CN113457635A - Preparation method and application of composite nanofiber adsorbing material based on ZIF-8 material - Google Patents
Preparation method and application of composite nanofiber adsorbing material based on ZIF-8 material Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a preparation method and application of a ZIF-8 material-based composite nanofiber adsorbing material, wherein natural silk fibers are selected as a carrier, and the pretreatment process of the carrier is simple; the composite fiber adsorption material with the surface immobilized with the ZIF-8 nano particles is prepared by a layer-by-layer growth method, so that the loading efficiency is high; hydration reaction activation is adopted before adsorption, so that the reaction rate can be greatly improved. Preliminary application shows that the prepared composite fiber adsorbing material based on the metal organic framework material has the advantages of high adsorption quantity, high adsorption rate, easy regeneration, simple and convenient solid-liquid separation step and low energy consumption, can be better applied to the practice of adsorbing and removing heavy metals in drinking water, and has important application value.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method and application of a composite nanofiber adsorbing material based on a ZIF-8 material.
Background
Arsenic-containing compounds (arsenic acid and arsenite) are highly toxic substances, and are easy to cause acute and chronic poisoning and even death after long-term exposure. The international organization for the research on cancer (IARC) and the United States Environmental Protection Agency (USEPA) have classified arsenic-containing compounds as class a carcinogens. According to the International Water Association (IWA) statistics, 2.2 million people worldwide are in arsenic-exposed environments, and about 2000 million people in China are affected by this. To avoid arsenic exposure to harm people, the most critical measure is to prevent arsenic poisoning by drinking water.
In order to remove arsenic-containing compounds in drinking water, porous materials such as activated carbon, porous alumina, porous iron oxide and the like are mainly used for enhancing the adsorption removal efficiency. Since then, considering that most arsenic-containing compounds in drinking water are trace and even trace arsenic, more and more nano-porous materials are being developed to improve the adsorption efficiency of trace pollutants. Among them, metal organic framework Materials (MOFs) are one of the most thermally and potentially applicable nanoporous materials due to their chemical and thermal stability, porosity, and spatial structure adjustability.
The types of MOFs materials are hundreds, even thousands, and can be classified into ZIFs series, MILs series, HKUST series and other types according to the major categories. ZIFs materials are collectively known as zeolite-like framework materials and are known for their good hydrothermal stability. Among them, the ZIF-8 material is the nano-porous material with the best hydrothermal stability, and since 2012, the ZIF-8 material is used for the adsorption and removal of various pollutants such as organic matters, heavy metals and the like, but cannot be applied in large scale all the time, and there are two important reasons for this: firstly, the ZIF-8 material is a powder material, so that solid-liquid separation is difficult and the use is inconvenient. If a static adsorption mode is adopted, the material is easy to lose, and the energy consumption is overhigh when centrifugal separation is adopted. If the filter is used for dynamic adsorption column filtration, high head loss is generated, the filtration speed is slow, and the water yield is low. Secondly, the reaction rate is slow, and Li et al (Zeolite enzyme frame-8 with high efficiency in trace area adsorption and removal from water) find that the university of adsorption equilibrium time needs 12h when ZIF-8 adsorbs pentavalent arsenate in drinking water, which means that the hydraulic retention time of more than 12h needs to be ensured in practical application, and the pool capacity exceeds tens of thousands of cubes, which obviously cannot be satisfied.
In order to solve the problem of solid-liquid separation of powder materials in use, research teams at home and abroad try from different directions. Song et al (ZIF-8) based polymer nanocomposite membranes for gas separation) prepared in advance were mixed with a polymer solution to prepare a ZIF-8 composite membrane by a membrane casting method; wu et al (electrically fibrous materials as slides to product free-standing MOF membranes) dope ZIF-8 crystal grains in an electrospinning fiber mother solution, and prepare a composite fiber membrane by an electrospinning technology; however, the above methods all disperse the ZIF-8 in the fiber, and the specific surface area of the ZIF-8 nanoparticles is lost, so that the activity and adsorption capacity of the particles are reduced. Another method is to fix ZIF-8 on the surface of a carrier, such as Pan (Effective separation of propylene/propylene alloys by ZIF-8 membranes) and Yao (vacuum-dispersion synthesis of ZIF-8 films on a polymer substrate) and the like, wherein a porous aluminum foil is used as a support, and a nylon material is selected as the carrier by Yao and the like, but the operation process is quite complex in atomic layer and involves pretreatment steps such as seed crystal modification, single activation and the like.
