CN110639534B - Oxygen evolution electrocatalytic material and preparation method and application thereof - Google Patents
Oxygen evolution electrocatalytic material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 43
- 239000001301 oxygen Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 30
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002135 nanosheet Substances 0.000 claims abstract description 13
- 239000011651 chromium Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 22
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- 239000002253 acid Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
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- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims description 4
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- 239000001257 hydrogen Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 239000010963 304 stainless steel Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明公开一种析氧电催化材料及其制备方法和应用。该催化材料含有铁镍铬层状双氢氧化物(FeNiCr‑LDH)和金属基底，所述FeNiCr‑LDH原位垂直生长在所述金属基底的表面，所述金属基底中含有铁元素、镍元素和铬元素。本发明采用一步水热合成法，以金属基底作为半牺牲模板，在2,5‑二羟基对苯二甲酸配体的调控下，超薄纳米片状的FeNiCr‑LDH原位生长在金属基底表面，得到电催化材料，并将其直接作为自支撑电极用于电催化析氧反应。本发明制备的电催化材料具有优异的电催化活性，良好的电化学稳定性，制备工艺简单易行，成本低廉，具有大规模工业化的应用前景。
The invention discloses an oxygen evolution electrocatalytic material and a preparation method and application thereof. The catalytic material contains iron-nickel-chromium layered double hydroxide (FeNiCr-LDH) and a metal substrate, the FeNiCr-LDH is vertically grown on the surface of the metal substrate in situ, and the metal substrate contains iron and nickel elements and chromium elements. The invention adopts a one-step hydrothermal synthesis method, uses a metal substrate as a semi-sacrificial template, and under the control of 2,5-dihydroxyterephthalic acid ligands, ultra-thin nano-sheet FeNiCr-LDH is grown in-situ on the surface of the metal substrate , obtained electrocatalytic materials, and used them directly as self-supporting electrodes for electrocatalytic oxygen evolution reaction. The electrocatalytic material prepared by the invention has excellent electrocatalytic activity, good electrochemical stability, simple and easy preparation process, low cost, and has the application prospect of large-scale industrialization.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to an oxygen evolution electrocatalytic material as well as a preparation method and application thereof.
Background
In recent years, with the shortage of energy, the warming of climate and the increasing problem of environmental pollution, the search for new renewable green energy has become one of the important subjects in the research field of materials and energy. Hydrogen energy is considered as a new energy source with the most potential to replace the traditional fossil fuel due to the advantages of high energy density, zero carbon emission, no pollution and the like. Water resources on the earth are extremely rich, and electrochemical water decomposition hydrogen production has immeasurable great advantages and application prospects. However, the Oxygen Evolution Reaction (OER) occurring at the anode during electrochemical water splitting involves a multi-step proton-coupled electron transfer process and a complex intermediate adsorption behavior with slow reaction kinetics. Therefore, there is a need for a highly efficient catalyst to reduce the reaction energy barrier and thereby increase the oxygen evolution reaction rate. Noble metal oxides such as RuO2And IrO2Is a high-activity oxygen evolution electrocatalyst which is generally accepted at present, but has rare reserves and high price, and greatly limits the industrial application of the electrocatalyst. Therefore, development and design of the oxygen evolution reaction electrocatalyst with low cost and excellent performance are the key for realizing the high-efficiency electrochemical water decomposition technology, and thus become a hotspot for research of extensive researchers.
At present, Layered Double Hydroxides (LDHs) as OER electrocatalysts have great potential for development in the field of electrocatalysis due to their tunable chemical composition and unique electronic structure. The FeNi-based LDH has active d electrons due to Fe and Ni elements, and a good synergistic effect can be formed between the Fe and Ni elements, so that the FeNi-based LDH can be used as an OER electrocatalyst with excellent performance to stand out in an LDH material. However, because of the structural and electrical conductivity limitations of the FeNi-based LDH, the active sites are not sufficiently exposed, so that the catalytic activity thereof cannot be utilized to the maximum extent. Therefore, the development of a simple, efficient and economical method for preparing the FeNi-based LDH material with high catalytic activity and conductivity has important practical significance for realizing large-scale industrial application of electrolyzed water.
