CN117417543A - A kind of scandium metal organic framework material and its preparation method and application - Google Patents
A kind of scandium metal organic framework material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a preparation method of scandium metal organic framework material, which comprises the steps of mixing soluble scandium salt and terephthalic acid, and then performing solvothermal reaction to obtain the scandium metal organic framework material, wherein the soluble scandium salt comprises any one or more of scandium chloride, scandium nitrate, scandium chloride hydrate and scandium nitrate hydrate. Meanwhile, the scandium metal organic framework material prepared by the invention is applied to the electrocatalytic reaction to convert 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid, and has good electrocatalytic conversion effect. Compared with the prior art, the preparation method for the scandium metal organic framework material has the advantages of simple process, wide applicability and capability of large-scale production, and the prepared scandium metal organic framework material has the advantages of larger specific surface area, smaller aperture, higher yield and Faraday efficiency of converting the electrocatalytic oxidation of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a scandium metal organic framework material, a preparation method and application thereof.
Background
Fossil fuels, also known as mineral resources, are non-renewable resources, and the problem of energy exhaustion of fossil fuels due to excessive consumption has attracted close attention in various countries around the world. The human beings cannot generate various pollutants in the process of using fossil fuel, so that the environment is damaged to a certain extent, and the global warming effect is caused, so that the requirements of environmental protection are not met. The selection of a renewable and sustainable energy source to replace the important duty cycle of fossil fuels in the global energy system has therefore become a major problem that is now in need of solution. Biomass, which is a novel renewable non-fossil-based carbon source, has outstanding advantages of environmental protection, compatibility, wide sources, etc., and has shown great potential in the production of biomass-based fuels and chemicals. 5-Hydroxymethylfurfural (HMF) is considered to be one of the most important biomass-derived industrial feedstocks at present, and valuable chemicals obtained by the catalysis of HMF can be used for the production of pharmaceuticals, polymers and fine chemicals, and have received increasing attention. Among them, 2, 5-furandicarboxylic acid (FDCA) produced by the oxidation of an aldehyde group of 5-hydroxymethylfurfural and hydroxymethyl has great economic value. The FDCA can be used as an effective substitute for fossil fuel, can reduce environmental pollution caused by production in the plastic industry, and meets the sustainable development requirement of green economy.
The traditional chemical method for preparing FDCA by using HMF catalytic oxidation generally uses noble metals such as gold, platinum, palladium and the like as catalysts, generally requires higher cost, has poor availability, is difficult to apply on a large scale and does not meet the development concept of green environmental protection. The electrocatalytic oxidation method is used for catalyzing the oxidation of HMF to prepare FDCA, and the method has the advantages of being green, free of pollution, mild in reaction condition, low in cost and simple and convenient to operate. Metal Organic Frameworks (MOFs) are a porous crystalline material, and MILs materials are a more specific MOFs material, and different types of MILs materials can be synthesized by coordination of trivalent metal ions (e.g., fe, al, and Cr) with carboxylic acid based ligands (e.g., terephthalic acid, trimesic acid), and have many excellent and unique properties such as ultra-low mass density, easy modification, high specific surface area, and sharp pore size distribution. It is these unique characteristics that make MILs material have been used in many fields such as catalysis, adsorption, hydrogen storage and medicine, and have great application prospects. Scandium (III) ions can form strong metal organic frameworks (MILs), and the method and steps for synthesizing scandium metal organic framework materials are easier and easier to handle. However, scandium ions are much less synthesized in MILs materials than other ions for use. The mesoporous metal-organic framework multi-center catalyst has the advantages of high specific surface area, excellent thermal stability and excellent chemical stability, and can be used for efficiently catalyzing and converting glucose into FDCA under the photo-thermal condition, but the application direction of generating FDCA by electrocatalytic HMF is relatively short about the mesoporous metal-organic framework material at present.
Therefore, how to provide a scandium metal organic framework material, which has a high specific surface area, can achieve the technical effect of effectively catalyzing the conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid, and is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
In view of the problems in the prior art, the technical problem to be solved by the invention is to provide a scandium metal organic framework material which has a high specific surface area, and is used as a catalyst in an electrocatalytic reaction to effectively catalyze the conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid.