Therefore, research on the composite fiber material capable of efficiently and conveniently immobilizing the ZIF-8 nanoparticles on the surface, simplification of solid-liquid separation efficiency and improvement of adsorption rate are urgent needs for promoting industrial production and application of related novel functional materials.
Disclosure of Invention
The invention aims to provide a composite fiber material based on a ZIF-8 material and a modification method, so that the adsorption rate of the composite fiber material on trace arsenic in water and the solid-liquid separation efficiency are remarkably improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a composite nanofiber material based on a ZIF-8 material comprises the following steps:
1) dissolving 2-methylimidazole in methanol, and marking as a solution A; dissolving zinc nitrate in methanol, marking as a solution B, sequentially putting the fiber carrier into the solution A and the solution B at the temperature of 25 ℃, and reacting for 2-6 h at constant temperature;
2) rinsing for 1 time before exchanging precursor mother liquor each time; rinsing in ethanol for 1 time before mother liquor exchange every time, not only can incompletely-reacted metal ions or organic ligands be removed, but also ZIF-8 crystals which are weak in binding force and adsorbed on the surface of silk can be removed, a compact ZIF-8 surface layer is formed, and the ZIF-8 surface layer is not easy to fall off.
3) Filtering the obtained solid after 5 cycles, washing with methanol for 3 times, adding at 80 deg.C, oven drying, and activating;
furthermore, in the step (1), the molar ratio of the 2-methylimidazole to the zinc nitrate to the methanol is (5-20) to 1 (1-2.5);
further, in the step 1), the isothermal reaction time was 4 hours.
Further, in the step 1), the fiber carrier is natural silk fiber with the mass of 30-60 mg, and the preparation method comprises the steps of cleaning the silkworm cocoons, boiling the silkworm cocoons in water and a sodium bicarbonate solution for about 30 minutes to degum, cleaning and then drying the silkworm cocoons at 80 ℃;
an application of a composite nanofiber material based on a ZIF-8 material in adsorption removal of heavy metals in drinking water comprises the following steps:
1) before use, the composite fiber material is immersed in an aqueous solution for full hydration reaction, so that the number of hydroxyl functional groups on the surface of the silk and the surface of the ZIF-8 is obviously increased;
2) after the composite fiber material is used, the composite fiber material is immersed in a regeneration solution for material regeneration, and after the reaction is carried out for 0.5-2.5 hours, the composite fiber material is cleaned and dried for standby use and can be recycled;
3) after regeneration, concentrating the regenerated liquid to extract salt;
further, in the step 1), the hydration reaction time is 0.5-2.5 hours.
Further, in the step 2), the regeneration solution is one or more reagents selected from methanol, ethanol, NaOH and water;
further, in the step 2), the regeneration time is 2 hours;
compared with the prior art, the invention has the beneficial effects that: the composite fiber adsorption material has mature preparation technology, easy operation, high adsorption quantity, high adsorption rate, easy regeneration, simple and convenient solid-liquid separation step and low energy consumption, can be better applied to the practice of adsorption and removal of heavy metals in drinking water, and has important application value.
Drawings
FIG. 1: SEM picture of ZIF-8 composite silk fiber (1 time of ZIF-8 growth on silk).
FIG. 2: SEM picture of ZIF-8 composite silk fiber (3 times of ZIF-8 growth on silk).
FIG. 3: SEM picture of ZIF-8 composite silk fiber (5 times of ZIF-8 growth on silk).
FIG. 4: comparison of adsorption rates of ZIF-8 composite silk fibers.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
A preparation method of a composite nanofiber adsorbing material based on a ZIF-8 material comprises the following steps:
1) dissolving 2-methylimidazole in methanol, and marking as a solution A; dissolving zinc nitrate in methanol to obtain solution B, sequentially adding the fiber carrier into the solution A and the solution B at 25 deg.C, and reacting at constant temperature for 4 hr.
2) Rinsing 1 time before exchanging precursor mother liquor each time.
3) After 5 cycles, the solid obtained is filtered, washed 3 times with methanol, dried and activated at 80 ℃ for further use.
In the step (1), the molar ratio of the 2-methylimidazole to the zinc nitrate to the methanol is (5-20) to 1 (1-2.5).
In the step (1), the reaction is carried out for 2-6 hours at constant temperature.
In the step (1), the fiber carrier is natural silk fiber with the mass of 30-60 mg, and the preparation method comprises the steps of cleaning the silkworm cocoons, boiling the silkworm cocoons in water and a sodium bicarbonate solution for about 30 minutes to degum, cleaning and then drying at 80 ℃.
