CN111647167A - Novel metal organic framework material Zn-MOF, and synthesis method and application thereof - Google Patents
Novel metal organic framework material Zn-MOF, and synthesis method and application thereof Download PDFInfo
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- CN111647167A CN111647167A CN202010610604.3A CN202010610604A CN111647167A CN 111647167 A CN111647167 A CN 111647167A CN 202010610604 A CN202010610604 A CN 202010610604A CN 111647167 A CN111647167 A CN 111647167A
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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Abstract
The invention discloses a novel metal organic framework material Zn-MOF, a synthesis method and application thereof, wherein the method comprises the steps of material proportioning and mixing, grinding, vacuumizing, heating and preserving heat, cooling, purifying and the like, wherein after the vacuum heating temperature is 120-200 ℃, the heat is preserved for a specific time, the heating time is 24-112 h, and the metal organic framework material Zn-MOF prepared by the method has the advantages that: the synthetic method has the advantages of simple operation, less consumed materials, lower cost and less waste generation; impurities in the solid-phase reaction product can be well removed, and the crystallization of Zn-MOF can be promoted; the novel Zn-MOF material obtained by the method can regulate and control the emission spectrum performance of the material through laser.
Description
Technical Field
The invention belongs to the field of synthesis of metal organic framework Materials (MOF), and particularly relates to a Zn-MOF material synthesized by metal oxide (ZnO) and organic 2-methylimidazole (C4H6N2), a synthesis method and application thereof.
Background
The traditional metal oxide material ZnO has a unique band gap structure and high electron mobility, so the ZnO has wide application in sensing electrochemistry and photocatalysis, but the detection efficiency of a detector needs to be further improved. The metal organic framework is a novel porous coordination composite material, and is widely applied to the aspects of gas separation, storage, catalysis and the like due to the high specific surface area, adjustable pore size, high-density active sites and high catalytic activity. Recent researches find that the metal organic framework has the characteristic of a large number of high-activity sites, and the metal organic framework can be used as a precursor to obtain metal oxide with unique structural characteristics by specific technical means such as calcination under certain conditions, so that the device application of the metal oxide in the fields of catalysis, energy, sensing and the like is improved.
The metal organic framework of zinc is a composite material with a space topological structure, which takes zinc ions as central ions and organic molecular chains as ligands, and due to the special topological structure, the thermal stability of the material is often poor, and related technologies still need to be improved. The existing synthesis methods of metal organic frameworks are various: aqueous (solution) thermal methods, diffusion methods, solid phase reaction methods, and the like. The common synthesis method is a solution thermal method, which is beneficial to full contact reaction of soluble reactants, and the product is usually solid precipitate and is easy to separate. However, most of the solution thermal methods have complex synthesis processes, a plurality of organic solvents are needed as combined solvents in the synthesis processes, and part of the medicines used in the synthesis processes have certain dangerousness. For example, the existing Zn-MOF hydrothermal synthesis technology mostly adopts nitrate containing zinc as a zinc source, and has the disadvantages of corrosivity, explosiveness, harm to the environment, harsh reaction conditions and the like. And a poorly soluble reactant (ZnO) is not suitable as a reactant in the solution heating method. While the solid-phase reaction method is suitable for the reaction of a poorly soluble reactant, the product obtained by the solid-phase reaction method is not easily separated and usually contains many impurities. For example, in other synthesis processes using solid-phase reaction, the reactants are placed in a quartz glass tube, sealed by calcining, and heated at a high temperature under the protection of nitrogen. The traditional solid phase reaction method has the defects of high manufacturing cost, low yield, complex synthesis process, low purity of the synthesized product and the like.
Disclosure of Invention
The solid phase reaction method used for MOF synthesis has the advantages of being beneficial to reaction of insoluble reactants, simple in operation, environment-friendly (less in use or not applicable to solution), and the like, but the product generally contains more impurities.