In order to achieve the above purpose, the invention provides a preparation method of scandium metal organic framework material, which comprises the following steps:
adding soluble scandium salt and terephthalic acid into an organic solvent, and stirring for 5-30 minutes at a stirring speed of 400-600 rpm to obtain a mixed solution A;
carrying out solvothermal reaction on the obtained mixed solution A to obtain a mixed solution B;
and filtering the obtained mixed solution B by using a filter membrane, collecting solids, washing the collected solids, and drying to obtain the scandium metal organic framework material.
In a first aspect, the performing a solvothermal reaction on the obtained mixed solution a to obtain a mixed solution B specifically includes: and (3) putting the obtained mixed solution A into a reaction kettle, screwing, then reacting for 12-72 hours at the temperature of 60-200 ℃, and cooling the reaction kettle to 15-30 ℃ after the reaction is finished to obtain the mixed solution B.
In the first aspect, the molar and volume ratio of the soluble scandium salt to the organic solvent is (0.4-1) mmol (8-10) mL.
In a first aspect, the organic solvent is N, N-dimethylformamide; or the organic solvent is a mixed solution of anhydrous ethanol and N, N-dimethylformamide with the volume ratio of 5 (3-4).
In a first aspect, the soluble scandium salt specifically comprises: any one or more of scandium chloride, scandium nitrate, a hydrate of scandium chloride, and a hydrate of scandium nitrate.
In the first aspect, the molar ratio of the terephthalic acid to the soluble scandium salt is (0.6-1): 0.4-1
In the first aspect, the pore size of the filter membrane used for filtering is 0.22-0.8 μm; the washing specifically comprises: the collected solids were washed with N, N-dimethylformamide and absolute ethanol respectively 2 to 4 times in sequence.
In the first aspect, the drying temperature of the drying is 60 to 100 ℃, and the drying time of the drying is 10 to 18 hours.
The invention also provides application of the scandium metal organic framework material, wherein the scandium metal organic framework material is used as a working electrode to electrically catalyze 5-hydroxymethylfurfural to convert into 2, 5-furandicarboxylic acid, and the scandium metal organic framework material is prepared by adopting the preparation method of the scandium metal organic framework material.
The beneficial effects are that:
due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages: 1) The scandium metal organic framework material is prepared by solvothermal reaction of soluble scandium salt, and the preparation method is simple, has wide applicability and can be used for mass production; 2) The scandium metal organic framework material prepared by the invention has higher catalytic activity, can catalyze the conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid in the electrocatalytic reaction process, and has higher yield and Faraday efficiency of the 2, 5-furandicarboxylic acid; 3) The scandium metal organic framework material prepared by the invention has high repetition efficiency in the reaction of electrocatalytic conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid, and has higher yield and Faraday efficiency of electrocatalytic conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid for 6 times, no obvious large-scale reduction, excellent stability, repeated utilization and use cost saving; 4) The scandium metal organic framework material prepared by the method has larger specific surface area and smaller aperture, is of an obvious mesoporous structure, and further improves the performance of the scandium metal organic framework material in the process of converting the electrocatalytic 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid; 5) The scandium metal organic framework material prepared by the invention has higher catalytic activity, the condition of the electrocatalytic process is mild, green and pollution-free in the process of converting 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid, the conversion rate of the raw material 5-hydroxymethylfurfural is better, the yield of the product 2, 5-furandicarboxylic acid is higher than 90% and approaches 95%, the Faraday efficiency is higher than 85% and approaches 90%, and the scandium metal organic framework material has good industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present description or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of the yield and Faraday efficiency of the scandium metal organic framework prepared according to examples 1-4 of the present invention to electro-catalyze 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid;
FIG. 2 is a linear sweep voltammogram of scandium metal organic framework prepared according to examples 1-4 of the present invention in the electrocatalytic production of 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural;
FIG. 3 is a BET characterization of the scandium metal organic framework according to example 1 of the present invention;
FIG. 4 is a BET characterization of the scandium metal organic framework according to example 2 of the present invention;
FIG. 5 is a BET characterization of scandium metal organic framework according to example 3 of the present invention;
FIG. 6 is a BET characterization of the scandium metal organic framework prepared according to example 4 of the present invention;
FIG. 7 is an XRD characterization of scandium metal organic frameworks prepared according to examples 1-4 of the present invention;
FIG. 8 is a plot of the product of the scandium metal organic framework electrocatalytic 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid reaction produced according to example 1 of the present invention as a function of coulomb level;
FIG. 9 is a transmission electron microscope image of scandium metal organic framework according to example 1 of the present invention;
FIG. 10 is a graph showing the yield and Faraday efficiency of the scandium metal organic framework prepared according to example 1 of the present invention in catalyzing 5-hydroxymethylfurfural to produce 2, 5-furandicarboxylic acid through 6 electrolysis experiments.
