CN115746323A - Preparation method and electrocatalysis application of Fe-based metal organic framework material - Google Patents
Preparation method and electrocatalysis application of Fe-based metal organic framework material Download PDFInfo
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Abstract
The invention discloses a preparation method and electrocatalysis application of a Fe-based metal organic framework material, belonging to the field of metal organic framework materials. The preparation method is a solvothermal method, and the Fe-based metal organic framework material is obtained by mixing and heating ferric salt, 5-nitrobenzimidazole, pyromellitic acid, N-dimethylformamide solution and the like for reaction, and then sequentially cooling, washing, filtering and drying. The Fe-based metal organic framework material is applied to an electrolytic water cathode reaction in a strong acid environment as a catalyst, has low cost and good catalytic effect, can stably exist in the strong acid environment, and breaks through the bottleneck encountered in the electrocatalytic application process of the current Fe-based metal organic framework material.
Description
Technical Field
The invention belongs to the field of metal organic framework materials, and relates to a preparation method and electrocatalysis application of a Fe-based metal organic framework material.
Background
In modern society, with the development of times, fossil fuels (coal, oil and natural gas) are gradually reduced, and it is difficult to meet the long-term needs and use of human beings, and the naturally formed fossil fuels emit a large amount of harmful gases (carbon dioxide, nitrogen oxides and the like) in the combustion process, thereby causing serious environmental pollution to the living homes of human beings.
The most effective way to solve the problem is to develop new energy sources that are renewable and clean, gradually replacing the fossil energy sources used at present. The new energy sources developed at present are clean energy sources such as wind energy, tidal energy, solar energy and hydrogen energy. Among them, electrolyzed water is considered as one of the most promising energy sources in the present day, and is called as a future energy source by researchers. The hydrogen production by the electrolysis of acid water is an important subject of research and development at the present stage, and one of the main reasons of large energy consumption and low efficiency in the water electrolysis process is that the oxygen evolution overpotential is high and the stability of the electrode is poor, which is a problem to be solved urgently. Therefore, it is important to develop an electrocatalytic hydrogen evolution reaction catalyst which is efficient, abundant in source, economical, and simple.
Organometallic Frameworks (MOFs) are a new class of porous materials that combine metal ions with organic ligaments to form their basic structure, with high crystallinity and order quality. MOFs materials are distinguished from other porous polymer materials by their high specific surface area, pore size and topology, adjustable chemical composition and surface function. The MOFs of the porous channel element may be combined with active site points having an oxidative contraction function to make active sites more effective, compared to conventional heterogeneous catalysts. However, the low electrical conductivity and chemical stability severely limit its application in the field of electrocatalysis.
The electrolyzed water has two half-reactions constituting its total reaction, respectively, anodic oxidation reaction (OER) and cathodic reduction reaction (HER), where OER has a greater overpotential than HER. Some precious metal catalysts are currently considered to be efficient OER catalysts, but since a great deal of cost is required to prepare an effective and widely-usable OER catalyst, development of an inexpensive, efficient and stable electrocatalyst is urgently required.
Disclosure of Invention
The invention aims to solve the technical problems that the existing Fe-based metal organic framework material resists strong base but does not resist strong acid and the catalyst used in the cathode reduction reaction in the prior art has high cost.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of an Fe-based metal organic framework material is a solvothermal method and comprises the following steps:
s1, uniformly mixing iron salt, 5-nitrobenzimidazole, pyromellitic acid, N-dimethylformamide, tetrapropylammonium hydroxide and trifluoroacetic acid to obtain a mixed solution.
Preferably, the iron salt is ferric chloride hexahydrate or ferric nitrate nonahydrate.
Preferably, the concentration range of the iron salt in the mixed solution is 12.0-24.0 g/L, the concentration range of the 5-nitrobenzimidazole in the mixed solution is 4.0-8.0 g/L, the concentration range of the pyromellitic acid in the mixed solution is 8.0-24.0 g/L, the concentration range of the N, N-dimethylformamide in the mixed solution is 379.5-758.9 g/L, the concentration range of the tetrapropylammonium hydroxide in the mixed solution is 200.0-400.0 g/L, and the concentration range of the trifluoroacetic acid in the mixed solution is 184.2-200.2 g/L.
