CN110560001A - Preparation method and application of Fe-MOFs nano material containing ionic liquid - Google Patents
Preparation method and application of Fe-MOFs nano material containing ionic liquid Download PDFInfo
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- CN110560001A CN110560001A CN201910860384.7A CN201910860384A CN110560001A CN 110560001 A CN110560001 A CN 110560001A CN 201910860384 A CN201910860384 A CN 201910860384A CN 110560001 A CN110560001 A CN 110560001A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
a preparation method of Fe-MOFs nano material containing ionic liquid is characterized in that soluble ferric salt, polycarboxylic acid ligand and phenanthroline are used as raw materials, the ionic liquid is used as a template, and the Fe-MOFs containing the ionic liquid is synthesized through hydrothermal reaction. The preparation method provided by the invention comprises the steps of providing a metal center by using ferric salt, taking terphenyl tetracarboxylic acid as a main ligand, taking phenanthroline as an auxiliary ligand, and taking ionic liquid as a template for synthesis; in the synthesis process, nonpolar alkyl of the ionic liquid extends into holes of Fe-MOFs, polar imidazole ends are remained outside the holes, and the adsorption effect of the obtained nano material is realized by physical adsorptionConverted into partial chemical adsorption, electrostatic action and pi-pi stacking combined action adsorption, so that the adsorption performance is greatly improved, the cationic dye Methylene Blue (MB) has excellent adsorption performance, and the adsorption amount of MB under the optimal condition is up to 500mg g‑1The above.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a preparation method and application of an Fe-MOFs nano material containing ionic liquid.
Background
The dye has the advantages of rich types, various classification methods and increasingly wide application, the usage amount of the dye in China reaches over 50 million tons in 2004, and new varieties are continuously emerged every year. When used in large quantities, the additive can add color to people's life and can inevitably enter industrial wastewater to cause serious water pollution, thereby affecting people's life and health (Chemical engineering journal,2016, (283), 1127-1136.). Methylene Blue (MB) is a common cationic dye, and prolonged direct contact with MB can cause increased heart rate, quadriplegia, or other physical damage in humans. Because the molecular structure of methylene blue dye is complex and quite stable, and is difficult to degrade (Journal of Colloid and interface science,2005, (286),90-100.), it is important to develop a proper method for treating methylene blue wastewater.
Heretofore, there have been various methods for treating dye wastewater, including photocatalytic degradation, reverse osmosis, adsorption, electrocatalytic degradation, biological methods, and the like (Journal of Environmental Management,2012, (113), 170-183.). The adsorption method is simple and cheap, and various adsorbents such as mesoporous carbon, waste cotton activated carbon, natural clay, modified pumice, zeolite material, silica, Fe @ Au bimetallic nanoparticles and bentonite are usedmethylene blue was removed from the wastewater (Arabian Journal of Chemistry,2018, (11), 615-623.). MOFs have the characteristics of high metal center content, large specific surface area, structural stability and the like, and are important adsorbents for removing methylene blue dyes in wastewater. Uio-66(International Journal of Environmental Science)&Technology,2017,(14),1-10.)、Fe3O4@MIL-100(Fe)(Chemical Engineering Journal,2016,(283),1127-1136)、MIL-101-SO3H(Microporous&Mesoporous Materials,2017,(237),268-274.)、MIL-53(Al)-NH2(Journal of Chemical&Engineering Data,2015, (60),3414-3422.) and Fe3O4MOF and MOF composite adsorbents such as-COOH/HKUST-1 (Applied organic Chemistry,2017, (31),3786-3798.) have been reported for MB adsorption, but the adsorption capacity of these adsorbents is susceptible to pH fluctuations.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a preparation method and application of Fe-MOFs nano material containing ionic liquid, the preparation method is simple and convenient to operate, the prepared nano material can efficiently remove MB in aqueous solution, the adsorption process of the IL-Fe-MOF nano material on the MB is well matched with a quasi-second-order kinetic model, and the adsorption amount of the IL-Fe-MOF nano material on the MB under the optimal condition is up to 558mg g-1Particularly has good adaptability to the fluctuation of the pH value of the water body.