The technical scheme is as follows:
a synthesis method of a novel metal organic framework material Zn-MOF comprises the following steps:
(1) step 1: weighing zinc oxide and 2-methylimidazole according to a certain mass ratio, and mixing the two powders;
(2) step 2: putting the mixed powder in the step (1) into an agate mortar, and grinding to mix uniformly;
(3) and step 3: putting the uniformly mixed powder in the step (2) into a specific container, putting the container into a vacuum constant-temperature drying oven, vacuumizing and keeping the pressure below 0.1 MPa;
(4) and 4, step 4: heating to 120-200 ℃ at a vacuum degree of more than 0.1MPa, and keeping the temperature for a certain time;
(5) and 5: cooling to room temperature at a vacuum degree of more than 0.1MPa after reaching the heat preservation time, and taking out the material;
(6) step 6: preparing an ammonium chloride solution with a certain concentration, putting the material obtained in the step (5) into the solution, uniformly stirring, placing in a heat preservation box, preserving heat for a certain time at a certain temperature, fully reacting the ammonium chloride solution with the residual zinc oxide, performing suction filtration, and drying to obtain the novel Zn-MOF material.
In addition, the invention also discloses a metal organic framework material Zn-MOF, which is prepared by the synthesis method of the novel metal organic framework material Zn-MOF.
The invention also discloses an application of the metal oxide in devices in the fields of catalysis, energy and sensing, wherein the application comprises the novel metal organic framework material Zn-MOF.
Has the advantages that:
1: the whole material synthesis method is simple to operate, low in material consumption, low in cost, low in waste generation amount, mainly water, safe and pollution-free. (by using a synthetic method based on a solid phase reaction method).
2: the purification process is simple and easy to operate.
Drawings
FIG. 1(1) is an XRD diffraction pattern before and after purification, wherein the second and third samples are heated to 160 ℃ for 84 hours and 112 hours; FIG. 1(2) is a purified XRD diffraction pattern of samples IV and V of the present invention after heating to 120 deg.C and holding at 200 deg.C for 112 hours;
FIG. 2 is SEM pictures of the holding time before and after purification, 24h, 84h and 112 h;
FIG. 3(1) MAF-4, ZnO and C prepared according to example III of the invention4H6N2Emission spectrum of the material under 265nm light excitation; FIG. 3(2) MAF-4, ZnO and C prepared for example three of the present invention4H6N2Emission spectrum of the material under 356nm light excitation.
Detailed Description
The present invention is not limited to the above embodiments, and any modifications, equivalent substitutions, improvements, etc. within the scope of the present invention should be included in the present invention.
A synthesis method of a novel metal organic framework material Zn-MOF comprises the following steps:
(1) weighing zinc oxide and 2-methylimidazole according to a certain mass ratio, and mixing. The coordination is carried out according to the coordination mode of the metal organic material, and the ratio of zinc oxide to 2-methylimidazole is about 1: 2;
(2) grinding: putting the mixed powder in the step (1) into an agate mortar, grinding the two kinds of powder for about 15 minutes to ensure that the reaction is fully carried out, grinding the two kinds of materials into fine powder and uniformly mixing;
(3) vacuumizing: placing the mixed powder in the step (2) into a specific container, placing the mixed powder into a vacuum constant-temperature drying oven for vacuumizing and keeping the pressure below 0.1MPa, wherein 2-methylimidazole can react with oxygen, so that the mixed powder cannot be in an aerobic environment in the heat preservation process;
(4) heating and heat preservation: heating to 120-200 ℃ below 0.1MPa of vacuum degree, and keeping the temperature for a certain time;
(5) and (3) cooling: cooling to room temperature under the vacuum degree of 0.1MPa after the heat preservation time is reached, and taking out the material;
(6) and (3) purification: the purity of Zn-MOF is affected by the presence of zinc oxide as an impurity in the product. This step is carried out for purification. Preparing an ammonium chloride solution with the concentration of 0.1-0.9M, putting the material obtained in the step (5) into the solution, uniformly stirring, placing the solution in a heat preservation box, preserving heat for 24 hours at the temperature of 60 ℃ so that the ammonium chloride solution and the residual zinc oxide fully react, filtering, and drying to obtain the novel Zn-MOF material.
