CN116173923A - Preparation method of MOFs-based aerogel loaded with titanium dioxide - Google Patents
Preparation method of MOFs-based aerogel loaded with titanium dioxide Download PDFInfo
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- CN116173923A CN116173923A CN202310223891.6A CN202310223891A CN116173923A CN 116173923 A CN116173923 A CN 116173923A CN 202310223891 A CN202310223891 A CN 202310223891A CN 116173923 A CN116173923 A CN 116173923A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 122
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 102
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 15
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- 238000000034 method Methods 0.000 claims abstract description 13
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
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- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 12
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- 125000005289 uranyl group Chemical group 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 230000000844 anti-bacterial effect Effects 0.000 description 13
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- 229910052770 Uranium Inorganic materials 0.000 description 12
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 12
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 241000209094 Oryza Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 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]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a preparation method of MOFs-based aerogel loaded with titanium dioxide, which is characterized in that cellulose is subjected to oxidative modification treatment to obtain carboxylated cellulose nanofiber; anatase type TiO 2 Adding the mixture into a carboxylated cellulose nanofiber dispersion liquid, and obtaining TiO with uniform and firm load through a freeze drying method after dispersion treatment 2 Carboxylated cellulose nanofiber aerogel; with TiO 2 Carboxylated cellulose nanofiber aerogel as matrix, inorganic metal ions (Zr 4+ ) Chelating on carboxyl of carboxylated cellulose nanofiber and serving as metal ion center, and using 2-amino terephthalic acid as organic ligand, and performing hydrothermal synthesis reaction on TiO 2 MOFs (UIO-66-NH) were grown in situ on carboxylated cellulose nanofiber aerogel 2 ) Obtaining the loadMOFs-based aerogels of titanium dioxide. The MOFs-based aerogel loaded with titanium dioxide has the characteristics of large specific surface area, high porosity, high chelating property, photocatalytic property and biological pollution resistance, and easy recovery and repeated use.
Description
Technical Field
The invention relates to a preparation method of MOFs-based aerogel loaded with titanium dioxide, and belongs to the field of functional composite material science.
Background
To achieve the goal of carbon peak and carbon neutralization, nuclear energy with extremely high energy density and no greenhouse gas emissions has been of great concern. Uranium is mainly used as nuclear fuel, so refining uranium is beneficial to sustainable development of energy industry. Currently, uranium is mainly obtained by mineral extraction. As energy demand increases, uranium will become a shortfall resource. The total amount of uranium in seawater is estimated to be 45 hundred million tons, which is 1000 times greater than the reserve of uranium on land. However, the concentration of uranium in seawater is quite low (≡3.3 ppb) and there are a large number of competing ions, which makes recovery of uranium from seawater challenging. At present, various physical and chemical methods have been and are being studied to extract uranium from aqueous solutions, including ion exchange, membrane separation, and adsorption. Among them, the solid-phase adsorption method is attracting attention because of its advantages of flexible structure, easy application, repeatability, reliable use, low cost, environmental protection, etc., and at the same time, these potential advantages are very advantageous for treating ultra-large volumes of seawater. One of the key and challenges of solid phase adsorption is the preparation of high performance uranium adsorbents with high adsorption capacity, selectivity, fast adsorption/desorption kinetics. However, to date, most adsorbent materials have generally failed to meet these requirements simultaneously.
Metal Organic Frameworks (MOFs) have the advantages of large specific surface area, high porosity, low density, structural controllability, chemical stability, and the like, and are widely considered as attractive uranium adsorbent candidate materials (Coordination Chemistry Reviews 475 (2023) 214917). MOFs are usually present in the form of nanopowders or colloidal crystals due to their crystalline nature. Thus, the recovery of MOFs adsorbents in natural seawater remains a challenge. In the field of separations and catalysis, MOFs crystals are often embedded in a layered porous polymer matrix to make composites (ACS Omega 2022,7,14430-14456). Therefore, the search for advanced porous substrate materials with high porosity, ultra-light density and low cost is a key to realize easy recovery and repeated use of MOFs adsorbent.