The technical scheme adopted by the invention for solving the technical problems is as follows:
A preparation method of Fe-MOFs nano material containing ionic liquid is characterized in that soluble ferric salt, polycarboxylic acid ligand and phenanthroline are used as raw materials, the ionic liquid is used as a template, and the Fe-MOFs containing the ionic liquid is synthesized through hydrothermal reaction.
Preferably, the soluble iron salt is selected from FeCl3、Fe(NO3)3And Fe2(SO4)3And their hydrates; more preferably, the soluble iron salt is FeCl3·6H2O。
Preferably, the polycarboxylic acid ligand is selected from one of the compounds shown in formula I to formula XI,
Preferably, the polycarboxylic acid ligand is a compound shown as a formula VIII.
Preferably, the ionic liquid is imidazole ionic liquid [ Cnmim]mx, wherein m is 1 or 2, X is Cl, Br, I, SO4、HSO4、CO3Ala, Pro or Cys; [ C ]nmim]+As shown in formula XII, wherein R1Selected from alkyl groups with carbon chain length of 3-16,
Preferably, X ═ Cl and R are selected1The alkyl is selected from alkyl with a carbon chain length of 3-12.
Preferably, said R is1The material is selected from linear alkyl with a carbon chain length of 3-8; more preferably, R is1Is n-butyl.
Preferably, the mass ratio of the iron element, the polycarboxylic acid ligand and the phenanthroline in the soluble iron salt is 4-8: 1-2; preferably, the amount ratio of the iron element, the polycarboxylic acid ligand and the phenanthroline in the soluble iron salt is 6:1: 1.
Preferably, the molar ratio of the iron element in the soluble iron salt to the ionic liquid is 1:5, 1:10 and 1:15, and more preferably, the molar ratio of the iron element in the soluble iron salt to the ionic liquid is 1: 5.
Preferably, the temperature of the hydrothermal reaction is 120-160 ℃; more preferably, the temperature of the hydrothermal reaction is 150 ℃.
Preferably, the time of the hydrothermal reaction is 48-96 h; more preferably, the hydrothermal reaction time is 72 h.
Preferably, the preparation method comprises the following specific steps:
preparing a mixed aqueous solution from soluble ferric salt, a polycarboxyl ligand and phenanthroline, adding ionic liquid and an alkali solution, uniformly mixing to form a reaction solution, heating the reaction solution to 120-160 ℃ for hydrothermal reaction for 48-96 h, cooling, washing and drying after the reaction is finished, thus obtaining the Fe-MOFs nano material containing the ionic liquid.
Preferably, in the reaction solution, Fe3+The amount of (B) was 0.6 mmol/L.
Preferably, the alkali solution is 0.5mol/L NaOH aqueous solution.
Preferably, the solubility of NaOH in the reaction solution is 0.0025 mol/L.
The application of the Fe-MOFs nano material prepared by the preparation method in the field of cationic dye adsorption also belongs to the protection scope of the invention. The cationic dye is methylene blue.
The invention has the beneficial effects that:
(1) The preparation method provided by the invention comprises the steps of providing a metal center by using ferric salt, taking terphenyl tetracarboxylic acid as a main ligand, taking phenanthroline as an auxiliary ligand, and taking ionic liquid as a template for synthesis; in the synthesis process, nonpolar alkyl of the ionic liquid extends into holes of Fe-MOFs, and polar imidazole ends are left outside the holes, so that the adsorption effect of the obtained nano material is converted from physical adsorption into partial chemical adsorption, electrostatic action and pi-pi stacking combined action adsorption, and the adsorption performance is greatly improved;
(2) The Fe-MOFs nano material prepared by the preparation method has the specific surface area of 24-60 m < 2 > -2 g-1, the pore diameter of 17-41 nm and the pore volume of 0.1-0.15 cm3g-1The surface of the material is electronegative, the Zeta potential is about-20 mV, the material is beneficial to adsorption of cationic dye, especially methylene blue, the material can efficiently remove the methylene blue in water, the adsorption capacity can reach 558mg/g, and the stable adsorption of the methylene blue can be realized in a wider pH range.
