CN113041863A - Preparation method and application of defect-free and pollution-resistant zirconium-based metal organic framework film - Google Patents
Preparation method and application of defect-free and pollution-resistant zirconium-based metal organic framework film Download PDFInfo
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Abstract
The invention belongs to the technical field of environmental membrane separation, and provides a preparation method and application of a defect-free and pollution-resistant zirconium-based metal organic framework membrane. The introduced titanium dioxide modification layer improves the macroporous defect and the surface chemical environment of the original ceramic carrier, and is beneficial to the nucleation of the UiO-66 crystal, and secondly, the strategy of seeding the nano crystal seeds in situ is used for replacing the traditional dip coating seeding mode, and the UiO-66 crystal seed layer which is uniformly distributed and has thinner thickness is prepared, so that the finally obtained membrane after secondary growth has a thin and compact UiO-66 crystal layer, and the foundation is laid for obtaining the membrane with high flux and high salt retention rate in subsequent saline water treatment.
Description
Technical Field
The invention belongs to the technical field of environmental membrane separation, and relates to a preparation method of a pollution-resistant metal organic framework film integrating carrier modification, nanocrystal in-situ seeding-secondary growth film formation and hydrophilic modification of the film surface, and application of the pollution-resistant metal organic framework film in high-salt organic wastewater treatment.
Background
With the development of industrialization and urbanization, the problem of water pollution is increasingly serious, the water resource crisis is increased continuously, and the development of a new process with low energy consumption and water treatment is an urgent need. Among them, the membrane separation technology is widely used in the treatment process of salt-containing wastewater such as petrochemical wastewater, printing and dyeing wastewater, desalination wastewater and the like due to its advantages of strong selectivity, simple operation process, low energy consumption and the like.
For membrane separation technology, development of a defect-free membrane material with good operation stability is always a research hotspot in the field. Metal Organic Frameworks (MOFs), also known as porous coordination polymers, are crystals of three-dimensional networks [ FURUKAWA H, CORDOVA K E, O' KEEFFE M, et al, the Chemistry and Applications of Metal-Organic Frameworks [ J].Science,2013,341(6149):974]. The MOF material has both organic component and inorganic component, so that compared with traditional polymer film material, the MOF material has the features of rich kinds, high functionality, great porosity, great specific surface area, high pore size controllability, high biocompatibility, etc. and is one kind of ideal film material. Among many MOF materials, zirconium-based MOFs have extremely high water stability due to their strong coordination bonds with ligands formed by Zr clusters and high coordination numbers. As one of the most representative zirconium-based metal organic framework materials, the UiO-66 material consists of Zr6O4(OH)4Coordinated as secondary structural units with terephthalic acid, in the basic unit of which an octahedral central cage and an adjacent tetrahedral corner cage pass through a triangular window (the largest sphere that can pass through)Form diameter of 0.8nm), has great potential in the field of separation of small molecules (such as water molecules), and is favored by membrane development technicians [ CAVKA J H, JAKOBSEN S, OLSBYE U, et al.A. New Zirconium Inorganic Building brik formation Metal Organic Frameworks with Experimental Stability [ J].Journal of the American Chemical Society,2008,130(42):13850-13851]。
The controlled fabrication of intact and intergranular defect-free UiO-66 films remains a great challenge due to the rigidity of the crystalline film itself and the harsh conditions under which the UiO-66 crystals nucleate to grow. Internationally, Li Kang et al first prepared UO-66 Membranes on Alumina ceramic supports self-made in the laboratory by in situ direct growth, but they are more demanding on the supports, require a suitable surface pore structure and Chemical environment, and have poor film formation repeatability, are prone to amorphous morphology, intercrystalline defects, and thick Membranes (film thickness of about 2 μm) [ LIU X, DEMIR N K, WU Z, et al, high Water-Stable Zirconium Metal-Organic Framework UO-66 Membranes Supported on Alumina ceramic Fibers for depletion [ J ]. Journal of the American Chemical Society,2015,137(22):6999 & 7002 ]. To solve these problems, the secondary growth method was introduced to the process of preparing the UiO-66 film by Zhangongfu et al, which can introduce previously prepared seed crystals of UiO-66 for guiding crystal growth on the surface of a support and then carry out secondary growth to form a film. However, the seed layer used in this method is obtained by a dip coating method, which is poor in thickness controllability (more than 2 μm), resulting in an excessively large film thickness (6 μm) obtained after secondary growth, an increase in mass transfer resistance [ WU F, LIN L, LIU H, et al. Another key problem with the use of the UiO-66membranes for water treatment applications today is their inadequate hydrophilicity (contact angles often in the range of 50-70 °) and susceptibility to membrane fouling (e.g., organic fouling) during long-term operation. Therefore, there is an urgent need to develop a new and versatile membrane preparation and modification technique to obtain a defect-free high performance (e.g., flux and selectivity) contamination resistant high quality UiO-66 membrane.
