CN110404510A - A kind of metal-organic framework materials and its preparation method and application of petal-shaped core-shell structure - Google Patents

A kind of metal-organic framework materials and its preparation method and application of petal-shaped core-shell structure Download PDF

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CN110404510A
CN110404510A CN201910697927.8A CN201910697927A CN110404510A CN 110404510 A CN110404510 A CN 110404510A CN 201910697927 A CN201910697927 A CN 201910697927A CN 110404510 A CN110404510 A CN 110404510A
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熊英
张蒙蒙
单炜军
王月娇
娄振宁
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Liaoning University
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Abstract

The present invention is applied to rare earth metal adsorption technology field, and in particular to a kind of metal-organic framework materials and its preparation method and application of petal-shaped core-shell structure.The technical solution adopted is as follows: 1) take zirconium chloride, 2- amino terephthalic acid (TPA), glacial acetic acid and N, dinethylformamide is stirred at room temperature, and is subsequently moved in hydrothermal reaction kettle, reacts at 120 DEG C for 24 hours, it is cooled to room temperature, the UiO-66-NH obtained after washing2, 2) and weigh UiO-66-NH2Ultrasonic disperse is in anhydrous methanol, after PVP stirring is then added, adds zinc nitrate hexahydrate stirring, then adds 2-methylimidazole, centrifugal drying after stirring obtains petal-shaped core-shell structure adsorbent UiO-66-NH2@ZIF-8.The preparation method is simple, green non-pollution, and the adsorbent prepared is high to rare earths separation bioaccumulation efficiency, has practical application.

Description

A kind of metal-organic framework materials of petal-shaped core-shell structure and preparation method thereof and Using
Technical field
The present invention is applied to rare earth metal adsorption technology field, and in particular to a kind of metal of petal-shaped core-shell structure is organic Framework material and its preparation method and application.
Background technique
17 kinds of elements that rare earth element is made of scandium (Sc), yttrium (Y) and 15 kinds of lanthanide series (Ln).Rare earth element is with it Unique magnetic, electrical property and optical property rapidly develop, and become electric car (Nd, La, Dy), optical fiber (Nd, Er, Eu) and section Key element in energy lamp (Gd, La, Eu, Tb, Yb).The whole world also substantially increases rare earth member to the interest of cleaning and green technology The overall market value of element.Therefore, the important source material that rare earth metal becomes China's economy and further develops.However, the whole world is dilute The control that native reserves limited (1.3 hundred million tons) and the main China, supply country of rare earth export rare earth, it is clear that exacerbate global rare earth Short supply.In addition, the waste containing excessive rare earth ion of the industrial plants discharge such as metallurgy, mining, manufacture may be to environment It is seriously affected with human health generation.Accordingly, it is considered to rare earth element accumulating in food chain and its to the toxicity of human body, system The friendly strategy of ecology of the fixed recovering rare earth element from mine wastewater or industry and municipal sewage is most important.
Currently, a variety of methods such as coprecipitation, ion-exchange, electrochemical process and solvent extraction have been widely used in The separation and preenrichment of rare earth.However, most of they need expensive chemistry or energy consumption, secondary pollution and have to environment It is harmful, inefficiency for rare earth especially low to concentration for the treatment of.For example, common solvent extraction technology needs are a large amount of organic Solvent carries out multiple sequence extraction process, generates a large amount of radioactive waste.In contrast, absorption can be by relatively simple Technique recycles metal ion from low concentration sources.Therefore, absorption method due to it is easy to operate, at low cost, nontoxic, reusable, High-efficient, secondary waste generates the advantages that relatively fewer, adsorbent enriches in nature, it is considered to be separation and adsorbing metal A kind of green alternative of ion.
