CN111905818A - MOF-based two-dimensional ultrathin electrocatalyst and preparation method and application thereof - Google Patents
MOF-based two-dimensional ultrathin electrocatalyst and preparation method and application thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000013110 organic ligand Substances 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 24
- 239000012621 metal-organic framework Substances 0.000 description 12
- 239000002086 nanomaterial Substances 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- B01J35/33—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- 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 an MOF-based two-dimensional ultrathin electrocatalyst and a preparation method thereof, wherein the preparation method comprises the following steps of: s1, dissolving organic ligand phthalic acid in an organic solvent, adding a divalent nickel salt, and stirring for 30-60 min; adding triethylamine, and continuously stirring for 30-60 min; carrying out ultrasonic treatment on the solution for 7-10h, and replacing water every two hours; cleaning the precipitate with absolute ethanol after the ultrasonic treatment; s2, dispersing the precipitate obtained in the step S1 in absolute ethyl alcohol, adding ferric salt, cobalt salt or manganese salt, controlling the concentration of the ferric salt, the cobalt salt or the manganese salt in the solution to be 5-30mM, and then carrying out ultrasonic treatment; and after the ultrasonic treatment is finished, reacting the solution for 6-10 hours under the stirring condition, and washing and precipitating with absolute ethyl alcohol to obtain the MOF-based two-dimensional ultrathin electrocatalyst. The invention also provides application of the MOF-based two-dimensional ultrathin electrocatalyst in water electrolysis. The MOF-based two-dimensional ultrathin electrocatalyst has good catalytic properties.
Description
Technical Field
The invention relates to the technical field of synthesis of electrocatalytic materials, in particular to a surface in-situ modification synthesis electrocatalyst based on ultrathin MOF nanosheets, a preparation method thereof and application thereof in electrolytic water.
Background
With the gradual increase of global environmental pollution and energy shortage, it is the focus of research at present to seek efficient clean energy to replace the existing fossil energy. The large consumption of traditional fossil energy such as coal, petroleum and natural gas not only brings about the rapid reduction of energy reserves, but also causes serious environmental pollution problems. Therefore, the development of new clean low-carbon energy such as new hydrogen energy has great significance for alleviating the problem of environmental pollution, solving the energy crisis faced at present and realizing the sustainable development of energy.
At present, the electrolysis of water to produce hydrogen using a catalyst is considered to be one of the effective ways to achieve the above-mentioned objects. Theoretically, water electrolysis is an effective strategy for producing hydrogen, however, the industrial application is greatly limited by a noble metal catalyst, so that the development of an efficient and stable non-noble metal electrocatalyst to replace the existing noble metal catalyst becomes a research hotspot, and the efficient electrode catalyst is crucial to green sustainable energy conversion and storage. The metal organic framework Materials (MOFs) with ordered topological structures, which are formed by coordination and complexation of metal ions and organic ligands, have the characteristics of periodic porous structures, high specific surface areas, adjustable structures, structural diversity and the like, and show unique advantages in the field of electrocatalysis as an electrocatalyst. However, the problems of the MOFs materials such as poor conductivity and easy collapse of the structure still remain to be solved.
Disclosure of Invention
The invention aims to provide an MOF-based two-dimensional ultrathin electrocatalyst which has good catalytic properties.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a preparation method of an MOF-based two-dimensional ultrathin electrocatalyst, which comprises the following steps:
s1, dissolving organic ligand phthalic acid in an organic solvent, adding a divalent nickel salt, and stirring for 30-60 min; adding triethylamine, and continuously stirring for 30-60 min; carrying out ultrasonic treatment on the solution for 7-10h, and replacing water every two hours; cleaning the precipitate with absolute ethanol after the ultrasonic treatment;
s2, dispersing the precipitate obtained in the step S1 in absolute ethyl alcohol, adding ferric salt, cobalt salt or manganese salt, controlling the concentration of the ferric salt, the cobalt salt or the manganese salt in the solution to be 5-30mM, and then carrying out ultrasonic treatment; and after the ultrasonic treatment is finished, reacting the solution for 6-10 hours under the stirring condition, and washing and precipitating with absolute ethyl alcohol to obtain the MOF-based two-dimensional ultrathin electrocatalyst.
Further, in step S1, the organic solvent is a mixed solvent of N, N-dimethylformamide, ethanol, and water.
Further, in step S1, the concentration of phthalic acid in the solution is 0.01 to 0.03mol/L, and the concentration of nickel salt is 0.015 to 0.025 mol/L.
Further, in step S1, the divalent nickel salt is nickel chloride, nickel sulfate, nickel acetate, or a hydrate thereof.
According to the invention, triethylamine is used as a surfactant, and the morphology of the synthesized Ni-MOFs can be controlled, so that the ultrathin Ni-MOFs nanosheet is obtained.