Example 1
(1) Preparing ingredients:
3.0121 g of zinc oxide with the purity of more than 99 percent and 6.0135 g of 2-methylimidazole (the mass ratio of the two is about 1:2) are put into an agate mortar to be ground for 15 minutes, the two reactants are fully contacted and homogenized, and the mixture is filled into a glass container.
(2) Vacuum heating and heat preservation:
and (3) putting the container in the step (1) into a vacuum constant-temperature drying oven, vacuumizing and keeping the pressure below 0.1MPa, heating to 160 ℃, and keeping the temperature for 24 hours. Then cooling to room temperature, deflating and taking out.
(3) And (3) purification:
preparing 150mL of 0.5M ammonium chloride aqueous solution, putting the product obtained in the step (2), soaking the product in the solution, heating to 60 ℃, and preserving heat for 24 hours. And then carrying out suction filtration and drying to obtain the novel Zn-MOF material.
Example 2
(1) Preparing ingredients:
3.0000 g of zinc oxide with the purity of more than 99 percent and 6.0009 g of 2-methylimidazole (the mass ratio of the two is about 1:2) are put into an agate mortar to be ground for 15 minutes, so that the two reactants are fully contacted and homogenized, and the mixture is filled into a glass container.
(2) Vacuum heating and heat preservation:
and (3) putting the container in the step (1) into a vacuum constant-temperature drying oven, vacuumizing and keeping the pressure below 0.1MPa, heating to 160 ℃, and keeping the temperature for 84 hours. Then cooling to room temperature, deflating and taking out.
(3) And (3) purification:
preparing 150mL of 0.5M ammonium chloride aqueous solution, putting the product obtained in the step (2), soaking the product in the solution, heating to 60 ℃, and preserving heat for 24 hours. And then carrying out suction filtration and drying to obtain the novel Zn-MOF material.
Example 3
(1) Preparing ingredients:
3.0098 g of zinc oxide with the purity of more than 99 percent and 6.0110 g of 2-methylimidazole (the mass ratio of the two is about 1:2) are put into an agate mortar to be ground for 15 minutes, the two reactants are fully contacted and homogenized, and the mixture is filled into a glass container.
(2) Vacuum heating and heat preservation:
and (3) putting the container in the step (1) into a vacuum constant-temperature drying oven, vacuumizing and keeping the pressure below 0.1MPa, heating to 160 ℃, and keeping the temperature for 112 hours. Then cooling to room temperature, deflating and taking out.
(3) And (3) purification:
preparing 150mL of 0.5M ammonium chloride aqueous solution, putting the product obtained in the step (2), soaking the product in the solution, heating to 60 ℃, and preserving heat for 24 hours. And then carrying out suction filtration and drying to obtain the novel Zn-MOF material.
Example 4
(1) Preparing ingredients:
3.0102 g of zinc oxide with the purity of more than 99 percent and 6.0036 g of 2-methylimidazole (the mass ratio of the two is about 1:2) are put into an agate mortar to be ground for 15 minutes, the two reactants are fully contacted and homogenized, and the mixture is filled into a glass container.
(2) Vacuum heating and heat preservation:
and (3) putting the container in the step (1) into a vacuum constant-temperature drying oven, vacuumizing and keeping the pressure below 0.1MPa, heating to 120 ℃, and preserving the temperature for 112 hours. Then cooling to room temperature, deflating and taking out.
(3) And (3) purification:
preparing 150mL of 0.5M ammonium chloride aqueous solution, putting the product obtained in the step (2), soaking the product in the solution, heating to 60 ℃, and preserving heat for 24 hours. And then carrying out suction filtration and drying to obtain the novel Zn-MOF material.
Example 5
(1) Preparing ingredients:
3.0007 g of zinc oxide with the purity of more than 99 percent and 6.0002 g of 2-methylimidazole (the mass ratio of the two is about 1:2) are put into an agate mortar to be ground for 15 minutes, the two reactants are fully contacted and homogenized, and the mixture is filled into a glass container.
