CN112266484B - Preparation method and application of iron-based metal organic framework composite material capable of continuously giving electrons - Google Patents

Preparation method and application of iron-based metal organic framework composite material capable of continuously giving electrons Download PDF

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CN112266484B
CN112266484B CN202010981196.2A CN202010981196A CN112266484B CN 112266484 B CN112266484 B CN 112266484B CN 202010981196 A CN202010981196 A CN 202010981196A CN 112266484 B CN112266484 B CN 112266484B
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CN112266484A (en
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李铁龙
李冰洁
王薇
高超林
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Nankai University
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Abstract

The invention provides a preparation method and application of an iron-based metal organic framework composite material capable of continuously giving electrons, and solves the problems that in the process of degrading pollutants, nano iron obstructs the electron transfer process due to a compact oxide layer formed on the surface, the reaction rate is reduced, even the reaction is stopped, the practical application efficiency is low, and the like. The method is characterized in that: while providing an organic framework with an organic ligand material to disperse and stabilize nano metallic iron, the ligand is used for complexing nano iron to reduce and degrade iron ions generated in the process of pollutants, so that iron oxide and iron hydroxide are deposited on the organic framework, and the nano iron is ensured to continuously give electrons. According to the invention, the nano-iron is modified by the organic ligand material, so that the prepared composite material has excellent stability and dispersibility, the generation of a passivation layer on the surface of the nano-iron can be inhibited, the continuous supply of iron electrons in the reduction reaction is ensured, and the full and effective utilization of the nano-iron material is realized.