Disclosure of Invention
According to one aspect of the application, the invention provides a novel, efficient and economical oxygen evolution electrocatalytic material, and a preparation method and application thereof. The catalytic material can be directly used as a self-supporting electrode for electrocatalytic oxygen evolution reaction, and can ensure the stability of the catalyst material while realizing the high-efficiency electrocatalytic oxygen evolution reaction.
The invention provides an oxygen evolution electrocatalytic material, which comprises FeNiCr-chromium layered double hydroxide (FeNiCr-LDH) and a metal substrate, wherein the FeNiCr-LDH is vertically grown in situ on the surface of the metal substrate, and the metal substrate contains iron element, nickel element and chromium element.
Wherein the metal substrate may be at least one of Stainless Steel (SS) and foamed iron-nickel-chromium (FNC), preferably stainless steel.
Illustratively, the catalytic material comprises a FeNiCr-chromium layered double hydroxide (FeNiCr-LDH) and Stainless Steel (SS), expressed as FeNiCr-LDH-SS, which is grown vertically in situ on the surface of the stainless steel.
Illustratively, the catalytic material comprises FeNiCr-layered double hydroxide (FeNiCr-LDH) and foamed FeNiCr alloy (FNC), represented by FeNiCr-LDH-FNC, which is vertically grown in situ on the surface of the foamed FeNiCr alloy.
According to the technical scheme of the invention, the FeNiCr-LDH forms an ultrathin two-dimensional nanosheet array. Wherein the nanoplatelets have a thickness of 0.5-5nm, such as 1-4nm, further such as 1.3-3 nm; illustratively, the thickness may be 0.8nm, 1.5nm, 1.69nm, 2nm, 2.5 nm.
According to the technical scheme of the invention, the electrocatalytic material has a three-dimensional open porous structure consisting of an ultrathin two-dimensional nanosheet array formed by FeNiCr-LDH.
The second aspect of the present invention provides a method for preparing the oxygen evolution electrocatalytic material, comprising the following steps:
uniformly stirring an organic solvent, an acid solution and 2, 5-dihydroxyterephthalic acid to form a mixed solution, putting a metal containing iron, nickel and chromium as a substrate and a metal source into the mixed solution, and performing hydrothermal reaction to prepare the oxygen evolution electrocatalytic material.
According to the technical scheme of the invention, the acid solution can be selected from a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution, and is preferably a hydrochloric acid solution or a nitric acid solution. Further, the acid solution has a concentration of 0.5 to 5mol/L, such as 1 to 4mol/L, and illustratively, a concentration of 1.5mol/L, 2mol/L, 3 mol/L.
According to the technical scheme of the invention, the organic solvent can be selected from at least one of N, N-dimethylacetamide and N, N-dimethylformamide. Further, the volume ratio of the organic solvent to the acid solution is 1:5 to 5:1, for example 1:3 to 3:1, exemplarily 1: 1.
According to the technical scheme, the mass-to-volume ratio (g/mL) of the metal to the organic solvent is (1-4):30, such as (1.3-3):30, and exemplarily, the mass-to-volume ratio (g/mL) is 1.6: 30. Further, the metal comprises 50-60% of iron element, 8-25% of nickel element and 18-25% of chromium element by mass percentage, and preferably comprises 50-60% of iron element, 8-11% of nickel element and 18-20% of chromium element by mass percentage. For example, the metal may be stainless steel or a foamed iron-nickel-chromium alloy, such as 304 stainless steel. In the method, metal is used as a semi-sacrificial template and used as a metal source and a substrate, and iron, nickel and chromium required by the reaction are all from metal materials.
According to the technical scheme of the invention, the metal can be pretreated before being added into the reaction kettle so as to remove an oxide layer and organic residues on the surface of the metal. Wherein, the operation of the preprocessing can be as follows: the metal is ultrasonically washed by sequentially immersing in an acid (e.g., dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid), ethanol, and water, and then dried.