(2) Vacuum heating and heat preservation:
and (3) putting the container in the step (1) into a vacuum constant-temperature drying oven, vacuumizing and keeping the pressure below 0.1MPa, starting heating to 200 ℃, and keeping the temperature for 112 hours. Then cooling to room temperature, deflating and taking out.
(3) And (3) purification:
preparing 150mL of 0.5M ammonium chloride aqueous solution, putting the product obtained in the step (2), soaking the product in the solution, heating to 60 ℃, and preserving heat for 24 hours. And then carrying out suction filtration and drying to obtain the novel Zn-MOF material.
By the above examples, the XRD diffraction pattern of the obtained novel Zn-MOF material is shown in figure 1. In the pattern (1) of figure 1, a and c are XRD diffraction patterns before and after 84h of purification at 160 ℃, b and d are XRD diffraction patterns before and after 112h of purification at 160 ℃, and the pattern comprises a simulated XRD pattern of Zn-MOF and a standard PDF card of ZnO and 2-methylimidazole. In the spectrum (2) of figure 1, the e and f curves are XRD diffraction patterns after purification at 120 ℃ and 200 ℃ for 112 h. The XRD pattern before purification according to the curves c and d in figure 1 shows that the synthesized novel Zn-MOF material contains more ZnO impurities, which results in the generated Zn-MOF with lower specific gravity and lower purity. The XRD pattern after purification according to the curves a and b in figure 1 shows that after the purification process, the peak value corresponding to ZnO is reduced, the peak value corresponding to Zn-MOF material is obviously increased, the specific gravity of Zn-MOF is strengthened, and the purity is improved. Compared with curves a, e and f, Zn-MOF can be generated under the conditions of heat preservation of 120 ℃ and heat preservation of 200 ℃, but obviously the specific gravity of the generated Zn-MOF is lower and the yield is lower. Therefore, 160 ℃ is the best temperature for synthesizing Zn-MOF.
The SEM microstructure image of the obtained Zn-MOF is shown in FIG. 2. In FIG. 2, a and b are SEM microstructure images of purification and non-purification after heat preservation at 160 ℃ for 24h, c and d are SEM microstructure images of purification and non-purification after heat preservation at 160 ℃ for 84h, and e and f are SEM microstructure images of purification and non-purification after heat preservation at 160 ℃ for 112 h. According to a, c and e in FIG. 2, Zn-MOF crystals are contained in the graph when the materials are not purified at each holding time, but other impurities are more visible from the graph and influence the performance of the materials. According to b, d and f in fig. 2, a large number of clearly visible Zn-MOF crystals are in the picture after the purification step under each heat preservation time, and the impurities are obviously reduced. And comparing the SEM images of b, d and f in FIG. 2 with different holding times, it can be seen that the longer the holding time is, the more sufficient the reaction is, and the less impurities are. By the synthesis method, the generated Zn-MOF is a high-purity crystal material and is convenient to use.
The emission spectrum of Zn-MOF under 265nm excitation is shown in FIG. 3(1), which is obtained by reacting with ZnO and 2-methylimidazole C4H6N2Compared with the emission spectrum of the material, the peak value of the synthesized novel material Zn-MOF (namely MAF-4) under the excitation of 265nm is shifted to the left than that of a ZnO material and is compared with 2-methylimidazole (C)4H6N2) The emission spectrum of the detector is narrow, and the detector is easily matched with a photomultiplier to improve the detection efficiency of the detector. The measured emission spectrum of Zn-MOF under 356nm excitation is shown in FIG. 3(2), and the synthesis is performed by comparing the emission spectrum with that under 265nm excitation in FIG. 3(1)The peak value of the novel material Zn-MOF (i.e. MAF-4) under 356nm excitation shows two peak values, which is obviously different from the emission spectrum under 265nm excitation, and the two peak values of the synthesized novel material Zn-MOF (i.e. MAF-4) under 356nm excitation are more concentrated than the two peak values of the ZnO material, which is beneficial to improving the photoelectric conversion efficiency of the back-end photomultiplier.