Renewable resources are an urgent need for sustainable development of humans, cellulose is the most abundant natural "organic" biological material on earth, and annual production is several billion tons worldwide. Cellulose Nanofibers (CNFs) are a unique nanoscale material that can be extracted from different natural sources (e.g., wood and cotton) by chemical and/or physical methods. The CNFs has the advantages of easy obtainment, regeneration, low cost, degradability, light weight, surface chemical control, environmental protection and the like, and can be used for preparing CNFs aerogel with communicated holes, high porosity, large specific surface and high strength by a freeze drying technology. It was found that carboxylated CNFs (Carboxylated CNFs) aerogels have abundant polar groups (e.g., hydroxyl and carboxyl groups), which provide a rich reaction site and strong binding for nucleation and growth of MOF crystals.
Research on MOFs based materials shows that MOFs have low binding force with a matrix material, so that the MOFs in the prepared composite material are small in quantity, and the MOFs lack groups with high affinity and selectivity to uranyl, so that the adsorption and separation effects on uranyl are not ideal (Applied Surface Science 597 (2022) 153659). Titanium dioxide (TiO 2) is taken as a semiconductor photocatalyst, has the advantages of radiochemical stability, acid-base stability, no toxicity, low price and the like, and is a well-known radionuclide adsorbent (Journal of Molecular Liquids 293 (2019) 111563). The MOFs (UiO-66-NH 2) is grown in situ on the TiO 2/carboxylated cellulose nanofiber through hydrothermal synthesis reaction, and is firmly combined in the aerogel through chemical chelation, and the MOFs are large in quantity. The MOFs (UIO-66-NH 2) crystal rich in high chelating carboxyl groups provides sites for a large number of binding sites of uranyl, and meanwhile, tiO2 is used for photocatalytic reduction of U (VI) into insoluble U (IV), so that more binding sites on the MOF crystal are used for further U (VI) adsorption. In addition, the MOFs-based aerogel loaded with titanium dioxide endows the MOFs-based aerogel with antimicrobial pollution capability, has easy recovery and reusability, and can realize efficient and selective enrichment of uranyl from a real water environment. Meanwhile, other MOFs/cellulose aerogel with excellent performance can be synthesized by utilizing different metal clusters and organic connecting agents, and the invention provides a very promising strategy for the MOFs-based adsorbent in commercial and industrial application.
Disclosure of Invention
In view of the above problems, the technical object of the present invention is to provide a titania-supported MOFs-based aerogel. Due to the limitation of the crystal structure of MOFs materials, the MOFs materials generally exist in powder or colloid form, so that the MOFs materials are difficult to recycle, have poor reusability and the like when applied to the adsorption field. At the same time, the lack of groups with high affinity and selectivity for uranyl severely limits the adsorptive properties of MOFs materials. Therefore, designing a MOFs-based composite material that is highly efficient and selectively enriched for uranyl is a problem that needs to be addressed. The invention provides MOFs-based aerogel loaded with titanium dioxide, which is characterized in that cellulose is subjected to oxidative modification treatment to obtain carboxylated cellulose nanofiber; anatase TiO with photocatalytic activity 2 Dispersing into carboxylated cellulose nanofiber solution, and freeze drying to obtain uniformly and firmly loaded TiO 2 Carboxylated cellulose nanofiber aerogel; with TiO 2 Carboxylated cellulose nanofiber aerogel as matrix, inorganic metal ions (Zr 4 + ) Chelating on carboxyl of carboxylated cellulose nanofiber and serving as metal ion center, and using 2-amino terephthalic acid as organic ligand, and performing hydrothermal synthesis reaction on TiO 2 MOFs (UIO-66-NH) were grown in situ on carboxylated cellulose nanofiber aerogel 2 ) Obtaining the MOFs-based aerogel loaded with titanium dioxide. The MOFs-based aerogel loaded with titanium dioxide has large specific surface area, high porosity, is rich in carboxyl groups with strong chelating property, has photocatalysis and biological pollution resistance, and is the same asThe method has the characteristics of easy recovery and repeated utilization, and is hopeful to be used as a novel MOFs-based adsorption material to realize efficient selective enrichment and separation of uranyl in aqueous solution.