Metal-organic framework materials (MOFs) are to be connected with each other the infinite net that inorganic metal node is constituted by strong covalent bond Shape structure.Due to its adjustable pore structure, biggish specific surface area, highdensity active site and enough stability, MOFs is considered as the candidate material in many potential application fields, including Selective Separation, sensor, heterogeneous catalysis, drug are passed It send, the storage of battery and gas.In recent years, MOFs has been to be concerned by more and more people as application of the adsorbent in water environment. Compared with conventional adsorbent, MOFs is high with specific surface area, aperture is adjustable, it is a variety of to be introduced by modification after simply synthesizing The advantages that function.Ahmed F.Abdel-Magied etc. reports classifying porous zeolite Asia imidazoles hydrochlorate frame nano particle to dilute Effective absorption of earth elements.Yu-Ri Lee etc. has synthesized the adsorbent absorption rare earth of modification different functional groups after Cr-MIL-101 Element, it can be seen that metal organic framework in terms of adsorption of metal ions for having broad application prospects.
But these researchs are relatively low to the adsorption capacity of rare earth, dynamic behavior is slow.In order to explore MOFs dilute Application potential in soil separation, it is necessary to which it is further improved.
Summary of the invention
To achieve the above object, the present invention provides a kind of metal-organic framework materials UiO-66- of petal-shaped core-shell structure The preparation method and applications of NH2@ZIF-8, the method for the present invention operation is succinct, and resource utilization is high, the absorption to rare earth element Performance is high, and process cycle is short, has very high practical value.
The present invention is achieved through the following technical solutions: a kind of metal-organic framework materials of petal-shaped core-shell structure UiO-66-NH2@ZIF-8, preparation method include the following steps: to take UiO-66-NH2PVP is added in anhydrous methanol in ultrasonic disperse Stirring adds zinc nitrate hexahydrate stirring, is eventually adding 2-methylimidazole, centrifugal drying after stirring obtains petal-shaped nucleocapsid Structure adsorbent UiO-66-NH2@ZIF-8。
Preferably, the metal-organic framework materials UiO-66-NH of above-mentioned a kind of petal-shaped core-shell structure2@ZIF-8, institute The UiO-66-NH stated2The preparation method is as follows: take zirconium chloride, 2- amino terephthalic acid (TPA), glacial acetic acid and N, N- dimethyl methyl Amide is stirred at room temperature, and is subsequently moved in hydrothermal reaction kettle, at 100-150 DEG C react 12~for 24 hours, be cooled to room temperature, The UiO-66-NH obtained after washing2。
Preferably, the metal-organic framework materials UiO-66-NH of above-mentioned a kind of petal-shaped core-shell structure2@ZIF-8, is pressed Molar ratio, zirconium chloride: 2- amino terephthalic acid (TPA)=1:1-3, by solid-to-liquid ratio, zirconium chloride: n,N-Dimethylformamide: ice Acetic acid=50-100mg:40-80mL:4-8mL.
Preferably, the metal-organic framework materials UiO-66-NH of above-mentioned a kind of petal-shaped core-shell structure2@ZIF-8, is pressed Solid-to-liquid ratio, UiO-66-NH2: anhydrous methanol=1mg:1mL-3mL.
Preferably, the metal-organic framework materials UiO-66-NH of above-mentioned a kind of petal-shaped core-shell structure2@ZIF-8, is pressed Mass ratio, UiO-66-NH2: PVP: zinc nitrate hexahydrate: 2-methylimidazole=1:1-10:10-30:10-30.
Preferably, the metal-organic framework materials UiO-66-NH of above-mentioned a kind of petal-shaped core-shell structure2@ZIF-8, institute The ultrasonic time stated is 30min-1h, and mixing time 6h-12h after zinc nitrate hexahydrate is added, and is stirred after 2-methylimidazole is added Time is 10min-50min.
The metal-organic framework materials UiO-66-NH of above-mentioned any petal-shaped core-shell structure2@ZIF-8 is dilute in recycling Application in earth elements.
Preferably, above-mentioned application, the rare earth element are Nd (III), Eu (III), Gd (III), in Er (III) It is one or more.
Preferably, above-mentioned application, steps are as follows: by any petal-shaped core-shell structure described in claim 1-6 Metal-organic framework materials UiO-66-NH2@ZIF-8 is added in earth solution, is vibrated for 24 hours in the oscillation case of 180r/min.