Compared with the prior art, the invention has the following advantages:
1: compared with the synthesis method based on the solid-phase reaction method adopted in the prior art, the whole material synthesis method is simple to operate, less in consumed materials, lower in cost, less in waste generation amount, mainly water, safe and pollution-free.
2: the purification process is simple and easy to operate, impurities in the solid-phase reaction product can be well removed through the purification process, and the crystallization of Zn-MOF can be promoted. (purification process by soaking, filtering, drying, etc. of NH4Cl solution in the method)
3: the novel Zn-MOF material obtained by the method can regulate and control the emission spectrum performance of the material through laser. (by measuring the emission spectra under excitation at 265nm and 356 nm)
4: in other synthesis methods, zinc hydroxide material is used, which decomposes at 125 ℃ and introduces impurities into the synthesis process. The zinc oxide material used in the method has better thermal stability and is convenient for reaction compared with the zinc hydroxide material.
5: the temperature selected in the synthesis method is 160 ℃ which is the optimal reaction temperature. The temperature is lower than 160 ℃, the reaction is not sufficiently carried out, and more impurities exist; above 160 ℃ the flash point of dimethylimidazole is reached, which is detrimental to the reaction.
In addition, the invention also discloses a metal organic framework material Zn-MOF, which is prepared by the synthesis method of the novel metal organic framework material Zn-MOF.
The invention also discloses an application of the metal oxide in devices in the fields of catalysis, energy and sensing, wherein the application comprises the novel metal organic framework material Zn-MOF.
In summary, each parameter selected in the process of the method for synthesizing the novel metal organic framework material Zn-MOF in the present invention is not necessarily selected by those skilled in the art, but is a result obtained through numerous experiments and scientific theoretical analysis by researchers with creative labor, and is not a routine technical means easily imaginable by those skilled in the art.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A synthesis method of a novel metal organic framework material Zn-MOF comprises the following steps:
step 1: weighing zinc oxide and 2-methylimidazole according to a certain mass ratio, and mixing the two powders;
step 2: putting the mixed powder in the step (1) into an agate mortar, and grinding to mix uniformly;
and step 3: putting the uniformly mixed powder in the step (2) into a specific container, putting the container into a vacuum constant-temperature drying oven, vacuumizing and keeping the pressure below 0.1 MPa;
and 4, step 4: heating to 120-200 ℃ at a vacuum degree of more than 0.1MPa, and then preserving heat for a certain time;
and 5: cooling to room temperature at a vacuum degree of more than 0.1MPa after reaching the heat preservation time, and taking out the material;
step 6: preparing an ammonium chloride solution with a certain concentration, putting the material obtained in the step (5) into the solution, uniformly stirring, placing in a heat preservation box, fully reacting the ammonium chloride solution with the residual zinc oxide, performing suction filtration, and drying to obtain the novel Zn-MOF material.
2. The synthesis method of a novel metal organic framework material Zn-MOF according to claim 1, characterized in that: the purity of the zinc oxide and the purity of the 2-methylimidazole are both more than 99%.
3. The synthesis method of a novel metal organic framework material Zn-MOF according to claim 1, characterized in that: the particular container is a glass container.
4. The synthesis method of a novel metal organic framework material Zn-MOF according to claim 1, characterized in that: the specific time of the heat preservation is 24 to 112 hours.
5. The synthesis method of a novel metal organic framework material Zn-MOF according to claim 1, characterized in that: the concentration of the ammonium chloride solution in the step 6 is 0.1M-0.9M.
6. A novel metal organic framework material Zn-MOF is characterized in that: the metal organic framework material Zn-MOF is prepared by the synthesis method of the novel metal organic framework material Zn-MOF as claimed in any one of claims 1 to 5.
7. An application of the metal oxide in the field of catalysis, energy and sensing is improved, which is characterized in that: comprising the novel metal organic framework material Zn-MOF of claim 6.
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