According to the technical scheme of the invention, in the reaction process, under the etching of an acid solution, Fe ions, Ni ions and Cr ions are dissolved out from the surface of a metal substrate, and at the same time, the FeNiCr-LDH material grows in situ on the metal surface. The added 2, 5-dihydroxyterephthalic acid ligand is used for regulating and controlling the thickness of the FeNiCr-LDH nano-sheet.
According to the technical scheme of the invention, the mass-to-volume ratio (mg/mL) of the 2, 5-dihydroxyterephthalic acid to the organic solvent is (1-10):3, such as (2-7):3, and further such as (3-5):3, and exemplarily, the mass-to-volume ratio (mg/mL) is 4: 3.
According to the technical scheme of the invention, the temperature of the hydrothermal reaction is 50-300 ℃, such as 100-200 ℃, and exemplarily 130 ℃, 150 ℃ and 170 ℃. Further, the hydrothermal reaction time is not more than 48 hours, such as 12 to 30 hours, and illustratively, the time is 15 hours, 18 hours, 24 hours.
According to the technical scheme of the invention, after the hydrothermal reaction is finished, the product is naturally cooled to room temperature, and then the product is washed. For example, the product is washed several times with ethanol and water (such as distilled or deionized water). Further, after completion of washing, the product was dried at 50 to 70 ℃.
According to an embodiment of the present invention, the method for preparing the oxygen evolution electrocatalytic material comprises the following steps:
a) uniformly mixing a hydrochloric acid solution, a 2, 5-dihydroxy terephthalic acid ligand and N, N-dimethylacetamide, adding a pretreated metal material, and placing the metal material in a polytetrafluoroethylene reaction kettle;
b) the reaction kettle is sealed, and is kept at the temperature of 50-300 ℃ for no more than 48 hours to carry out hydrothermal reaction, so that the oxygen evolution electrocatalytic material is obtained after the reaction is finished.
A third aspect of the present invention provides an oxygen evolution electrocatalytic material obtained by the above preparation method.
A fourth aspect of the invention provides the use of the above oxygen evolution electrocatalytic material for electrocatalytic oxygen evolution reactions, preferably as a self-supporting electrode in the reaction.
The invention has the beneficial effects that:
(1) the FeNiCr-LDH grows on the surface of metal (such as stainless steel) in situ, and the FeNiCr-LDH and the metal (such as stainless steel) are in close and firm contact, so that the overall conductivity and stability of the catalyst are enhanced.
(2) The electrocatalytic material provided by the invention has a three-dimensional open porous structure formed by an ultrathin two-dimensional nanosheet array, can expose more catalytic active sites, and is favorable for the permeation of electrolyte to promote the transfer of electrons and mass, thereby accelerating the catalytic reaction kinetics.
(3) The electrocatalytic material provided by the invention can be directly used as a self-supporting electrode for electrocatalytic oxygen evolution reaction, avoids the use of an adhesive, reduces the electrode preparation steps, and is simple, convenient and quick.
(4) The electrocatalytic material provided by the invention can be applied to oxygen evolution reaction under alkaline electrolyte to obviously reduce overpotential, and when the current density is 10 and 100mA cm-2The required overpotential is only 202mV and 242mV, with a smaller Tafel slope.
(5) The electrocatalytic material provided by the invention takes metal (such as stainless steel) as a raw material, adopts a one-step hydrothermal synthesis method, has low cost, simple and convenient operation and excellent performance, and can realize larger current density in the catalysis process, so that the oxygen evolution electrocatalytic material has wide application prospects in the fields of energy conversion, energy storage and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of FeNiCr-LDH powder grown on the surface of stainless steel in example 1.
FIG. 2 is a scanning electron micrograph of FeNiCr-LDH-SS prepared in examples 1 to 4.
FIG. 3 is an atomic force microscope image of FeNiCr-LDH-SS prepared in example 1.
FIG. 4 is an X-ray photoelectron spectrum of FeNiCr-LDH-SS prepared in example 1.