Preferably, above-mentioned application, the concentration of the earth solution are 20-40mg L-1。
Beneficial effects of the present invention:
It 1) is the important channel for extending the application program based on MOF by the way that a kind of MOF type is integrated into another MOF, Because MOF composite material usually shows the even unprecedented characteristic of enhancing compared with single MOF.These preceding institutes are not The advantages of having, provides a very promising approach for the aqueous solution functional material of exploitation absorption rare earth.Have in a large amount of metal In machine framework material, UiO-66-NH2Have the characteristics that good porosity, large specific surface area, stability is good in water with ZIF-8.It is special It is not due to ZIF-8 and UiO-66-NH2With highdensity coordination site, adsorption process can make rare earth preenrichment, further drop Low equilibration time.It is that structure directing agent extends to the outside life using inside at room temperature with polyvinylpyrrolidone (PVP) Long mode carries out the metal-organic framework materials UiO-66-NH of synthesis petal-shaped core-shell structure2@ZIF-8.The method of the present invention operation Succinctly, resource utilization is high, high to the absorption property of rare earth element, and process cycle is short.
2)UiO-66-NH2Contain a large amount of-NH with ZIF-82, coordination can occur with rare earth for-COOH, Zn-OH, different The composite material that MOF is compounded to form overcomes the low disadvantage of adsorbance of single MOF.
3) the function adsorbent separation and concentration prepared of the present invention is high-efficient, absorption that can be selective from mixed ion solutions Rare earth ion.Method of the invention adsorbent large amount of adsorption easy to operate, widely applicable, obtained has practical application.
4) present invention utilizes the bigger serface of metal organic framework, and high chemical stability and existing coordination are not Saturation metal center can carry out the coordination advantages such as functionalization, and the adsorbent material of preparation can be used for waste water, the rare earth element in waste residue Recycling.
5) modified metal organic framework material prepared by the present invention has the rare earth in solution larger under certain acidity Adsorbance, be 249.90mg g to the maximal absorptive capacity of neodymium-1, the saturated extent of adsorption to europium is 295.28mg g-1, to gadolinium Saturated extent of adsorption is 326.22mg g-1, the saturated extent of adsorption to erbium is 340.95mg g-1。
In conclusion adsorbent prepared by the present invention can effectively adsorb rare earth ion, and adsorbent preparation is convenient, Adsorption rate is high, has actual practicability.
Detailed description of the invention
Fig. 1 is UiO-66-NH2The synthesis schematic diagram of@ZIF-8.
Fig. 2 a is UiO-66-NH2The scanning electron microscope (SEM) photograph of@ZIF-8.
Fig. 2 b is UiO-66-NH2@ZIF-8、ZIF-8、UiO-66-NH2Infrared spectrogram.
Fig. 2 c is UiO-66-NH2The XRD diagram of@ZIF-8.
Fig. 2 d is UiO-66-NH2@ZIF-8 under different acidity to rare earth element nd (III), Eu (III), Gd (III), The absorption property figure of Er (III).
Fig. 3 is UiO-66-NH2@ZIF-8 adsorbent adsorbs Nd (III), Eu (III), Gd (III), the absorption of Er (III) Thermoisopleth.
Fig. 4 is UiO-66-NH2@ZIF-8 adsorbent under the interference of other coexisting ions under the absorption property of rare earth is analyzed Figure.
