CN113981469A - Organic ligand modified transition metal layered hydroxide electrocatalytic material and preparation method and application thereof - Google Patents
Organic ligand modified transition metal layered hydroxide electrocatalytic material and preparation method and application thereof Download PDFInfo
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- CN113981469A CN113981469A CN202111299537.9A CN202111299537A CN113981469A CN 113981469 A CN113981469 A CN 113981469A CN 202111299537 A CN202111299537 A CN 202111299537A CN 113981469 A CN113981469 A CN 113981469A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 51
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000013110 organic ligand Substances 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 19
- -1 transition metal salt Chemical class 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 2
- 229910003321 CoFe Inorganic materials 0.000 description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
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- 238000001179 sorption measurement Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention relates to an organic ligand modified transition metal layered hydroxide electrocatalytic material and a preparation method and application thereof. The preparation method of the electrocatalytic material comprises the following steps: step 1): adding a transition metal salt A, a transition metal salt B, urea and ammonium fluoride into water, stirring to obtain a mixed solution, transferring the mixed solution into a reaction kettle, and then putting a conductive substrate into the reaction kettle for hydrothermal reaction to obtain a conductive substrate with the surface coated with a mixture of the two transition metals; step 2): and placing the conductive substrate coated with the mixture of the two transition metals on the surface in a culture dish, immersing the conductive substrate into an organic ligand molecular solution, standing for 10-60 min, and drying to obtain the organic ligand modified LDH electro-catalytic material. The organic ligand modified LDH electro-catalytic material provided by the invention has excellent oxygen evolution activity when being used as an electro-catalyst for oxygen evolution reaction, has very small overpotential and stability under large current density, has good long-term stability and has a commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts containing metal or metal oxide or hydroxide, and particularly relates to an organic ligand modified transition metal layered hydroxide electrocatalytic material and a preparation method and application thereof.
Background
Hydrogen energy is regarded as one of the most ideal renewable energy sources as a secondary energy source with high energy density, zero carbon emission and wide sources. At present, the cost of hydrogen production by water electrolysis is higher, and the hydrogen production by water electrolysis is 3-4 times of the technical routes of natural gas reforming, coal hydrogen production and the like in view of the assembly cost, so that the development of a high-performance electrocatalyst is urgently needed to reduce the cost of hydrogen production by water electrolysis. The electrolyzed water mainly comprises Hydrogen Evolution Reaction (HER) at a cathode and Oxygen Evolution Reaction (OER) at an anode, wherein the OER relates to a complex four-electron transfer process, the kinetics is slow, the overpotential of the decomposed water is too high, and the electrolysis efficiency is seriously influenced. Therefore, as a mainstream technology of hydrogen production in the future, it is important to develop a high-activity OER electrocatalyst, reduce the overpotential of water decomposition, and further improve the hydrogen production efficiency. The noble metal Ir and Ru-based material has excellent OER performance, but the Ir and Ru have scarce reserves, high price and poor stability, and the wide application of the material is seriously restricted. Therefore, research and development of an OER catalyst with low cost, environmental friendliness, excellent catalytic activity and stable performance becomes an important way to solve the current energy dilemma.
Transition metal layered hydroxides (LDH) are widely concerned due to the advantages of low price, stable structure and the like, have certain commercial application prospect, but still have the defects of large adsorption capacity to intermediates, poor conductivity, insufficient exposure of active sites and the like, and cause the insufficient high efficiency of catalytic oxygen evolution. The scheme of the invention can adjust the bonding strength of LDH to the OER intermediate product, improve the reaction activity of the catalyst and accelerate the reaction rate.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides an organic ligand modified LDH electro-catalytic material, a preparation method and an application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
provides an organic ligand modified transition metal layered hydroxide electrocatalytic material, and the preparation method comprises the following steps:
step 1): mixing transition metal salt A, transition metal salt B, urea and ammonium fluoride (NH)4F) Adding water, stirring until the mixture is clear to obtain a mixed solution, transferring the mixed solution into a reaction kettle, then putting a conductive substrate into the reaction kettle for hydrothermal reaction, naturally cooling after the reaction is finished, taking out the conductive substrate, cleaning and drying to obtain the conductive substrate with the surface coated with the mixture of the two transition metals;
step 2): placing the conductive substrate coated with the mixture of the two transition metals on the surface obtained in the step 1) in a culture dish, immersing the conductive substrate into an organic ligand molecular solution, standing for 10-60 min, taking out, and drying by using a vacuum oven to obtain the organic ligand modified LDH electro-catalytic material.