Drawings
FIG. 1 is the present inventionNanomaterial [ C ] prepared in inventive example 14mim]Scanning electron micrographs of Cl-Fe-tpta-5;
FIG. 2 is an infrared spectrum of 3 different nanomaterials prepared in examples 1 to 3 of the present invention;
FIG. 3 is an infrared spectrum of 3 different nanomaterials prepared in examples 1, 4 and 5 of the present invention;
FIG. 4 shows a nanomaterial [ C ] prepared in example 1 of the present invention4mim]Zeta potential diagram of Cl-Fe-tpta-5;
FIG. 5 is a graph of the relationship between adsorption capacity and time for adsorbing methylene blue by 3 different nanomaterials prepared in examples 1 to 3, respectively, of the present invention;
FIG. 6 is a graph of adsorption capacity versus time for methylene blue adsorbed by 3 different nanomaterials prepared according to examples 1, 4 and 5 of the present invention;
FIG. 7 shows a nanomaterial [ C ] prepared by the method of example 1 of the present invention4mim]An adsorbent dosage investigation graph for adsorbing methylene blue by Cl-Fe-tpta-5;
FIG. 8 shows a nanomaterial [ C ] prepared by the method of example 1 of the present invention4mim]An initial concentration investigation graph of methylene blue adsorbed by Cl-Fe-tpta-5;
FIG. 9 shows a nanomaterial [ C ] prepared by the method of example 1 of the present invention4mim]Initial pH effect of Cl-Fe-tpta-5 adsorbing methylene blue was investigated.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
The reagents and materials used in the following examples are commercially available or prepared by conventional methods unless otherwise specified.
Example 1
The specific steps of this example are as follows: 0.162g FeCl was weighed in turn3·6H2O (0.6mmol), 0.040g of terphenyltetracarboxylic acid (0.1mmol) and 0.0198g of phenanthroline (0.1mmol) are placed in a reaction kettle, a certain amount of deionized water is added for dissolution, then 0.5240g of 1-butyl-3-methylimidazole chloride (3mmol) is added into the reaction kettle, and then 0.1mL of 0.5M NaOH is added to ensure thatH in the reaction kettle220mL of O solvent, uniformly stirring, placing the reaction kettle in an oven, setting the temperature to be 150 ℃, reacting for 3d, cooling, washing and drying to obtain orange powdery solid which is marked as (C)4mim]Cl-Fe-tpta-5。
also for [ C ] prepared in this example4mim]Cl-Fe-tpta-5, scanning by transmission electron microscope, and obtaining the grain-shaped nanometer material [ C ] shown in figure 14mim]The surface of Cl-Fe-tpta-5 is not smooth and radial, so that the contact area with the dye molecules is increased during the process of adsorbing methylene blue molecules.
Nanomaterial [ C4mim]The IR spectrum of Cl-Fe-tpta-5 is shown in FIG. 2, from which 574cm was observed-1A very obvious characteristic absorption peak of Fe-O coordination bonds is formed, which indicates that the coordination of the Fe metal center and the ligand is generated; 1698cm-1The carboxyl group of (b) shows a stretching vibration absorption peak, which indicates that the ligand terphenyltetracarboxylic acid is not completely deprotonated.
For further study [ C4mim]The adsorption Performance of Cl-Fe-tpta-5, on which the porosity characteristics were investigated, Using N2adsorption specific surface area Analyzer to determine [ C4mim]The surface area, pore volume, pore diameter, etc. of Cl-Fe-tpta-5, and the results are shown in Table 1. [ C ]4mim]The specific surface area of Cl-Fe-tpta-5 was 29.1m2g-1。[C4mim]The pore size of Cl-Fe-tpta-5 was 22.5 nm.
At the same time, electrophoresis is also adopted to treat [ C ] under different pH values4mim]Zeta potential of Cl-Fe-tpta-5 was measured, and the result is shown in FIG. 4, [ C ]4mim]The surface charge of Cl-Fe-tpta-5 in a solution having a pH of 4 to 9 is negative and [ C ] is a cationic dye because methylene blue is a cationic dye4mim]And the Cl-Fe-tpta-5 and methylene blue have good electrostatic interaction, so that the adsorption can be promoted.
