CN113842886A - Modified UiO-66-NH2Material, preparation method and application thereof - Google Patents
Modified UiO-66-NH2Material, preparation method and application thereof Download PDFInfo
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- CN113842886A CN113842886A CN202111113984.0A CN202111113984A CN113842886A CN 113842886 A CN113842886 A CN 113842886A CN 202111113984 A CN202111113984 A CN 202111113984A CN 113842886 A CN113842886 A CN 113842886A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 80
- 239000000463 material Substances 0.000 claims abstract description 73
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 47
- RDIMQHBOTMWMJA-UHFFFAOYSA-N 4-amino-3-hydrazinyl-1h-1,2,4-triazole-5-thione Chemical compound NNC1=NNC(=S)N1N RDIMQHBOTMWMJA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006683 Mannich reaction Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 15
- 230000004048 modification Effects 0.000 abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 239000003463 adsorbent Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 125000004434 sulfur atom Chemical group 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000013207 UiO-66 Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PJDVOLYULHZZAG-UHFFFAOYSA-N ethylmercury Chemical compound CC[Hg] PJDVOLYULHZZAG-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- -1 mercury ions Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a modified UiO-66-NH2Material, preparation method and application thereof, and modified UiO-66-NH2The material is made of UiO-66-NH2The compound is obtained by Mannich reaction of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole and formaldehyde under the condition of hydrochloric acid as a catalyst. The invention adopts post-synthesis modification strategy to UiO-66-NH2The one-step modification is carried out to improve the UiO-66-NH2The adsorption performance and selectivity of Hg (II) show rapid Hg (II) removal capacity, the adsorption equilibrium is reached at 90min, the adsorption capacity at 298K and pH (5) is 327.88mg/g, and the modified UiO-66-NH is2The material shows good selectionThe performance and the cycling stability can be used as a potential adsorbent material to be applied to the treatment of wastewater containing heavy metal ions.
Description
Technical Field
The invention relates to a modified UiO-66-NH2A material, a preparation method thereof and application thereof as an Hg (II) remover, belonging to the technical field of water treatment.
Background
With the rapid development of industrialization and urbanization, a large amount of wastewater containing heavy metal ions is discharged into a water body, which has resulted in serious heavy metal pollution. Mercury (Hg) is one of the heavy metals with extremely strong hazard, and has the characteristics of high toxicity, easy conversion of chemical forms, strong bioaccumulation, nondegradable property and the like. Inorganic mercury ions (hg (ii)) as the main form of existence are easily converted into more toxic methyl mercury and ethyl mercury under the action of microorganisms, thus posing a great threat to the environment and human health. Therefore, there is a pressing need to provide an effective and feasible solution to the problem of hg (ii) pollution in aqueous environments. At present, the method for removing Hg (II) in the water body mainly comprises chemical precipitation, membrane separation, ion exchange, microbial treatment and adsorption. In which, chemical precipitation, membrane separation, ion exchange, and microbial treatment all face the problems of high cost, poor selectivity, complex operation, etc., in comparison, the adsorption method has lower cost and convenient operation, and the adsorption capacity and selectivity can be adjusted by material modification. The metal organic framework Material (MOF) becomes an important research object in the field of heavy metal adsorption due to the advantages of accurate structure, high specific surface area, easy modification and the like. However, most of the MOF materials reported so far suffer from structural stability problems, thus limiting their applications. The UiO-66 series MOF materials have been widely researched and applied to heavy metal adsorption due to the characteristics of excellent structural stability, easy functionalized modification and the like, but the materials still have the problems of small adsorption capacity, poor selectivity and the like, so that a modification strategy for improving the adsorption performance and selectivity of the materials is needed to be researched.
Disclosure of Invention
For UiO-66-NH2The invention aims to provide a modified UiO-66-NH, which has the problems of small adsorption capacity, poor selectivity and the like2The material, the preparation method thereof and the application of the material as Hg (II) remover adopt post-synthesis modification mode to UiO-66-NH2The one-step modification is successfully carried out on UiO-66-NH2The surface of (2) is grafted with functional molecules rich in N and S atoms, the surface of the material shows rapid Hg (II) removal capacity, the adsorption equilibrium is achieved at 90min, the adsorption capacity at 298K and pH (5) is 327.88mg/g, and the performance is improved by 227.46mg/g compared with that before the material is not modified. Furthermore, modified UiO-66-NH2The material shows good selectivity to Hg (II) under the condition of coexistence of a plurality of metal ions and shows cycling stability when being recycled for a plurality of times, and can be widely applied to actual treatment of waste water containing Hg (II) as a potential adsorbent material.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
modified UiO-66-NH2Material of UiO-66-NH2The compound is obtained by Mannich reaction of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole and formaldehyde under the condition of hydrochloric acid as a catalyst.