According to the scheme, the transition metal salt A and the transition metal salt B in the step 1) are selected from two different metal salts of iron salt, cobalt salt and nickel salt.
Preferably, the transition metal salt a is a cobalt salt, and the transition metal salt B is an iron salt.
According to the scheme, the cobalt salt is one or more of cobalt chloride, cobalt nitrate and cobalt acetate.
According to the scheme, the ferric salt is one or more of ferric chloride, ferric nitrate and ferric acetate.
According to the scheme, the nickel salt is one or more of nickel chloride, nickel nitrate and nickel acetate.
According to the scheme, the molar ratio of the metal element, the urea and the ammonium fluoride in the mixed solution in the step 1) is 1: 1.4-1.5: 3.0 to 3.2. Urea and NH4F provides a buffer environment of weak alkaline solution, and is beneficial to the deposition of the catalyst on the conductive substrate.
According to the scheme, the molar ratio of cobalt to iron elements in the mixed solution is 1: 0.2-5, and the concentration of cobalt ions in the mixed solution is 0.01-0.05 mol/L.
According to the scheme, the conductive substrate in the step 1) is one of foamed Nickel (NF), foamed iron, foamed copper and carbon cloth.
According to the scheme, the hydrothermal reaction conditions in the step 1) are as follows: reacting for 2-6 hours at 45-120 ℃.
According to the scheme, the organic ligand molecule solution in the step 2) is an aqueous solution of one of 2-methylimidazole (MIM), terephthalic acid, 2, 5-thiophenedicarboxylic acid and 1-methylimidazole, and the concentration of the organic ligand molecule solution is 1.0-2.5 mol/L. The organic ligand molecule has the function of chelating with metal, so that the electronic structure of the metal is regulated, the adsorption energy of an active intermediate in the OER process of a metal active site is effectively improved, and the energy barrier of a reaction path is optimized.
The invention also comprises a preparation method of the organic ligand modified transition metal layered hydroxide electrocatalytic material, which comprises the following steps:
step 1): adding a transition metal salt A, a transition metal salt B, urea and ammonium fluoride into water, stirring until the mixture is clear to obtain a mixed solution, transferring the mixed solution into a reaction kettle, then putting a conductive substrate into the reaction kettle for hydrothermal reaction, naturally cooling after the reaction is finished, taking out the conductive substrate, cleaning and drying to obtain the conductive substrate with the surface coated with a mixture of the two transition metals;
step 2): placing the conductive substrate coated with the mixture of the two transition metals on the surface obtained in the step 1) in a culture dish, immersing the conductive substrate into an organic ligand molecular solution, standing for 10-60 min, taking out, and drying by using a vacuum oven to obtain the organic ligand modified LDH electro-catalytic material.
The transition metal layered hydroxide electrocatalytic material modified by the organic ligand is used as an oxygen evolution catalyst and a working electrode in the oxygen evolution reaction.
The LDH prepared by the method has a nano flower-shaped structure, has larger specific surface area, smaller mass transfer resistance and shorter mass transfer path, and can improve the exposure of active sites and the transmission of OER active substances. Two transition metals (such as Co and Fe in CoFe LDH, and the two metals have synergistic effect and have better performance) coated on the surface of the material are widely considered as main active sites of OER reaction, organic ligand micromolecules can be tightly combined with the transition metals in the LDH through chelation, the electronic structure of the metals is regulated and controlled, the electronic structure becomes more stable, the adsorption energy of active intermediates in the OER process of the metal active sites is effectively improved, and the energy barrier of a reaction path is optimized.