In the step (2), the mother liquor is rinsed in ethanol for 1 time before each time of exchange, so that not only can incompletely reacted metal ions or organic ligands be removed, but also ZIF-8 crystals which are weak in binding force and are adsorbed on the surface of silk can be removed, a compact ZIF-8 surface layer is formed, and the surface layer is not easy to fall off.
The preparation process is described below by means of specific examples.
Specific example 1:
washing silkworm cocoon with water, floating, adding into clear water and 0.1M sodium hydroxide solution, and soaking and boiling at 100 deg.C for 30min to complete degumming process. Rinsing with clear water, and drying at 80 deg.C for use.
Referring to FIG. 1, 0.438g 2-methylimidazole was dissolved in 10mL methanol and designated as solution A; dissolving 0.183g of zinc nitrate in 10mL of methanol to obtain a solution B, sequentially adding silk into the solution A and the solution B at 25 ℃, reacting at constant temperature for 4 hours, rinsing in an ethanol solution for 1 time before exchanging the reaction kettle each time, washing the obtained solid with alcohol for 3 times after 1 cycle, and drying for later use.
Specific example 2:
the difference from the example 1 is that the cycle number in the loading process is different, and is increased from 1 to 3.
Washing silkworm cocoon with water, floating, adding into clear water and 0.1M sodium hydroxide solution, and soaking and boiling at 100 deg.C for 30min to complete degumming process. Rinsing with clear water, and drying at 80 deg.C for use.
Referring to FIG. 2, 0.438g 2-methylimidazole was dissolved in 10mL methanol and designated as solution A; dissolving 0.183g of zinc nitrate in 10mL of methanol to obtain a solution B, sequentially adding silk into the solution A and the solution B at 25 ℃, reacting at constant temperature for 4 hours, rinsing in an ethanol solution for 1 time before exchanging the reaction kettle each time, washing the obtained solid with alcohol for 3 times after 3 cycles, and drying for later use.
Specific example 3:
the difference from the example 1 is that the cycle number in the loading process is different, and is increased from 1 to 5.
Washing silkworm cocoon with water, floating, adding into clear water and 0.1M sodium hydroxide solution, and soaking and boiling at 100 deg.C for 30min to complete degumming process. Rinsing with clear water, and drying at 80 deg.C for use.
Referring to FIG. 3, 0.438g 2-methylimidazole was dissolved in 10mL methanol and designated as solution A; dissolving 0.183g of zinc nitrate in 10mL of methanol to obtain a solution B, sequentially adding silk into the solution A and the solution B at 25 ℃, reacting at constant temperature for 4 hours, rinsing in an ethanol solution for 1 time before exchanging the reaction kettle each time, washing the obtained solid with alcohol for 3 times after 5 cycles, and drying for later use.
The preparation method of the composite fiber adsorption material selects the natural silk fiber as the carrier, and the pretreatment process of the carrier is simple; the composite fiber adsorption material with the surface immobilized with the ZIF-8 nano particles is prepared by a layer-by-layer growth method, so that the loading efficiency is high; hydration reaction activation is adopted before adsorption, so that the reaction rate can be greatly improved. Preliminary application shows that the prepared composite fiber adsorbing material based on the metal organic framework material has the advantages of high adsorption quantity, high adsorption rate, easy regeneration, simple and convenient solid-liquid separation step and low energy consumption, can be better applied to the practice of adsorbing and removing heavy metals in drinking water, and has important application value.
The invention also discloses an application of the composite nanofiber material based on the ZIF-8 material, and a using method for adsorbing and removing heavy metals in drinking water, which comprises the following steps:
1) before use, the composite fiber material is immersed in an aqueous solution for full hydration reaction, and the number of hydroxyl functional groups on the surface of the silk and the surface of the ZIF-8 is obviously increased.
2) After the composite fiber material is used, the composite fiber material is immersed in a regeneration solution for material regeneration, and after 2 hours of reaction, the composite fiber material is washed and dried for standby and can be recycled.
3) After regeneration, the regenerated liquid is concentrated to extract salt.
More specifically, in the step (1), the hydration reaction time is 0.5-2.5 hours.
More specifically, in the step (2), the regeneration solution is one or more of methanol, ethanol, NaOH and water.
More specifically, in the step (2), the regeneration time is 0.5-2.5 hours.