Description

Preparation method and application of iron-based metal organic framework composite material capable of continuously giving electrons
Technical Field
The invention relates to preparation and application of an iron-based metal organic framework composite material capable of continuously giving electrons, and belongs to the technical field of nano material modification.
Background
The nano-iron has high surface activity and strong reducibility, can degrade various pollutants, has wide application prospect in the aspect of soil and underground water environmental pollution treatment, and is a hot spot of domestic and foreign research. At present, the nano iron material can be mainly prepared by methods such as a high-energy ball milling method, a liquid phase reduction method, a micro-emulsion method, a carbonyl iron pyrolysis method and the like, but products prepared by the methods still have some defects in the aspects of stability, dispersibility, oxidation resistance and the like, and practical application of the products is limited.
The surface of the nano zero-valent iron is modified, and the aggregation of the nano iron is inhibited by utilizing the electrostatic action and the steric hindrance action of the modifier, so that the dispersibility and the stability of the particles can be improved, and the mobility and the reactivity of the nano material in underground water and soil can be enhanced. The commonly used modifying agents at present comprise polyethylene glycol (PEG) nonionic surfactants, Tween series, Span series, oleylamine, oleic acid and the like, the materials are mainly used for solving the problems of nano-iron agglomeration, air stability and the like, and the problem of low utilization efficiency of nano-iron due to the fact that a passivation layer is easily generated on the surface in the process of actually degrading pollutants by nano-iron is still not effectively solved.
In the process of reducing and degrading pollutants, nano iron is oxidized into iron ions or ferrous ions, and is easily combined with hydroxyl ions in water to generate precipitates to be deposited on the iron surface. The compact oxide film can prevent the further reaction of the nano iron, greatly reduce the degradation reaction efficiency and ensure that the nano iron can not be fully utilized. The researches of Zhangxian et al find that the main component of the passivation layer on the surface of the nano iron is iron oxide or hydroxide, the structure of the passivation layer is stable, the transmission of electrons from metallic iron to a solution can be blocked, and the nano zero-valent iron core has very strong corrosion resistance. (Nanoencapsulation of High resolution chemical mapping of the migration layer,2018,4-13) the corrosion resistance seriously reduces the utilization efficiency of the nano-iron in the field in-situ remediation, and causes the waste of nano-iron materials. Based on the structure, the organic material is used for providing the framework to synthesize, disperse and stabilize the nano iron, and the complexing group is used for combining iron ions generated in the corrosion process of the nano iron to the organic framework, so that the deposition of the iron ions is inhibited, the formation of a passivation layer on the surface of the nano iron is prevented, the nano iron can continuously and efficiently give out electrons, and the degradation of pollutants is promoted. The patent provides a preparation method of a continuous electron-donating iron-based metal organic framework composite material, and the continuous electron-donating iron-based metal organic framework composite material is applied to reduction treatment of Cr (VI).
Disclosure of Invention
The invention aims to provide a preparation method and application of an iron-based metal organic framework composite material capable of continuously giving electrons.
The iron-based metal organic framework composite material capable of continuously supplying electrons, which is provided by the method, inhibits the accumulation of corrosion products on the surface of nano iron by utilizing the strong complexing effect of hydroxyl of an organic ligand in the framework material on inorganic metal oxidation products, ensures that the nano iron can continuously supply electrons, and improves the service efficiency of the nano iron. In addition, the organic ligand can provide steric hindrance for the nano-iron, and the modified nano-iron has negative charges, so that electrostatic steric hindrance exists between particles, and the stability of the particles is ensured. The aqueous layer medium is generally negatively charged, and repulsive force potential energy can be generated between the negatively charged nano iron particles and the aqueous layer medium, so that the mobility of the nano material in the aqueous layer is improved.
In order to realize the purpose of the invention, the technical method adopted by the invention is as follows:
(1) measuring 45ml of deionized water, placing the deionized water in a three-neck flask, deoxidizing for 20min, adding an organic ligand material, and fully stirring and dissolving to obtain an organic framework solution.
(2) And (2) adding an iron salt compound into the organic framework obtained in the step (1), and stirring at the rotating speed of 3000-5000 r/min to fully and uniformly mix the iron salt compound and the organic framework to obtain a metal organic solution.
(3) Under the condition of stirring, a reducing agent solution with a proper concentration is dripped into the system, and the mixture is continuously stirred for reaction for 30min after the dripping is finished, so as to ensure the complete reaction.
(4) And after the reaction is finished, separating the nano iron particles by using a magnetic separation method, then respectively cleaning the nano iron particles by using deoxygenated deionized water and absolute ethyl alcohol for three times, and drying the nano iron particles in vacuum to obtain the iron-based metal organic framework material.
The organic ligand material in the step (1) is tannic acid, and the molar ratio of iron to the organic ligand material is 1: (5-80).
The iron salt compound in the step (2) is FeCl3、FeCl3·6H2O、Fe(NO3)3·9H2O、FeCl2·4H2O、FeSO4·7H2And one or more of O.
The reducing agent in the step (3) includes, but is not limited to, sodium borohydride, potassium borohydride, hydrazine hydrate, sodium hydrosulfite and the like, wherein the molar ratio of iron to the reducing agent is 1: (3-8).
The vacuum drying temperature in the step (4) is 60-70 ℃, and the drying time is 10-30 h.
The invention has the advantages that:
(1) the method solves the problem of low actual utilization rate of the nano iron in the field repairing process. The iron, ferrous and other metal ions generated in the process of complexing and degrading the organic ligand in the iron-based metal organic framework material are utilized to inhibit the oxidative deposition on the surface of the nano iron, so that the nano iron can continuously give out electrons, the degradation reaction is continuously generated, and the utilization efficiency of the nano iron is improved.
(2) In the iron-based metal organic framework composite material with continuous electron supply, the organic framework can provide steric hindrance for nano iron, and the surface of the modified nano iron is provided with negative charges, so that electrostatic steric hindrance exists between nano particles, repulsive potential energy exists between the particles and a negatively charged water-containing layer medium, and the nano iron is ensured to have good dispersibility, stability and mobility in field application.
(3) The preparation method provided by the invention can generate the nano-iron particles which have small and uniform particle size, large specific surface area, strong stability, high reaction activity and can continuously output electrons, effectively ensures the degradation capability of the nano-iron in the actual field repairing application process, and can be widely applied to the field of repairing of various environmental pollutions.
Drawings
Fig. 1 is a TEM image of the prepared persistent electron donating iron-based metal organic framework composite material.
FIG. 2 shows the effect of the metal organic framework material on the degradation of contaminants (in the case of hexavalent chromium).
FIG. 3 is an XPS plot of the persistent electron donating iron-based metal organic framework material after degradation of contaminants (hexavalent chromium for example); wherein a is the second period experimental result, b is the third period experimental result, and c is the fourth period experimental result.
Fig. 4 is an XPS plot of the composite after reaction.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
A method for preparing an iron-based metal organic framework composite material for continuous electron supply, taking tannic acid as an organic framework as an example, comprises the following specific steps:
preparation of iron-based metal organic framework material example 1:
(1) measuring 45ml of deionized water, placing the deionized water in a three-neck flask, removing oxygen for 20min, adding 0.3046g of tannic acid, and fully stirring for dissolving to obtain an organic framework solution.
(2) 0.2420g FeCl was added to the organic framework solution obtained in step (1)3·6H2O(FeCl3·6H2The molar ratio of O to tannic acid is 1:5), stirring for 0.3h at the rotating speed of 1000r/min, and fully mixing to obtain the metal organic solution.
(3) Under the condition of stirring, 5mL of 0.54mol/L sodium borohydride aqueous solution is dripped into the system, and the stirring reaction is continued for 30min after the dripping is finished, so as to ensure the complete reaction.
(4) And after the reaction is finished, separating the nano iron particles by using a magnetic separation method, then respectively cleaning the nano iron particles by using deoxygenated deionized water and absolute ethyl alcohol for three times, and drying the nano iron particles in vacuum to obtain the iron-based metal organic framework material. Wherein the vacuum drying temperature is 70 ℃, and the drying time is 20 h.
Preparation of iron-based metal organic framework material example 2:
(1) 45ml of deionized water is weighed and placed in a three-neck flask for 20min of oxygen removal, 0.1523g of tannic acid is added, and the mixture is fully stirred and dissolved to obtain an organic framework solution.
(2) 0.2420g FeCl was added to the organic framework solution obtained in step (1)3·6H2O(FeCl3·6H2The molar ratio of O to tannic acid is 1:10), stirring for 0.3h at the rotating speed of 1000r/min, and fully mixing to obtain the metal organic solution.
(3) Under the condition of stirring, 5mL of 0.54mol/L sodium borohydride aqueous solution is dripped into the system, and the stirring reaction is continued for 30min after the dripping is finished, so as to ensure the complete reaction.
(4) And after the reaction is finished, separating the nano iron particles by using a magnetic separation method, then respectively cleaning the nano iron particles by using deoxygenated deionized water and absolute ethyl alcohol for three times, and drying the nano iron particles in vacuum to obtain the iron-based metal organic framework material. Wherein the vacuum drying temperature is 70 ℃, and the drying time is 20 h.
Metal organic framework material preparation example 3:
(1) 45ml of deionized water is weighed and placed in a three-neck flask for deoxygenation for 20min, 0.0762g of tannic acid is added, and the mixture is fully stirred and dissolved to obtain an organic framework solution.
(2) 0.2420g FeCl was added to the organic framework solution obtained in step (1)3·6H2O(FeCl3·6H2The molar ratio of O to tannic acid is 1:20), stirring for 0.3h at the rotating speed of 1000r/min, and fully mixing to obtain the metal organic solution.
(3) Under the condition of stirring, 5mL of 0.54mol/L sodium borohydride aqueous solution is dripped into the system, and the stirring reaction is continued for 30min after the dripping is finished, so as to ensure the complete reaction.
(4) And after the reaction is finished, separating the nano iron particles by using a magnetic separation method, then respectively cleaning the nano iron particles by using deoxygenated deionized water and absolute ethyl alcohol for three times, and drying the nano iron particles in vacuum to obtain the iron-based metal organic framework material. Wherein the vacuum drying temperature is 70 ℃, and the drying time is 20 h.
Metal organic framework material preparation example 4:
(1) 45ml of deionized water is weighed and placed in a three-neck flask for deoxygenation for 20min, 0.0381g of tannic acid is added, and the mixture is fully stirred and dissolved to obtain an organic framework solution.
(2) 0.2420g FeCl was added to the polymer solution obtained in step (1)3·6H2O(FeCl3·6H2The molar ratio of O to tannic acid is 1:40), stirring for 0.3h at the rotating speed of 1000r/min, and fully mixing to obtain the metal organic solution.
(3) Under the condition of stirring, 5mL of 0.54mol/L sodium borohydride aqueous solution is dripped into the system, and the stirring reaction is continued for 30min after the dripping is finished, so as to ensure the complete reaction.
(4) And after the reaction is finished, separating the nano iron particles by using a magnetic separation method, then respectively cleaning the nano iron particles by using deoxygenated deionized water and absolute ethyl alcohol for three times, and drying the nano iron particles in vacuum to obtain the iron-based metal organic framework material. Wherein the vacuum drying temperature is 70 ℃, and the drying time is 20 h. FIG. 1 shows FeCl3·6H2Iron-based metal organic bone with continuous electron donor prepared when molar ratio of O to tannic acid is 1:40According to a TEM image of the frame composite material, the particle size of the nano iron particles is only 4nm and almost no agglomeration phenomenon can be seen, and the method is proved to be capable of obtaining the nano iron material with small particle size and strong dispersibility.
Metal organic framework material preparation example 5:
(1) measuring 45ml of deionized water, placing the deionized water in a three-neck flask, deoxidizing for 20min, adding 0.0190g of tannic acid, and fully stirring and dissolving to obtain an organic framework solution.
(2) 0.2420g FeCl was added to the organic framework solution obtained in step (1)3·6H2O，FeCl3·6H2The molar ratio of O to tannic acid is 1:80), stirring for 0.3h at the rotating speed of 1000r/min, and fully mixing to obtain the metal organic solution.
(3) Under the condition of stirring, 5mL of 0.54mol/L sodium borohydride aqueous solution is dripped into the system, and the stirring reaction is continued for 30min after the dripping is finished, so as to ensure the complete reaction.
(4) And after the reaction is finished, separating the nano iron particles by using a magnetic separation method, then respectively cleaning the nano iron particles by using deoxygenated deionized water and absolute ethyl alcohol for three times, and drying the nano iron particles in vacuum to obtain the iron-based metal organic framework material. Wherein the vacuum drying temperature is 70 ℃, and the drying time is 20 h.
The organic ligand material in the invention is not limited to Tannic Acid (TA) in the embodiment, and polyacrylic acid (PAA), Polyacrylamide (PAM), sodium carboxymethylcellulose (CMC) can be selected; the iron salt is not limited to FeCl in the examples3·6H2O, optionally FeCl3、Fe(NO3)3·9H2O、FeCl2·4H2O、FeSO4·7H2O, which has the same effect as the embodiment of the present invention.
The application of the iron-based metal organic framework material in the aspect of removing pollutants, taking hexavalent chromium as an example, comprises the following steps:
degradation experiments example 1:
(1) deoxidizing the Cr (VI) aqueous solution for 20-30 min in advance.
(2) 100ml of an initial 120mg/L Cr (VI) aqueous solution was quickly introduced into a plasma bottle containing a suitable amount of nano-iron slurry (iron content 0.05g) prepared as described above by means of a vacuum line.
(3) Placing the mixed solution in a constant temperature oscillator, reacting at room temperature and at the rotating speed of 200r/min, and sampling at a certain time interval, wherein the sampling amount is 1mL each time.
(4) After being filtered by a filter membrane of 0.22 mu m, the concentration of Cr (VI) in a water sample is determined by a dibenzoyl dihydrazide spectrophotometry, and the degradation effect is shown in figure 2. The composite material prepared by the method has the advantage that the Cr (VI) removal efficiency is increased along with the increase of the using amount of the tannic acid, and the Cr (VI) can be completely removed within 2.5min at the fastest speed.
Degradation experiment example 2:
(1) the solution after the reaction of degradation experiment example 1 was washed with deionized water, and the supernatant was removed by magnetic separation.
(2) The second reaction was carried out by adding 100mL of 120mg/L aqueous Cr (VI) solution.
Repeating the steps (1) and (2) to carry out the third and fourth phase reactions. The experimental degradation effect is shown in fig. 3. After four period experiments, the prepared iron-based metal organic framework material can still completely remove Cr (VI), and the iron-based metal organic framework material is proved to be capable of continuously giving electrons.
Degradation experiment example 3:
the composite material after the reaction of the degradation experiment example 1 was subjected to photoelectron spectroscopy (XPS) detection, and the result is shown in fig. 4. As can be seen, the photoelectron peaks at 709.9eV and 722.8eV are FeCr2O42p of1/2And 2p3/2A small peak at 705.7eV evidences the presence of zero-valent iron (Fe 2 p)3/2). The peak positions at 709.3, 710.6 and 712.1eV are Fe2O3，In conclusion, the surface of the composite material after reaction is mainly FeCr2O4、Fe2O3And the like. This shows that no compact passivation layer is formed on the surface of the nano iron, and the iron-based metal organic framework material can continuously give electrons.