Example 2
The specific steps of this example are as follows: 0.162g FeCl was weighed in turn3·6H2O (0.6mmol), 0.040g (0.1mmol) of terphenyl tetracarboxylic acid and 0.0198g of phenanthroline (0.1mmol) are placed in a reaction kettle, and a certain amount of deionized water is addedWater was dissolved, and 0.8600g of 1-octyl-3-methylimidazole chloride (3mmol) were added to the reaction vessel followed by 0.1mL of 0.5M NaOH to ensure that the reaction vessel had H220mL of O solvent, uniformly stirring, placing the reaction kettle in an oven, setting the temperature at 150 ℃, reacting for 3d, cooling, washing and drying to obtain orange powdery solid, and marking as [ (. C) ]8mim]Cl-Fe-tpta-5。
For [ C ] obtained in this example8mim]As a result of IR spectroscopy of Cl-Fe-tpta-5, 574cm was observed as shown in FIG. 2-1A very obvious characteristic absorption peak of Fe-O coordination bonds is formed, which indicates that the coordination of the Fe metal center and the ligand is generated; 1698cm-1The carboxyl group of (b) shows a stretching vibration absorption peak, which indicates that the ligand terphenyltetracarboxylic acid is not completely deprotonated.
Porosity characteristics were also investigated, including specific surface area and the like. Using N2Adsorption specific surface area Analyzer to determine [ C4mim]The surface area, pore volume, pore diameter, etc. of Cl-Fe-tpta-5, and the results are shown in Table 1. [ C ]8mim]The specific surface area of Cl-Fe-tpta-5 was 48.7m2g-1。[C8mim]The pore size of Cl-Fe-tpta-5 was 20.5 nm.
Example 3
The specific steps of this example are as follows: 0.162g FeCl was weighed in turn3·6H2O (0.6mmol), 0.040g of terphenyltetracarboxylic acid (0.1mmol) and 0.0198g of phenanthroline (0.1mmol) are placed in a reaction kettle, a certain amount of deionized water is added for dissolution, then 0.8600g of 1-dodecyl-3-methylimidazole chloride (3mmol) is added into the reaction kettle, then 0.1mL of 0.5M NaOH is added to ensure H in the reaction kettle220mL of O solvent, uniformly stirring, placing the reaction kettle in an oven, setting the temperature at 150 ℃, reacting for 3d, cooling, washing and drying to obtain orange powdery solid, and marking as (C)12mim]Cl-Fe-tpta-5。
For [ C ] of this example12mim]As a result of IR spectroscopy of Cl-Fe-tpta-5, 574cm was observed as shown in FIG. 2-1a very obvious characteristic absorption peak of Fe-O coordination bonds is formed, which indicates that the coordination of the Fe metal center and the ligand is generated; 1698cm-1The carboxyl group of (b) shows a stretching vibration absorption peak, which indicates that the ligand terphenyltetracarboxylic acid is not completely deprotonated.
Porosity characteristics were also investigated, including specific surface area, etc., using N2Adsorption specific surface area Analyzer to determine [ C4mim]The surface area, pore volume, pore diameter, etc. of Cl-Fe-tpta-5, and the results are shown in Table 1. [ C ]12mim]The specific surface area of Cl-Fe-tpta-5 was 60.0m2g-1。[C12mim]The pore size of Cl-Fe-tpta-5 was 17.2 nm.
Example 4
The specific steps of this example are as follows: 0.162g FeCl was weighed in turn3·6H2O (0.6mmol), 0.040g of terphenyltetracarboxylic acid (0.1mmol) and 0.0198g of phenanthroline (0.1mmol) are placed in the inner liner of a reaction kettle, a certain amount of deionized water is added for dissolution, then 1.7200g of 1-butyl-3-methylimidazole chloride (6mmol) is added into the reaction kettle, then 0.1mL of 0.5M NaOH is added to ensure that H in the reaction kettle220mL of O solvent, uniformly stirring, placing the reaction kettle in an oven, setting the temperature at 150 ℃, reacting for 3d, cooling, washing and drying to obtain orange powdery solid, and recording as4mim]Cl-Fe-tpta-10。
For [ C ] obtained in this example4mim]As a result of IR spectroscopy of Cl-Fe-tpta-10, 574cm was observed as shown in FIG. 3-1A very obvious characteristic absorption peak of Fe-O coordination bonds is formed, which indicates that the coordination of the Fe metal center and the ligand is generated; 1698cm-1The carboxyl group of (b) shows a stretching vibration absorption peak, which indicates that the ligand terphenyltetracarboxylic acid is not completely deprotonated. 2924cm-1、2851cm-1The stretching vibration absorption peak of alkyl C-H on the side chain of the ionic liquid is obviously enhanced.