The invention provides a preparation method of MOFs-based aerogel loaded with titanium dioxide, which comprises the following components in parts by weight 2 0.1-0.5 part of UiO-66-NH 2 1-5 parts of crystal, and the preparation method comprises the following steps:
S1：TiO 2 preparation of carboxylated cellulose nanofiber Dispersion, anatase TiO 2 Adding into 1.5-10wt% carboxylated cellulose nanofiber dispersion liquid, placing into an ultrasonic cell crusher for treatment, setting the power to be 500-1000W and the treatment time to be 1-5 h to obtain the TiO 2 Carboxylated cellulose nanofiber dispersion;
S2：TiO 2 preparing carboxylated cellulose nanofiber aerogel, performing ultrasonic deaeration on the dispersion liquid, injecting the dispersion liquid into a mould, and freezing at-80 ℃ for 2-10 h, and performing vacuum drying to obtain TiO 2 Carboxylated cellulose nanofiber aerogel;
s3: preparation of MOFs-based aerogel carrying titanium dioxide, and ZrCl 4 Dissolved in N, N-dimethylformamide solution, wherein ZrCl 4 The mass concentration of (2) is 0.1-0.5 wt%, and TiO is continuously added into the solution 2 Carboxylated cellulose nanofiber aerogel, and then dispersing the solution in an ultrasonic cell crusher to make Zr 4+ Chelating on free carboxyl of carboxylated cellulose nanofiber, and continuously adding 2-amino terephthalic acid and 1ml glacial acetic acid into the solution, wherein the 2-amino terephthalic acid and ZrCl 4 The molar mass ratio was 1:1, and finally the mixed solution was transferred to a solvothermal reactor and reacted in an oven at 95 ℃ for 24 hours. And after the reaction is finished and cooled to room temperature, taking out a product from the reaction solution, and washing with DMF and absolute ethyl alcohol to obtain the MOFs-based aerogel loaded with titanium dioxide.
Further, the preparation steps of the carboxylated cellulose nanofiber in the step S1 are as follows:
step 1, placing cellulose in a NaOH solution with the concentration of 1-5 wt% according to the bath ratio of 1:100-1:50, boiling for 30-120 min, adding absolute ethyl alcohol and sodium chloroacetate into the solution, wherein the absolute ethyl alcohol is in an amount of 1:10-1:50 according to the bath ratio of the cellulose, the molar mass of the sodium chloroacetate and the cellulose is 1:1, keeping the mixture at 71 ℃ for 4 hours, filtering after the reaction is finished, drying the filtrate, and washing the filtrate with deionized water to obtain the cellulose nanofiber;
and 2, dispersing cellulose nanofibers in deionized water according to a bath ratio of 1:20-1:100, adding nitric acid and phosphoric acid with a volume ratio of 1-5:1 into the solution, reacting for 3-5 hours at room temperature with a total acid concentration of 10-20%, continuously adding sodium nitrite into the solution, reacting for 12-48 hours at room temperature with a concentration of 0.5-5% of sodium nitrite, filtering, washing and drying to obtain carboxylated cellulose nanofibers, and dispersing the carboxylated cellulose nanofibers into deionized water to obtain carboxylated cellulose nanofiber dispersion with a weight percentage of 1.5-10%.
Further, the anatase TiO in step S1 2 The content of (C) is 0.1-0.5 wt%.
Further, the TiO in step S3 2 The amount of the carboxylated cellulose nanofiber aerogel is 1 to 5 weight percent.
Further, the dispersion treatment conditions in the ultrasonic cell disruptor in step S3 are as follows: the power is set to be 500-1200W, and the treatment time is 0.5-5 h.
Further, the anatase TiO in step S1 2 The grain diameter is 80-800 nm.
Further, the cellulose in the step 1 is one or a mixture of cotton linters, wood, rice straw and wheat straw.
The invention has the beneficial effects that:
(1) TiO with large specific surface area and high porosity 2 The carboxylated cellulose aerogel is used as a substrate material, and the MOFs and the substrate material are compounded, so that the problems of difficult recovery and poor reusability of the MOFs-based material in application can be solved.
(2)TiO 2 CarboxylationCellulose aerogel is rich in a large amount of carboxyl groups, and inorganic metal ions (Zr) chelated by the carboxyl groups 4 + ) As a center, in TiO 2 MOFs (UIO-66-NH) are grown in situ on the surface of carboxylated cellulose aerogel by hydrothermal synthesis 2 ) MOFs are firmly bound to TiO by chemical chelation 2 Carboxylated cellulose aerogel, and the loading is high. Overcomes the problems of poor combination and low load caused by directly compounding MOFs and a matrix in the conventional process.
(3) The MOFs-based aerogel loaded with titanium dioxide has large specific surface area, high porosity and MOFs (UiO-66-NH) rich in high chelating carboxyl groups 2 ) The crystal has the advantages of photocatalysis, lasting antimicrobial pollution, excellent mechanical property, easy recovery and reusability, and shows the capability of highly-efficient selective enrichment of uranyl.
