine ions in water and can be recycled.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a NH2-UiO-66@ LS composite material, taking pretreated natural Loofah Sponge (LS) as a carrier, and adding NH2-UiO-66 is loaded on the pretreated LS.
The invention provides the NH2The preparation method of the-UiO-66 @ LS composite material takes pretreated LS as a carrier and adopts an in-situ growth mode to react NH2-UiO-66 is loaded on the pretreated LS.
Further, the preparation method also comprises an LS pretreatment process: and (2) cutting LS into cylinders with the diameter of 30mm and the length of 30mm, soaking the cylinders in a sodium hydroxide solution, then sequentially washing the cylinders with distilled water and ethanol until the washing liquid is neutral, and airing and collecting the cylinders at room temperature for later use.
Further, the in-situ growth process comprises: reacting ZrCl4Dissolving in N, N-Dimethylformamide (DMF), stirring and ultrasonically treating until the solution is completely dissolved, then adding 2-aminoterephthalic acid for stirring, then adding acetic acid into the solution, uniformly stirring the solution, mixing the solution with the pretreated LS for reaction, cooling the solution to room temperature, taking out the reacted LS, and washing the LS with ethanol and water to obtain NH2-UiO-66@ LS composite.
Further, the reaction temperature was 115-125 ℃.
Further, LS and NH after pretreatment2-UiO-66 in a mass ratio of 1: 1.
further, ZrCl4The mass ratio to 2-aminoterephthalic acid was 175.1: 135.9.
The invention provides the NH2-UiO-66@ LS composite material for removing harmful ions in water.
The invention provides the NH2The application of the-UiO-66 @ LS composite material in removing the fluorine ions in water can specifically and efficiently adsorb the fluorine ions in the water, and the composite material can be efficiently recycled.
The invention discloses the following technical effects:
(1) the invention converts NH into2combining-UiO-66 with pretreated LS, using pretreated LS as carrier, adding NH2-UiO-66 loading on pretreated LS surface to obtain NH2-UiO-66@ LS composite material, the loofah sponge is a porous net structure, and NH is added2the-UiO-66 is loaded on the surface of the loofah sponge and can make NH2the-UiO-66 is uniformly distributed on the loofah spongeThe prepared composite material can effectively prevent the material from agglomerating on the net structure, and the preparation process is simple, the raw materials are easy to obtain, and the large-scale preparation can be realized.
(2) The invention takes the fluoride ions in the sewage as the target to adsorb the fluoride ions, greatly improves the efficiency of adsorbing the fluoride ions compared with LS only after pretreatment, and carries out F treatment-The adsorption rate of the composite material reaches 77.59%, and under the condition of coexistence of other anions, the composite material can have specific adsorption performance on the fluorine ions in the sewage, and can be efficiently recycled, which shows that the composite material has good application prospect in removing the fluorine ions in the sewage.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic diagram of the synthesis steps of the composite material of the present invention;
FIG. 2 shows LS and NH after pretreatment in example 12-XRD pattern of UiO-66@ LS composite;
FIG. 3 shows LS and NH after pretreatment in example 12-an infrared spectrum of the UiO-66@ LS composite;
FIG. 4 shows LS and NH after pretreatment in example 12SEM pictures of the UiO-66@ LS composite material at different times, wherein a is the SEM picture of the pretreated LS at the time of 100 times, b is the SEM picture of the pretreated LS at the time of 1000 times, and c is NH at the time of 100 times2SEM picture of-UiO-66 @ LS composite material, d is NH at 1000 times2-SEM image of UiO-66@ LS composite;
FIG. 5 shows NH prepared in example 12-EDS diagram of UiO-66@ LS composite;
FIG. 6 is F plotted according to example 2-A concentration standard curve graph;
FIG. 7 shows LS and NH after pretreatment in example 12-UiO-66@ LS complexA comparison graph of the composite material adsorbing fluorine ions;
FIG. 8 is NH prepared in example 12-effect of UiO-66@ LS composite on adsorption rate at different initial concentrations of fluoride ion;
FIG. 9 shows NH prepared in example 12-the effect of the UiO-66@ LS composite on the adsorption of fluoride ions in water under conditions of anion competition;
FIG. 10 shows NH prepared in example 12-UiO-66@ LS composite material adsorption effect graph after three repeated experiments.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated value or intervening value in a stated range, and any other stated or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the "5% sodium hydroxide" of the present invention, "%" means mass fraction.
Example 1
Preprocessing LS:
cutting natural retinervus Luffae fructus (LS) into cylinders with diameter of 30mm and length of 30mm, soaking in 5% sodium hydroxide solution for 24 hr, sequentially cleaning with distilled water and ethanol for several times until the cleaning solution is neutral, air drying at room temperature, and collecting;
NH2-preparation of UiO-66@ LS composite:
using pretreated 30mg LS as a carrier, and adopting an in-situ growth method to prepare NH2-UiO-66@ LS composite: 0.8g of ZrCl4(3.43mmol) was dissolved in 50mL of DMF, sonicated to complete dissolution, and then 0.57g of 2-aminoterephthalic acid (H) was added2BDC, 3.43mmol) was stirred for five minutes, then 0.48g of acetic acid was added to it, stirred well, then charged to a 100mL liner and the pretreated LS was placed in the liner. And (3) putting the reaction kettle into a drying box at 120 ℃ for reaction for 24 hours. After cooling, the LS after reaction is taken out of the reaction kettle and washed with ethanol and water for a plurality of times to obtain NH2-UiO-66@ LS composite.