Further research into porosity characteristics, including specific surface area, etc., was conducted. Using N2Adsorption specific surface area Analyzer to determine [ C4mim]The surface area, pore volume, pore diameter, etc. of Cl-Fe-tpta-10, and the results are shown in Table 1. [ C ]4mim]The specific surface area of Cl-Fe-tpta-10 was 23.9m2g-1。[C12mim]The pore size of Cl-Fe-tpta-5 was 41.2 nm.
example 5
The specific steps of this example are as follows: 0.162g FeCl was weighed in turn3·6H2O (0.6mmol), 0.040g (0.1mmol) of terphenyl tetracarboxylic acid, 0.0198g of phenanthroline (0.1mmol) are placed in a reaction kettle, a certain amount of deionized water is added for dissolution, then 2.5800g of 1-n-butyl-3-methylimidazole chloride (9mmol) is added into the reaction kettle, then 0.1mL of 0.5M NaOH is added to ensure H in the reaction kettle220mL of O solvent, uniformly stirring, placing the reaction kettle in an oven, setting the temperature at 150 ℃, reacting for 3d, cooling, washing and drying to obtain orange powdery solid, and marking as fifth [ C ]4mim]Cl-Fe-tpta-15。
For [ C ] obtained in this example4mim]As a result of IR spectroscopy of Cl-Fe-tpta-15, 574cm was observed as shown in FIG. 2-1A very obvious characteristic absorption peak of Fe-O coordination bonds is formed, which indicates that the coordination of the Fe metal center and the ligand is generated; 1698cm-1The carboxyl group of (b) shows a stretching vibration absorption peak, which indicates that the ligand terphenyltetracarboxylic acid is not completely deprotonated. 2924cm-1、2851cm-1The stretching vibration absorption peak of alkyl C-H on the side chain of the ionic liquid is obviously enhanced.
porosity characteristics were also investigated, including comparative surface area, etc. Using N2Adsorption specific surface area Analyzer to determine [ C4mim]The surface area, pore volume, pore diameter, etc. of Cl-Fe-tpta-15, and the results are shown in Table 1. [ C ]4mim]The specific surface area of Cl-Fe-tpta-15 was 51.4m2g-1。[C12mim]The pore size of Cl-Fe-tpta-5 was 20.5 nm.
The infrared spectrum results of the 5 kinds of nanomaterials prepared in examples 1 to 5 are shown in FIG. 3, and it can be seen from the figure that: 574cm can be observed in IL-Fe-tpta-1A very obvious characteristic absorption peak of Fe-O coordination bonds is formed, which indicates that the coordination of the Fe metal center and the ligand is generated; 1698cm-1The carboxyl group of (b) shows a stretching vibration absorption peak, which indicates that the ligand terphenyltetracarboxylic acid is not completely deprotonated. It is noteworthy that 2924cm when the ratio of metal ions to ionic liquid reaches 1:10-1、2851cm-1The stretching vibration absorption peak of alkyl C-H on the side chain of the ionic liquid is obviously enhanced.
The porosity characteristics of the different nanomaterials obtained in examples 1-5 are shown in Table 1, and the specific surface area of IL-Fe-MOF is 23.9-60.0m2g-1In which is [ C ]12mim]The maximum specific surface area of Cl-Fe-tpta-5 is 60.0m2g-1. The pore size range of this series of MOFs is 17.2 to 41.2nm, [ C ]12mim]The pore size of Cl-Fe-tpta-5 is minimal.
