CN115505135B - Fe-Zr MOFs and preparation method and application thereof - Google Patents

Fe-Zr MOFs and preparation method and application thereof Download PDF

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CN115505135B
CN115505135B CN202211179423.5A CN202211179423A CN115505135B CN 115505135 B CN115505135 B CN 115505135B CN 202211179423 A CN202211179423 A CN 202211179423A CN 115505135 B CN115505135 B CN 115505135B
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ligand
mofs
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zrocl
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CN115505135A (en
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丁宇
唐晓亮
朱浩
曲毅
杨宏旺
王翠辉
王玥
王小丽
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Lanrun Environmental Protection Technology Yantai Co ltd
Lanzhou University
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Lanzhou University
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Abstract

The invention discloses Fe-ZrMOFs and a preparation method and application thereof, and belongs to the technical field of MOFs. The preparation method comprises the following steps: preparation of ligand HL 2 Fe (BF) 4 ) 2 ·6H 2 O, ligand HL 2 And anhydrous DMSO are stirred at normal temperature to prepare ligand Fe-HL 2 ZrOCl is used as the material 2 ·H 2 O, ligand Fe-HL 2 And (3) reacting DMF with formic acid at 120 ℃ for 3d to obtain crystals, filtering and collecting the crystals, and washing and drying to obtain the Fe-ZrMOFs. The invention has the advantages that: (1) The process flow is simple, the operability is strong, the yield is high, the batch amplification synthesis can be realized, and the repeatability is good; (2) The prepared Fe-ZrMOFs has higher catalytic activity and good stability, and the Fe-ZrMOFs participates in the photocatalytic reduction of CO 2 Reaction and CO 2 Cyclic carbonate synthesis reaction CO 2 The utilization ratio of the (C) is very high.

Description

Fe-Zr MOFs and preparation method and application thereof
Technical Field
The invention relates to MOFs and a preparation method and application thereof, in particular to Fe-Zr MOFs and a preparation method thereof and CO reduction in photocatalysis 2 Chemically fixing CO 2 Belongs to the technical field of metal organic frame materials.
Background
Excessive CO emission 2 Causes serious environmental problems, and develops and utilizes CO in a green and efficient way 2 Is beneficial to relieving the greenhouse effect and changing waste into valuable, and has important significance.
In recent years, a number of processes have been developed to efficiently store and convert CO 2 . The natural photosynthesis is taken as inspiration, and a relatively promising mode is that the sunlight is used for CO under the action of a photocatalyst 2 To valuable fuels or other chemicals such as CO, formic acid, methane, etc. In addition, CO 2 Cycloaddition with epoxide, which is another promising method, can convert CO 2 Is converted into various chemical substances. However, due to CO 2 The molecules are very stable, activate CO 2 A large amount of energy is required. Thus, effective artificial catalysts were developed to activate and convert CO 2 Transformation is very important.
Metal-organic framework Materials (MOFs) are coordination framework materials formed based on self-assembly of Metal ions and organic ligands, which may have metallic properties, may have organic ligand properties, and may have new properties that are not present in both Metal and organic ligands. As an emerging porous material with the characteristics of high specific surface area, multiple active sites, tailorable structure, easy functionalization and the like, MOFs have shown important application prospects in the fields of gas storage and separation, molecular sensing, photoelectric materials, drug carriers, catalysis and the like. In recent years, MOFs have been increasingly focused and studied in the catalytic field due to their excellent thermal and chemical stability.
At present, CO is reduced by photocatalysis 2 In the reaction, MOFs used as photocatalysts mainly take the following three forms:
(1) Pure MOFs is used as a catalyst, and the components are single, so that the catalytic performance is limited, the solar energy utilization efficiency is low, and the CO is low 2 The adsorption force is weak;
(2) MOFs catalysis participated by the metal complex is a homogeneous system, so that the metal complex lacks long-term stability and is difficult to separate in the catalysis process, product pollution can be caused, and the recycling of the catalyst can not be realized;
(3) The choice of a suitable semiconductor-MOFs composite catalyst is critical because the photocatalysis of the semiconductor-MOFs composite forms an effective schottky barrier only if the semiconductor has the proper fermi level matching.