Among a plurality of membrane separation processes, the pervaporation technology is an ideal treatment technology for high-salinity wastewater due to the advantages of reasonable utilization of heat and weak sensitivity to salinity. However, the pervaporation membranes currently suffer from low flux, which leads to huge energy consumption [ CASTRO-
R.Breakthroughs on tailoring pervaporation membranes for water desalination:A review[J].Water Research,2020,187(116428)]. Traditional polymer membrane materials are widely developed due to simple preparation process, but most of the materials are compact and amorphous structures, so that the balance problem of permeability and selectivity often occurs, and the flux is difficult to continue to be improved on the premise of ensuring the separation efficiency. The novel inorganic membrane materials such as zeolite and MOF molecular sieve are expected to overcome the problem and realize high flux under high salt rejection rate. However, current research is limited to desalination studies of single brines, and performance evaluation of treatment of organic-containing brines and modification strategies in the presence of membrane fouling are lacking.
Disclosure of Invention
The invention provides a robust anti-pollution UiO-66membrane preparation strategy comprising carrier modification, in-situ seeding and secondary growth membrane formation of nano-crystals and hydrophilic modification of the membrane surface and application thereof in high-salinity wastewater treatment. The introduced titanium dioxide modification layer improves the macroporous defect and the surface chemical environment of the original ceramic carrier, and is beneficial to the nucleation of the UiO-66 crystal, and secondly, the traditional dip coating seeding mode is replaced by the strategy of seeding the nano crystal seeds in situ, and the UiO-66 crystal seed layer which is uniformly distributed and has thinner thickness is prepared, so that the finally obtained membrane after secondary growth has a thin and compact UiO-66 crystal layer, and the foundation is laid for obtaining the membrane with high flux and high salt rejection rate in subsequent saline water treatment.
The technical scheme of the invention is as follows:
a method for preparing a defect-free pollution-resistant zirconium-based metal organic framework film comprises the following steps:
(1) preparation of metal oxide modification layer
(1.1) cleaning the hollow fiber ceramic carrier, and fully drying;
and (1.2) preparing a titanium dioxide modification layer. Preparing a commercial titanium dioxide suspension with the mass fraction of 10-20% by taking water as a disperse phase, and introducing a titanium dioxide modification layer on the surface of the hollow fiber ceramic carrier by using a dipping coating-sintering process; wherein, the dipping time is 5-10s, the sintering temperature is 500-900 ℃, and the process is repeated for 2-3 times to obtain a complete titanium dioxide middle modified layer;
(2) preparation of UiO-66 film
(2.1) in situ seeding of UiO-66 nanocrystals. Zirconium chloride and terephthalic acid are sequentially added in an amount of 5-10 mmol.L-1Is dissolved in N, N-dimethylformamide solvent, and then glacial acetic acid is added to the solution in an amount to make the concentration of acetic acid in the solution reach 0.4-1.2 mol.L-1Fully stirring to prepare reaction mother liquor; then, putting the reaction mother liquor and the carrier modified by the metal oxide into a reaction kettle together, and reacting for 1-2 days at the temperature of 100-150 ℃ to obtain the carrier with the surface uniformly distributed UiO-66 nano seed crystals;
(2.2) two-stage growth of UiO-66 to form a film. In order to obtain a compact and flawless UiO-66 separation membrane, placing the carrier after in-situ seeding in the reaction mother liquor of the UiO-66membrane for secondary growth; in this process, the ratio of zirconium chloride: terephthalic acid: water: acetic acid: preparing UiO-66membrane reaction mother liquor according to the molar ratio of N, N-dimethylformamide (1: 1:0.5-2: 100) and 200: 500) and 800, then placing the UiO-66membrane reaction mother liquor and a carrier loaded with seed crystals into a reaction kettle together, and reacting for 2-3 days at the temperature of 100 and 150 ℃ to obtain a compact defect-free UiO-66 membrane;
(3) hydrophilic modification of UiO-66membranes
(3.1) preparation of PVA (polyvinyl alcohol) modification solution. Adding PVA and P (AA-AMPS) (poly (acrylic acid-co-2-acrylamide-2-methyl propane sulfonic acid)) into deionized water to prepare a solution with the mass fraction of 0.3-0.5 wt%, wherein the mass ratio of PVA to P (AA-AMPS) is 1.5-2.5, and the pH of the solution is adjusted to be less than 3; after the solution is uniformly mixed, standing for 24 hours for defoaming to obtain a PVA modified solution;
(3.2) preparation of PVA modified layer. The PVA modified layer is introduced through a dip coating process; immersing the prepared UiO-66membrane into a PVA modified solution to introduce a PVA modified layer on the surface of the membrane; after the film is completely dried at room temperature, the film is treated for 10-30min at 80-120 ℃ to ensure that PVA is fully crosslinked. The hollow fiber ceramic carrier can be ceramic films such as an alumina film, a zirconia film, a mullite film and the like.