Preferably, the tetrapropylammonium hydroxide is used for providing an alkaline environment required by synthesis, controlling the pore size of the synthesized iron-based metal organic framework material and promoting pyromellitic acid guest molecules to enter to form a coordination compound.
Preferably, the trifluoroacetic acid is a catalyst for reaction, so as to promote the crystallization process and improve the crystallinity of the Fe-based metal organic framework material.
And S2, sealing the mixed solution, and then carrying out heating reaction to obtain a solid-liquid mixture.
Preferably, the temperature of the heating reaction is 120-140 ℃, the time of the heating reaction is 24-48 h, and the heating rate of the heating reaction is 3-5 ℃/min.
And S3, sequentially cooling, washing, filtering and drying the solid-liquid mixture to obtain the Fe-based metal organic framework material.
Preferably, the cooling process finally cools the temperature to room temperature.
Preferably, the washing process is performed using a solution of N, N-dimethylformamide.
Preferably, the filtration process uses an organic microporous filter membrane with the pore diameter of 0.22 μm to complete suction filtration through a suction filtration machine.
Preferably, in the drying process, 1-5 drops of anhydrous methanol are dropped into the solid obtained by filtering to accelerate drying, and then the solid is placed in a 60 ℃ oven for drying.
Use of an Fe-based metal-organic framework material as a catalyst in an electrocatalytic cathode reaction, for use in a strongly acidic environment.
Preferably, the chemical substance on the surface of the Fe-based metal organic framework material does not exist a great amount of H in a strong acid solution with the pH = 0-1 + Free ions of reaction, so the material is resistant to strong acids and structurally stable in acidic environments.
Compared with the prior art, the technical scheme provided by the invention has the beneficial effects that at least:
the Fe-based metal organic framework material prepared by the solvothermal method is novel in structure and resistant to strong acid, and compared with the high-stability Fe-based metal organic framework material synthesized by the prior art, the high-stability Fe-based metal organic framework material generally has the oxygen evolution catalytic performance under the alkaline condition (pH =13 KOH), is good in stability in an alkaline solution, and does not pay much attention to whether the Fe-based metal organic framework material is stable in an acidic solution. The Fe-based metal organic framework material provided by the invention can stably exist in a strong acid solution with the pH = 0-1, so that the bottleneck encountered in the electrocatalytic application process of the current Fe-based metal organic framework material can be broken through.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a three-dimensional structural view of a Fe-based metal-organic framework material synthesized in example 1 of the present invention;
FIG. 2 is a comparative XRD pattern before and after acid leaching of Fe-based metal organic framework material synthesized in example 1 of the present invention: (a) is a spectrum of a pure Fe-based metal organic framework material; (b) Is a spectrum of Fe-based metal organic framework material soaked at pH = 0; (c) Is a spectrum of Fe-based metal organic framework material soaked at pH = 1;
fig. 3 is an XRD contrast before and after the Fe-based metal-organic framework material synthesized in example 1 of the present invention adsorbs metal ions: (a) is a spectrum of a pure Fe-based metal organic framework material; (b) For soaking in Ni (NO) 3 ) 2 The spectrum of the Fe-based metal organic framework material of (a); (c) For soaking in Co (NO) 3 ) 2 The spectrum of the Fe-based metal organic framework material of (a); (d) For soaking in Ni (NO) 3 ) 2 With Co (NO) 3 ) 2 A spectrum of the Fe-based metal organic framework material of the mixed solution;
FIG. 4 shows IR spectra before and after acid leaching of Fe-based metal organic framework material synthesized in example 1 of the present invention: (a) infrared spectra of pure Fe-based metal organic framework materials; (b) Soaking the Fe-based metal organic framework material in a pH =0HCl solution for 6 h;