In CO 2 MOFs used as catalysts in the cyclic carbonate synthesis reaction mainly comprise rare earth metal organic frameworks (Ln-MOFs) and transition metal organic framework materials, and most MOFs have low catalytic efficiency, are sensitive to air, require auxiliary solvents and have high temperature>130 ℃ high pressure [ ]>1 MPa) conditions, etc.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for reducing CO in photocatalysis 2 Reaction and CO 2 MOFs with high catalytic activity in cyclic carbonate synthesis reaction, and method for preparing MOFs with simple process flow and high yield 2 And CO 2 Use in the synthesis of cyclic carbonates.
In order to achieve the above object, the present invention adopts the following technical scheme:
a method for preparing Fe-Zr MOFs, comprising the steps of:
(1) Preparation of ligand HL 2 ；
(2) With Fe (BF) 4 ) 2 ·6H 2 O, ligand HL 2 And anhydrous DMSO as raw materials, wherein Fe (BF) 4 ) 2 ·6H 2 O and ligand HL 2 The mass ratio of the substances is 1:2, stirring at normal temperature to prepare ligand Fe-HL 2 ；
(3) With ZrOCl 2 ·H 2 O, ligand Fe-HL 2 DMF and formic acid are used as raw materials, wherein ZrOCl 2 ·H 2 O and ligand Fe-HL 2 The mass ratio of (2) is 3:1, and the mixture is reacted for 3 days at 120 ℃ in a reaction kettle to prepare crystals;
(4) Filtering the reaction liquid, collecting crystals, washing and drying the crystals to obtain Fe-Zr MOFs;
wherein the ligand HL 2 And ligand Fe-HL 2 The structural formula of (a) is shown below respectively:
preferably, in step (1), ligand HL is prepared 2 The method of (2) is as follows: mixing methyl p-formylbenzoate, 2-acetylpyridine, ammonia water and potassium hydroxide, wherein the mass ratio of the methyl p-formylbenzoate to the 2-acetylpyridine is 1:2, placing the mixed solution into a round-bottom flask, adding ethanol, and reacting at 80 ℃ for 24 hours to obtain ligand HL 2 。
Preferably, in step (2), the ligand Fe-HL is prepared 2 The method of (2) is as follows: fe (BF) 4 ) 2 ·6H 2 O and ligand HL 2 Mixing, adding anhydrous DMSO, and stirring at normal temperature for 4h to obtain ligand Fe-HL 2 。
Preferably, in the step (3), the method for preparing the crystal is specifically as follows: ligand Fe-HL 2 Adding into DMF, ultrasonic treatment, and then addingInto ZrOCl 2 ·H 2 O, ultrasonic treatment, adding formic acid, ultrasonic treatment to make ligand Fe-HL 2 And ZrOCl 2 ·H 2 O is completely dissolved, the mixed solution is transferred into a reaction kettle and is put into a baking oven at 120 ℃ for 3d reaction, and the crystal is prepared.
Preferably, in step (4), the method for washing the crystals is specifically as follows: the crystals were washed 3 times with DMF and then 3 times with acetonitrile.
An Fe-Zr MOFs prepared by a method as claimed in any one of the preceding claims.
The Fe-Zr MOFs as the catalyst for photocatalytic reduction of CO 2 Applications in the catalysis of CO 2 Use in the synthesis of cyclic carbonates.