The metal oxide modified layer can be a gamma-alumina layer besides the titanium oxide layer.
The hydrophilic modification layer of the UiO-66membrane can be a polydopamine layer besides a PVA layer.
The prepared membrane can be used for a high-salinity wastewater treatment process based on a pervaporation technology.
The invention has the beneficial effects that:
(1) the invention provides a general carrier modification strategy, which weakens the harsh requirements of the UiO-66 film growth on a ceramic carrier by introducing a commercial metal oxide modification layer, so that various ceramic carriers have the growth conditions of the UiO-66 film.
(2) By adopting the film preparation method of 'nanocrystal in-situ seeding-secondary growth film forming', the UO-66 nanocrystals can be uniformly distributed on the surface of the ceramic carrier, and compared with the traditional dip coating seeding mode, the method can obtain the UO-66 seed crystals with smaller thickness and more uniform distribution, and lays a foundation for the preparation of defect-free UO-66 films.
(3) After PVA is subjected to hydrophilic modification, the prepared UiO-66membrane can be used for a high-salt wastewater treatment process based on a pervaporation technology, can realize higher water flux and salt retention rate of nearly 100 percent, and has equivalent organic pollution resistance.
Drawings
Fig. 1 is an electron microscope photograph of a titanium dioxide modified carrier, wherein fig. 1a is an electron microscope photograph of a surface of the titanium dioxide modified carrier, and fig. 1b is an electron microscope photograph of a cross section of the titanium dioxide modified carrier.
FIG. 2 is an electron microscope photograph of the surface morphology of the UiO-66 nano seed crystal layer obtained after in-situ seeding.
FIG. 3 is a photograph of a UiO-66 film obtained after the secondary growth, in which FIG. 3a is a photograph of the surface morphology of the UiO-66 film, and FIG. 3b is a photograph of the cross-sectional morphology of the UiO-66 film, from which the original ceramic support and TiO are clearly seen2The middle layer and the UiO-66 film layer have a three-layer structure, wherein the thickness of the UiO-66 film layer is about 1 mu m.
FIG. 4 shows the one-component gas permeability of the membrane (N for each of the test gases)2、CH4、CO2)。
FIG. 5 shows the desalination performance of the membrane under different conditions, wherein FIG. 5a shows UiO-66 desalination performance influenced by the salt concentration of the feed liquid, and FIG. 5b shows UiO-66 desalination performance influenced by the temperature of the feed liquid.
FIG. 6 is the long term operational stability of membrane desalination.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings and technical solutions.
(1) Preparation of metal oxide modification layer
(1.1) the hollow fiber ceramic support was washed with 50 vol.% alcohol and deionized water in this order and dried thoroughly in an oven at 60 ℃.
(1.2) preparation of TiO2And (3) suspension. Weighing anatase type commercial titanium dioxide with the mass fraction of 12%, adding polyacrylic acid solution 1 (with the molecular weight of 20000) and polyacrylic acid solution 2 (with the molecular weight of 5000) in parts by mass of 4-5%, adding deionized water with the mass fraction of 78-80%, and performing ball milling for more than one day to obtain uniformly mixed slurry. Finally, ammonia water is used for adjusting the pH value of the slurry to be 9.5-10.5, and TiO which is evenly and stably dispersed can be obtained2And (3) suspension.
And (1.3) preparing a titanium dioxide modification layer. The preparation method mainly adopts a dip-coating and dip-coating process to prepare the titanium dioxide modification layer, and specifically, the hollow fiber ceramic carrier with two sealed ends is immersed in a titanium dioxide suspension liquid at a constant speed, stands for 5-10s, is pulled out at a constant speed, and is dried in a closed space with constant humidity overnight. After drying, the titanium dioxide modification layer is burntThe sintering is realized by fixing, the sintering atmosphere is air atmosphere, and the sintering procedure is determined to be 2-3 ℃ per minute-1Heating to 700--1Cooling to 500 deg.C, and naturally cooling to room temperature to obtain the final product (figure 1) of the titanium dioxide modified ceramic carrier, wherein the above steps are repeated for 1-2 times to ensure the uniformity of modification.