The invention has the beneficial effects that: 1. the organic ligand modified LDH electro-catalytic material provided by the invention has excellent oxygen evolution activity when being used as an electro-catalyst for oxygen evolution reaction, has very small overpotential and stability under large current density, has good long-term stability and has a commercial application prospect. 2. The invention regulates the performance of the LDH catalyst by using the organic ligand through a simple method, and the preparation method has the advantages of mild reaction conditions, simple steps, low cost and easy industrial production implementation.
Drawings
FIG. 1 is a field emission scanning electron microscope image of MIM-CoFe LDH @ NF prepared in example 1 of the present invention at a 100 μm scale;
FIG. 2 is a field emission scanning electron microscope image of MIM-CoFe LDH @ NF prepared in example 1 on a 1 μm scale;
FIG. 3 is a graph of high angle renewing dark field scanning transmission electron microscopy (HAADF-STEM) and element distribution testing of MIM-CoFe LDH @ NF samples prepared in example 1;
FIG. 4 is an XRD plot of MIM-CoFe LDH @ NF and CoFe LDH @ NF prepared in example 1;
FIG. 5 is an FTIR plot of MIM-CoFe LDH @ NF and CoFe LDH @ NF prepared in example 1;
FIG. 6 is an XPS plot of MIM-CoFe LDH @ NF versus CoFe LDH @ NF prepared in example 1;
FIG. 7 is a plot of the OER polarization for different samples prepared in example 1;
FIG. 8 is the results of the OER stability test of MIM-CoFe LDH @ NF prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Example 1
Preparation of 2-methylimidazole modified CoFe-LDH coated foamed nickel material (MIM-CoFe LDH @ NF):
1) 2.224g (7.6mmol) Co (NO)3)2·6H2O、0.6128g(1.5mmol)Fe(NO3)3·9H2O, 0.8049g (13.4mmol) Urea and 1.045g (28.2mmol) NH4F, adding 175mL of ultrapure water, stirring vigorously for 15min to obtain a clear solution, and transferring the solution to a polytetrafluoroethylene reaction kettle;
2) ultrasonically cleaning foamed nickel (2.0cm multiplied by 4.0cm, the thickness of 1cm) with 3mol/L HCl solution and ultrapure water for 15 minutes in sequence, then vertically putting the foamed nickel into a reaction kettle, transferring the foamed nickel into a 120 ℃ oven for reaction for 2 hours, naturally cooling, taking out the foamed nickel, cleaning the foamed nickel with ethanol, and drying in vacuum at 60 ℃ to obtain a sample (CoFe-LDH @ NF, the total weight of the foamed nickel is increased by 2 mg/cm)2The thickness of the coating layer is about tens of microns);
3) and (3) placing the sample CoFe-LDH @ NF into a culture dish, adding 50mL of 2-methylimidazole water solution (the concentration range is 2.5mol/L), soaking for 10min, and drying for 5h in a vacuum oven at 60 ℃ to obtain a final product (MIM-CoFe LDH @ NF).
Scanning MIM-CoFe LDH @ NF at 100 μm by using a field emission scanning electron microscope (model number FESEM, JEOL, FEG-XL30S, manufacturer JEOL electron company, Japan), wherein the obtained scanning electron micrograph is shown in figure 1, and the MIM-CoFe LDH sample is uniformly loaded on a foam nickel skeleton; the MIM-CoFe LDH @ NF is scanned under the condition of 1 mu m, and an obtained scanning electron microscope image is shown in figure 2, so that the ultrathin nanosheets are densely and orderly gathered into a nanoflower-shaped appearance, the ultrathin and mutually crosslinked nanosheets provide enough channels for rapid electron transfer, and the nanosheets have abundant open gaps, have larger specific surface area, smaller mass transfer resistance and shorter mass transfer path, and can improve the exposure of active sites and the transmission speed of OER active substances.
Scanning MIM-CoFe LDH @ NF by using a transmission electron microscope (model is JEOL JEM-2100F, the manufacturer is JEOL electronics company in Japan), and changing the high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) and element distribution test of a sample into a new dark-field scanning transmission electron microscope and an element distribution test chart as shown in figure 3, so that the elements C, N, O, Co and Fe are uniformly distributed in the whole system structure, and the fact that 2-methylimidazole is successfully combined on the surface of CoFe LDH @ NF is verified.