FIG. 5 is a polarization curve obtained by Linear Sweep Voltammetry (LSV) for the products of examples 1-4.
FIG. 6 is a constant current stability test chart of the product of example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The information on the instruments used in the following examples is shown in Table 1, and the information on the reagents used in the examples is shown in Table 2.
TABLE 1 Instrument information Table used in the examples
TABLE 2 information Table of reagents used in examples
Example 1
(1) Pretreatment of the substrate: 0.8g of stainless steel (SS, 304, containing 50-60 wt% of Fe, 8-11 wt% of Ni, 18-20 wt% of Cr, 1000 mesh) having a size of 4cm × 2.5cm was immersed in dilute hydrochloric acid (2.0mol/L HCl), ethanol and distilled water in this order, ultrasonically washed to remove a surface oxide layer and organic residues thereof, and then dried in an oven at 60 ℃.
(2) To a polytetrafluoroethylene reaction vessel (50mL) were added 20.0mg of 2, 5-dihydroxyterephthalic acid, 15mL of hydrochloric acid solution (2.0mol/L) and 15mL of N, N-Dimethylacetamide (DMA) and stirred well to form a mixed solution. And (2) putting the stainless steel sheet pretreated in the step (1) into a reaction kettle to be used as a growth substrate and a metal source. The sealed reaction kettle is placed in an oven to be heated and kept at 150 ℃ for 18 hours. After natural cooling to room temperature, the obtained dark green FeNiCr-LDH-SS was washed several times with ethanol and distilled water and dried at 60 ℃.
Example 2
(1) The pretreatment of the substrate was the same as in step (1) of example 1.
(2) A polytetrafluoroethylene reaction vessel (50mL) was charged with 15mL of a hydrochloric acid solution (2.0mol/L) and 15mL of N, N-Dimethylacetamide (DMA) and stirred well to form a mixed solution. Then the pretreated stainless steel sheet is put into a reaction kettle to be used as a growth substrate and a metal source. The sealed reaction kettle is placed in an oven to be heated and kept at 150 ℃ for 18 hours. After natural cooling to room temperature, the obtained dark green FeNiCr-LDH-SS was washed several times with ethanol and distilled water and dried at 60 ℃.
Example 3
(1) The pretreatment of the substrate was the same as in step (1) of example 1.
(2) 5mg of 2, 5-dihydroxyterephthalic acid, 15mL of a hydrochloric acid solution (2.0mol/L) and 15mL of N, N-Dimethylacetamide (DMA) were added to a polytetrafluoroethylene reaction vessel (50mL) and stirred uniformly to form a mixed solution. Then the pretreated stainless steel sheet is put into a reaction kettle to be used as a growth substrate and a metal source. The sealed reaction kettle is placed in an oven to be heated and kept at 150 ℃ for 18 hours. After natural cooling to room temperature, the obtained dark green FeNiCr-LDH-SS was washed several times with ethanol and distilled water and dried at 60 ℃.
Example 4
(1) The pretreatment of the substrate was the same as in step (1) of example 1.
(2) To a polytetrafluoroethylene reaction vessel (50mL) were added 35mg of 2, 5-dihydroxyterephthalic acid, 15mL of a hydrochloric acid solution (2.0mol/L) and 15mL of N, N-Dimethylacetamide (DMA) and stirred well to form a mixed solution. Then the pretreated stainless steel sheet is put into a reaction kettle to be used as a growth substrate and a metal source. The sealed reaction kettle is placed in an oven to be heated and kept at 150 ℃ for 18 hours. After natural cooling to room temperature, the obtained dark green FeNiCr-LDH-SS was washed several times with ethanol and distilled water and dried at 60 ℃.
Example 5
(1) The pretreatment of the substrate was the same as in step (1) of example 1.
(2) To a polytetrafluoroethylene reaction vessel (50mL) were added 20mg of 2, 5-dihydroxyterephthalic acid, 15mL of nitric acid solution (2.0mol/L) and 15mL of N, N-Dimethylacetamide (DMA) and stirred well to form a mixed solution. Then the pretreated stainless steel sheet is put into a reaction kettle to be used as a growth substrate and a metal source. The sealed reaction kettle is placed in an oven to be heated and kept at 150 ℃ for 18 hours. After natural cooling to room temperature, the obtained dark green FeNiCr-LDH-SS was washed several times with ethanol and distilled water and dried at 60 ℃.