Detailed Description
The technical solutions of the embodiments of the present specification will be clearly and completely described below with reference to the drawings in the embodiments of the present specification, and it is apparent that the described embodiments are only some embodiments of the present specification, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments in this specification are within the scope of the invention.
Example 1
The first embodiment provides a preparation method of a scandium metal organic framework material, which specifically includes: adding soluble scandium salt and terephthalic acid into an organic solvent, and stirring for 5-30 minutes at a stirring speed of 400-600 rpm to obtain a mixed solution A; carrying out solvothermal reaction on the obtained mixed solution A to obtain a mixed solution B; and filtering the obtained mixed solution B by using a filter membrane, collecting solids, washing the collected solids, and drying to obtain the scandium metal organic framework material.
Compared with the prior art, the preparation method of the scandium metal organic framework material provided by the embodiment of the invention has the following advantages: 1) The scandium metal organic framework material is prepared by carrying out solvothermal reaction on the mixture of soluble scandium salt and terephthalic acid, the preparation method is simple, the applicability of the preparation method is wide, and the scandium metal organic framework material can be produced in a large scale; 2) The scandium metal organic framework material prepared by the invention has higher catalytic activity, can catalyze the conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid in the electrocatalytic reaction process, and has higher yield and Faraday efficiency of the 2, 5-furandicarboxylic acid; 3) The scandium metal organic framework material prepared by the invention has high repetition efficiency in the reaction of electrocatalytic conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid, and has higher yield and Faraday efficiency of electrocatalytic conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid for 6 times, no obvious large-scale reduction, excellent stability, repeated utilization and use cost saving; 4) The scandium metal organic framework material prepared by the method has larger specific surface area and smaller aperture, is of an obvious mesoporous structure, and further improves the performance of the scandium metal organic framework material in the process of converting the electrocatalytic 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid; 5) The scandium metal organic framework material prepared by the invention has higher catalytic activity, the condition of the electrocatalytic process is mild, green and pollution-free in the process of converting 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid, the conversion rate of the raw material 5-hydroxymethylfurfural is better, the yield of the product 2, 5-furandicarboxylic acid is higher than 90% and approaches 95%, the Faraday efficiency is higher than 85% and approaches 90%, and the scandium metal organic framework material has good industrial application prospect.
In some possible implementations, the performing a solvothermal reaction on the obtained mixed solution a to obtain a mixed solution B specifically includes: putting the obtained mixed solution A into a reaction kettle, screwing, then reacting for 12-72 hours at the temperature of 60-200 ℃, and cooling the reaction kettle to 15-30 ℃ after the reaction is finished to obtain a mixed solution B; the molar ratio and the volume ratio of the soluble scandium salt to the organic solvent are (0.4-1) mmol (8-10) mL; the organic solvent is N, N-dimethylformamide; or the organic solvent is a mixed solution of anhydrous ethanol and N, N-dimethylformamide with the volume ratio of 5 (3-4).
Specifically, in the solvothermal reaction process, the solvent has a certain influence on the finally obtained product, and the scandium metal organic framework material can be obtained by solvothermal reaction by using N, N-dimethylformamide or a mixed solution of anhydrous ethanol and N, N-dimethylformamide with the volume ratio of 5 (3-4) as an organic solvent to dissolve soluble scandium salt and terephthalic acid; wherein, the scandium metal organic framework material prepared by adopting the mixed solution of anhydrous ethanol and N, N-dimethylformamide with the volume ratio of 5 (3-4) as the organic solvent has better performance.