In a preferred embodiment, the UiO-66-NH2The dosage ratio of the 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, formaldehyde and hydrochloric acid is 1 g: 0.1-10 g: 1-100 mL: 0.2-20 mL, wherein the mass fraction of the hydrochloric acid is 37 wt%; more preferably 1 g: 0.5-5 g: 5-50 mL: 0.5-10 mL.
The invention also provides the modified UiO-66-NH2The preparation method of the material takes hydrochloric acid as a catalyst and takes UiO-66-NH2Adding 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole and formaldehyde into water, and mixing and reacting to obtain the final product.
In a preferred embodiment, the UiO-66-NH2Has a molecular formula of C48H34N6O32Zr6The molecular weight is 1754.16 g/mol; belongs to a triclinic system, the space group is P1, the unit cell parameters are:
α＝59.9570°，β＝59.8930°，γ＝59.9760°，
Dcalc＝1.27384g·cm-3。
in a preferred embodiment, the UiO-66-NH2The dosage ratio of the 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, formaldehyde and hydrochloric acid is 1 g: 0.1-10 g: 1-100 mL: 0.2-20 mL, wherein the mass fraction of the hydrochloric acid is 37 wt%; more preferably 1 g: 0.5-5 g: 5-50 mL: 0.5-10 mL.
In a preferred embodiment, the UiO-66-NH2The concentration of the water is 0.01-0.2 g/mL.
In a preferred embodiment, the reaction conditions are as follows: preserving the heat for 2-36 h at the temperature of 25-150 ℃; further preferably, the temperature is kept at 50-100 ℃ for 4-24 h.
In a preferred scheme, the crude product obtained after the reaction is washed by deionized water and ethanol, collected and dried in vacuum for 4-24 hours at the temperature of 40-100 ℃.
The invention adopts Mannich reaction, selects 4-amino-3-hydrazino-5-sulfydryl-1, 2, 4-triazole as functional molecule, uses formaldehyde as bridging molecule, and reacts on UiO-66-NH under the condition that hydrochloric acid is used as catalyst2And (4) carrying out modification. Wherein, the hydrochloric acid provides an acid environment to accelerate the reaction; formaldehyde provides-CH2Promoting UiO-66-NH2Of (2) is-NH2The group reacts with-SH of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole to generate N-C-S bond, thereby grafting 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole molecule on UiO-66-NH2The purpose of the surface. Modified UiO-66-NH2The surface of the material contains abundant N and S atoms, provides a large number of adsorption sites, and can be combined with Hg (II) in water in a complex forming mode to achieve the aim of removing Hg (II). In addition, the S atom and Hg (II) are easy to form stable Hg-S bond, and modified UiO-66-NH can be improved2Selectivity and affinity of the material to hg (ii).
The invention also provides the modified UiO-66-NH2Use of a material as an hg (ii) remover for the adsorptive removal of hg (ii).
Modified UiO-66-NH of the invention2The adsorbent is applied to removal of Hg (II) in water body as an adsorbing material, and shows rapid removal efficiency, high adsorption capacity, selectivity and circulationAnd (4) stability.
Modified UiO-66-NH of the invention2The material is subjected to adsorption performance study at the temperature of 298K, the adsorption time of 3h, the initial Hg (II) concentration of 100mg/L and different pH values (2-9), and the modified UiO-66-NH is found2The material reaches a maximum removal rate of 90% of Hg (II) at pH 5; at pH 2-4, the removal rate was low, mainly due to excess H in the solution+Competes with hg (ii), inhibiting the adsorption process; mercury is susceptible to hydrolysis at pH 6-9, predominantly in hg (oh)+Or Hg (OH)2Exist in the form of (1).
Modified UiO-66-NH of the invention2The material is subjected to adsorption performance research at the temperature of 298K, the initial Hg (II) concentration of 200mg/L, pH ═ 5 and different adsorption time (10-180min), and the modified UiO-66-NH is found2The adsorption rate of the material is rapidly increased within 40min, and the removal rate reaches 70.4 percent. Subsequently, the adsorption process gradually slowed down, approaching equilibrium at 90 min. The dynamic research finds that the modified UiO-66-NH2The adsorption behavior of the material conforms to a pseudo-second order kinetic model, which shows that the chemisorption is dominant in the adsorption process, and the adsorption amount of Hg (II) is positively correlated with the number of binding sites.