Example 6
(1) Foamed iron-nickel-chromium alloy (abbreviated as FNC, in mass percent: 50% iron, 25% nickel, 25% chromium) was used as a substrate, and the pretreatment of the substrate was the same as in step (1) of example 1.
(2) To a polytetrafluoroethylene reaction vessel (50mL) were added 20.0mg of 2, 5-dihydroxyterephthalic acid, 15mL of hydrochloric acid solution (2.0mol/L) and 15mL of N, N-Dimethylacetamide (DMA) and stirred well to form a mixed solution. And (2) putting the foam iron nickel chromium alloy sheet pretreated in the step (1) into a reaction kettle to be used as a growth substrate and a metal source. The sealed reaction kettle is placed in an oven to be heated and kept at 150 ℃ for 18 hours. After natural cooling to room temperature, the obtained dark green FeNiCr-LDH-FNC ethanol and distilled water were washed several times and dried at 60 ℃.
Structure characterization of the products of examples 1-4
The product obtained in example 1 was subjected to ultrasonic treatment to collect FeNiCr-LDH powder grown on the surface of stainless steel, and X-ray powder diffraction analysis of the FeNiCr-LDH powder was performed, where (a) is a theoretical powder X-ray diffraction pattern of FeNi-based LDH and (b) is an experimentally measured powder X-ray diffraction pattern of the powder of example 1 in fig. 1. As can be seen from the figure, the XRD spectrum obtained by the powder experiment in example 1 is basically consistent with the theoretical spectrum, thereby showing that FeNi-based LDH grows on the surface of the stainless steel in example 1.
FIG. 2 is a scanning electron micrograph of the products of examples 1 to 4. In FIG. 2, (a) is the SEM image of the product of example 2, (b) is the SEM image of the product of example 3, (c) is the SEM image of the product of example 1, and (d) is the SEM image of the product of example 4. As can be clearly seen from the figure, the thickness of the nanosheets formed in (a) to (d) is gradually reduced along with the increase of the adding amount of the ligand 2, 5-dihydroxyterephthalic acid, and the three-dimensional open porous structure can still be maintained on the whole. When the amount of the ligand added is too large as in (d), although the thickness of the nanosheet is further reduced, curling occurs due to the thinness of the nanosheet, so that a three-dimensional open porous structure cannot be formed, thereby affecting catalytic performance. Therefore, the ligand plays a crucial role in forming an open porous structure consisting of an ultrathin two-dimensional nanosheet array. The experimental result shows that the product of the example 1 has the optimal morphology structure and the optimal catalytic performance. As can be seen from the atomic force microscope image of the product in example 1 in FIG. 3, the thickness of the ultrathin nanosheet is only 1.69 nm.
The ultrathin two-dimensional nanosheet and the open porous structure formed by the product in the embodiment 1 can avoid serious aggregation of the catalyst, expose more catalytic active sites, and facilitate permeation of electrolyte to promote electron and mass transfer, so that catalytic reaction kinetics is accelerated.
FIG. 4 is an X-ray photoelectron spectrum of the product of example 1. The presence of Fe, Ni and Cr elements in example 1 was confirmed. Namely, in example 1, the surface of the stainless steel is grown with trimetal FeNiCr-LDH.
(II) electrocatalytic oxygen evolution performance test of the products of examples 1-4
The electro-catalytic oxygen evolution performance test of the embodiment adopts a three-electrode test system, and the above-mentioned embodiments 1E to E4 FeNiCr-LDH-SS made of the product is used as a working electrode, and the electrode area is 1 multiplied by 1cm2The platinum mesh was used as a counter electrode and the silver/silver chloride electrode as a reference electrode. The electrolyte is a 1mol/L KOH solution. The scanning rate at 25 ℃ is 5mV s-1Recording Linear Sweep Voltammetry (LSV) under the conditions of (a) to obtain a polarization curve, as shown in fig. 5, it can be seen that the product of example 1 shows the most excellent catalytic performance at 10mA cm-2And 100mA cm-2The minimum overpotential of (a) is only 201mV and 242 mV. All electrode potential data were 95% iR compensated.