The invention has the advantages that:
(1) The method for preparing the Fe-Zr MOFs has simple process flow and can prepare the ligand Fe-HL at normal temperature 2 The operability is strong, the batch amplification synthesis can be realized, and the repeatability is good;
(2) The method for preparing the Fe-Zr MOFs has high yield (more than 65 percent) and can realize industrialized preparation;
(3) The Fe-Zr MOFs prepared by the method provided by the invention has very stable structure, has two metal ions of Fe (II) and Zr (IV) and 2,2':6', 2' -terpyridine ligand, thus having higher catalytic activity and participating in photocatalytic reduction of CO 2 Reaction and CO 2 Cyclic carbonate synthesis reaction CO 2 The utilization rate of the system is very high;
(4) The residual mass of the Fe-Zr MOFs prepared by the method provided by the invention is 50% after the thermogravimetric analysis measurement is finished, and the PXRD diffraction patterns after the Fe-Zr MOFs are soaked in different solvents for 3 days and calcined at 150 ℃ for 2 hours show that the Fe-Zr MOFs have good chemical stability and thermal stability;
(5) The Fe-Zr MOFs prepared by the method provided by the invention has holes and can adsorb and capture CO 2 。
Drawings
FIG. 1 is an X-ray diffraction pattern of Fe-Zr MOFs-1 prepared in example 1;
FIG. 2 is a drawing of the Fe-HL produced in example 1 2 And Fe-Zr MOFs-1;
FIG. 3 is a thermogram of Fe-Zr MOFs-1 prepared in example 1;
FIG. 4 is a PXRD diffraction pattern of the Fe-Zr MOFs-1 prepared in example 1 after 3d immersion in different solvents;
FIG. 5 is a PXRD diffraction pattern of Fe-Zr MOFs-1 prepared in example 1 after calcination at 150℃for 2 hours;
FIG. 6 is a schematic illustration of participation in photocatalytic reduction of CO 2 X-ray diffraction pattern of Fe-Zr MOFs-1 after the reaction;
FIG. 7 is a diagram of the product of the cyclic carbonate synthesis reaction 1 H NMR spectrum.
Detailed Description
The invention is described in detail below with reference to the drawings and the specific embodiments.
1. Preparation of Fe-Zr MOFs
Example 1
Ligand HL 2 And ligand Fe-HL 2 The structural formula of (a) is shown below respectively:
2.46g (15 mmol) of methyl p-formylbenzoate, 3.4mL (30 mmol) of 2-acetylpyridine, 3mL (45 mmol) of ammonia water and 2.56g (45 mmol) of potassium hydroxide are mixed, put into a round-bottomed flask, 250mL of ethanol is added, and reacted at 80 ℃ for 24 hours to obtain ligand HL 2 。
101.3mg (0.3 mmol) of Fe (BF 4 ) 2 ·6H 2 O and 212.4mg (0.6 mmol) of ligand HL 2 Mixing, adding 9mL anhydrous dimethyl sulfoxide (DMSO), stirring at normal temperature for 4h to obtain deep purple ligand Fe-HL 2 。
10mg (0.014 mmol) of ligand Fe-HL 2 Added to 2.5mLN, N-Dimethylformamide (DMF), sonicated for 5min, then 30mg (0.17 mmol) ZrOCl was added 2 ·H 2 O, ultrasonic for 10min, adding 1000 mu L of formic acid, ultrasonic for 5min,by reacting the ligand Fe-HL 2 And ZrOCl 2 ·H 2 O is completely dissolved, the mixed solution is transferred into a reaction kettle and is put into a baking oven at 120 ℃ for 3d reaction, and the purple-black crystal is obtained.
The reaction solution was filtered, and the crystals were collected, washed with 20mL of DMF 3 times, then with 20mL of acetonitrile 3 times, and dried to obtain Fe-Zr MOFs-1.
The yield of Fe-Zr MOFs-1 was calculated to be 66%.
Example 2
Ligand Fe-HL 2 The preparation method is exactly the same as that of the embodiment 1, and is not repeated.
11mg (0.015 mmol) of ligand Fe-HL 2 Added to 3.0mL DMF and sonicated for 5min before 33mg (0.19 mmol) ZrOCl was added 2 ·H 2 O, ultrasonic for 10min, adding 1000 μL formic acid, ultrasonic for 5min to obtain ligand Fe-HL 2 And ZrOCl 2 ·H 2 O is completely dissolved, the mixed solution is transferred into a reaction kettle and is put into a baking oven at 120 ℃ for 3d reaction, and purple black crystals and filtrate are obtained. The crystals were filtered and collected, washed 3 times with 20mL DMF and then 3 times with 20mL acetonitrile, and dried to give Fe-Zr MOFs-2.