Modified UiO-66-NH of the invention2The material is subjected to adsorption performance research at the temperature of 298K, pH ═ 5 and the adsorption time of 3h and different concentrations of Hg (II) solution (100mg/L-600mg/L), and the modified UiO-66-NH is found2The maximum adsorption capacity of the material is 293.22mg/g, compared with unmodified UiO-66-NH2The improvement of 227.46mg/g indicates the success of the modification strategy described in the present invention. The adsorption isotherm research finds that the modified UiO-66-NH2The adsorption behavior of the material conforms to the Langmuir model, and shows that the modified UiO-66-NH2The adsorption of the material to Hg (II) is single-layer adsorption.
Modified UiO-66-NH of the invention2The material is subjected to adsorption performance research under the conditions that the pH value is 5, the adsorption time is 3h, the concentration of Hg (II) solution is 100mg/L-600mg/L and different temperatures (298K, 308K and 318K) are adopted, and the modified UiO-66-NH is found2The maximum adsorption amount of the material at 298K is 293.22mg/g, and the adsorption amount gradually increases with the increase of the temperatureAnd reached 326.32mg/g at 318K, mainly due to the increased temperature of the modified UiO-66-NH2The contact probability of the adsorption sites on the surface of the material and Hg (II) is increased, thereby improving the adsorption capacity.
Modified UiO-66-NH of the invention2The material is repeatedly adsorbed and desorbed for 7 times under the conditions of 298K, pH ═ 5, adsorption time of 3h and Hg (II) solution concentration of 100mg/L, and the removal rate of Hg (II) is between 88.12% and 80.25%, and the reduction of the removal rate can be attributed to the loss of the quality of the adsorbent in the process of multiple cycles. As can be seen from the results of 7 cycles, the modified UiO-66-NH2The material has long term cycling stability when applied to removal of hg (ii).
Modified UiO-66-NH of the invention2The material shows obvious selectivity to Hg (II) under the condition that Hg (II), Mg (II), Cu (II), Pb (II), Cd (II), Ni (II), Al (III), Co (II) and Cr (III) coexist (the concentration of metal ions is 100mg/L), the adsorption capacity reaches 87.9mg/g, and the material shows very low adsorption performance to other metal ions.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the invention provides modified UiO-66-NH2The material adopts Mannich reaction, selects 4-amino-3-hydrazino-5-sulfydryl-1, 2, 4-triazole as functional molecule, uses formaldehyde as bridging, and reacts on UiO-66-NH under the condition that hydrochloric acid is used as catalyst2Carrying out post-synthesis modification. Modified UiO-66-NH2The surface of the material contains abundant N and S atoms, provides a large number of adsorption sites, and can be combined with Hg (II) in water in a complex formation mode, so that the aim of effectively removing Hg (II) is fulfilled. In addition, the S atom and Hg (II) are easy to form stable Hg-S bond, and modified UiO-66-NH can be improved2Selectivity and affinity of the material to hg (ii).
2. The invention provides modified UiO-66-NH2The material shows rapid removal efficiency, high adsorption capacity, selectivity and circulation stability to Hg (II) in a water body, and can be used as a potential water treatment agent to be applied to actual treatment of mercury-containing wastewater.
Drawings
FIG. 1 is UiO-66-NH prepared in example 1 of the present invention2And modified UiO-66-NH2X-ray powder diffraction pattern of (a).
FIG. 2 shows UiO-66-NH prepared in example 1 of the present invention2And modified UiO-66-NH2Infrared spectrum of (1).
FIG. 3 is a modified UiO-66-NH prepared in example 1 of the present invention2Adsorption performance of the material at different pH values.
FIG. 4 is a modified UiO-66-NH prepared in example 1 of the present invention2Adsorption performance of the material under different adsorption time.
FIG. 5 is a modified UiO-66-NH prepared in example 1 of the present invention2Adsorption performance of the material at different initial hg (ii) concentrations and different temperatures.
FIG. 6 is a modified UiO-66-NH prepared in example 1 of the present invention2The cycle stability performance of the material.
FIG. 7 is a modified UiO-66-NH prepared in example 1 of the present invention2The material has the adsorption performance under the coexistence of various metal ions.
Detailed Description
In order to better explain the technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to the embodiments. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as those skilled in the art will be able to make insubstantial modifications and variations of this invention in light of the above teachings, and will nevertheless fall within the scope of this invention.