The following description is given with reference to specific embodiments:
specific example 4:
50mg of ZIF-8 composite silk fiber material is immersed in 10ml of water, and the activation reaction is carried out for 0.5 hour; taking 50mg of ZIF-8 composite silk fiber material and 10ml of water, and carrying out no contact reaction; the two silk composite fiber materials (water) are respectively added into a pentavalent sodium arsenate solution (500 mL) with the concentration of 5 mg/L, and the shaking reaction is carried out for a period of time. The adsorption rate was analyzed by sampling at 3min, 10min, 20min, 40min, 1h, 1.5h, 2h, 3h, 5h, 8.5h, 12h, and 24h, respectively, see FIG. 4.
Specific example 5:
50mg of the ZIF-8 composite silk fiber material which is saturated by adsorption is immersed in 50 ml of NaOH aqueous solution, and the activation reaction is carried out for 2 hours; then the regeneration process can be finished by cleaning and drying with pure water. The saturated adsorption capacity after 3 times of regeneration can still be maintained above 75%.
The composite fiber adsorbing material prepared by the invention has the following advantages:
firstly, the composite fiber material based on ZIF-8 is prepared, so that the solid-liquid separation step is greatly facilitated, the loss of powder materials can be effectively avoided, and the energy consumption level in the adsorption process is reduced;
secondly, silk is used as a carrier, so that surface active groups of the silk can be fully utilized, and links such as seed crystal inoculation, surface modification and the like are avoided;
in addition, the surface characteristic and the pore channel structure of the nano material cannot be sacrificed in the silk surface loading mode, and the good porous characteristic of the nano material can be maintained. And the layer-by-layer growth principle can obviously improve the load efficiency, so that the ZIF-8 crystal and the silk are tightly combined, and the phenomenon of crystal falling cannot occur.
Furthermore, before the adsorption reaction, the silk composite fiber adsorption material is pretreated by skillfully utilizing the hydration reaction, so that the adsorption rate can be increased, and the adsorption rate of the ZIF-8 material to trace arsenic in water can be obviously enhanced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of a composite nanofiber material based on a ZIF-8 material is characterized by comprising the following steps of:
1) dissolving 2-methylimidazole in methanol, and marking as a solution A; dissolving zinc nitrate in methanol, marking as a solution B, sequentially putting the fiber carrier into the solution A and the solution B at the temperature of 25 ℃, and reacting for 2-6 h at constant temperature;
2) rinsing for 1 time before exchanging precursor mother liquor each time; rinsing in ethanol for 1 time before mother liquor exchange every time, not only can incompletely-reacted metal ions or organic ligands be removed, but also ZIF-8 crystals which are weak in binding force and adsorbed on the surface of silk can be removed, a compact ZIF-8 surface layer is formed, and the ZIF-8 surface layer is not easy to fall off;
3) after 5 cycles, the solid obtained is filtered, washed 3 times with methanol, dried and activated at 80 ℃ for further use.
2. The preparation method of the ZIF-8 material-based composite nanofiber material as claimed in claim 1, wherein: in the step (1), the molar ratio of the 2-methylimidazole to the zinc nitrate to the methanol is (5-20) to 1 (1-2.5).
3. The preparation method of the ZIF-8 material-based composite nanofiber material as claimed in claim 1 or 2, wherein: in the step 1), the reaction time is 4 hours at constant temperature.
4. The preparation method of the ZIF-8 material-based composite nanofiber material as claimed in claim 3, wherein: in the step 1), the fiber carrier is natural silk fiber with the mass of 30-60 mg, and the preparation method comprises the steps of cleaning the silkworm cocoons, boiling the silkworm cocoons in water and a sodium bicarbonate solution for about 30 minutes to degum, cleaning the silkworm cocoons, and drying the silkworm cocoons at 80 ℃.
5. The application of the composite nanofiber material based on the ZIF-8 material in adsorption removal of heavy metals in drinking water is characterized by comprising the following steps of:
1) before use, the composite fiber material is immersed in an aqueous solution for full hydration reaction, so that the number of hydroxyl functional groups on the surface of the silk and the surface of the ZIF-8 is obviously increased;
2) after the composite fiber material is used, the composite fiber material is immersed in a regeneration solution for material regeneration, and after the reaction is carried out for 0.5-2.5 hours, the composite fiber material is cleaned and dried for standby use and can be recycled;
3) after regeneration, concentrating the regenerated liquid to extract salt;
the application of the ZIF-8 material-based composite nanofiber material as claimed in claim 5, wherein in the step 1), the hydration reaction time is 0.5-2.5 hours.