(2) Preparation of UiO-66 film
(2.1) in situ seeding of UiO-66 nanocrystals. Zirconium chloride (0.1305g, 0.56mmol), terephthalic acid (0.093g, 0.56mmol) and glacial acetic acid (1.6ml, 28mmol) are sequentially dissolved in 70ml of N, N-dimethylformamide solvent, the mixture is uniformly stirred to obtain seed crystal mother liquor, then the seed crystal mother liquor and the titanium oxide modified carrier are placed in a reaction kettle together for reaction for 1-2 days at 120 ℃, and after the reaction is finished, the excessive UiO-66 crystals on the surface of the carrier are removed by wiping with cotton to obtain the UiO-66 nano seed crystal layer with the particle size of about 200nm (figure 2).
(2.2) Secondary growth of UiO-66 film. Zirconium chloride, terephthalic acid, water and glacial acetic acid are sequentially dissolved in N, N-dimethylformamide solvent, a seed crystal mother solution is prepared according to the molar ratio of 1:1:0.5-2:50-150:500, then a carrier with the seed crystal is placed in the mother solution and reacts for 3 days at the temperature of 120-130 ℃, and a UiO-66 film with good crystal intergrowth can be obtained (figure 3).
(2.3) activation of UiO-66 film. And (3) washing the prepared UiO-66membrane by using N, N-dimethylformamide, placing the washed membrane in methanol, standing for 2 days to exchange the solvent, replacing fresh methanol for 2-3 times, then placing the UiO-66membrane subjected to solvent exchange in a vacuum drying oven, and performing vacuum drying at 60 ℃ for 1 day to obtain the UiO-66membrane capable of performing performance test.
(3) Integrity evaluation of UiO-66 film.
Intact defect-free UiO-66membranes are a prerequisite for achieving good separation performance, and to verify membrane integrity, the single component gas permeability of the prepared UiO-66membranes was tested using a soap film flow meter (fig. 4). The test result shows that the permeability of single-component gas of the UiO-66membrane is always kept in a certain range and is slightly influenced by the change of transmembrane pressure, which shows a mechanism of molecular sieve diffusion and proves that the membrane has no large defects.
(4) Hydrophilic modification of UiO-66membranes
(4.1) preparation of PVA modification solution. Adding a certain volume of PVA and P (AA-AMPS) into deionized water to prepare a solution with the mass fraction of 0.4 wt.%, wherein the mass ratio of PVA to P (AA-AMPS) is controlled to be 7:3, and adjusting the pH value of the solution to be 1 by using sulfuric acid. And (3) after uniformly mixing the solution, standing for 24 hours for defoaming to obtain a modified solution.
And (4.2) preparing a PVA hydrophilic modified layer. Introducing the modified layer through a dip coating process, and immersing the prepared UiO-66membrane into a PVA modified solution to introduce the PVA modified layer on the surface of the membrane, wherein the preferable dip coating parameters are as follows: 1cm s-1A falling speed of (2), a soaking time of 1min and a length of 0.4cm · s-1In order to maintain the single-sided coating, both ends of the hollow fiber membrane were sealed before dip coating. After the membrane was completely dried, the membrane was treated at 100 ℃ for 15min to crosslink the PVA.
(5) UiO-66membrane pervaporation desalination.
(5.1) saline handling properties of UiO-66 membranes. The pervaporation desalination performance of the UiO-66membrane was first tested at different salt concentrations (1-7 wt.%), and the membrane salt rejection exceeded 99.9% at all feed concentrations, confirming the effectiveness of the UiO-66membrane in treating brine. The desalination performance of the membranes was then tested at different feed solution temperatures and it was found that as the temperature was increased, the water production of the membranes increased and a high salt rejection rate was maintained (fig. 5). In addition, the stability of the membrane for long-term operation was tested using a 7 wt.% NaCl solution.
(5.2) the fouling resistance of the modified UiO-66 membrane. The fouling resistance of the membranes when treating high salinity organic wastewater was tested using 7 wt.% brine containing high concentrations of HA (humic acid, natural organic matter) as the feed solution.