The yield of Fe-Zr MOFs-2 was calculated to be 68%.
Example 3
Ligand Fe-HL 2 The preparation method is exactly the same as that of the embodiment 1, and is not repeated.
9mg (0.012 mmol) of ligand Fe-HL 2 Added to 2.0mL DMF and sonicated for 5min before adding 27mg (0.16 mmol) ZrOCl 2 ·H 2 O, ultrasonic for 10min, adding 1000 μL formic acid, ultrasonic for 5min to obtain ligand Fe-HL 2 And ZrOCl 2 ·H 2 O is completely dissolved, the mixed solution is transferred into a reaction kettle and is put into a baking oven at 120 ℃ for 3d reaction, and purple black crystals and filtrate are obtained. The crystals were filtered and collected, washed 3 times with 20mL DMF and then 3 times with 20mL acetonitrile, and dried to give Fe-Zr MOFs-3.
The yield of Fe-Zr MOFs-3 was calculated to be 65%.
2. Characterization of Fe-Zr MOFs prepared by the method
1. X-ray diffraction
The prepared Fe-Zr MOFs-1, fe-Zr MOFs-2 and Fe-Zr MOFs-3 were subjected to X-ray diffraction, diffraction data collection was performed on a D8 ADVANCE diffractometer, and continuous scanning was performed using graphite-monochromatized copper target X-rays (Cu K.alpha.) in the range of 3.1℃to 50 ℃.
The X-ray diffraction pattern of Fe-Zr MOFs-1 is shown in FIG. 1. As can be seen from FIG. 1, the peak positions of the Fe-Zr MOFs-1 match the peak positions of the simulated Fe-Zr MOFs. This demonstrates that example 1 successfully produced Fe-Zr MOFs.
The X-ray diffraction patterns of Fe-Zr MOFs-2 and Fe-Zr MOFs-3 were substantially identical to those of FIG. 1, and the peak positions were also identical to those of the simulated Fe-Zr MOFs. This illustrates that example 2 and example 3 also work to produce Fe-Zr MOFs.
2. Infrared spectrum
Adopting NEXUS 670 spectrometer, using KBr as base, at 400-4000 cm -1 Fe-HL obtained by measuring in the range 2 IR spectra of Fe-Zr MOFs-1, fe-Zr MOFs-2 and Fe-Zr MOFs-3.
Fe-HL 2 And Fe-Zr MOFs-1, see FIG. 2. As can be seen from FIG. 2, fe-HL 2 And the peak shape of Fe-Zr MOFs-1 are substantially identical, and the wave number is 3063cm in the infrared spectrum of Fe-Zr MOFs-1 -1 Point 16 cm -1 The peak at the position disappeared and the wave number was 3063cm -1 The disappearance of the peak at this point indicates the ligand Fe-HL 2 The O-H of carboxylic acid coordinates with metal ion, wave number is 1699cm -1 The disappearance of the peak at this point indicates the ligand Fe-HL 2 C=o of carboxylic acid coordinates with metal ion, which also indicates that example 1 successfully produced fe—zr MOFs.
The infrared spectra of Fe-Zr MOFs-2 and Fe-Zr MOFs-3 were substantially identical to those of FIG. 2. This illustrates that example 2 and example 3 also work to produce Fe-Zr MOFs.
3. Single crystal diffraction
Single crystal diffraction was performed on Fe-Zr MOFs-1 prepared in example 1, and the obtained crystallographic data were as follows:
TABLE 1 crystallographic data of Fe-Zr MOFs-1
a R＝Σ(||F 0 |-|F C ||)/Σ|F 0 |； b wR＝[Σw(|F 0 | 2 -|F C | 2 ) 2 /Σw(F 0 2 )] 1/2
The above-mentioned crystallographic data indicate that Fe (II) and Zr (IV) are both metal ions in the framework of Fe-Zr MOFs-1, fe (II) and the ligands HL from two 2 Is coordinated by six N atoms; zr (IV) and HL from two ligands 2 O atoms on the carboxyl group of (2) and O atoms on four formic acids are linked to form [ Fe Zr (HCOO) 4 (HL 2 ) 2 ]One-dimensional chains, a plurality of one-dimensional chains are further connected together through pi interaction and hydrogen bonds to form the three-dimensional Fe-Zr MOFs.