In some possible implementations, the soluble scandium salt specifically includes: any one or more of scandium chloride, scandium nitrate, a hydrate of scandium chloride, and a hydrate of scandium nitrate; the mole ratio of the terephthalic acid to the soluble scandium salt is (0.6-1) to (0.4-1).
Specifically, scandium chloride, scandium nitrate, hydrates of scandium chloride and hydrates of scandium nitrate can be used as scandium sources of scandium metal organic framework materials, wherein scandium metal organic framework materials prepared by scandium nitrate and terephthalic acid are better in performance.
In some possible implementations, the filter membrane used for the filtration has a pore size of 0.22-0.8 μm; the washing specifically comprises: respectively washing the collected solids with N, N-dimethylformamide and absolute ethyl alcohol for 2-4 times in sequence; the drying temperature of the drying is 60-100 ℃, and the drying time of the drying is 10-18 hours.
Specifically, the solid obtained after filtration by the filter membrane is scandium metal organic framework material mixed with part of unreacted impurity, and the impurity in the scandium metal organic framework material can be washed off by utilizing N, N-dimethylformamide and absolute ethyl alcohol to obtain the scandium metal organic framework material.
Example two
The second embodiment of the invention provides a scandium metal organic framework material, which is prepared by the preparation method in the first embodiment, and a person skilled in the art can understand that the scandium metal organic framework material is prepared by performing solvothermal reaction on a mixture of soluble scandium salt and terephthalic acid, and has the advantages of large specific surface area, high electrocatalytic efficiency and the like. It should be noted that, the scandium metal organic framework material in the second embodiment is prepared by the preparation method according to the first embodiment, so the performance principle of the scandium metal organic framework material in the second embodiment is not described herein, and the detailed part of the description is not limited to the first embodiment.
Example III
The third embodiment of the invention provides an application of a scandium metal organic framework material, which specifically comprises that foam nickel modified by the scandium metal organic framework material is used as a working electrode to electrically catalyze 5-hydroxymethylfurfural to convert the 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid, wherein the scandium metal organic framework material is the scandium metal organic framework material in the second embodiment. The scandium metal organic framework material in the second embodiment is prepared by the preparation method according to one embodiment.
In order to further describe the technical solution of the present application in detail to support the technical problem to be solved by the present application, the following specific examples of the preparation method are described, as examples 1 to 4.
Example 1
Scandium nitrate hydrate of 0.58mmol and terephthalic acid of 0.64mmol were added to a mixed solution of 4mL of N, N-dimethylformamide and 5mL of absolute ethyl alcohol, and stirred at a stirring speed of 500 rpm for 20 minutes to obtain a mixed solution A;
putting the obtained mixed solution A into a high-pressure reaction kettle, screwing, then reacting for 24 hours at the temperature of 80 ℃, and cooling the reaction kettle to 25 ℃ after the reaction is finished to obtain a mixed solution B;
the obtained mixed solution B was filtered with a 0.45 μm filter membrane and the solid was collected, and then the collected solid was washed with N, N-dimethylformamide and absolute ethyl alcohol in this order 3 times, and then the washed solid was dried at 60℃for 12 hours, to obtain scandium metal organic framework material.
Example 2
Adding 0.435mmol of scandium nitrate hydrate, 0.145mmol of scandium chloride hexahydrate and 0.64mmol of terephthalic acid into a mixed solution of 4mL of N, N-dimethylformamide and 5mL of absolute ethyl alcohol, and stirring at a stirring speed of 500 rpm for 20 minutes to obtain a mixed solution A;
putting the obtained mixed solution A into a high-pressure reaction kettle, screwing, then reacting for 24 hours at the temperature of 80 ℃, and cooling the reaction kettle to 25 ℃ after the reaction is finished to obtain a mixed solution B;
the obtained mixed solution B was filtered with a 0.45 μm filter membrane and the solid was collected, and then the collected solid was washed with N, N-dimethylformamide and absolute ethyl alcohol in this order 3 times, and then the washed solid was dried at 60℃for 12 hours, to obtain scandium metal organic framework material.