Drawings
FIG. 1 is a scanning electron microscope image of a titania-supported MOFs-based aerogel.
FIG. 2 is a scanning electron microscope image of a titanium dioxide loaded MOFs based aerogel partially magnified.
FIG. 3 is an infrared spectrum of a titania-supported MOFs-based aerogel.
Detailed Description
The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
The invention provides a preparation method of MOFs-based aerogel loaded with titanium dioxide, which comprises the following components in parts by weight 2 0.1-0.5 part of UiO-66-NH 2 1-5 parts of crystal, and the preparation method comprises the following steps:
S1：TiO 2 preparation of carboxylated cellulose nanofiber Dispersion, anatase TiO 2 Adding into 1.5-10wt% carboxylated cellulose nanofiber dispersion liquid, placing into an ultrasonic cell crusher for treatment, setting the power to be 500-1000W and the treatment time to be 1-5 h to obtain the TiO 2 Carboxylated cellulose nanofiber dispersion;
S2：TiO 2 preparing carboxylated cellulose nanofiber aerogel, performing ultrasonic deaeration on the dispersion liquid, injecting the dispersion liquid into a mould, and freezing at-80 ℃ for 2-10 h, and performing vacuum drying to obtain TiO 2 Carboxylated cellulose nanofiber aerogel;
s3: preparation of MOFs-based aerogel carrying titanium dioxide, and ZrCl 4 Dissolved in N, N-dimethylformamide solution, wherein ZrCl 4 The mass concentration of (2) is 0.1-0.5 wt%, and TiO is continuously added into the solution 2 Carboxylated cellulose nanofiber aerogel, and then dispersing the solution in an ultrasonic cell crusher to make Zr 4+ Chelating on free carboxyl of carboxylated cellulose nanofiber, and continuously adding 2-amino terephthalic acid and 1ml glacial acetic acid into the solution, wherein the 2-amino terephthalic acid and ZrCl 4 The molar mass ratio was 1:1, and finally the mixed solution was transferred to a solvothermal reactor and reacted in an oven at 95 ℃ for 24 hours. And after the reaction is finished and cooled to room temperature, taking out a product from the reaction solution, and washing with DMF and absolute ethyl alcohol to obtain the MOFs-based aerogel loaded with titanium dioxide.
Further, the preparation steps of the carboxylated cellulose nanofiber in the step S1 are as follows:
step 1, placing cellulose in a NaOH solution with the concentration of 1-5 wt% according to the bath ratio of 1:100-1:50, boiling for 30-120 min, adding absolute ethyl alcohol and sodium chloroacetate into the solution, wherein the absolute ethyl alcohol is in an amount of 1:10-1:50 according to the bath ratio of the cellulose, the molar mass of the sodium chloroacetate and the cellulose is 1:1, keeping the mixture at 71 ℃ for 4 hours, filtering after the reaction is finished, drying the filtrate, and washing the filtrate with deionized water to obtain the cellulose nanofiber;
and 2, dispersing cellulose nanofibers in deionized water according to a bath ratio of 1:20-1:100, adding nitric acid and phosphoric acid with a volume ratio of 1-5:1 into the solution, reacting for 3-5 hours at room temperature with a total acid concentration of 10-20%, continuously adding sodium nitrite into the solution, reacting for 12-48 hours at room temperature with a concentration of 0.5-5% of sodium nitrite, filtering, washing and drying to obtain carboxylated cellulose nanofibers, and dispersing the carboxylated cellulose nanofibers into deionized water to obtain carboxylated cellulose nanofiber dispersion with a weight percentage of 1.5-10%.
Further, the cellulose is one or a mixture of cotton linters, wood, rice straw and wheat straw.