3. The stability of the Fe-Zr MOFs prepared by the invention was analyzed
1. Thermogravimetric analysis
Thermogravimetric analysis was carried out on the Fe-Zr MOFs-1 prepared in example 1, and the obtained thermogravimetric analysis spectrum was shown in FIG. 3.
As is clear from FIG. 3, the residual mass of Fe-Zr MOFs-1 after the end of the measurement was 50%. This indicates that Fe-Zr MOFs-1 has relatively high thermal stability.
2. PXRD diffraction analysis
The obtained PXRD diffraction pattern is shown in FIG. 4 after soaking the Fe-Zr MOFs-1 prepared in example 1 in different solvents (water, methanol and acetonitrile) for 3 d.
The Fe-Zr MOFs-1 prepared in example 1 was calcined at 150℃for 2 hours, and the obtained PXRD diffraction pattern was shown in FIG. 5.
As can be seen from FIGS. 4 and 5, fe-Zr MOFs-1 has good thermal and chemical stability.
In conclusion, the Fe-Zr MOFs prepared by the method have good thermal stability and chemical stability.
4. Application of research Fe-Zr MOFs
1. Photocatalytic reduction of CO 2 Reaction
Fe-Zr MOFs-1 was immersed in fresh acetonitrile for 3d, the solvent was changed 2 times per day, and the influence of the possibly adsorbed solvent on the activity test was removed.
Dispersing 20mg of Fe-Zr MOFs-1 (photocatalyst) into 40mL of acetonitrile, adding 100mg of eosin Y as a photosensitizer, adding 10mL of triethanolamine as a sacrificial agent, transferring the mixed solution into a 250mL quartz reactor, sealing and stirring, continuously adding high-purity CO 2 Bubbling into the reactor for 30min, and continuously leading out the gas in the reactor to remove the residual gas oxygen and the dissolved oxygen in the water in the reactor. Sealing the reactor, and slowly introducing CO 2 Into the reactor. This step requires the addition of a backflow water device.
A 300W xenon lamp was used as an external light source to illuminate the reactor through a quartz window on top. Photocatalytic reduction of CO 2 The reaction was continued for 6 hours, and the content of formic acid was detected 1 time every 1 hour by ion chromatography (using sodium carbonate and sodium bicarbonate as leacheate).
The content of formic acid was found to be 0. Mu. Mol, 13.7. Mu. Mol, 17.5. Mu. Mol, 22.0. Mu. Mol, 23.0. Mu. Mol, 28.1. Mu. Mol, 31.8. Mu. Mol, respectively, over the 6 h.
Calculated conversion of formic acid was 265. Mu. Mol g -1 h -1 。
Fe-Zr MOFs-1 was recovered, and the reacted Fe-Zr MOFs-1 was subjected to X-ray diffraction characterization, and the results are shown in FIG. 6.
As is clear from FIG. 6, the position of the diffraction peak of the reacted Fe-Zr MOFs-1 was matched with the position of the diffraction peak of the reacted Fe-Zr MOFs-1. This indicates that the catalyst Fe-Zr MOFs-1 was very stable.
2. Cyclic carbonate synthesis reaction
10mmol of epoxy styrene, 0.001mmol (0.01 mol%) of Fe-Zr MOFs-1 and 0.08mmol (0.8 mol%) of tetrabutylammonium bromide (cocatalyst) were added in sequence to a polytetrafluoroethylene-lined stainless steel autoclave with a magneton in the absence of any organic solvent.
The autoclave was screwed down and with CO 2 The steel cylinders are connected. First CO 2 The air in the kettle is replaced by gas, the process is repeated for 3 times, and then CO with the pressure of 0.5MPa is filled 2 The temperature of the oil bath pot is set to 120 ℃, and stirring is started.