Example 2
Preparing a sodium fluoride standard stock solution:
preparing standard stock solution of sodium fluoride by a fluoride ion selective electrode method, firstly weighing 4.2g of NaF (0.1mol), dissolving in deionized water, and then fixing the volume to 1L to obtain 0.1 mol.L-1The prepared sodium fluoride ion solutions are respectively diluted to be 1 x 10-2mol·L-1、1×10-3mol·L-1、1×10-4mol·L-1、2×10-4mol·L-1、1×10- 5mol·L-1、2×10-5mol·L-1、2×10-6mol·L-1Respectively measuring 10mL of F with different concentrations-The standard solution was placed in a 50mL beaker and 10mL of Total Ionic Strength Adjusting Buffer (TISAB) was added. Under the condition of stirring stability, testing a series of standard solutions by a fluoride ion selective electrode to obtain lg (C)F -) The standard equation with E is E-55.84385X-218.43254, R20.99251. During the experiment, the corresponding potential value was measured by the fluoride ion selective electrode and substituted into lg (C)F -) And obtaining the corresponding fluorine ion concentration by using a standard equation of the E, and further calculating the adsorption amount and the adsorption rate of the composite material to the fluorine ions.
Example 3
Pretreated LS and NH2-UiO-66@ LS composite adsorption on fluoride ion:
under the condition of room temperature, the influence of different materials on the adsorption of fluorine ions is researched. LS and NH after adsorbent pretreatment2The amount of the-UiO-66 @ LS composite was 1g, pH 5, F-Has an initial concentration of 1.10-3mol·L-1. LS and NH2-UiO-66@ LS composite material for adsorbing F in water-. In the course of the experiment, F-The concentration is from 1 to 10-3mol·L-1Reduced to 2.3.10-4mol·L-1The adsorption capacity is 8.03.10-5mol·L-1The adsorption rate reaches 77.59%. NH can be seen2The modification of pretreated LS by-UiO-66 was very effective for F-The main reason for the improvement of the adsorption capacity is NH2Zr in-UiO-664+To F-Has adsorption capacity; furthermore, NH2-UiO-66 has a rich pore structure, which is F-Provides sufficient space for adsorption.
Example 4
NH2-effect of UiO-66@ LS composite on fluoride ion adsorption at different initial concentrations of fluoride ion:
under the condition of room temperature, the method can be used,exploration of NH2-UiO-66@ LS composite effect on fluoride ion adsorption at different initial concentrations of fluoride ion. Adsorbent NH2-UiO-66@ LS composite in an amount of 1g, pH 5, F-The initial concentrations of (A) are 100mg/L, 300mg/L and 500mg/L, respectively, using NH2the-UiO-66 @ LS composite material adsorbs fluorine ions in water. Experiments show that NH is continuously increased along with the initial concentration of fluorine ions2The adsorption capacity of the-UiO-66 @ LS composite material to fluorine ions is continuously enhanced.
Example 5
NH2-effect of UiO-66@ LS composite on fluoride ion adsorption in water under anion competitive conditions:
exploration of NH under ambient conditions2-effect of UiO-66@ LS composite on fluoride ion adsorption in water under anion competitive conditions. Adsorbent NH2-UiO-66@ LS composite in an amount of 1g, pH 5, Cl-、F-、NO3-Has an initial concentration of 1.10-3mol·L-1. Experiments show that under the coexistence of other anions, F-Does not change much, F-The concentration is from 1 to 10-3mol·L-1Reduced to 2.626 & 10-4mol·L-1The adsorption rate reaches 73.74 percent, namely NH2-UiO-66@ LS composite material pair F-Has a certain specificity.
Example 6
NH2-UiO-66@ LS composite material pair F-Three replicate adsorption experiments were performed:
at room temperature, using NH2-UiO-66@ LS composite material pair F-Three replicates of the adsorption experiments were performed. Adsorbent NH2-UiO-66@ LS composite in an amount of 1g, pH 5, F-Is 1X 10-3mol·L-1. After one-time adsorption, the sample is put into a hydrochloric acid solution for washing, naturally dried at room temperature, and the experiment is repeated after drying. Experiments show that NH2The adsorption effect of the-UiO-66 @ LS composite material is obviously reduced after the composite material is recycled, and F-The adsorption rate of (A) is reduced from 77.59% to 59.91%, but still has a certain valueAnd (4) reusability.
Example 1 pretreated LS and NH2The XRD contrast of the-UiO-66 @ LS composite material is shown in FIG. 2, the infrared spectrum contrast is shown in FIG. 3, the SEM contrast is shown in FIG. 4, and NH2The EDS diagram of the-UiO-66 @ LS composite is shown in FIG. 5.