The stability test was carried out on the product of example 1 at 10mA cm-2And 20mA cm-2When the test voltage is maintained for 15 hours under the condition of alternating constant current density, as shown in figure 6, the test voltage does not change obviously in the test process, and the example 1 has higher stability. The test result shows that the catalyst of the example 1 has excellent catalytic performance and high stability, and is one of the oxygen evolution electrocatalysts with the best performance so far.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The preparation method of the oxygen evolution electrocatalytic material is characterized by comprising the following steps of:
uniformly stirring an organic solvent, an acid solution and 2, 5-dihydroxyterephthalic acid to form a mixed solution, putting a metal containing iron, nickel and chromium as a substrate and a metal source into the mixed solution, and preparing the oxygen evolution electrocatalytic material through a hydrothermal reaction;
the prepared oxygen evolution electrocatalytic material contains FeNiCr-chromium layered double hydroxide (FeNiCr-LDH) and a metal substrate, wherein the FeNiCr-LDH vertically grows on the surface of the metal substrate in situ, and the metal substrate contains iron elements, nickel elements and chromium elements.
2. The method for preparing an oxygen evolution electrocatalytic material as set forth in claim 1, wherein the acid solution is selected from a hydrochloric acid solution, a sulfuric acid solution, or a nitric acid solution.
3. The method for preparing an oxygen evolution electrocatalytic material as set forth in claim 2, wherein the concentration of the acid solution is 0.5-5 mol/L.
4. The method for preparing an oxygen evolution electrocatalytic material as set forth in claim 1, wherein the organic solvent is at least one selected from the group consisting of N, N-dimethylacetamide and N, N-dimethylformamide.
5. The method for preparing the oxygen evolution electrocatalytic material as set forth in any one of claims 1 to 4, wherein the volume ratio of the organic solvent to the acid solution is 1:5 to 5: 1.
6. The method for preparing the oxygen evolution electrocatalytic material as set forth in claim 1 or 4, wherein the mass-to-volume ratio of the metal to the organic solvent is (1-4) g:30 mL.
7. The method for preparing the oxygen evolution electrocatalytic material as set forth in claim 1 or 4, wherein the mass-to-volume ratio of the 2, 5-dihydroxyterephthalic acid to the organic solvent is (1-10) mg:3 mL.
8. The method of claim 1, wherein the metal is pretreated to remove oxide layers and organic residues from the metal surface before being added to the reaction vessel.
9. The method for preparing the oxygen evolution electrocatalytic material as set forth in claim 1, wherein the hydrothermal reaction temperature is 50-300 ℃ and the reaction time is not more than 48 hours.
10. The method for preparing the oxygen evolution electrocatalytic material as set forth in claim 1, wherein after the hydrothermal reaction is completed, the product is naturally cooled to room temperature and then washed.
11. The method of claim 1, wherein the metal substrate is at least one of stainless steel and a foamed iron-nickel-chromium alloy.
12. The oxygen evolution electrocatalytic material produced by the method of any one of claims 1 to 11, wherein said FeNiCr-LDH forms an ultra-thin two-dimensional nanosheet array; the electrocatalytic material has a three-dimensional open porous structure consisting of an ultrathin two-dimensional nanosheet array formed from FeNiCr-LDH.
13. The oxygen evolution electrocatalytic material of claim 12, wherein said nanoplatelets have a thickness of 0.5-5 nm.
14. Use of the oxygen evolution electrocatalytic material of claim 12 or 13 for electrocatalytic oxygen evolution reactions.
15. Use according to claim 14, wherein the oxygen electrocatalytic material is used as a self-supporting electrode in electrocatalytic oxygen evolution reactions.
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