An X-ray diffractometer (model number Burker-AXS D8, manufactured by Burker of Germany) is used for testing MIM-CoFe LDH @ NF, and the obtained XRD pattern is shown in figure 4, and the result shows that the 2-methylimidazole modification treatment has little influence on the structure of CoFe LDH.
The samples before and after the CoFe LDH @ NF is treated by 2-methylimidazole are subjected to infrared test by a spectrum two-wo type infrared spectrometer, and the obtained infrared spectrogram is shown in figure 5, which proves that the 2-methylimidazole is successfully combined on the surface of the CoFe LDH @ NF.
An X-ray photoelectron spectroscopy is used for testing MIM-CoFe LDH @ NF and CoFe LDH @ NF, an obtained XPS diagram is shown in figure 6, signal peaks of elements C, N, O, Co and Fe can be seen, and meanwhile, the fact that 2-methylimidazole is successfully combined on the surface of CoFe LDH @ NF is confirmed, and the result is consistent with the element distribution test result.
Comparative example 1
RuO was prepared using a commercial catalyst in place of the transition metal layer and the organic ligand modification layer of example 12/NF：
1) 4mg of RuO2Adding a catalyst into a mixed solution of 395 mu L of ultrapure water, 100 mu L of absolute ethyl alcohol and 5 mu L of Nafion solution (the mass percentage concentration is 5 percent), and performing ultrasonic dispersion for 30 minutes to obtain an evenly dispersed ink solution;
2) ultrasonically cleaning foamed nickel (2.0cm multiplied by 4.0cm, thickness 1cm) with 3mol/L HCl solution and ultrapure water for 15 minutes, then coating 250 mu L of the ink solution on the foamed nickel, and finally placing the foamed nickel into an oven for drying to obtain a sample RuO2/NFMiddle RuO2The catalyst loading was about 2mg cm-2。
Electrochemical testing: a1.0 mol/L KOH solution was used as an electrolyte, and a three-electrode system was used to prepare the MIM-CoFe LDH @ NF electrode and CoFe-LDH @ NF electrode prepared in example 1, and the RuO prepared in this comparative example2Respectively taking a/NF electrode and the cleaned foamed Nickel (NF) as working electrodes, taking a calomel electrode as a reference electrode and taking a graphite electrode as a counter electrode, and measuring MIM-CoFe LDH @ NF, CoFe-LDH @ NF and RuO2Linear sweep voltammograms for/NF and cleaned Nickel Foam (NF).
MIM-CoFe LDH @ NF, CoFe-LDH @ NF, RuO obtained in example 1 and comparative example 12The electrochemical performance of/NF and cleaned Nickel Foam (NF) was tested by an electrochemical workstation, chenhua electrochemical workstation, model No. CHI 660E.
An OER performance test is carried out on MIM-CoFe LDH @ NF and CoFe LDH @ NF by utilizing a linear sweep voltammetry, an obtained OER polarization curve graph (LSV graph) is shown in figure 7, a sample MIM-CoFe LDH @ NF after 2-methylimidazole treatment shows the optimal performance, has the minimum overpotential under the same current density and has a very small overpotential under a large current density, and the feasibility of regulating the electrocatalytic oxygen evolution performance of the transition metal layered hydroxide is proved.
OER stability test is carried out on MIM-CoFe LDH @ NF by using a current-time scanning method, and the current is set to be 20mA/cm2And 50mA/cm2And as shown in FIG. 8, OER stability test results show that MIM-CoFe LDH @ NF has excellent stability under different current densities, and the current density is not obviously attenuated within 24 h.
The organic ligand modified CoFe-LDH electro-catalytic material provided by the invention has excellent electro-catalytic oxygen evolution performance, and has excellent catalytic activity and cycle stability under high current density, thereby being beneficial to commercial application.