Claims (4)

1. A preparation method of an iron-based metal organic framework composite material capable of continuously giving electrons is characterized by comprising the following steps:
1) dissolving an organic ligand material in distilled water, and fully stirring and dissolving to prepare an organic framework solution;
2) adding iron salt into the organic framework solution obtained in the step 1), and stirring and complexing at the rotating speed of 3000-5000 r/min to obtain a metal organic solution;
3) under the condition of stirring, dropwise adding a reducing agent solution with a certain concentration into the system, and continuously stirring until the reaction is complete after the dropwise adding is finished;
4) after the reaction is finished, separating out nano iron by a magnetic separation method, and then washing, separating and drying in vacuum to obtain the iron-based metal organic framework material;
the reducing agent in the step 3) comprises sodium borohydride, potassium borohydride, hydrazine hydrate and sodium hydrosulfite, wherein the molar ratio of iron to the reducing agent is 1: (3-8);
the organic ligand material is tannic acid TA.
2. The method for preparing a sustained electron-donating iron-based metal organic framework composite material according to claim 1, wherein: the molar ratio of the ferric salt to the organic ligand material in the step 1) is 1: (5-80).
3. The method for preparing a sustained electron-donating iron-based metal organic framework composite material according to claim 1, wherein: the iron salt compound in the step 2) is FeCl3、FeCl3·6H2O、Fe(NO3)3·9H2O 、FeCl2·4H2O、FeSO4·7H2And one or more of O.
4. The method of preparing a sustained electron-donating iron-based metal-organic framework composite material according to claim 1, wherein: and in the step 4), washing is carried out by respectively cleaning with deoxidized deionized water and absolute ethyl alcohol for three times, wherein the vacuum drying temperature is 60-70 ℃, and the drying time is 10-30 h.
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CN114409916B (en) * 2022-01-25 2023-03-14 汕头大学 Nano tannin and preparation method and application thereof
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