Further, in step S1, the cell is treated by ultrasonic treatment with a cell crusher, the ultrasonic power is 50-100W, and the frequency setting range is respectively operated for 1-4S and stopped for 2-5S. And the cell crusher is adopted for ultrasonic treatment, so that the precipitate can be dispersed more uniformly.
Further, in step S2, the iron salt includes ferrous chloride, ferrous sulfate, or a hydrate thereof, the cobalt salt includes cobalt chloride or a hydrate thereof, and the manganese salt includes manganese chloride or a hydrate thereof.
In a second aspect, the invention provides MOF-based two-dimensional ultrathin electrocatalysts prepared by the method of the first aspect.
In a third aspect of the invention, there is provided the use of a MOF-based two-dimensional ultrathin electrocatalyst according to the second aspect in the electrolysis of water.
The invention has the beneficial effects that:
1. according to the invention, iron, cobalt or manganese is adopted to replace Ni in the Ni-MOF nanosheets through an atom replacement reaction, so that the MOF-based two-dimensional ultrathin nanomaterial with Fe, Co or Mn elements modified on the surface is obtained, the nanomaterial not only has an ultrathin nanostructure, but also has an optimized atomic structure on the interface, and has good electrocatalytic performance.
2. The MOFs-based nano material disclosed by the invention is simple in preparation method, cheap and easily available in raw materials, and can be popularized and used as a commercial electro-catalytic material.
Drawings
FIG. 1: a transmission electron microscope image of Fe @ Ni-MOFs;
FIG. 2: XPS comparison of Fe @ Ni-MOFs with Ni-MOFs and co-deposited Fe-Ni-MOFs;
FIG. 3: comparing CV curves of Fe @ Ni-MOFs, Ni-MOFs and co-deposited Fe-Ni-MOFs in a 1mol/L potassium hydroxide solution;
FIG. 4: comparing LSV curves of Fe @ Ni-MOFs, Ni-MOFs and co-deposited Fe-Ni-MOFs in a 1mol/L potassium hydroxide solution;
FIG. 5: the Tafel curves of Fe @ Ni-MOFs were compared with Ni-MOFs and co-deposited Fe-Ni-MOFs in a 1mol/L potassium hydroxide solution.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
Example 1: synthesis of ultrathin Ni-MOF nanosheet
(1) Preparing a reaction solvent: adding 32ml of N, N-Dimethylformamide (DMF), 2ml of ethanol and 2ml of water into a 100ml beaker, and stirring until complete mixing;
(2) weighing 0.75mmol of phthalic acid, adding into the solution while stirring, and stirring for 30-60min until the solution is clear for later use;
(3) to the clear solution was added 0.75mmol of NiCl2·6H2O, continuously stirring for 30-60 min;
(4) adding 0.8ml of triethylamine into the solution, and continuing stirring for 30-60 min;
(5) and finally, carrying out ultrasonic treatment on the stirred solution by using a cell crusher, wherein the ultrasonic power is 60W, the frequency is set to be 2s + 3s, the total ultrasonic time is 8h, distilled water is changed every two hours, and after the treatment is finished, the obtained precipitate is cleaned for 3-5 times by using absolute ethyl alcohol to obtain the ultrathin Ni-MOF nanosheet.
Example 2: preparation of Fe @ Ni-MOFs nano material
(1) Fully dispersing the precipitate obtained in the example 1 by 50ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min for later use;
(2) adding ferrous chloride into the solution to obtain Fe2+The concentration range of (A) is 10mM, and ultrasonic treatment is carried out for 30 min;
(3) and (3) reacting the solution after the ultrasonic treatment for 6-10 hours under magnetic stirring, and washing and precipitating by using absolute ethyl alcohol to obtain the Fe @ Ni-MOFs nano material.
As shown in FIG. 1, Fe @ Ni-MOFs has a nanosheet structure and is uniform in thickness. The results of FIG. 2 show that Fe is successfully replaced on the surface of the nanosheet, and the doping amount of Fe is greater than that of Fe-Ni-MOFs prepared by co-doping.
Comparative example 1: preparation of co-deposited Fe-Ni-MOFs nano material
(1) Preparing a reaction solvent: adding 32ml of N, N-Dimethylformamide (DMF), 2ml of ethanol and 2ml of water into a 100ml beaker, and stirring until complete mixing;
(2) weighing 0.75mmol of phthalic acid, adding into the solution while stirring, and stirring for 30-60min until the solution is clear for later use;
(3) to the clear solution was added 0.75mmol of NiCl2·6H2O and 0.75mmol of ferrous chloride, and continuously stirring for 30-60 min;
(4) adding 0.8ml of triethylamine into the solution, and continuing stirring for 30-60 min;
(5) and finally, carrying out ultrasonic treatment on the stirred solution by using a cell crusher, wherein the ultrasonic power is 60W, the frequency is set to be 2s + 3s, the total ultrasonic time is 8h, distilled water is changed every two hours, and after the treatment is finished, the obtained precipitate is cleaned for 3-5 times by using absolute ethyl alcohol to obtain the co-deposition Fe-Ni-MOFs nano material.
