CN113751037A - Metal carbide Fe combined with organic metal framework3C/Mo2Preparation and use of C - Google Patents
Metal carbide Fe combined with organic metal framework3C/Mo2Preparation and use of C Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 19
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 229960003638 dopamine Drugs 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- -1 iron salt inorganic compound Chemical class 0.000 claims abstract description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 4
- 239000002135 nanosheet Substances 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 5
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- 238000009826 distribution Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010411 electrocatalyst Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract description 2
- 150000001875 compounds Chemical group 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 11
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- 238000010438 heat treatment Methods 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 238000001514 detection method Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000710013 Lily symptomless virus Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000000635 electron micrograph Methods 0.000 description 1
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method and application of metal carbide combined with a metal organic framework, which has a unique compound structure of nanocubes and nanosheets. The preparation method of the material comprises the following steps: 1) firstly, compounding an iron salt inorganic compound and an organic high molecular material to obtain Fe-MOFs of an iron-based metal organic framework; 2) mixing Fe-MOFs and a molybdate according to a certain mass ratio, uniformly stirring, and naturally evaporating and drying water at 60 ℃; 3) uniformly dispersing the sample prepared in the step 3) and dopamine in an alkaline solution according to a certain mass ratio, stirring, collecting the precipitate, and centrifugally drying; 4) finally, the dried sample prepared in the step 3) is put in nitrogen gasAnnealing treatment under atmosphere to obtain the final product Fe3C/Mo2C. The electrocatalyst prepared by the invention is applied to Oxygen Evolution Reaction (OER) in electrolyzed water, compared with commercialized RuO2、IrO2And most other electrocatalysts, the material prepared by the invention has higher reaction activity, catalytic performance and cycling stability.
Description
Technical Field
The invention relates to the field of organic metal frameworks and electrocatalysis, in particular to preparation of organic metal frameworks, preparation of an electrocatalytic oxygen evolution electrode material and performance exploration of the electrocatalytic oxygen evolution electrode material.
Background
Future economic and strategic developments in human society leave sustainable energy systems. As a renewable alternative energy source to fossil fuels, hydrogen energy has clean, efficient, and friendly characteristics, and can play an important role in green energy and chemical conversion. Recently, more and more hydrogen evolution reaction catalysts have been reported, and in addition, they have conducted extensive studies on electrochemical water decomposition. Electrochemical water splitting is divided into two half-reactions: hydrogen Evolution Reaction (HER), Oxygen Evolution Reaction (OER), wherein the development of electrochemical water splitting is severely limited due to higher overpotential and poorer cycle performance in the electrochemical reaction of OER.
The effective oxygen evolution catalysts found to date are: (1) noble metal oxides, e.g. IrO2And RuO2Etc.; (2) perovskite materials with catalytic activity, e.g. LaCoO4And PrCoO4Etc.; (3) metal oxides, e.g. Co3O4And NiO2And the like. These materials are materials with excellent performance in the electrolytic water oxygen evolution reaction, but still have some problems which cannot be solved in a short time, such as expensive precious metals, low reserves, low conductivity of perovskite materials and the like. It has been shown that the activity and cycling stability of electrocatalysts in hydrolysis reactions are related to their microscopic crystal size structure. In recent years, research reports about Metal Organic Framework (MOF) materials have been widely applied to electrochemical hydrolysis reactions. The materials have a hollow structure, high material compatibility and extremely high size controllability, so that the materials can achieve high activity, good conductivity and stable cycle performance in catalytic reaction. However, the metal organic framework has low catalytic performance and needs to be further compounded with other materials.
Therefore, it is of great significance to research and develop an OER electrode catalyst with higher activity, conductivity and low price and abundant reserves.
Disclosure of Invention
The invention provides an oxygen evolution reaction electrocatalyst combined with a metal organic framework, which aims to solve the problem that a common catalyst in the prior art is low in catalytic performance in an OER reaction process.
The invention also provides an oxygen evolution reaction electrocatalyst combined with the organic metal framework, which is prepared by the method and has a unique nanocube and nanosheet composite structure and OER activity.
The invention also provides the oxygen evolution reaction electrocatalyst combined with the organic metal framework, which is prepared by the method and has good conductivity and cycling stability.
The experimental scheme adopted by the invention to solve the technical problems is as follows:
an electrocatalyst for oxygen evolution reactions, characterized in that said catalyst is a composite material consisting of a metal organic framework and a metal carbide; the metal carbide of the material is interacted on the surface of the composite metal organic framework through molecules to form a lamellar structure and be compounded with a cubic structure with a certain shape.