TABLE 1 porosity characteristics of the nanomaterials of the examples
In order to further verify the adsorption performance of the nano material on cationic dyes, methylene blue adsorption tests are carried out on different nano materials obtained in examples 1-5, and factors such as adsorption time, adsorbent dosage, methylene blue initial concentration and pH are also investigated.
1. Adsorption of methylene blue test
1) Preparation of methylene blue aqueous solution
The methylene blue solution is prepared by adopting the principle of being prepared on site and using a volumetric flask to prepare the methylene blue solution with the concentration of 250 mg/L.
(2) Adsorption experiment procedure
a) Accurately weighing 5mg of adsorbent (C)4mim]Cl-Fe-tpta-5、②[C8mim]Cl-Fe-tpta-5、③[C12mim]Cl-Fe-tpta-5、④[C4mim]Cl-Fe-tpta-10 and (C)4mim]Cl-Fe-tpta-15, and placing the Cl-Fe-tpta-15 into 5 250mL conical flasks with ground openings respectively, adding 50mL methylene blue solution, plugging the conical flasks, rapidly placing the conical flasks into a constant-temperature water bath oscillator with preset experimental parameters, starting timing oscillation, carrying out adsorption experiments, and sampling at regular intervals of 20 min.
b) After adsorption is finished, centrifuging the experimental sample, taking supernatant, diluting by 100 times, measuring the absorbance of the solution, calculating the mass concentration of the solution after adsorption by using a standard curve equation of the methylene blue solution, and calculating the adsorption quantity according to an adsorption quantity calculation formula of the adsorbent.
the methylene blue adsorption amount calculation formula:
qt＝(c0-ct)V/m
(in the formula: q)t，mg g-1；c0、ct，mg L-1；V，L；m，g.)
The results are shown in fig. 5 and 6, the speed of the adsorption of methylene blue is high in the initial stage of adsorption, a high adsorption amount can be achieved after 5min, and all adsorbents can reach adsorption equilibrium within 70min, because a large number of available vacancy adsorption sites exist on the surface of the IL-Fe-MOF in the initial stage of adsorption, the number of available vacancies is reduced with the passage of time, and the adsorption sites become saturated. As can also be seen from the figure, [ C ]4mim]The adsorption amount of Cl-Fe-tpta-5 is obviously larger than that of Fe-MOF adsorbent prepared by taking other ionic liquid as a template, and the [ C ] is shown4mim]The Cl-Fe-tpta-5 has more excellent adsorption performance.
2. Sorbent dosage investigation test
1) Preparation of methylene blue aqueous solution
The methylene blue solution is prepared by adopting the principle of being prepared on site and using a volumetric flask to prepare the methylene blue solution with the concentration of 250 mg/L.
(2) Adsorption experiment procedure
a) Accurately weighing 5mg, 10mg and 15mg of adsorbents (C)4mim]and Cl-Fe-tpta-5, respectively placing the Cl-Fe-tpta-5 into 3 250mL ground conical bottles, adding 50mL of methylene blue solution, plugging the bottles, quickly placing the bottles into a constant-temperature water bath oscillator with preset experimental parameters, starting timing oscillation, carrying out adsorption experiments, and sampling regularly every 20 min.
b) After adsorption is finished, centrifuging the experimental sample, taking supernatant, diluting by 100 times, measuring the absorbance of the solution, calculating the mass concentration of the solution after adsorption by using a standard curve equation of the methylene blue solution, and calculating the adsorption quantity according to an adsorption quantity calculation formula of the adsorbent.
The methylene blue adsorption amount calculation formula:
qt＝(c0-ct)V/m
(in the formula: q)t，mg g-1；c0、ct，mg L-1；V，L；m，g.)
The results are shown in FIG. 7, [ C ]4mim]The results of the study of the amount of Cl-Fe-tpta-5 on MB adsorption showed that the amount of methylene blue adsorbed rapidly decreased with increasing mass of the adsorbent. When using 5mg of [ C4mim]When Cl-Fe-tpta-5 is present, the maximum adsorption amount of 335mg g is reached-1. This may be due to [ C ]4mim]When the dosage of Cl-Fe-tpta-5 is less, the surface of the material can fully adsorb methylene blue; it is also possible to use larger amounts of adsorbent particles [ C ]4mim]Cl-Fe-tpta-5 aggregates in solution resulting in a reduction in surface area and an increase in diffusion path length.