Example 1
(1)UiO-66-NH2The preparation of (1):
adding 20g of zirconium tetrachloride and 40g of 2-amino terephthalic acid into 200mL of N, N-dimethylformamide, adding 5mL of 0.6mol/L hydrochloric acid, reacting at 80 ℃ for 6h, washing the obtained pale yellow powdery solid with N, N-dimethylformamide for three times, collecting, and drying at 60 ℃ in vacuum to obtain UiO-66-NH2；
(2)UiO-66-NH2Modification of (2):
mixing UiO-66-NH2Adding 1g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole 0.5g, 5mL of formaldehyde and 0.5mL of HCl into 15mL of deionized water, reacting at 50 ℃ for 12h, washing the obtained dark yellow powder solid with deionized water and ethanol for three times, collecting, and drying at 80 ℃ for 6h in vacuum to obtain modified UiO-66-NH2。
Example 2
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH2Adding 1g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, 1g of formaldehyde and 0.5mL of HCl0 into 15mL of deionized water, reacting at 50 ℃ for 12h, washing the obtained deep yellow powder solid with deionized water and ethanol for three times, collecting, and drying at 80 ℃ for 6h in vacuum to obtain modified UiO-66-NH2。
Example 3
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH21g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, 1.5g of formaldehyde and 0.5mL of HCl are added into 15mL of deionized water, the mixture reacts for 12h at 50 ℃, the obtained dark yellow powder solid is washed three times by deionized water and ethanol, and then is collected and dried for 6h in vacuum at 80 ℃, and the modified UiO-66-NH is obtained2。
Example 4
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH2Adding 1g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole 0.5g, 15mL of formaldehyde and 0.5mL of HCl into 15mL of deionized water, reacting at 50 ℃ for 12h, washing the obtained dark yellow powder solid with deionized water and ethanol for three times, collecting, and drying at 80 ℃ for 6h in vacuum to obtain modified UiO-66-NH2。
Example 5
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH21g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, 0.5g of formaldehyde and 1.5mL of HCl are added into 25mL of deionized water and reacted for 12h at 50 ℃, and the obtained dark yellow powder solid is washed by deionized water and ethanolWashing for three times, collecting and drying for 6 hours in vacuum at the temperature of 80 ℃ to obtain the modified UiO-66-NH2。
Example 6
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH2Adding 1g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole 0.5g, 15mL of formaldehyde and 0.5mL of HCl into 15mL of deionized water, reacting for 8h at 80 ℃, washing the obtained dark yellow powder solid with deionized water and ethanol for three times, collecting, and drying for 6h at 80 ℃ in vacuum to obtain modified UiO-66-NH2。
Example 7
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH2Adding 1g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole 0.5g, 15mL of formaldehyde and 0.5mL of HCl into 15mL of deionized water, reacting for 4h at 100 ℃, washing the obtained dark yellow powder solid with deionized water and ethanol for three times, collecting, and drying for 6h at 80 ℃ in vacuum to obtain modified UiO-66-NH2。
Example 8
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH2Adding 1g, 0.5g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, 15mL of formaldehyde and 2.5mL of HCl into 25mL of deionized water, reacting for 4h at 100 ℃, washing the obtained dark yellow powder solid with deionized water and ethanol for three times, collecting, and drying for 6h at 80 ℃ in vacuum to obtain modified UiO-66-NH2。
Example 9
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH2Adding 1g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole 2.5g, 25mL of formaldehyde and 2.5mL of HCl into 25mL of deionized water, reacting for 4h at 100 ℃, washing the obtained dark yellow powder solid with deionized water and ethanol for three times, collecting, and drying for 4h at 100 ℃ in vacuum to obtain modified UiO-66-NH2。
Example 10
UiO-66-NH2The preparation is the same as example 1;
mixing UiO-66-NH2Adding 1g of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole 5g, 25mL of formaldehyde and 5mL HCl into 50mL of deionized water, reacting at 100 ℃ for 4h, washing the obtained dark yellow powder solid with deionized water and ethanol for three times, collecting, and drying at 100 ℃ for 4h in vacuum to obtain modified UiO-66-NH2。
For UiO-66-NH prepared in example 1 of the invention2And modified UiO-66-NH thereof2X-ray powder diffraction analysis was performed, and as shown in FIG. 1, UiO-66-NH was prepared2And modified UiO-66-NH thereof2The diffraction peaks of (A) were consistent with the theoretical simulated diffraction peaks of UiO-66, indicating that UiO-66-NH was successfully prepared according to example 12Modified material thereof, and modified UiO-66-NH obtained by post-synthesis modification method2The crystal form and the structural stability of the original framework are not changed.