In the technical scheme, the metal carbide is prepared by coating and calcining metal salt carbon.
The oxygen evolution reaction electrocatalyst is prepared by firstly preparing a required metal organic framework, preparing a precursor from the metal organic framework and metal salt with different mass ratios, and then carrying out heat treatment on the precursor to obtain a product of the lamellar structure and a cubic structure with a certain shape.
In the above technical scheme, the ratio of the metal organic framework to the metal salt is 2: 1, 1: 2, 1: 4.
A preparation method of an oxygen evolution reaction electrocatalyst combined with a metal organic framework comprises the following steps:
(1) compounding an iron salt inorganic compound and an organic polymer material, uniformly stirring, heating at constant temperature, centrifuging, collecting precipitate, cleaning and drying to obtain the Fe-MOFs of the iron-based metal organic framework.
(2) Mixing the iron-based metal organic frame prepared in the step (1) with molybdate according to a certain mass ratio, then carrying out ultrasonic dispersion, and then stirring at a certain temperature until water is evaporated, so that the molybdate is coated on the surface of Fe-MOFs to form Fe-MOFs/molybdate.
(3) And (3) uniformly dispersing the dried sample obtained in the step (2) and dopamine in an alkaline solution according to a certain mass ratio, stirring for a certain time, finally collecting and cleaning the precipitate, and drying in vacuum.
(4) And (4) annealing the product obtained in the step (3) at a high temperature for a certain time under the protection of a nitrogen atmosphere to obtain a final product.
In the above technical scheme, the iron salt selected in step (1) includes ferric nitrate nonahydrate, ferric chloride hexahydrate, potassium ferricyanide and the like, and the organic polymer material includes polyvinylpyrrolidone, terephthalic acid, trimesic acid and the like. Preferably, potassium ferricyanide and polyvinylpyrrolidone are used in the present invention.
In the step (1), the constant temperature heating is carried out in water bath for 30-50 hours at 60-80 ℃. The centrifugal speed is 8000-10000 turns, and the time is 8-10 minutes. Preferably, the invention adopts constant temperature water bath at 80 ℃ for 48 hours, and centrifugation is carried out for 8 minutes at 10000 revolutions.
In the technical scheme, the proportion of Fe-MOFs to molybdate in the step (2) is 2: 1, 1: 2 and 1: 4. Preferably, the molybdate adopted by the invention is ammonium molybdate, and the ratio is 1: 2.
In the step (2), the ultrasonic dispersion time is 30-60 minutes, and the stirring temperature is 60-80 ℃. Preferably, the invention adopts ultrasonic dispersion for 30 minutes, and stirring evaporation is carried out at 60 ℃.
In the technical scheme, the mass ratio of the sample to the dopamine in the step (3) is 90-105: 45-60, and the mass ratio of the sample to the alkaline solution is 90-105: 120-140. The alkaline solution is generally Tris buffer solution, the pH value of the solution is 7.0-9.0, and the stirring time is 20-30 hours. Preferably, the mass ratio of the sample to the dopamine is 90: 45, the mass ratio of the sample to the alkaline solution is 90: 120, the pH value of the solution is 8.8, and the stirring time is 24 hours.
And (3) centrifugally collecting and cleaning the precipitate, wherein the centrifugal rotation speed is 8000-10000 r, the centrifugal time is 8-15 minutes, and the vacuum drying temperature is 60 ℃ for 10-12 hours. Preferably, the invention adopts the centrifugal rotating speed of 8000 min and vacuum drying at 60 ℃ for 12 h.
In the above technical scheme, the annealing temperature of the sample in the step (4) is 700-900 ℃, and the time is 1-3 hours. Preferably, the annealing temperature adopted by the invention is 800 ℃ and the time is 2 hours.
The invention has the beneficial effects that:
the invention provides a simple and convenient method for synthesizing the material with the unique nano cubic block and nano lamellar composite structure, the cubic blocks have the same size, uniform distribution and uniform lamellar thickness, and the structural characteristics of the metal organic framework are fully utilized. Compared with the traditional electrocatalyst and the commercialized RuO2、IrO2The invention prepares Fe3C/Mo2C has higher catalytic activity, good stability and structural novelty. And the raw material reserves are abundant, the cost is lower, solve noble metal catalyst with high costs, resource scarce scheduling problem to a certain extent.
Drawings
FIG. 1 shows Fe obtained in example 1 of the present invention3C/Mo2X-ray diffraction pattern (XRD) of C.