FIG. 5 is a photograph synthesized in example 1 of the present inventionThe IR spectra before and after Ni ion adsorption of the Fe-based metal organic framework material are as follows: (a) is the infrared spectrum of the pure Fe-based metal organic framework material; (b) Soaking Fe-based metal organic frame material in Ni (NO) 3 ) 2 Infrared spectrum of 48h in solution;
FIG. 6 shows IR spectra before and after Co ion adsorption of Fe-based metal organic framework material synthesized in example 1 of the present invention: (a) is the infrared spectrum of the pure Fe-based metal organic framework material; (b) Soaking Fe-based metal organic frame material in Co (NO) 3 ) 2 Infrared spectrum of the solution for 48 h;
fig. 7 is a HER curve comparison graph of the Fe-based metal organic framework material synthesized in example 1 of the present invention, wherein the pure Fe-based metal organic framework material is loaded on a nickel mesh, and a blank nickel mesh, the HER performance of the electrocatalyst is shown when pH = 0: (a) is a curve of a pure blank nickel screen; (b) Curve of Fe-based metal organic framework material-blank nickel mesh;
FIG. 8 is the Ni-impregnated Fe-based metal-organic framework material synthesized in example 1 of the present invention 2+ Solution, soaking in Co 2+ Solution and simultaneous immersion in Ni 2+ And Co 2+ HER curves with solutions loaded on nickel mesh in pH =0 solutions, fe-based metal organic framework materials synthesized electrocatalytic HER performance at pH = 0: (a) For soaking in Ni 2+ Curves in solution; (b) For soaking in Co 2+ Curves in solution; (c) For soaking in Co 2+ And Ni 2+ Curves in solution;
FIG. 9 shows the Fe-based metal-organic framework material synthesized in comparative example 1 of the present invention immersed in Ni 2+ Solution, soaking in Co 2+ Solution and simultaneous immersion in Ni 2+ And Co 2+ HER curve of solution loaded on nickel mesh in pH =0 solution, current Fe-based metal organic framework material electrocatalytic HER performance at pH = 0: (a) For soaking in Ni 2+ Curves in solution; (b) For soaking in Co 2+ Curves in solution; (c) For soaking in Co 2+ And Ni 2+ Curves in solution.
Detailed Description
The following describes technical solutions and technical problems to be solved in the embodiments of the present invention with reference to the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the patent of the invention, and not all embodiments.
Example 1
S1, weighing 0.03g of ferric chloride hexahydrate, 0.01g of 5-nitrobenzimidazole and 0.03g of pyromellitic acid in a reaction bottle, dissolving in a mixed solvent of 1mL of N, N-dimethylformamide, 0.5mL of tetrapropylammonium hydroxide and 0.3mL of trifluoroacetic acid, and stirring at room temperature for 15min to uniformly mix to obtain a mixed solution.
S2, placing the reaction bottle filled with the mixed solution in an oven, wherein the heating rate is 3 ℃/min, and the heating reaction temperature is 120 ℃.
And S3, after the reaction is finished and the temperature of the system is reduced to room temperature, observing the morphological characteristics of the generated product under a microscope, adding a solvent, washing, performing suction filtration by using a Buchner funnel, and drying the mixture in a 60 ℃ drying oven to obtain the red Fe-based metal organic framework material.
Example 2
S1, weighing 0.06g of ferric chloride hexahydrate, 0.02g of 5-nitrobenzimidazole and 0.06g of pyromellitic acid into a reaction bottle, dissolving in a mixed solvent of 2mL of N, N-dimethylformamide, 1mL of tetrapropylammonium hydroxide and 0.3mL of trifluoroacetic acid, and stirring at room temperature for 15min to uniformly mix to obtain a mixed solution.
S2, placing the reaction bottle filled with the mixed solution in an oven, wherein the heating rate is 4 ℃/min, and the heating reaction temperature is 125 ℃.
And S3, after the reaction is finished and the temperature of the system is reduced to room temperature, adding a solvent, washing, performing suction filtration by using a Buchner funnel, and drying the mixture in a 60 ℃ drying oven to obtain the red Fe-based metal organic framework material.
Example 3
S1, weighing 0.03g of ferric nitrate nonahydrate, 0.02g of 5-nitrobenzimidazole and 0.02g of pyromellitic acid in a reaction bottle, dissolving in a mixed solvent of 1mL of N, N-dimethylformamide, 0.5mL of tetrapropylammonium hydroxide and 0.3mL of trifluoroacetic acid, and stirring at room temperature for 15min to uniformly mix to obtain a mixed solution.