Further on UiO-66-NH2And modified UiO-66-NH thereof2The structure of (A) was analyzed by infrared spectroscopy, as shown in FIG. 2, at 1572 and 1655cm-1Infrared absorption peak at (A) is attributed to asymmetric stretching vibration of the carboxylate, indicating the carboxylic acid ligand and Zr4+Has been coordinated at 3470cm-1Then is assigned to-NH2Stretching vibration of (2) indicating UiO-66-NH2The successful preparation. From modified UiO-66-NH2The infrared spectrum of (2) found to be 2974cm-1，1572cm-1And 768--1Are respectively assigned to-CH2C ═ N and C — S bonds, these newly appearing characteristic peaks indicate that 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole molecules have been successfully grafted to UiO-66-NH2On the framework of (2).
Application example 1
Modified UiO-66-NH prepared in inventive example 12The material was subjected to adsorption performance studies at a temperature of 298K, an adsorption time of 3h, an initial Hg (II) concentration of 100mg/L and various pH values (2-9), and the results are shown in FIG. 3. As can be seen from the figure, the modified UiO-66-NH2The material reaches a maximum removal rate of 90% of Hg (II) at pH 5; at pH 2-4, the removal rate is relatively low, mainly due to excess H in solution+Compete with Hg (II) and inhibitThe adsorption process is adopted; at pH 6-9, however, mercury is susceptible to hydrolysis, mainly in Hg (OH)+Or Hg (OH)2Exist in the form of (1).
Application example 2
Modified UiO-66-NH prepared in inventive example 12The material was subjected to adsorption performance studies at a temperature of 298K, an initial hg (ii) concentration of 200mg/L, pH ═ 5 and at different adsorption times (10-180min), the results are shown in fig. 4. As can be seen from the figure, the modified UiO-66-NH2The adsorption rate of the material rapidly increased within 40min, at which point the removal rate reached 70.4%. Subsequently, the adsorption process gradually slowed down, approaching equilibrium at 90 min. The dynamic research finds that the modified UiO-66-NH2The adsorption behavior of the material conforms to a pseudo-second order kinetic model, which shows that the chemisorption is dominant in the adsorption process, and the adsorption amount of Hg (II) is positively correlated with the number of binding sites.
Application example 3
Modified UiO-66-NH prepared in inventive example 12The material was subjected to adsorption performance studies at a temperature of 298K, pH ═ 5, an adsorption time of 3h, and various concentrations of hg (ii) solutions (100mg/L to 600mg/L), the results of which are shown in fig. 5. The modified UiO-66-NH can be seen from the figure2The maximum adsorption capacity of the material is 293.22mg/g, compared with unmodified UiO-66-NH2The improvement is 227.46 mg/g. The adsorption isotherm research finds that the modified UiO-66-NH2The adsorption behavior of the material conforms to the Langmuir model, and shows that the modified UiO-66-NH2The adsorption of the material to Hg (II) is single-layer adsorption.
Application example 4
Modified UiO-66-NH prepared in inventive example 12The material was subjected to adsorption performance studies at pH 5, adsorption time 3h, Hg (II) solution concentration of 100mg/L to 600mg/L and different temperatures (298K, 308K and 318K), and the results are shown in fig. 5. As can be seen from the figure, the modified UiO-66-NH2The maximum adsorption capacity of the material at 298K is 293.22mg/g, the adsorption capacity is gradually increased along with the increase of the temperature and reaches 326.32mg/g at 318K, mainly because the temperature rise is increased to modify UiO-66-NH2Adsorption sites on the surface of the materialThe probability of contact with hg (ii) increases the adsorption capacity.
Application example 5
Modified UiO-66-NH prepared in inventive example 12The material was repeatedly adsorbed and desorbed 7 times under the conditions of 298K, pH ═ 5, adsorption time 3h and Hg (II) solution concentration of 100mg/L, and the removal rate of Hg (II) was between 88.12% and 80.25%, and the results are shown in FIG. 6. The decrease in removal rate can be attributed to loss of adsorbent quality over multiple cycles. As can be seen from the results of 7 cycles, the modified UiO-66-NH2The material has long-term circulation stability when applied to removal of Hg (II).