Specific embodiment
The metal-organic framework materials UiO-66-NH of 1 petal-shaped core-shell structure of embodiment2The preparation of@ZIF-8
(1) the metal-organic framework materials UiO-66-NH of petal-shaped core-shell structure2The preparation of@ZIF-8: synthesis process is such as Shown in Fig. 1,
1) 0.0745g zirconium chloride, 0.072g 2- amino terephthalic acid (TPA), 5.5mL glacial acetic acid and 50mLN, N- diformazan are taken Base formamide is stirred at room temperature, and is subsequently moved in hydrothermal reaction kettle, reacts for 24 hours, is cooled to room temperature at 120 DEG C, washing The UiO-66-NH obtained afterwards2。
2) 10mg UiO-66-NH is weighed2In round bottom beaker, in 19ml anhydrous methanol, ultrasonic time is ultrasonic disperse 1h after 20mg PVP stirring 12h is then added, adds 0.2g zinc nitrate hexahydrate stirring 12h, 0.25g 2- then is being added Methylimidazole is centrifuged after stirring 45min, dry, obtains target product petal-shaped core-shell structure adsorbent UiO-66-NH2@ZIF- 8。
(2) the metal-organic framework materials UiO-66-NH of petal-shaped core-shell structure2The characterization of@ZIF-8
1. electron microscope analysis: can be seen that UiO-66-NH by Fig. 2 a2Three-dimensional structure is presented in@ZIF-8, size in 1um or so, Simultaneously it can be seen that lamellar structure, the whole shape that similar flower is presented is presented in the ZIF-8 that outer layer is presented.
2. infrared analysis: Fig. 2 b respectively illustrates UiO-66-NH2,ZIF-8,UiO-66-NH2The infrared spectroscopy of@ZIF-8 Figure.1379 in figure, 1679,3369,3471cm-1Belong to the C-N stretching vibration peak of aromatic amine, N-H flexural vibrations peak, carboxylic acid The symmetrical stretching vibration peak of C=O stretching vibration peak and amido, in addition, 422,1579,2929 and 3133cm-1Belong to Zn-N Characteristic peak, C=N stretching vibration peak, the stretching vibration peak of the C-N on c h bond and imidazole ring.It is all these all to confirm UiO-66-NH2It is successfully combined with each other with ZIF-8.
3.XRD analysis: by Fig. 2 c it can be found that the UiO-66-NH after compound2The XRD diagram of@ZIF-8 and original UiO-66-NH2It is compared with the XRD diagram of ZIF-8, there is no apparent change occurs, it was demonstrated that the adsorbent after compound is still kept Original crystalline structure.
2 UiO-66-NH of embodiment2@ZIF-8 is under different acidity to Nd (III), Eu (III), Gd (III), Er (III) Adsorption effect
1. method: weighing 10mg UiO-66-NH respectively2@ZIF-8, being separately added into 10mL concentration is 30mg L-1Nd (III), Eu (III), Gd (III), Er (III) solution, the pH of solution is respectively 2,3,4,5,6, at 30 DEG C, the vibration of 180r/min It swings in case and vibrates for 24 hours.UiO-66-NH2@ZIF-8 adsorbs the process of Nd (III) as shown in Figure 1, absorption result such as Fig. 2 d.
2. with the increase of pH value, UiO-66-NH it can be seen from Fig. 2 d2@ZIF-8 to the adsorption rate of rare earth ion by It is cumulative plus, in pH=5, to the adsorption rate of rare earth all up to 90% or more, to realize to rare earth element nd (III), Eu (III), the recycling of Gd (III), Er (III).
3 UiO-66-NH of embodiment2@ZIF-8 adsorbent adsorbs Nd (III), Eu (III), Gd (III), the suction of Er (III) Attached thermoisopleth
1. method: compound concentration is 20mgg respectively-1, 30mgg-1, 50mgg-1, 80mgg-1, 100mgg-1, 150mg·g-1, 200mgg-1, 300mgg-1, 500mgg-1Rare-earth ion solution, adjust pH be 5.It weighs respectively 10mgUiO-66-NH2@ZIF-8, addition 10mL concentration are 20~500mg L-1Nd (III), Eu (III), Gd (III), Er (III) solution, the pH of solution are 5, are vibrated for 24 hours in 30 DEG C, the oscillation case of 180r/min.As a result such as Fig. 3.
2. as seen from Figure 3, UiO-66-NH2@ZIF-8 to rare earth ion to Nd (III), Eu (III), Gd (III) and The maximum adsorption ability of Er (III) is respectively 249.90,295.28,316.22 and 340.95mg g-1.Adsorbent to rare earth most Big adsorption capacity follows Nd (III) < Eu (III) < Gd (III) < Er (III) sequence, this sequentially with metal ion half Diameter, electronegativity are consistent with charge density.These show UiO-66-NH2@ZIF-8 being capable of high efficiente callback rare earth ion.