S2, placing the reaction bottle filled with the mixed solution in an oven, wherein the heating rate is 5 ℃/min, and the heating reaction temperature is 120 ℃.
And S3, after the reaction is finished and the temperature of the system is reduced to room temperature, adding a solvent, washing, performing suction filtration by using a Buchner funnel, and drying the mixture in a 60 ℃ drying oven to obtain the red Fe-based metal organic framework material.
Comparative example 1
An existing commercially available Fe-based metal organic framework material is used.
The Fe-based metal organic framework materials of example 1 and comparative example 1 were analyzed with respect to structural morphology, acid stability, structural stability and electrocatalytic hydrogen production performance, and the results were as follows:
(1) Structural morphology identification analysis
FIG. 1 is a three-dimensional structure diagram of the Fe-based metal organic framework material synthesized in example 1 of the present invention. The structure was found to be a novel structure.
(2) Acid resistance stability analysis
And (3) after drying, characterizing the pure Fe-based metal organic framework material by using X-ray diffraction, then taking a small amount of the material to soak in HCl solutions with the pH =0 and the pH =1 for 6h, and drying the acid-soaked sample and then performing X-ray diffraction and infrared spectrum analysis to compare with the sample before soaking acid.
FIG. 2 is a comparative XRD pattern of Fe-based metal organic framework material synthesized in example 1 of the present invention before and after acid leaching.
FIG. 4 is an IR chart of the Fe-based metal-organic framework material synthesized in example 1 of the present invention before and after acid leaching.
As can be seen from the figure, it is clear that the peak positions are almost consistent, the peak types are similar, and the structure of the Fe-based metal organic framework material is not damaged after soaking in HCl solution with pH =0 and pH =1, and the Fe-based metal organic framework material has good acid resistance stability.
(3) Analysis of structural stability
And after drying, characterizing the pure Fe-based metal organic framework material by using X-ray diffraction, then taking a small amount of material to soak in a Ni ion salt solution and a Co ion salt solution for 48 hours respectively, and drying the acid-soaked sample to perform X-ray diffraction and infrared spectrum analysis for comparison with before pickling.
FIG. 3 is an XRD contrast before and after the Fe-based metal-organic framework material synthesized in example 1 of the present invention adsorbs metal ions.
FIG. 5 shows IR spectra before and after Ni ions are adsorbed by the Fe-based metal organic framework material synthesized in example 1 of the present invention.
FIG. 6 shows IR spectra before and after Co ions are adsorbed by the Fe-based metal organic framework material synthesized in example 1 of the present invention.
As can be seen from the figure, the characteristic absorption peak after soaking the metal salt is consistent with the wave number of the characteristic absorption peak of the pure Fe-based metal organic framework material, which indicates that the original structure is still maintained after adsorbing the metal ions, and further indicates that the prepared catalyst has good structural stability.
(4) Analysis of electrocatalytic hydrogen production performance
Accurately weighing 0.0100g of Fe-based metal organic framework catalyst prepared in example 1, adding 350. Mu.L of absolute ethanol, 100. Mu.L of deionized water and 50. Mu.L of membrane solution into a small centrifuge tube, ultrasonically cleaning for 30min, and depositing 20. Mu.L of dispersion solution on an electrode substrate (nickel mesh, geometric area of 0.5 cm) for multiple times 2 ) The upper electrode is used as a working electrode, a Pt electrode is used as an auxiliary electrode, ag/AgCl is used as a reference electrode, and the concentration is 0.5 mol.L -1 H 2 SO 4 (pH = 0) aqueous solution as electrolyte solution, and CHI760E type electrochemical workstation of Housekeeping instrument was selected to respond to photocurrent of related substances and components.
When the catalyst is characterized by linear sweep voltammetry in the experiment, the range of the applied electrode potential is-1.2V-0.2V, and the scanning rate is 0.005 V.s -1 。
FIG. 7 shows that the Fe-based metal organic framework material synthesized in example 1 of the present invention is loaded on a nickel mesh and a blank nickel mesh (NF) in an acidic solution of 0.5 mol. L -1 H 2 SO 4 The comparative graph of HER curve of the catalytic activity of the electro-catalytic hydrogen production shows that the current density reaches 10mA cm -2 When the material is used, the overpotential of pure NF is 243mV, and the overpotential of Fe-based metal organic framework material loaded on NF is 191mV, which is 52mV lower than that of pure NF.