FIG. 2 shows Fe obtained in example 1 of the present invention3C/Mo2Electron Micrograph (SEM) of C.
FIG. 3 shows Fe obtained in example 1 of the present invention3C/Mo2High resolution transmission electron microscopy (HR-TEM) image of C.
FIG. 4 shows Fe prepared by the present invention3C/Mo2C、Fe3C、Mo2C with commercial RuO2OER polarization profile of the catalyst.
FIG. 5 shows Fe prepared by the present invention3C/Mo2C、Fe3C、Mo2C with commercial RuO2The Tafel profile of the catalyst in the OER reaction corresponds.
Detailed Description
Example 1
131.7mg of K3[Fe(CN)6]And 3.0g PVP (K30) was dissolved in 40ml 0.01M HCl solution and stirred for 30 minutes to disperse it evenly. Then placing into a hot water bath, and heating at 80 ℃ for 48 h. And after the constant temperature is finished, centrifuging to collect precipitates, wherein the centrifugal speed is 10000 r, and the centrifugal time is 8 minutes. The sample was washed three times with deionized water and two times with ethanol. Vacuum drying at 60 deg.CAnd drying in a drying oven for 12 hours to obtain Fe-MOFs.
100mg of pre-prepared Fe-MOFs was mixed with 200mg (NH)4)6Mo7O2·4H2O is dispersed in 15ml of water and dispersed by ultrasonic. And then stirring the solution at 60 ℃, and coating a layer of molybdate on the surface of the Fe-MOFs after water is evaporated. The dried solid powder and dopamine were uniformly dispersed in Tris base buffer at pH 8.8 and stirred for 24 hours. Finally, collecting and cleaning the precipitate, drying the precipitate, and calcining the dried precipitate for 2 hours at 800 ℃ in a nitrogen atmosphere to obtain black powder Fe3C/Mo2And C, a composite material.
Example 2
The procedure is as in example 1, except that Fe-MOFs and (NH)4)6Mo7O2·4H2The amount of O was changed to 100 mg: 100mg and dispersed in 10ml of water.
Example 3
The procedure is as in example 1, except that Fe-MOFs and (NH)4)6Mo7O2·4H2The amount of O was changed to 100 mg: 400mg and dispersed in 30ml of water.
Example 4
The procedure is as in example 1, except that Fe-MOFs and (NH)4)6Mo7O2·4H2The amount of O was changed to 200 mg: 100mg, and dispersed in 15ml of water.
Example 5
The procedure was followed as in example 1, except that the temperature of the final nitrogen heat treatment was changed to 700 ℃.
Example 6
The procedure was followed as in example 1, except that the temperature of the final nitrogen heat treatment was changed to 900 ℃.
Example 7
The procedure is as in example 1, except that the pH of the Tris base buffer is changed to 7.4.
Example 8
The procedure is as in example 1, except that the pH of the Tris base buffer is changed to 8.0.
Comparative example 1
131.7mg of K3[Fe(CN)6]And 3.0g PVP (K30) was dissolved in 40ml 0.01M HCl solution and stirred for 30 minutes to disperse it evenly. Then placing into a hot water bath, and heating at 80 ℃ for 48 h. And after the constant temperature is finished, centrifuging to collect precipitates, wherein the centrifugal speed is 10000 r, and the centrifugal time is 8 minutes. The sample was washed three times with deionized water and two times with ethanol. And drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain Fe-MOFs.
The prepared 0.4g Fe-MOFs and 0.2g dopamine were uniformly dispersed in Tris base buffer solution of pH 8.8, stirred for 24 hours, then the washed precipitate was collected and dried in a vacuum oven at 60 ℃ for 10 hours. Finally, the product is heated and treated for 2 hours in nitrogen at 800 ℃ to obtain a solid sample Fe3C。
Comparative example 2
0.8g of (NH)4)6Mo7O2·4H2O and 0.2g of dopamine are uniformly dispersed in Tris alkali buffer solution with the pH value of 8.8, and the sample is uniformly dispersed by ultrasonic treatment for 60 minutes. Then the reaction was stirred for 6 hours, centrifuged at 10000 rpm for 10min, the solid was washed with water and dried in a vacuum oven at 60 ℃ for 12 hours. Finally, the product is heated and treated for 2 hours in nitrogen at 800 ℃ to obtain a solid sample Mo2C。
Detection example 1
Fe obtained in Experimental example 13C/Mo2C and Fe obtained in comparative examples 1 and 23C、Mo2C, carrying out an X-ray diffraction (XRD) test, wherein the test result is shown in figure 1, and the obtained samples are target products by comparing the XRD pattern of the sample with a standard JCPDF card.