Example 1
Anatase TiO with particle size of 80-800 nm 2 Added into 5wt% of carboxylated cellulose nanofiber dispersion, wherein the titanium ore type TiO in the dispersion 2 The amount is 0.3wt percent, then the mixture is placed in an ultrasonic cell grinder for treatment, the power is set to be 800W, and the treatment time is 3 hours, thus obtaining the TiO 2 Carboxylated cellulose nanofiber dispersion; ultrasonic defoaming the dispersion liquid, injecting into a mould, freezing at-80 ℃ for 5 hours, and vacuum drying to obtain TiO 2 Carboxylated cellulose nanofiber aerogel; zrCl is added to 4 Dissolved in N, N-dimethylformamide solution, wherein ZrCl 4 The mass concentration of (2) was 0.3wt%, and then the addition of TiO to the solution was continued 2 Carboxylated cellulose nanofiber aerogel, wherein TiO 2 The carboxylated cellulose nanofiber aerogel amount is 3 weight percent, the solution is put into an ultrasonic cell crusher for dispersion treatment, the power is set to 1000W, the treatment time is 2 hours, and Zr is caused 4+ Chelating on free carboxyl groups of carboxylated cellulose nanofibers, adding 2-amino terephthalic acid and 1ml glacial acetic acid to the solution, wherein the 2-amino terephthalic acid and ZrCl 4 The molar mass ratio was 1:1, and the mixed solution was transferred to a solvothermal reactor and reacted in an oven at 95 ℃ for 24 hours. And after the reaction is finished and cooled to room temperature, taking out a product from the reaction solution, and repeatedly washing with DMF and absolute ethyl alcohol to obtain the MOFs-based aerogel loaded with titanium dioxide.
Referring to fig. 1, there are a large number of holes in the titanium dioxide loaded MOFs-based aerogel, which demonstrates that the aerogel has high porosity and large specific surface area.
Referring to FIG. 2, tiO is prepared by hydrothermal synthesis reaction 2 In situ growth on carboxylated cellulose nanofiber aerogelMOFs(UiO-66-NH 2 ) And the MOFs have regular morphology and uniform size, and can be uniformly and firmly combined with the TiO 2 Carboxylated cellulose nanofiber aerogel surfaces, mainly due to the presence of TiO in the present invention 2 Carboxylated cellulose nanofiber aerogel as matrix, inorganic metal ions (Zr 4+ ) Chelating on carboxyl of carboxylated cellulose nanofiber and serving as metal ion center, the hole of aerogel and the adjacent metal ion center distance can limit the growth of MOFs, so that the synthesized MOFs are regular in morphology and uniform in size. Chelation of large amounts of Zr in the aerogel 4+ The increased nucleation centers in the MOFs hydrothermal synthesis reaction allow for the preparation of aerogels with a strong, uniform loading of large amounts of MOFs by the present invention.
Referring to fig. 3, fig. 3 (a) is untreated cellulose and fig. 3 (b) is a titania-loaded MOFs-based aerogel. As can be seen from FIG. 3 (b), the MOFs based aerogel loaded with titanium dioxide was at 1730cm -1 There appears a significant telescopic vibration absorption band of carboxyl c=o, and 1644cm -1 The characteristic vibration peak of the nearby adsorbed water is obviously enhanced, which indicates that the carboxylated cellulose nanofiber still contains a large amount of un-mixed Zr 4+ The chelated carboxyl groups simultaneously increase the affinity of the MOFs-based aerogel loaded with titanium dioxide to water molecules due to the presence of carboxylated cellulose nanofibers.
Referring to table 1, table 1 shows adsorption performance of the titania-supported MOFs-based aerogel on uranyl in solution. To test the uranyl selective enrichment performance of titanium dioxide loaded MOFs-based aerogels, 5mg samples were added to 1.0L of uranyl nitrate solutions of different concentrations, respectively, and the solutions were then exposed to uv lamps for a period of time. Dark field environments were used for the control experiments. At intervals, a certain amount of the solution is taken out, the uranyl concentration is measured by an arsenical azo arsine III method (the uranyl solution before and after adsorption is added into a mixed solution containing deionized water (3 mL), azo arsine (0.2 mL,1 mM) and hydrochloric acid (0.8 mL, 0.1M), and the absorbance at 652nm is measured by an ultraviolet-visible spectrophotometerAnd calculating the adsorption capacity. As can be seen from the table, a single MOFs (UiO-66-NH 2 ) The adsorption capacity of the crystal material to uranyl is 205mg/g, and the adsorption capacity of the MOFs-based aerogel loaded with titanium dioxide under the condition of no illumination to uranyl is 290mg/g, which shows that the MOFs (UiO-66-NH) is increased by a large number of carboxyl groups with strong chelating property in the MOFs-based aerogel loaded with titanium dioxide 2 ) The adsorption sites of crystals to uranyl are confirmed by the analysis of FIG. 3, which shows that carboxylated cellulose nanofibers still contain a significant amount of un-neutralized Zr in titania-loaded MOFs-based aerogels 4+ Chelating carboxyl groups. At the same time, under no light conditions, single MOFs (UiO-66-NH 2 ) Crystals and titanium dioxide-loaded MOFs-based aerogel are used for enriching uranyl ions in a solution only by adsorption, and if the adsorption capacity of the MOFs-based material is further improved, a material with various enrichment modes needs to be developed. From the table, it is shown that the adsorption capacity of the MOFs-based aerogel loaded with titanium dioxide for uranyl reaches 355mg/g under the illumination condition, which further illustrates the capability of enhancing the selective enrichment of the MOFs-based aerogel loaded with titanium dioxide for uranyl by utilizing the photocatalysis principle, mainly because of the fact that under the illumination condition, tiO 2 The U (VI) chelated in the MOFs crystals is reduced to insoluble U (IV) by a photocatalytic reaction, resulting in more free binding sites on the MOFs crystals for further U (VI) adsorption, which also embodies the selective enrichment of uranyl by titania-loaded MOFs-based aerogels.