6. The use of the ZIF-8 based composite nanofiber material as claimed in claim 6, wherein in the step 2), the regeneration solution is one or more of methanol, ethanol, NaOH, and water.
7. Use of a ZIF-8 based composite nanofiber material as claimed in claim 7, wherein in the above step 2), the regeneration time is 2 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116422295A (en) * | 2023-01-13 | 2023-07-14 | 北京理工大学唐山研究院 | Copper-based monoatomic adsorbent and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497017A (en) * | 2014-12-11 | 2015-04-08 | 浙江大学 | Method for growing metal-organic framework seeds in gelatin layer |
| CN104629080A (en) * | 2015-03-06 | 2015-05-20 | 武汉理工大学 | Method for synthesizing ZIF-8 aerogel on basis of cellulose hard template |
| CN106955604A (en) * | 2017-04-17 | 2017-07-18 | 宁波大学 | One kind is based on the preparation method of the dimethyl silicone polymer MULTILAYER COMPOSITE gas separation membranes of PPSU/ZIF 8/ |
| CN107051398A (en) * | 2017-04-26 | 2017-08-18 | 浙江大学 | A kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film |
| CN107469467A (en) * | 2017-09-21 | 2017-12-15 | 陕西科技大学 | A kind of preparation method of efficient gas absorbent-type air filting material |
| CN109235044A (en) * | 2018-08-29 | 2019-01-18 | 华南理工大学 | A kind of polyvinylidene fluoride nanometer tunica fibrosa and its preparation method and application loading ZIF-8 |
| CN109908871A (en) * | 2019-03-21 | 2019-06-21 | 沈阳药科大学 | A kind of magnetic Fe3O4The preparation method and applications of@MIL-100 |
| CN112237850A (en) * | 2019-07-19 | 2021-01-19 | 中能科泰（北京）科技有限公司 | Membrane and preparation method and application thereof |
| CN112811537A (en) * | 2021-02-07 | 2021-05-18 | 河海大学 | Preparation method and application of iron-nitrogen doped carbon nanotube electrode |
-
2021
- 2021-08-05 CN CN202110898497.3A patent/CN113457635A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497017A (en) * | 2014-12-11 | 2015-04-08 | 浙江大学 | Method for growing metal-organic framework seeds in gelatin layer |
| CN104629080A (en) * | 2015-03-06 | 2015-05-20 | 武汉理工大学 | Method for synthesizing ZIF-8 aerogel on basis of cellulose hard template |
| CN106955604A (en) * | 2017-04-17 | 2017-07-18 | 宁波大学 | One kind is based on the preparation method of the dimethyl silicone polymer MULTILAYER COMPOSITE gas separation membranes of PPSU/ZIF 8/ |
| CN107051398A (en) * | 2017-04-26 | 2017-08-18 | 浙江大学 | A kind of method for preparing silk-fibroin nanofiber-metal organic frame laminated film |
| CN107469467A (en) * | 2017-09-21 | 2017-12-15 | 陕西科技大学 | A kind of preparation method of efficient gas absorbent-type air filting material |
| CN109235044A (en) * | 2018-08-29 | 2019-01-18 | 华南理工大学 | A kind of polyvinylidene fluoride nanometer tunica fibrosa and its preparation method and application loading ZIF-8 |
| CN109908871A (en) * | 2019-03-21 | 2019-06-21 | 沈阳药科大学 | A kind of magnetic Fe3O4The preparation method and applications of@MIL-100 |
| CN112237850A (en) * | 2019-07-19 | 2021-01-19 | 中能科泰（北京）科技有限公司 | Membrane and preparation method and application thereof |
| CN112811537A (en) * | 2021-02-07 | 2021-05-18 | 河海大学 | Preparation method and application of iron-nitrogen doped carbon nanotube electrode |
Non-Patent Citations (2)
| Title |
|---|
| ZHISHANG LI ET AL.: ""Biomineralization-mimetic preparation of hybrid membranes with ultra-high loading of pristine metal–organic frameworks grown on silk nanofibers for hazard collection in water"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 马小亮等: ""类沸石金属有机框架材料吸附去除饮用水中微量砷的研究"", 《绿色科技》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116422295A (en) * | 2023-01-13 | 2023-07-14 | 北京理工大学唐山研究院 | Copper-based monoatomic adsorbent and preparation method and application thereof |
| CN116422295B (en) * | 2023-01-13 | 2023-08-29 | 北京理工大学唐山研究院 | Copper-based monoatomic adsorbent and preparation method and application thereof |
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