Claims (6)
1. The preparation method of the defect-free pollution-resistant zirconium-based metal organic framework film is characterized by comprising the following steps of:
(1) preparation of metal oxide modification layer
(1.1) cleaning the hollow fiber ceramic carrier, and fully drying;
(1.2) preparing a titanium dioxide modification layer; preparing a titanium dioxide suspension with the mass fraction of 10-20% by taking water as a disperse phase, and introducing a titanium dioxide modification layer on the surface of the hollow fiber ceramic carrier by using a dipping coating-sintering process; wherein, the dipping time is 5-10s, the sintering temperature is 500-900 ℃, and the process is repeated for 2-3 times to obtain a complete titanium dioxide middle modified layer;
(2) preparation of UiO-66 film
(2.1) in-situ seeding of UiO-66 nanocrystals; zirconium chloride and terephthalic acid are sequentially added in an amount of 5-10 mmol.L-1Is dissolved in N, N-dimethylformamide solvent, and glacial acetic acid is added thereto so that the concentration of acetic acid in the solution becomes 0.4 to 1.2 mol. L-1Fully stirring to prepare reaction mother liquor; then, putting the reaction mother liquor and the carrier modified by the metal oxide obtained in the step (1) into a reaction kettle together, and reacting for 1-2 days at the temperature of 100-150 ℃ to obtain the carrier with the surface uniformly distributed UiO-66 nano seed crystals;
(2.2) carrying out secondary growth of UiO-66 to form a film; in order to obtain a compact and flawless UiO-66 separation membrane, placing the carrier after in-situ seeding in the reaction mother liquor of the UiO-66membrane for secondary growth; in this process, the ratio of zirconium chloride: terephthalic acid: water: acetic acid: preparing UiO-66membrane reaction mother liquor according to the molar ratio of N, N-dimethylformamide (1: 1:0.5-2: 100) and 200: 500) and 800, then placing the UiO-66membrane reaction mother liquor and a carrier with the surface uniformly distributed with UiO-66 nanometer crystal seeds in a reaction kettle together, and reacting for 2-3 days at the temperature of 100 and 150 ℃ to obtain a compact defect-free UiO-66 membrane;
(3) hydrophilic modification of UiO-66membranes
(3.1) preparing a PVA modification solution; adding PVA and P (AA-AMPS) into deionized water to prepare a solution with the mass fraction of 0.3-0.5 wt.%, wherein the mass ratio of the PVA to the P (AA-AMPS) is 1.5-2.5, and the pH of the solution is adjusted to be less than 3; uniformly mixing the solution, standing for 24 hours for defoaming to obtain a PVA modified solution;
(3.2) preparing a PVA modified layer; the PVA modified layer is introduced through a dip coating process; immersing the prepared UiO-66membrane into a PVA modified solution to introduce a PVA modified layer on the surface of the membrane; and after the film is completely dried at room temperature, treating at 80-120 ℃ for 10-30min to fully crosslink PVA, thus obtaining the defect-free pollution-resistant zirconium-based metal organic framework film.
2. The method according to claim 1, wherein the hollow fiber ceramic support is an alumina film, a zirconia film or a mullite film.
3. The method according to claim 1 or 2, wherein the titanium dioxide modification layer is replaced with a gamma-alumina modification layer.
4. The method according to claim 1 or 2, wherein the PVA modifying layer is replaced by a polydopamine layer.
5. The method according to claim 3, wherein the PVA modified layer is replaced by a polydopamine layer.
6. A defect-free and pollution-resistant zirconium-based metal organic framework membrane is used for a high-salinity wastewater treatment process based on a pervaporation technology.
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| CN114316319A (en) * | 2022-01-11 | 2022-04-12 | 天津大学 | Method for preparing oriented MOF film by steam assistance and separation application |
| CN114887502A (en) * | 2022-03-24 | 2022-08-12 | 大连理工大学 | Method for preparing Zr-MOF molecular sieve membrane by using zirconium cluster as metal source under mild reaction condition |
| CN115894955A (en) * | 2022-12-14 | 2023-04-04 | 中国科学技术大学 | Zirconium-based metal organic framework material, and synthesis method and application thereof |
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| CN115894955B (en) * | 2022-12-14 | 2023-11-17 | 中国科学技术大学 | Zirconium-based metal organic framework material, synthesis method and application thereof |
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Inventor after: Dong Yingchao Inventor after: Li Haotian Inventor after: Wang Dong Inventor after: Fu Mao Inventor before: Wang Dong Inventor before: Li Haotian Inventor before: Dong Yingchao Inventor before: Fu Mao |
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