Example 3
Adding 0.29mmol of scandium nitrate hydrate, 0.29mmol of scandium chloride hexahydrate and 0.64mmol of terephthalic acid into a mixed solution of 4mL of N, N-dimethylformamide and 5mL of absolute ethyl alcohol, and stirring at a stirring speed of 500 rpm for 20 minutes to obtain a mixed solution A;
putting the obtained mixed solution A into a high-pressure reaction kettle, screwing, then reacting for 24 hours at the temperature of 80 ℃, and cooling the reaction kettle to 25 ℃ after the reaction is finished to obtain a mixed solution B;
the obtained mixed solution B was filtered with a 0.45 μm filter membrane and the solid was collected, and then the collected solid was washed with N, N-dimethylformamide and absolute ethyl alcohol in this order 3 times, and then the washed solid was dried at 60℃for 12 hours, to obtain scandium metal organic framework material.
Example 4
Scandium chloride hexahydrate (0.58 mmol) and terephthalic acid (0.64 mmol) were added to a mixed solution of 4mL of N, N-dimethylformamide and 5mL of absolute ethyl alcohol, and the mixture was stirred at a stirring speed of 500 rpm for 20 minutes to obtain a mixed solution A;
putting the obtained mixed solution A into a high-pressure reaction kettle, screwing, then reacting for 24 hours at the temperature of 80 ℃, and cooling the reaction kettle to 25 ℃ after the reaction is finished to obtain a mixed solution B;
the obtained mixed solution B was filtered with a 0.45 μm filter membrane and the solid was collected, and then the collected solid was washed with N, N-dimethylformamide and absolute ethyl alcohol in this order 3 times, and then the washed solid was dried at 60℃for 12 hours, to obtain scandium metal organic framework material.
The scandium metal organic framework materials prepared according to examples 1 to 4 were used and tested as follows:
electrolytic testing of electrocatalytic oxidation HMF: firstly, preparing a working electrode, and performing an electrocatalytic reaction test by using the scandium metal organic framework material modified porous foam nickel prepared in examples 1-4 as the working electrode, wherein the preparation method of the scandium metal organic framework material modified porous foam nickel specifically comprises the following steps: 10mg of scandium metal organic framework material prepared by the method is taken and ground to obtain scandium metal organic framework material powder; dispersing 100 mu L of Nafion solution with the concentration of 5wt% into 900 mu L of absolute ethyl alcohol, adding the absolute ethyl alcohol into the obtained scandium metal organic framework material powder, performing ultrasonic treatment for 30min to form uniform ink-shaped dispersion liquid, taking the dispersion liquid, dripping the dispersion liquid onto 1cm multiplied by 2cm foam nickel, irradiating and drying the foam nickel by an infrared lamp, and finally placing the foam nickel in air for drying to obtain scandium metal organic framework material modified porous foam nickel; then, an electrocatalytic reaction test is carried out, wherein the electrocatalytic reaction test comprises the following steps: adopting a three-electrode system to perform catalytic oxidation in an H-type electrolytic tank; the porous foam nickel modified by scandium metal organic framework material is used as a working electrode, a mercury/mercury oxide electrode is used as a reference electrode, a platinum wire is used as a counter electrode, 10mL of catholyte in a catholyte chamber is 1mol/L potassium hydroxide aqueous solution, 10mL of anolyte in an anolyte chamber is 1mol/L potassium hydroxide aqueous solution containing 5-hydroxymethylfurfural, the concentration of 5-hydroxymethylfurfural is 0.01mol/L, an electrocatalytic reactor is formed by the working electrode, the reference electrode, the counter electrode, the catholyte and the anolyte, 1.48V of voltage is applied to an anode, then sampling tests are carried out on different electric charges in the reaction process by using a high-performance liquid chromatograph, and the yield and Faraday efficiency of 2, 5-furandicarboxylic acid are calculated according to the results, and the results are shown in figure 1.