TABLE 1
Table 2 shows the antibacterial properties of titania-loaded MOFs-based aerogels against Staphylococcus aureus and Escherichia coli. The experiment selects two representative antibacterial experiments of gram negative bacteria and positive bacteria (staphylococcus aureus, S.aureus and escherichia coli, E.coli) and simulates and verifies the antimicrobial pollution performance of MOFs-based aerogel loaded with titanium dioxide. To facilitate the operation of bacteriostasis experiments, aerogels were tested prior to testingCompressed into a sheet form. Evaluation of antimicrobial Properties of textiles according to GB/T20944.3-2008 part 3: vibration method, in which MOFs base aerogel samples loaded with titanium dioxide are respectively sheared and put into a flask, 70ml of phosphate buffer solution (PBS, pH is approximately 7.2) and 5ml of bacterial liquid (3X 105-4X 105 cfu/ml) are added, and then the flask is vibrated for 18 hours at 24 ℃; taking out 1ml of culture solution, diluting, uniformly dispersing in an agar plate, incubating at 37 ℃ for 24-48 hours, counting the number of colonies growing, and calculating according to a formula to obtain the antibacterial rate. As can be seen from table 2, the MOFs-based aerogel loaded with titanium dioxide also has a certain antibacterial performance on staphylococcus aureus and escherichia coli under the condition of no illumination, but the antibacterial effect is quite unsatisfactory. Under the condition of no illumination, the antibacterial effect of the MOFs-based aerogel loaded with titanium dioxide on staphylococcus aureus and escherichia coli is 19.14% and 10.47%, and the antibacterial rate after 30 times of washing is 10.92% and 6.73%, which shows that the MOFs-based aerogel loaded with titanium dioxide has obvious inhibition effect on escherichia coli with larger antibacterial activity on staphylococcus aureus, because the cell wall of staphylococcus aureus consists of teichoic acid, and the carboxylated cellulose nanofiber in the MOFs-based aerogel loaded with titanium dioxide contains a large amount of carboxyl groups, and the carboxylated cellulose nanofiber and teichoic acid have similar compatibility principle, so that the aerogel is easier to damage the cell wall of staphylococcus aureus, and the bacterial structure is damaged to die. The outer cell of the escherichia coli is provided with a thicker Lipoid Polysaccharide (LPS) layer which can prevent external macromolecular substances, so that the inhibition effect of the escherichia coli is poor. Meanwhile, after multiple times of water washing, the MOFs-based aerogel loaded with the titanium dioxide still has certain antibacterial property, which indicates that the antibacterial effect is durable. It is shown from the table that under the illumination condition, the antibacterial effect of MOFs-based aerogel loaded with titanium dioxide on staphylococcus aureus and escherichia coli is 97.95% and 92.38%, respectively, mainly because the MOFs-based aerogel contains the inhibition effect of carboxylated cellulose nanofiber on bacteria, and under the illumination condition, the MOFs-based aerogel is subjected to H 2 In the presence of O and dissolved oxygen, photo-induced active oxygen (e.g.. O) 2 - 、H 2 O 2 And OH) raw materialsAnd (3) forming the finished product. These highly reactive free radicals first damage the cell wall and then further oxidize and damage the cytoplasmic membrane of the bacteria, which breaks down resulting in free flow of the cell contents. At the same time, DNA/RNA may be directly attacked by ROS, thereby accelerating bacterial cell death. This demonstrates that the photocatalytic properties of titania-loaded MOFs-based aerogels not only enhance the selective enrichment of uranyl by MOFs-based materials, but also impart antimicrobial contamination resistance. Meanwhile, after 30 times of washing, the antibacterial rate of the MOFs-based aerogel loaded with titanium dioxide on staphylococcus aureus and escherichia coli still reaches more than 90% and 85%, which shows that the antibacterial effect is durable, and the possibility is provided for recycling the adsorbent for multiple times. In conclusion, the bacteriostasis effect of the aerogel is verified by different bacteriostasis effects, so that the MOFs-based aerogel loaded with titanium dioxide solves the problem that in a real marine environment, the adsorbent is inevitably attacked by marine bacteria to seriously destroy the binding sites, so that the adsorption capacity of uranium is reduced. The MOFs-based aerogel loaded with titanium dioxide has the capability of resisting microbial contamination, and provides theoretical support and potential for adsorption application in a real environment.