3. And (4) examining the initial mass concentration of the methylene blue.
1) Preparation of methylene blue aqueous solution
The methylene blue solution is prepared into methylene blue solutions with the concentrations of 50mg/L, 250mg/L and 500mg/L by using a volumetric flask according to the principle of preparation in situ.
(2) adsorption experiment procedure
a) Accurately weighing 3 parts of 5mg adsorbent (C)4mim]And Cl-Fe-tpta-5, respectively placing the Cl-Fe-tpta-5 into 3 250mL conical flasks with ground openings, respectively adding 50mL of 50, 100 and 250mg/L methylene blue solutions, plugging the conical flasks, quickly placing the conical flasks into a constant-temperature water bath oscillator with preset experimental parameters, starting timing oscillation, carrying out adsorption experiments, and sampling at regular intervals of 20 min.
b) After adsorption is finished, centrifuging the experimental sample, taking supernatant, diluting by 100 times, measuring the absorbance of the solution, calculating the mass concentration of the solution after adsorption by using a standard curve equation of the methylene blue solution, and calculating the adsorption quantity according to an adsorption quantity calculation formula of the adsorbent.
The methylene blue adsorption amount calculation formula:
qt＝(c0-ct)V/m
(in the formula: q)t，mg g-1；c0、ct，mg L-1；V，L；m，g.)
As a result, as shown in FIG. 8, [ C ] was adsorbed4mim]The amount of methylene blue on Cl-Fe-tpta-5 increased with increasing initial mass concentration, when the concentration was 500mg L-1When is in [ C ]4mim]The equilibrium adsorption quantity of Cl-Fe-tpta-5 to MB is up to 558mg g-1This is because the concentration gradient increases with the initial mass concentration of MB, and the adsorption driving force increases accordingly. [ C ]4mim]The adsorption capacity of Cl-Fe-tpta-5 is obviously better than that of common MOF materials.
4. Influence of initial pH on adsorption.
1) Preparation of methylene blue aqueous solution
The methylene blue solution was prepared as it is and then used in a volumetric flask to prepare 250mg/L methylene blue solutions having pH values of 4, 5, 6, 7, 8 and 9, respectively.
(2) adsorption experiment procedure
a) Accurately weighing 6 parts of 5mg adsorbent (C)4mim]And Cl-Fe-tpta-5, respectively placing the Cl-Fe-tpta-5 into 6 250mL conical flasks with ground openings, respectively adding 50mL of 50, 100 and 250mg/L methylene blue solutions, plugging the conical flasks, quickly placing the conical flasks into a constant-temperature water bath oscillator with preset experimental parameters, starting timing oscillation, carrying out adsorption experiments, and sampling at regular intervals of 20 min.
b) After adsorption is finished, centrifuging the experimental sample, taking supernatant, diluting by 100 times, measuring the absorbance of the solution, calculating the mass concentration of the solution after adsorption by using a standard curve equation of the methylene blue solution, and calculating the adsorption quantity according to an adsorption quantity calculation formula of the adsorbent.
The methylene blue adsorption amount calculation formula:
qt＝(c0-ct)V/m
(in the formula: q)t，mg g-1；c0、ct，mg L-1；V，L；m，g.)
As a result, referring to FIG. 9, when the pH of the solution was changed from 4 to 9, the amount of methylene blue adsorbed was 298mg g-1to 361mg g-1the adsorption amount is not greatly influenced by pH due to the change of the range. It is shown that pH is not the main factor affecting the adsorption effect, and [ C ] can be seen4mim]Cl-Fe-tpta-5 is not damaged in the pH range of 4-9, has good stability and is suitable for a wide pH value fluctuation range.
Claims (10)
1. The preparation method of the Fe-MOFs nano material containing the ionic liquid is characterized in that soluble ferric salt, polycarboxylic acid ligand and phenanthroline are used as raw materials, the ionic liquid is used as a template, and the Fe-MOFs nano material containing the ionic liquid is synthesized through hydrothermal reaction.