XRD analysis of materials
X-ray diffraction (XRD) of pretreated LS, NH2Analysis of the-UiO-66 @ LS composite, see FIG. 2, and NH, as can be seen in FIG. 22Characteristic peak of-UiO-66 @ LS composite material and reported NH2The characteristic peak of-UiO-66 is consistent, indicating NH2Successful loading of-UiO-66.
Infrared spectroscopic analysis of materials
By infrared treatment of LS, NH after pretreatment2the-UiO-66 @ LS composite was tested, see FIG. 3, and NH can be seen from FIG. 32Infrared of-UiO-66 with reported NH2The IR of-UiO-66 is essentially unity.
SEM analysis of materials
LS and NH after pretreatment in example 12The SEM pictures of the-UiO-66 @ LS composite material under different times are shown in figure 4, wherein a is the SEM picture of the LS after pretreatment under the condition of 100 times, and b is the SEM picture of the LS after pretreatment under the condition of 1000 times, the surface of the composite material is rough, and the growth of crystals is facilitated. c is NH at a multiple of 1002SEM picture of-UiO-66 @ LS composite material, d is NH at 1000 times2SEM image of-UiO-66 @ LS composite material, NH was observed2The compact and uniform distribution of UiO-66 on the pretreated LS surface (no agglomeration) indicates successful loading.
EDS map analysis of materials
For NH prepared in example 12The energy spectrum test of the-UiO-66 @ LS composite material is carried out, the result is shown in FIG. 5, the Zr and Cl elements are uniformly distributed on the pretreated LS surface as can be seen from FIG. 5, and NH is further illustrated2Successful loading of-UiO-66.
FIG. 6 is F plotted according to example 2-A concentration standard curve graph;
FIG. 7 shows LS and NH after pretreatment in example 12-UiO-66@A comparison graph of LS composite material adsorbing fluorine ions; experiments show that NH is obtained by modifying pretreated LS2The adsorption performance of the-UiO-66 @ LS composite material is greatly improved;
FIG. 8 shows LS and NH after pretreatment in example 12-effect of UiO-66@ LS composite on adsorption rate at different initial concentrations of fluoride ion; experiments show that NH is continuously increased along with the initial concentration of fluorine ions2The adsorption rate of the UiO-66@ LS composite material to fluorine ions is increased continuously;
FIG. 9 shows LS and NH after pretreatment in example 12-effect of UiO-66@ LS composite on fluoride ion adsorption in water under anion competitive conditions; under the influence of other anions, F-Does not change much, i.e. NH2-UiO-66@ LS composite material pair F-The adsorption of (A) has a certain specificity;
FIG. 10 shows LS and NH after pretreatment in example 12-UiO-66@ LS composite material adsorption effect diagram obtained by three repeated experiments, NH2The adsorption effect of the-UiO-66 @ LS composite material is obviously reduced after the composite material is recycled, and F-The adsorption rate of the adsorbent is reduced from 77.59% to 59.91%, and the adsorbent still has certain reusability.
NH of the invention2the-UiO-66 @ LS composite material can be used for removing F in sewage-The adsorption rate of the ions reaches 73.74 percent. In Cl-、F-、NO3-In the presence of anions, F-The adsorption amount of (A) is not obviously changed, which shows that NH is2-UiO-66@ LS composite material pair F-The adsorption is specific. Three replicates of experiment, F-The adsorption rate of (A) is reduced from 77.59% to 59.91%, and still has certain repeatability.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. NH (hydrogen sulfide)2-UiO-66@ LS composite material, characterized in that NH is carried out by taking pretreated natural loofah sponge as carrier2the-UiO-66 is loaded on the pretreated natural loofah sponge carrier.
2. An NH according to claim 12The preparation method of the-UiO-66 @ LS composite material is characterized in that NH is carried out in an in-situ growth mode by taking pretreated natural loofah sponge as a carrier2the-UiO-66 is loaded on the pretreated natural loofah sponge carrier.
3. The preparation method according to claim 2, further comprising a natural luffa pretreatment process: cutting natural retinervus Luffae fructus, soaking in sodium hydroxide solution, sequentially washing with distilled water and ethanol until the washing solution is neutral, air drying at room temperature, and collecting.
4. The method of claim 2, wherein the in-situ growth comprises: reacting ZrCl4Dissolving in N, N-dimethylformamide, stirring and ultrasonically treating until the solution is completely dissolved, adding 2-aminoterephthalic acid, stirring, adding acetic acid, stirring, mixing with pretreated natural retinervus Luffae fructus, reacting, cooling to room temperature, taking out, washing with ethanol and water to obtain NH2-UiO-66@ LS composite.
5. The method as claimed in claim 4, wherein the reaction temperature is 115-125 ℃.
6. The method according to claim 4, wherein the pretreated natural luffa is reacted with NH2-UiO-66 in a mass ratio of 1: 1.
7. the method according to claim 4, wherein ZrCl is used4The mass ratio of the 2-amino terephthalic acid to the 2-amino terephthalic acid is 175.1:135.9。
8. NH according to claim 42-UiO-66@ LS composite material for removing harmful ions in water.
9. NH according to claim 42-UiO-66@ LS composite material for removing fluoride ions from water.
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