Detection example 2
Fe obtained in example 13C/Mo2And C, respectively carrying out Scanning Electron Microscope (SEM) and high-resolution transmission electron microscope (HR-TEM) tests, wherein the test results are respectively shown in fig. 2 and fig. 3. As can be seen from FIG. 2, the catalyst prepared by the invention is a composite structure of nano-cubic blocks and nano-sheet layers, the cubic blocks are regular in shape and uniform in size, the size is about 200nm, and the nano-cubic plates are uniform in sizeThe layer structure has uniform thickness and uniform distribution. From fig. 3, it can be seen that in the high-resolution transmission electron microscope (HR-TEM) image, the existence of crystal images of the two substances is clearly shown.
Detection example 3
Fe obtained in example 13C/Mo2C. Fe obtained in comparative examples 1 and 23C、Mo2C and commercial RuO2The catalyst powder was used as a test sample, and an electrode was prepared as follows:
mixing 950 μ L of anhydrous ethanol and 50 μ L of 5% Nafion solution, adding 5mg of sample, performing ultrasonic dispersion for 30min to obtain liquid sample, dropping 10 μ L of sample on disc electrode (ring disc electrode), and air drying to obtain electrode with catalyst loading of 40mg cm-2。
The electrode prepared above was subjected to OER electrochemical performance testing in a 1.0M KOH solution using a three-electrode system. Measured Fe3C/Mo2C. Fe3C, Mo2C and commercial RuO2The OER polarization curve of the catalyst is shown in FIG. 4. As can be seen from FIG. 4, when 10mA cm is reached-2Current density of (1), Fe3C/Mo2The overpotential required for C is 275mV, lower than that of Fe3C、Mo2C and commercial RuO2This indicates that it has superior activity in catalyzing OER in alkaline media.
As can be seen from FIG. 5, Fe3C/Mo2Tafel slope fit to C was 36.18mV dec-1Is significantly less than Fe3C(66.23mV dec-1)、Mo2C(102.51mV dec-1) And RuO2(50.82mV dec-1) And shows better OER dynamic performance.
The above LSVs and Tafel results collectively demonstrate that this metal organic framework-bound oxygen evolution reaction electrocatalyst, Fe3C/Mo2The high activity of C in catalyzing oxygen evolution indicates that C can be used as an excellent electrode material for electrochemical oxygen evolution reaction.
Claims (10)
1. Metal carbide Fe combined with metal organic framework3C/Mo2And C, the material is characterized by having a unique nanocube and nanosheet layer composite structure, the cubes are uniform in size and distribution, and the size of the cubes is 200 nm.
2. A metal carbide Fe in combination with a metal organic framework according to claim 13C/Mo2The preparation method of C comprises the following steps:
1) mixing an iron salt inorganic compound and an organic high polymer material to obtain Fe-MOFs of the iron-based metal organic framework;
2) uniformly mixing Fe-MOFs and a molybdate according to a certain mass ratio, stirring at 60 ℃ to naturally evaporate and dry water;
3) uniformly dispersing the sample prepared in the step 3) and dopamine in an alkaline solution according to a certain mass ratio, stirring, collecting the precipitate, and centrifugally drying;
4) finally, annealing the dried sample prepared in the step 3) in a nitrogen atmosphere to obtain a final product Fe3C/Mo2C。
3. The method according to claim 2, wherein the mixing of the iron salt inorganic compound with an organic polymer material in step 1) requires a constant temperature water bath of 80 ℃ for 40 to 50 hours.
4. The method according to claim 2, wherein the mass ratio of the sample to the dopamine in step 2) is 1: 1-4.
5. The method according to claim 2, wherein the mass ratio of the sample to dopamine in step 3) is 90-105: 45-60, and the pH value of the alkaline solution is 8.0-9.0.
6. The method as claimed in claim 2, wherein the nitrogen treatment temperature in step 4) is 700-900 ℃ for 2-3 h.
7. The method of any one of claims 2 to 5, wherein the mixing is carried out by stirring for a certain period of time.
8. The production method according to any one of claims 2 to 5, wherein the drying is carried out at 60 ℃ under vacuum.
9. The preparation method according to any one of claims 2 to 6, wherein the sample is dried under vacuum at 60 to 80 ℃ for 1 to 6 hours before the annealing treatment under the nitrogen condition.
10. Fe having a unique structure as set forth in claim 13C/Mo2The application of C in electrocatalytic oxygen evolution reaction.
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