After 8h of reaction, stirring is stopped, the kettle is rapidly placed into ice water bath for cooling, and after about 30min, a valve is slowly opened to release residual CO 2 . Opening the kettle, taking a proper amount of sample as 1 H NMR。
Detected, sample 1 The H NMR spectrum is shown in FIG. 7.
The yield of the reaction was calculated to be 90%.
It can be seen that the photocatalytic reduction of CO is participated in by Fe-Zr MOFs 2 Reaction and cyclic carbonate Synthesis reaction, CO 2 The utilization of (3) is very high.
In combination, fe-Zr MOFs contribute to CO 2 Has wide application prospect in the fields of energy and catalysis.
It should be noted that the above-mentioned examples of the present invention are only examples for clearly illustrating the present invention, and are not limiting to the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. Not all embodiments are exhaustive. All obvious changes or modifications which come within the spirit of the invention are desired to be protected.

Claims (4)

1. A method for preparing Fe-Zr MOFs, comprising the steps of:
(1) Preparation of ligand HL 2 : mixing methyl p-formylbenzoate, 2-acetylpyridine, ammonia water and potassium hydroxide, wherein the mass ratio of the methyl p-formylbenzoate to the 2-acetylpyridine is 1:2, placing the mixed solution into a round-bottom flask, adding ethanol, and reacting at 80 ℃ for 24 hours to obtain ligand HL 2 ；
(2) With Fe (BF) 4 ) 2 ·6H 2 O, ligandHL 2 And anhydrous DMSO as raw materials, wherein Fe (BF) 4 ) 2 ·6H 2 O and ligand HL 2 The mass ratio of the substances is 1:2, fe (BF 4 ) 2 ·6H 2 O and ligand HL 2 Mixing, adding anhydrous DMSO, stirring at normal temperature for 4h to prepare ligand Fe-HL 2 ；
(3) With ZrOCl 2 ·H 2 O, ligand Fe-HL 2 DMF and formic acid are used as raw materials, wherein ZrOCl 2 ·H 2 O and ligand Fe-HL 2 The mass ratio of (2) is 3:1, and the mixture is reacted for 3 days at 120 ℃ in a reaction kettle to prepare crystals;
(4) Filtering the reaction liquid, collecting crystals, washing and drying the crystals to obtain Fe-Zr MOFs;
wherein the ligand HL 2 And ligand Fe-HL 2 The structural formula of (a) is shown below respectively:
。
2. the method according to claim 1, wherein in step (3), the method for preparing the crystals is specifically as follows:
ligand Fe-HL 2 Adding into DMF, ultrasonic treating, and adding ZrOCl 2 ·H 2 O, ultrasonic treatment, adding formic acid, ultrasonic treatment to make ligand Fe-HL 2 And ZrOCl 2 ·H 2 O is completely dissolved, the mixed solution is transferred into a reaction kettle and is put into a baking oven at 120 ℃ for 3d reaction, and the crystal is prepared.
3. The method according to claim 1, wherein in step (4), the method of washing the crystals is specifically as follows:
the crystals were washed 3 times with DMF and then 3 times with acetonitrile.
4. Catalytic CO using Fe-Zr MOFs prepared by the method of any one of claims 1-3 as catalysts 2 Synthesis of cyclic carbonic acidThe use of esters, characterized in that the Fe-Zr MOFs catalyze CO 2 The method for synthesizing the cyclic carbonate comprises the following steps:
(1) Sequentially adding epoxy styrene, fe-Zr MOFs and tetrabutylammonium bromide into a stainless steel autoclave with a polytetrafluoroethylene lining with a magneton under the condition of no addition of any organic solvent;
(2) The autoclave was screwed down and with CO 2 The steel cylinders are connected by CO 2 The gas displaces the air in the kettle and is then filled with CO with the pressure of 0.5MPa 2 The temperature of the oil bath pot is set to 120 ℃, and stirring is started;
(3) After the reaction is finished, stopping stirring, rapidly putting the kettle into an ice water bath for cooling, and slowly opening a valve to release residual CO after 30min 2 。
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