Linear sweep voltammetry test in electrocatalytic process: the porous foam nickel modified by scandium metal organic framework material in the test of the electrocatalytic reaction is used as a working electrode, a mercury/mercury oxide electrode is used as a reference electrode, a platinum wire is used as a counter electrode, 5mL of catholyte in a catholyte chamber is 1mol/L potassium hydroxide aqueous solution, 5mL of anolyte in an anolyte chamber is 1mol/L potassium hydroxide aqueous solution containing 5-hydroxymethylfurfural, wherein the electrocatalytic reactor formed by 0.01mol/L of 5-hydroxymethylfurfural is used for linear sweep voltammetry curve test, the voltage interval applied to an anode is 0-0.7V (v.s.Hg/HgO) in the test process, the voltage sweep speed is 5mV/s, the change value of the test current along with the voltage is plotted, and the result is shown in figure 2.
BET test: characterization tests are carried out on scandium metal organic framework materials prepared in examples 1-4 by using a specific surface area and porosity analyzer (BET), and the results are shown in figures 3-6.
XRD test: the scandium metal organic framework materials prepared in examples 1-4 were subjected to characterization test by using an X-ray diffraction analyzer, and the characterization results are shown in FIG. 7.
Product distribution test as a function of coulomb during electrocatalytic reaction: in the above application in electrolytic test, the high performance liquid chromatography instrument was used to sample and test different amounts of electric charges during the reaction, and the result is shown in fig. 8.
TEM test: the scandium metal organic framework material prepared in example 1 was subjected to characterization test by using a transmission electron microscope, and the characterization result is shown in fig. 9.
And (3) cyclic test: the scandium metal organic framework material prepared in example 1 was subjected to the test for electrocatalytic conversion of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid by using the test method applied to the electrocatalytic reaction, the electrolytic test under the same voltage (1.48V) was repeated 6 times, and the yield and faraday efficiency of 2, 5-furandicarboxylic acid were calculated according to the results, and the results are shown in fig. 10.
As can be seen from the analysis of the yield and Faraday efficiency chart of the scandium metal organic framework electrocatalytic 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid, which is shown in the figure 1, the porous foam nickel modified by the scandium metal organic framework material prepared in the example 1 is used as a working electrode to electrocatalytic 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid, the yield of the 2-5-furandicarboxylic acid is approximately 95%, the yields of the examples 2-4 are all less than 90%, and the yield of the 2, 5-furandicarboxylic acid is in high-low order: example 1 > example 2 > example 3 > example 4; meanwhile, the faraday efficiency of example 1 is significantly better than examples 2-4, and the faraday efficiency is ranked as follows: example 1 > example 2 > example 3 > example 4.
From an analysis of the linear sweep voltammogram of the scandium metal-organic framework of fig. 2 in the electrocatalytic production of 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural, the voltage of example 1 was significantly shifted to the left compared to the other, which means that a higher current density could be achieved at the same voltage. Therefore, compared with scandium metal organic frameworks prepared in examples 2-4, the scandium metal organic framework in example 1 has a good catalytic effect.
As can be seen from the BET diagram analysis of the scandium metal organic frameworks of FIGS. 3 to 6, the specific surface areas of the scandium metal organic frameworks prepared in examples 1 to 4 were 283.2m, respectively 2 /g、122.3m 2 /g、90.5m 2 /g、68.2m 2 And (3) sequencing the specific surface area as follows: example 1 > example 2 > example 3 > example 4; higher reaction rate and catalytic activity can be obtained by high specific surface area. Meanwhile, as can be seen from FIGS. 3 to 6, the pore size distribution is smaller than 30nm, and the pore size is smaller.
As can be seen from the XRD characterization diagram analysis of the scandium metal organic framework of fig. 7, examples 1 and examples 2, 3, and 4 do not belong to the same scandium metal organic framework, and the crystal forms have a certain gap.
As can be seen from an analysis of the graph of the change in coulomb quantity of the scandium metal-organic framework electrocatalytic reaction for producing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural prepared in example 1 of fig. 8, since the scandium metal-organic framework electrocatalytic reaction for producing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural is divided into two reaction pathways, the first reaction pathway is that 5-Hydroxymethylfurfural (HMF) is oxidized into 2, 5-furandicarboxaldehyde (DFF), then oxidized into 5-formyl-2-furancarboxylic acid (FFCA) and finally oxidized into 2, 5-furandicarboxylic acid (FDCA); the second reaction route is that of oxidizing 5-hydroxymethyl furfural (HMF) into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), then oxidizing 5-formyl-2-furancarboxylic acid (FFCA) and finally oxidizing 2, 5-furandicarboxylic acid (FDCA), and the figure shows that the scandium metal organic framework material prepared in example 1 is mainly the first reaction route of electrocatalytically oxidizing 5-hydroxymethyl furfural into 2, 5-furandicarboxylic acid.