Application example 6
Modified UiO-66-NH prepared in inventive example 12The material shows obvious selectivity to Hg (II), the adsorption capacity reaches 87.9mg/g, and shows very low adsorption performance to other metal ions under the condition that Hg (II), Mg (II), Cu (II), Pb (II), Cd (II), Ni (II), Al (III), Co (II) and Cr (III) coexist (the metal ion concentration is all 100mg/L), and the result is shown in figure 7.
In conclusion, the modified UiO-66-NH provided by the invention2The material shows rapid removal capability to Hg (II) in a water body, shows very high adsorption capacity and excellent selectivity and cycle stability, and can be widely applied to actual treatment of mercury-containing wastewater as a potential water treatment agent. Furthermore, the modified UiO-66-NH2Compared with the adsorption performance of the material before modification, the adsorption performance of the material is improved by three times, which shows the success of the modification strategy, and the functional modification method can provide reference for designing the UiO-66-based adsorption material with high adsorption capacity.
Claims (10)
1. Modified UiO-66-NH2A material characterized by: from UiO-66-NH2The compound is obtained by Mannich reaction of 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole and formaldehyde under the condition of hydrochloric acid as a catalyst.
2. The modified UiO-66-NH of claim 12A material characterized by: the UiO-66-NH2The dosage ratio of the 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, formaldehyde and hydrochloric acid is 1 g: 0.1-10 g: 1-100 mL: 0.2-20 mL, and the mass fraction of the hydrochloric acid is 37 wt%.
3. The modified UiO-66-NH of claim 22A material characterized by: the UiO-66-NH2The dosage ratio of the 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, formaldehyde and hydrochloric acid is 1 g: 0.5-5 g: 5-50 mL: 0.5-10 mL.
4. The modified UiO-66-NH of any of claims 1 to 32The preparation method of the material is characterized by comprising the following steps: using hydrochloric acid as a catalyst, and reacting UiO-66-NH2Adding 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole and formaldehyde into water, and mixing and reacting to obtain the final product.
5. The method of claim 4, wherein: the UiO-66-NH2Has a molecular formula of C48H34N6O32Zr6The molecular weight is 1754.16 g/mol; belongs to a triclinic system, the space group is P1, the unit cell parameters are:
α＝59.9570°，β＝59.8930°，γ＝59.9760°，
Dcalc＝1.27384g·cm-3。
6. the method of claim 4, wherein: the UiO-66-NH2The dosage ratio of the 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, formaldehyde and hydrochloric acid is 1 g: 0.1-10 g: 1-100 mL: 0.2-20 mL, and the mass fraction of the hydrochloric acid is 37 wt%.
7. The method of claim 6, wherein the method comprisesIs characterized in that: the UiO-66-NH2The dosage ratio of the 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, formaldehyde and hydrochloric acid is 1 g: 0.5-5 g: 5-50 mL: 0.5-10 mL.
8. The method of claim 4, wherein: the UiO-66-NH2The concentration of the water is 0.01-0.2 g/mL.
9. The method of claim 4, wherein: the reaction condition is that the temperature is kept at 25-150 ℃ for 2-36 h, and a crude product obtained after the reaction is washed by deionized water and ethanol, collected and dried in vacuum at 40-100 ℃ for 4-24 h.
10. The modified UiO-66-NH of any of claims 1 to 32Material or modified UiO-66-NH obtainable by the preparation process according to any one of claims 4 to 92The application of the material is characterized in that: the catalyst is used as an Hg (II) remover for the adsorption removal of Hg (II).
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| EP3498368A1 (en) * | 2017-12-18 | 2019-06-19 | Centre National De La Recherche Scientifique | Aliphatic zr-, hf-, and ln-based inorganic-organic hybrid solid mof materials, methods for preparing same and uses thereof |
| CN113045767A (en) * | 2021-03-24 | 2021-06-29 | 肇庆市武大环境技术研究院 | Nitrogen heterocyclic ring molecule modified UiO-66-NH with stable structure2Material and method for the production thereof |
| CN113206279A (en) * | 2021-03-24 | 2021-08-03 | 武汉大学 | Modified UiO-66-NH2Use of materials as proton conducting materials |
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| EP3498368A1 (en) * | 2017-12-18 | 2019-06-19 | Centre National De La Recherche Scientifique | Aliphatic zr-, hf-, and ln-based inorganic-organic hybrid solid mof materials, methods for preparing same and uses thereof |
| CN113045767A (en) * | 2021-03-24 | 2021-06-29 | 肇庆市武大环境技术研究院 | Nitrogen heterocyclic ring molecule modified UiO-66-NH with stable structure2Material and method for the production thereof |
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