4 UiO-66-NH of embodiment2@ZIF-8 adsorbent is in the presence of other coexisting ions to the absorption property of rare earth point Analysis figure
1. weighing 10mg UiO-66-NH respectively2@ZIF-8, addition 10mL concentration are 20mg L-1Cd (II), Zn (II), Cu (II), Mn (II), Co (II), Nd (III), Eu (III), Gd (III), Er (III) solution, the pH of solution is 5,30 DEG C, it is vibrated for 24 hours in the oscillation case of 180r/min.As a result such as Fig. 4.
2. in the case where there is the interference of other coexistent metallic ions, adsorbent UiO-66-NH2@ZIF-8 to Nd (III), Eu (III), Gd (III), Er (III) adsorption rate still reach 80% or more.Show adsorbent UiO-66-NH2The selectivity of@ZIF-8 is inhaled It is attached functional.

Claims (10)

1. a kind of metal-organic framework materials UiO-66-NH of petal-shaped core-shell structure2@ZIF-8, which is characterized in that preparation method Include the following steps: to take UiO-66-NH2Ultrasonic disperse is added PVP stirring, adds zinc nitrate hexahydrate in anhydrous methanol Stirring, is eventually adding 2-methylimidazole, centrifugal drying after stirring obtains petal-shaped core-shell structure adsorbent UiO-66-NH2@ ZIF-8。
2. a kind of metal-organic framework materials UiO-66-NH of petal-shaped core-shell structure according to claim 12@ZIF-8, It is characterized in that, the UiO-66-NH2The preparation method is as follows: take zirconium chloride, 2- amino terephthalic acid (TPA), glacial acetic acid Be stirred at room temperature, be subsequently moved in hydrothermal reaction kettle with n,N-Dimethylformamide, at 100-150 DEG C react 12~ For 24 hours, it is cooled to room temperature, the UiO-66-NH obtained after washing2。
3. a kind of metal-organic framework materials UiO-66-NH of petal-shaped core-shell structure according to claim 22@ZIF-8, It is characterized in that, in molar ratio, zirconium chloride: 2- amino terephthalic acid (TPA)=1:1-3, by solid-to-liquid ratio, zirconium chloride: N, N- bis- Methylformamide: glacial acetic acid=50-100mg:40-80mL:4-8mL.
4. a kind of metal-organic framework materials UiO-66-NH of petal-shaped core-shell structure according to claim 12@ZIF-8, It is characterized in that, pressing solid-to-liquid ratio, UiO-66-NH2: anhydrous methanol=1mg:1mL-3mL.
5. a kind of metal-organic framework materials UiO-66-NH of petal-shaped core-shell structure according to claim 12@ZIF-8, It is characterized in that, in mass ratio, UiO-66-NH2: PVP: zinc nitrate hexahydrate: 2-methylimidazole=1:1-10:10-30:10- 30。
6. a kind of metal-organic framework materials UiO-66-NH of petal-shaped core-shell structure according to claim 12@ZIF-8, It is characterized in that, the ultrasonic time is 30min-1h, mixing time 6h-12h after zinc nitrate hexahydrate is added, 2- first is added Mixing time is 10min-50min after base imidazoles.
7. the metal-organic framework materials UiO-66-NH of any petal-shaped core-shell structure described in claim 1-62@ZIF-8 Application in recovering rare earth element.
8. application according to claim 7, which is characterized in that the rare earth element is Nd (III), Eu (III), Gd (III), one of Er (III) or a variety of.
9. application according to claim 8, which is characterized in that steps are as follows: by any flower described in claim 1-6 The metal-organic framework materials UiO-66-NH of petaloid core-shell structure2@ZIF-8 is added in earth solution, in the vibration of 180r/min It swings in case and vibrates for 24 hours.
10. application according to claim 9, which is characterized in that the concentration of the earth solution is 20-40mg L-1。
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CN112680601A (en) * 2020-12-02 2021-04-20 昆山鸿福泰环保科技有限公司 Method for recovering silver and gold from silver and gold-containing anode slime
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