As can be seen from the analysis of the transmission electron microscope of the scandium metal organic framework prepared in example 1 of fig. 9, the scandium metal organic framework prepared in example 1 of the present invention has a rhombohedral structure, and a regular shape.
According to the analysis of the yield and Faraday efficiency chart of the scandium metal organic framework prepared in the example 1 in the figure 10 for catalyzing and oxidizing 5-hydroxymethylfurfural to generate 2, 5-furandicarboxylic acid through 6 times of electrocatalytic experiments, the yield and Faraday efficiency of the scandium metal organic framework prepared in the example 1 after repeated 6 times of cyclic electrolysis tests are not obviously reduced in large scale and float at about 90%, and the result shows that the scandium metal organic framework material has good catalytic effect and excellent stability.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. A method for preparing scandium metal organic framework material, which is characterized by comprising the following steps:
adding soluble scandium salt and terephthalic acid into an organic solvent, and stirring for 5-30 minutes at a stirring speed of 400-600 rpm to obtain a mixed solution A;
carrying out solvothermal reaction on the obtained mixed solution A to obtain a mixed solution B;
and filtering the obtained mixed solution B by using a filter membrane, collecting solids, washing the collected solids, and drying to obtain the scandium metal organic framework material.
2. The method for preparing scandium metal organic framework material according to claim 1, wherein the step of performing solvothermal reaction on the obtained mixed solution a to obtain a mixed solution B specifically comprises:
and (3) putting the obtained mixed solution A into a reaction kettle, screwing, then reacting for 12-72 hours at the temperature of 60-200 ℃, and cooling the reaction kettle to 15-30 ℃ after the reaction is finished to obtain the mixed solution B.
3. The method for preparing scandium metal organic framework material according to claim 2, wherein: the molar ratio and the volume ratio of the soluble scandium salt to the organic solvent are (0.4-1) mmol (8-10) mL.
4. A method for preparing scandium metal organic framework material according to claim 3, wherein:
the organic solvent is N, N-dimethylformamide;
or alternatively, the first and second heat exchangers may be,
the organic solvent is a mixed solution of anhydrous ethanol and N, N-dimethylformamide with the volume ratio of 5 (3-4).
5. The method for preparing scandium metal organic framework material according to claim 4, wherein the soluble scandium salt specifically comprises:
any one or more of scandium chloride, scandium nitrate, a hydrate of scandium chloride, and a hydrate of scandium nitrate.
6. The method for preparing scandium metal organic framework material according to claim 5, wherein: the mole ratio of the terephthalic acid to the soluble scandium salt is (0.6-1) to (0.4-1).
7. The method for preparing scandium metal organic framework material according to claim 6, wherein: the pore diameter of the filter membrane used for filtering is 0.22-0.8 mu m; the washing specifically comprises: the collected solids were washed with N, N-dimethylformamide and absolute ethanol respectively 2 to 4 times in sequence.
8. The method for preparing scandium metal organic framework material according to claim 7, wherein: the drying temperature of the drying is 60-100 ℃, and the drying time of the drying is 10-18 hours.
9. A scandium metal organic framework material according to any one of claims 1-8, characterized in that it is prepared by a method for preparing a scandium metal organic framework material.
10. The application of the scandium metal organic framework material is characterized in that foam nickel modified by the scandium metal organic framework material is used as a working electrode to electrically catalyze 5-hydroxymethylfurfural to convert into 2, 5-furandicarboxylic acid, and the scandium metal organic framework material is the scandium metal organic framework material according to claim 9.
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| CN119823406A (en) * | 2025-01-08 | 2025-04-15 | 中国人民解放军陆军工程大学 | Scandium-based MOF crystal material, preparation method and application thereof |
| CN119823406B (en) * | 2025-01-08 | 2026-01-02 | 中国人民解放军陆军工程大学 | A scandium-based MOF crystal material, its preparation method and its application |
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