2. The method for preparing Fe-MOFs nanomaterials containing ionic liquids according to claim 1, wherein said soluble iron salt is selected from FeCl3、Fe(NO3)3And Fe2(SO4)3And their hydrates.
3. The preparation method of Fe-MOFs nanomaterials containing ionic liquids according to claim 1 or 2, wherein said polycarboxylic acid ligand is selected from one of the compounds represented by formulas I to XI,
4. The preparation method of the Fe-MOFs nano-materials containing the ionic liquid according to any one of claims 1 to 3, wherein the ionic liquid is imidazole-based ionic liquid [ C ]nmim]mX, wherein m is 1 or 2, X is Cl, Br, I, SO4、HSO4、CO3Ala, Pro or Cys; [ C ]nmim]+As shown in formula XII, wherein R1Selected from carbon chain length of 3-16The alkyl group of (a) is,
5. The method for preparing Fe-MOFs nanomaterials containing ionic liquids according to any of claims 1 to 4, wherein X is Cl and R is1Alkyl with a carbon chain length of 3-12 is selected; preferably, said R is1The material is selected from linear alkyl with a carbon chain length of 3-8; more preferably, R is1Is n-butyl.
6. The preparation method of the Fe-MOFs nano-materials containing the ionic liquid according to any one of claims 1 to 5, wherein the amount ratio of the iron element, the polycarboxylic acid ligand and the phenanthroline in the soluble iron salt is 4-8: 1-2; preferably, the mass ratio of the iron element, the polycarboxylic acid ligand and the phenanthroline in the soluble iron salt is 6:1: 1; the mass ratio of the iron element in the soluble ferric salt to the ionic liquid is 1: 4-15; more preferably, the mass ratio of the iron element to the ionic liquid in the soluble iron salt is 1: 5.
7. The preparation method of the Fe-MOFs nano-materials containing the ionic liquid according to any one of claims 1 to 6, wherein the temperature of the hydrothermal reaction is 120-160 ℃; more preferably, the temperature of the hydrothermal reaction is 150 ℃; preferably, the time of the hydrothermal reaction is 48-96 h; more preferably, the hydrothermal reaction time is 72 h.
8. The preparation method of Fe-MOFs nanomaterials containing ionic liquid according to any one of claims 1 to 7, characterized by comprising the following specific steps: preparing a mixed aqueous solution from soluble ferric salt, a polycarboxyl ligand and phenanthroline, adding ionic liquid and an alkali solution, uniformly mixing to form a reaction solution, heating the reaction solution to 120-160 ℃ for hydrothermal reaction for 48-96 h, cooling, washing and drying after the reaction is finished, thus obtaining the Fe-MOFs nano material containing the ionic liquid.
9. The method for preparing Fe-MOFs nanomaterials containing ionic liquids according to any one of claims 1 to 7, wherein said alkali solution is a 0.5mol/L aqueous NaOH solution; preferably, in the reaction solution, Fe3+The concentration of (A) is 0.6 mmol/L; preferably, the concentration of NaOH in the reaction solution is 0.0025 mol/L.
10. The application of the Fe-MOFs nano material prepared by the preparation method of any one of claims 1 to 9 in the field of cationic dye adsorption; preferably, the cationic dye is methylene blue.
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| CN113493225A (en) * | 2021-08-11 | 2021-10-12 | 洛阳理工学院 | Preparation method and application of Co/Fe layered double-metal hydroxide nanosheets |
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| CN114715870B (en) * | 2022-03-30 | 2023-12-08 | 合肥国轩高科动力能源有限公司 | Porous carbon layer coated lithium iron phosphate material and preparation method and application thereof |
| CN114685803A (en) * | 2022-04-01 | 2022-07-01 | 山东师范大学 | Coreactant embedded electrochemical luminescence double-ligand infinite coordination polymer nano particle and preparation method and application thereof |
| CN114685803B (en) * | 2022-04-01 | 2023-01-31 | 山东师范大学 | Coreactant embedded electrochemical luminescence double-ligand infinite coordination polymer nano particle and preparation method and application thereof |
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