Claims (10)
1. An organic ligand modified transition metal layered hydroxide electrocatalytic material is characterized by comprising the following preparation method steps:
step 1): adding a transition metal salt A, a transition metal salt B, urea and ammonium fluoride into water, stirring until the mixture is clear to obtain a mixed solution, transferring the mixed solution into a reaction kettle, then putting a conductive substrate into the reaction kettle for hydrothermal reaction, naturally cooling after the reaction is finished, taking out the conductive substrate, cleaning and drying to obtain the conductive substrate with the surface coated with the mixture of the two transition metals;
step 2): placing the conductive substrate coated with the mixture of the two transition metals on the surface obtained in the step 1) in a culture dish, immersing the conductive substrate into an organic ligand molecular solution, standing for 10-60 min, taking out, and drying by using a vacuum oven to obtain the organic ligand modified LDH electro-catalytic material.
2. The organic ligand-modified transition metal layered hydroxide electrocatalytic material as claimed in claim 1, wherein the transition metal salt A and the transition metal salt B in step 1) are selected from two different metal salts selected from iron salt, cobalt salt and nickel salt.
3. The organic ligand-modified transition metal layered hydroxide electrocatalytic material as set forth in claim 2, wherein the cobalt salt is one or more of cobalt chloride, cobalt nitrate, and cobalt acetate; the ferric salt is one or more of ferric chloride, ferric nitrate and ferric acetate; the nickel salt is one or more of nickel chloride, nickel nitrate and nickel acetate.
4. The organic ligand-modified transition metal layered hydroxide electrocatalytic material as claimed in claim 2, wherein the transition metal salt a is a cobalt salt, the transition metal salt B is an iron salt, and the molar ratio of cobalt to iron in the mixed solution in step 1) is 1: 0.2-5, and the concentration of cobalt ions in the mixed solution is 0.01-0.05 mol/L.
5. The organic ligand-modified transition metal layered hydroxide electrocatalytic material as set forth in claim 1, wherein the molar ratio of the metal element, urea and ammonium fluoride in the mixed solution of step 1) is 1: 1.4-1.5: 3.0 to 3.2.
6. The organic ligand-modified transition metal layered hydroxide electrocatalytic material as claimed in claim 1, wherein the conductive substrate of step 1) is one of nickel foam, iron foam, copper foam, and carbon cloth.
7. The organic ligand-modified transition metal layered hydroxide electrocatalytic material as set forth in claim 1, wherein the hydrothermal reaction conditions of step 1) are: reacting for 2-6 hours at 45-120 ℃.
8. The organic ligand-modified transition metal layered hydroxide electrocatalytic material as claimed in claim 1, wherein the organic ligand molecule solution in step 2) is an aqueous solution of one of 2-methylimidazole, terephthalic acid, 2, 5-thiophenedicarboxylic acid, and 1-methylimidazole, and the concentration of the organic ligand molecule solution is 1.0-2.5 mol/L.
9. A method for preparing the organic ligand modified transition metal layered hydroxide electrocatalytic material as described in any one of claims 1 to 8, which comprises the following steps:
step 1): adding a transition metal salt A, a transition metal salt B, urea and ammonium fluoride into water, stirring until the mixture is clear to obtain a mixed solution, transferring the mixed solution into a reaction kettle, then putting a conductive substrate into the reaction kettle for hydrothermal reaction, naturally cooling after the reaction is finished, taking out the conductive substrate, cleaning and drying to obtain the conductive substrate with the surface coated with a mixture of the two transition metals;
step 2): placing the conductive substrate coated with the mixture of the two transition metals on the surface obtained in the step 1) in a culture dish, immersing the conductive substrate into an organic ligand molecular solution, standing for 10-60 min, taking out, and drying by using a vacuum oven to obtain the organic ligand modified LDH electro-catalytic material.
10. The use of the organic ligand-modified transition metal layered hydroxide electrocatalytic material as set forth in any one of claims 1 to 8, wherein the organic ligand-modified transition metal layered hydroxide electrocatalytic material is used as an oxygen evolution catalyst and a working electrode in an oxygen evolution reaction.
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