FIG. 8 is synthesized in example 1 of the present inventionSoaking Fe-based metal organic frame material in Ni 2+ Solution, co 2+ Solution and simultaneous immersion in Ni 2+ And Co 2+ HER curves in pH =0 solutions with solutions loaded on nickel mesh. As can be seen from the graph, the current density reached 10mA cm -2 In the process, the Fe-based metal-organic framework material adsorbs Ni 2+ Adsorbing Co 2+ And adsorption of Ni 2+ And Co 2+ The overpotentials of the solutions were 124, 134 and 107mV, respectively, indicating simultaneous adsorption of Ni 2+ And Co 2+ The electrocatalytic effect of the mixed solution is optimal. Compared with the pure Fe-based metal organic framework material of FIG. 7, ni is adsorbed 2+ And Co 2+ After the metal ions are adsorbed, the electrocatalytic performance is obviously improved, which shows that the HER catalytic activity of the pure Fe-based metal organic framework material is improved after the metal ions are adsorbed.
FIG. 9 shows the Fe-based metal-organic framework material of comparative example 1 soaked in Ni 2+ Solution, co 2+ Solution and simultaneous immersion in Ni 2+ And Co 2+ HER curves in pH =0 solutions with solutions loaded on nickel mesh. As can be seen from the graph, the current density reached 10mA cm -2 In the process, the Fe-based metal-organic framework material adsorbs Ni 2+ Adsorbing Co 2+ And adsorption of Ni 2+ And Co 2+ The overpotentials of the solutions were 170, 149, and 112mV, respectively. Under the same conditions, the overpotential values are all larger than that of the Fe-based metal organic framework material synthesized in the embodiment 1 of the invention, so that the Fe-based metal organic framework material provided by the embodiment 1 of the invention has more excellent properties in the aspect of electrocatalytic hydrogen production performance.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A preparation method of an Fe-based metal organic framework material is a solvothermal method, and is characterized by comprising the following steps of:
s1, uniformly mixing iron salt, 5-nitrobenzimidazole, pyromellitic acid, N-dimethylformamide, tetrapropylammonium hydroxide and trifluoroacetic acid to obtain a mixed solution;
s2, sealing the mixed solution, and then carrying out heating reaction to obtain a solid-liquid mixture;
and S3, sequentially cooling, washing, filtering and drying the solid-liquid mixture to obtain the Fe-based metal organic framework material.
2. The method according to claim 1, wherein in step S1, the iron salt is ferric chloride hexahydrate or ferric nitrate nonahydrate;
the concentration range of the iron salt in the mixed solution is 12.0-24.0 g/L, the concentration range of the 5-nitrobenzimidazole in the mixed solution is 4.0-8.0 g/L, the concentration range of the pyromellitic acid in the mixed solution is 8.0-24.0 g/L, the concentration range of the N, N-dimethylformamide in the mixed solution is 379.5-758.9 g/L, the concentration range of the tetrapropylammonium hydroxide in the mixed solution is 200.0-400.0 g/L, and the concentration of the trifluoroacetic acid in the mixed solution is 184.2-200.2 g/L.
3. The method according to claim 1, wherein in step S2, the temperature of the heating reaction is 120 to 140 ℃, the time of the heating reaction is 24 to 48 hours, and the heating rate of the heating reaction is 3 to 5 ℃/min.
4. The method according to claim 1, wherein in step S3, the cooling process is finally cooled to room temperature; the washing process uses N, N-dimethylformamide solution for washing;
in the filtering process, an organic microporous filter membrane with the aperture of 0.22 mu m is used for completing suction filtration through a suction filter;
in the drying process, 1-5 drops of anhydrous methanol are dropped into the solid obtained by filtration to accelerate drying, and then the solid is placed in a 60 ℃ oven to be dried.
5. An Fe-based metal-organic framework material obtained by the production method according to any one of claims 1 to 4.
6. Use of the Fe-based metal organic framework material according to claim 5, wherein the Fe-based metal organic framework material is used as a catalyst in an electrocatalytic cathode reaction in a strongly acidic environment.
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