TABLE 2
Example 2
Anatase TiO with particle size of 80-800 nm 2 Added into 1.5wt% of carboxylated cellulose nanofiber dispersion, wherein the titanium ore type TiO in the dispersion 2 The amount is 0.1wt percent, then the mixture is placed in an ultrasonic cell grinder for treatment, the power is set to be 500W, and the treatment time is 1h, thus obtaining the TiO 2 Carboxylated cellulose nanofiber dispersion; ultrasonic defoaming the dispersion liquid, injecting into a mould, freezing at-80 ℃ for 2h, and vacuum drying to obtain TiO 2 Carboxylated cellulose nanofiber aerogel; zrCl is added to 4 Dissolved in N, N-dimethylformamide solution, wherein ZrCl 4 The mass concentration of (2) was 0.1wt%, and then the addition of TiO to the solution was continued 2 Carboxylic acidCellulose nanofiber aerogel, wherein TiO 2 The carboxylated cellulose nanofiber aerogel with the weight of 1 percent is put into an ultrasonic cell crusher to be dispersed and treated, the power is set to be 500W, the treatment time is 0.5h, and Zr is caused 4+ Chelating on free carboxyl groups of carboxylated cellulose nanofibers, adding 2-amino terephthalic acid and 1ml glacial acetic acid to the solution, wherein the 2-amino terephthalic acid and ZrCl 4 The molar mass ratio was 1:1, and the mixed solution was transferred to a solvothermal reactor and reacted in an oven at 95 ℃ for 24 hours. And after the reaction is finished and cooled to room temperature, taking out a product from the reaction solution, and repeatedly washing with DMF and absolute ethyl alcohol to obtain the MOFs-based aerogel loaded with titanium dioxide.
Example 3
Anatase TiO with particle size of 80-800 nm 2 Added into 10wt% of carboxylated cellulose nanofiber dispersion, wherein the titanium ore type TiO in the dispersion 2 The amount is 0.5wt percent, then the mixture is placed in an ultrasonic cell grinder for treatment, the power is set to be 1000W, and the treatment time is 5 hours, thus obtaining the TiO 2 Carboxylated cellulose nanofiber dispersion; ultrasonic defoaming the dispersion liquid, injecting into a mould, freezing at-80 ℃ for 10 hours, and vacuum drying to obtain TiO 2 Carboxylated cellulose nanofiber aerogel; zrCl is added to 4 Dissolved in N, N-dimethylformamide solution, wherein ZrCl 4 Is 0.5wt% and then continuing to add TiO to the solution 2 Carboxylated cellulose nanofiber aerogel, wherein TiO 2 The carboxylated cellulose nanofiber aerogel with the weight of 5 percent is put into an ultrasonic cell crusher to be dispersed and treated, the power is set to 1200W, the treatment time is 5 hours, and Zr is caused 4+ Chelating on free carboxyl groups of carboxylated cellulose nanofibers, adding 2-amino terephthalic acid and 1ml glacial acetic acid to the solution, wherein the 2-amino terephthalic acid and ZrCl 4 The molar mass ratio was 1:1, and the mixed solution was transferred to a solvothermal reactor and reacted in an oven at 95 ℃ for 24 hours. Cooling to room temperature after the reaction is finished, taking out the product from the reaction solution, and repeatedly washing with DMF and absolute ethanol to obtainTo titania-loaded MOFs-based aerogels.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (7)
1. A preparation method of MOFs-based aerogel loaded with titanium dioxide is characterized in that the aerogel comprises the following components in parts by weight, 5-10 parts of carboxylated cellulose nanofiber and anatase TiO 2 0.1-0.5 part of UiO-66-NH 2 1-5 parts of crystal, and the preparation method comprises the following steps:
S1：TiO 2 preparation of carboxylated cellulose nanofiber Dispersion, anatase TiO 2 Adding into 1.5-10wt% carboxylated cellulose nanofiber dispersion liquid, placing into an ultrasonic cell crusher for treatment, setting the power to be 500-1000W and the treatment time to be 1-5 h to obtain the TiO 2 Carboxylated cellulose nanofiber dispersion;