Example 3: electrocatalytic testing
Respectively preparing Fe @ Ni-MOFs, Ni-MOFs and Fe-Ni-MOFs into paste by using carbon black and Nafion solution, dripping the paste on a glassy carbon electrode for electrochemical test, wherein the electrolyte is 1mol/L potassium hydroxide solution, and the rotating speed of a working electrode is 1600 rpm.
FIG. 3 is a graph comparing CV curves of Fe @ Ni-MOFs, Ni-MOFs and co-deposited Fe-Ni-MOFs in a 1mol/L potassium hydroxide solution, and it can be seen that Fe @ Ni-MOFs has a higher polarization current.
FIG. 4 is a comparison of LSV curves of the three, and after IR correction, Fe @ Ni-MOFs showed better electrocatalytic performance at 10mAcm-2The overpotential is 279mV, which is obviously better than Ni-MOFs and co-deposited Fe-Ni-MOFs.
FIG. 5 is a Tafel curve comparison of the three, and it can be seen from the graph that the Tafel slope of Ni-MOFs is 90.05, the Tafel slope of Fe-Ni-MOFs is 56.46, and the Tafel slope of Fe @ Ni-MOFs of the present invention is 39.84, which shows that the Fe @ Ni-MOFs of the present invention has better electrocatalytic properties.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (8)
1. A preparation method of an MOF-based two-dimensional ultrathin electrocatalyst is characterized by comprising the following steps of:
s1, dissolving organic ligand phthalic acid in an organic solvent, adding a divalent nickel salt, and stirring for 30-60 min; adding triethylamine, and continuously stirring for 30-60 min; carrying out ultrasonic treatment on the solution for 7-10h, and replacing water every two hours; cleaning the precipitate with absolute ethanol after the ultrasonic treatment;
s2, dispersing the precipitate obtained in the step S1 in absolute ethyl alcohol, adding ferric salt, cobalt salt or manganese salt, controlling the concentration of the ferric salt, the cobalt salt or the manganese salt in the solution to be 5-30mM, and then carrying out ultrasonic treatment; and after the ultrasonic treatment is finished, reacting the solution for 6-10 hours under the stirring condition, and washing and precipitating with absolute ethyl alcohol to obtain the MOF-based two-dimensional ultrathin electrocatalyst.
2. The method for preparing the MOF-based two-dimensional ultrathin electrocatalyst according to claim 1, wherein in the step S1, the organic solvent is a mixed solvent of N, N-dimethylformamide, ethanol and water.
3. The method for preparing the MOF-based two-dimensional ultrathin electrocatalyst according to claim 1, wherein in step S1, the concentration of phthalic acid in the solution is 0.01-0.03mol/L, and the concentration of nickel salt is 0.015-0.025 mol/L.
4. The method for preparing the MOF-based two-dimensional ultrathin electrocatalyst according to claim 1, wherein in step S1, the divalent nickel salt is nickel chloride, nickel sulfate, nickel acetate or hydrate thereof.
5. The preparation method of the MOF-based two-dimensional ultrathin electrocatalyst, according to claim 1, characterized in that in step S1, the cell crusher is used for ultrasonic treatment, the ultrasonic power is 50-100W, and the frequency setting range is respectively run for 1-4S and stopped for 2-5S.
6. The method for preparing the MOF-based two-dimensional ultrathin electrocatalyst according to claim 1, wherein in step S2, the iron salt comprises ferrous chloride and ferrous sulfate, the cobalt salt comprises cobalt chloride, and the manganese salt comprises manganese chloride.
7. A MOF-based two-dimensional ultrathin electrocatalyst prepared according to the method of any one of claims 1-6.
8. Use of a MOF-based two-dimensional ultrathin electrocatalyst according to claim 7 in the electrolysis of water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112481639A (en) * | 2020-12-01 | 2021-03-12 | 中国海洋大学 | Preparation method and application of hierarchical porous nickel-based metal organic framework electrocatalytic material |
| CN115322387A (en) * | 2021-05-11 | 2022-11-11 | 南京理工大学 | Method for preparing two-dimensional metal-organic framework electrocatalyst through double-regulator competitive coordination |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112481639B (en) * | 2020-12-01 | 2022-02-11 | 中国海洋大学 | Preparation method and application of hierarchical porous nickel-based metal organic framework electrocatalytic material |
| CN115322387A (en) * | 2021-05-11 | 2022-11-11 | 南京理工大学 | Method for preparing two-dimensional metal-organic framework electrocatalyst through double-regulator competitive coordination |
| CN115322387B (en) * | 2021-05-11 | 2023-10-31 | 南京理工大学 | Method for preparing two-dimensional metal organic framework electrocatalyst by double-regulator competitive coordination |
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