S2：TiO 2 preparing carboxylated cellulose nanofiber aerogel, performing ultrasonic deaeration on the dispersion liquid, injecting the dispersion liquid into a mould, and freezing at-80 ℃ for 2-10 h, and performing vacuum drying to obtain TiO 2 Carboxylated cellulose nanofiber aerogel;
s3: preparation of MOFs-based aerogel carrying titanium dioxide, and ZrCl 4 Dissolved in N, N-dimethylformamide solution, the ZrCl 4 The mass concentration of (2) is 0.1-0.5 wt%, and TiO is continuously added into the solution 2 Carboxylated cellulose nanofiber aerogel, and then dispersing the solution in an ultrasonic cell crusher to make Zr 4+ Chelating on free carboxyl of carboxylated cellulose nanofiber, and continuing to add 2-amino terephthalic acid and 1ml glacial acetic acid to the solution, wherein the 2-amino terephthalic acid and the ZrCl 4 Molar massAnd finally transferring the mixed solution into a solvothermal reaction kettle in a ratio of 1:1, reacting for 24 hours in an oven at 95 ℃, cooling to room temperature after the reaction is finished, taking out a product from the reaction solution, and washing with DMF and absolute ethyl alcohol to obtain the MOFs-based aerogel loaded with titanium dioxide.
2. The method for preparing the titanium dioxide-loaded MOFs-based aerogel according to claim 1, wherein the preparation steps of the carboxylated cellulose nanofiber dispersion in step S1 are as follows:
step 1, placing cellulose in a NaOH solution with the concentration of 1-5 wt% according to the bath ratio of 1:100-1:50, boiling for 30-120 min, adding absolute ethyl alcohol and sodium chloroacetate into the solution, wherein the absolute ethyl alcohol is in an amount of 1:10-1:50 according to the bath ratio of the cellulose, the molar mass of the sodium chloroacetate and the cellulose is 1:1, keeping the mixture at 71 ℃ for 4 hours, filtering after the reaction is finished, drying the filtrate, and washing the filtrate with deionized water to obtain the cellulose nanofiber;
and 2, dispersing cellulose nanofibers in deionized water according to a bath ratio of 1:20-1:100, adding nitric acid and phosphoric acid with a volume ratio of 1-5:1 into the solution, reacting for 3-5 hours at room temperature with a total acid concentration of 10-20%, continuously adding sodium nitrite into the solution, reacting for 12-48 hours at room temperature with a concentration of 0.5-5% of sodium nitrite, filtering, washing and drying to obtain carboxylated cellulose nanofibers, and dispersing the carboxylated cellulose nanofibers into deionized water to obtain carboxylated cellulose nanofiber dispersion with a weight percentage of 1.5-10%.
3. The method for preparing MOFs based aerogel supporting titanium dioxide according to claim 1, wherein the anatase type TiO is selected in step S1 2 The content of (C) is 0.1-0.5 wt%.
4. The method for preparing MOFs based aerogel supporting titanium dioxide according to claim 3 wherein the TiO in step S3 is 2 The amount of the carboxylated cellulose nanofiber aerogel is 1 to 5 weight percent.
5. The method for preparing titanium dioxide-loaded MOFs based aerogel according to claim 4, wherein the conditions of the dispersion treatment in the ultrasonic cell disruptor in step S3 are as follows: the power is set to be 500-1200W, and the treatment time is 0.5-5 h.
6. The method for preparing MOFs based aerogel supporting titanium dioxide according to claim 5 wherein the anatase TiO is selected in step S1 2 The grain diameter is 80-800 nm.
7. The method of preparing titania-supported MOFs based aerogel according to claim 2, wherein the cellulose in step 1 is a mixture of one or more of cotton linters, wood, rice straw, wheat straw.
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